Source: http://www.allindianpatents.com/patents/258483-water-absorbing-resin-with-improved-internal-structure-and-manufacturing-method-tehrefor
Timestamp: 2018-06-23 06:08:34
Document Index: 138445147

Matched Legal Cases: ['art 1', 'art 1', 'art 1', 'art 1', 'art 1', 'art 1']

Indian Patents. 258483:WATER ABSORBING RESIN WITH IMPROVED INTERNAL STRUCTURE AND MANUFACTURING METHOD TEHREFOR
WATER ABSORBING RESIN WITH IMPROVED INTERNAL STRUCTURE AND MANUFACTURING METHOD TEHREFOR
According to the present invention, the manufacturing method for the water absorbing resin involves the step of polymerizing a water-soluble unsaturated monomer, 0.06 of 5 mol% of which is composed of an internal crosslinking agent; and the step of drying a water-containing gel which has a thermally decomposing radical initiator content index of 40 to 100 at 100 to 250°C. The water absorbing resin of the present invention contains a water-soluble unsaturated monomer as a repeat unit for a major chain, 90 mol% of the monomer being composed of an acrylic acid and/or salt thereof, the resin having an internal crosslinking structure and exhibiting a weight-average molecular weight Mw of 360, 000 to 1, 000, 000 daltons and an intrinsic viscosity IV of 2.1 to 6.0 dL/g where the weight-average molecular weight Mw and the intrinsic viscosity IV are measured after treatment under set 2 of hydrolysis conditions.
WITH IMPROVED INTERNAL STRUCTURE
AND MANUFACTURING METHOD THEREFOR
The present invention relates in general to water absorbing resins with improved internal structure and manufacturing methods for the resins and in particular to water absorbing resins and water absorbent cores which are suitably applicable to sanitary/bygienic materials for disposable diapers, sanitary napkins, so-called incontinent pads, and similar goods, and also to manufacturing methods for the water absorbing resins,
Water absorbent cores containing hydrophilic fiber, such as pulp, and a water absorbing resin arc widely used conventionally so that sanitary /hygienic materials, such as disposable diapers, sanitary napkins, and incontinent pads, can absorb body fluids. The water absorbent core is used in sanitary/hygienic materials, such as disposable diapers, sanitary napkins, and incontinent pads, to absorb body fluids.
There are recent demands for these sanitary/ hygienic materials to be reduced in thickness for better usability. To this end, water absorbent cores are manufactured with a decreasing ratio of hydrophllic fiber, which has a relatively low bulk density, and an increasing ratio of water absorbing resin, which exhibits excellent water absorption and a relatively high bulk density. The relative quantity of water absorbing resin particles -used in the water absorbent core is hence increased, which in turn reduces the thickness of the sanitary/hygienic materials without compromising water absorbency and other physical properties.
The ratio of the hydrophllic fiber may be decreased* but not further below i minimum quantity required. For further reduction in thickness of the sanitary/hygienic materials, the physical properties of the water absorbing resin need to be improved. Examples of such physical properties of the water absorbing resin include centrifuge retention capacity, saline flow conductivity, absorbency against pressure, fixed height absoibency,, mass-average particle diameter, and extraetable polymer content, The water absorbing resin needs to have these physical properties together in actual use.
These physical properties can be improved by any one of the following four methods: (1) by improving the internal structure of the water absorbing resin, (2) by improving a surface crosslink process, (3) with a liquid permeability
improver or other additive, and (4) through the regulation of particle shape and particle siase distribution.
Taking the first approach among them, the present invention is intended to Improve the internal structure of the water absorbing resin. We have chosen this approach because the improvement of the internal structure is effective not only single handedly, bat it also works symergiatiealiy with the improvement of the surface crosslink process and the use of additives.
Some technologies are documented that are intended to improve the internal structure. For example, patent document 1 discloses a water absorbing resin that has a particular particle &izt distribution, particular CRCs, particular AAPs> and a particular chemical crosslink index (or chemical crosslink index under load}. The document discloses also a manufacturing method in which a particular polymerisation method is used to obtain a water absorbing resin. The resin has a high degree of crosslink, a high retention capacity, and a swelling pressure of gel layer of 35,0 kdyne/cm2 or higher. The resin is processed to exhibit a particular particle size distribution (Particles ranging from 106 urn, inclusive, to 850 urn, exclusive, account for 95 wt% or more of the entire resin content. The particle size distribution has a logarithmic standard deviation of of 0.25 to 0.45). After that, the resin is subjected to surface crossiinking, and mixed with a liquid
permeability improver. The technology improves, gel strength toy relatively increasing chemical cros&linking points.
Patent document 2 discloses a method in which alkali metal silicate is added hefore water-containing gci is dried.
Patent document 3 discloses a method in which two kinds of 2 crosslinking agents are used together.
Patent document 4 discloses a superabsorbent cro&slinked polymer material for aqueous liquids which contains a partially neutralised, monocthylcnic, unsaturated, acid group-containing monomer, any other monomer copoiymerizable with said monomer, and any polymer suited for use as a graft base.
Techniques- that are similar to the present invention, but have a different objective are those involving mixing a polymerized water-containing gel with an. additive, such as a persulfate. The techniques are intended to lower residual monomers in water absorbing resins and therefore based on a different technical concept from the present invention. The techniques indeed achieve reduction of the residual monomers, ' but fall short of improving the internal structure of the water absorbing resins due to the quantities of the additives being different and for other reasons. An example of such techniques is the method disclosed in patent document 5, According to the method, a water-containing gel is mixed with fine particles of a water absorbing resin as well as with a
polymerisation initiator or a reduction agent Another example in disclosed, in patent document 6. According to the method, a water-containing gel is upon comminution misted with fine particles of a water absorbing resin as well as with a polymerization initiator, such as a peraulfate, A further example is disclosed in patent document 7. According to the method, a water-containing gel m mixed with a persulfate. Another example i* disclosed in patent document 8 whereby fine particles arc upon agglomeration arc mixed with a per sulfate.
[Patent Document 11 International Application Published
under PCT WO20Q5/279S6
[Patent Document 2j European Patent 1137678B1
(Patent Document 3] Specification of U.S. Published Patent
Application 2004/0014901
{Patent Document 4] International Application Published
under PCT WO97/019116
[Patent Document 5] Japanese Unexamined Patent Publication
05-43610/1993 (Tokukaihei 05-43610}
IPateat Document 6] Japanese Unexamined Patent Publication
(Tokukai) 2001-79829
[Patent Document 7] European Patent 1358224B1
(Patent Document 8] European Patent 16&08S7A '
The above-mentioned conventional techniques have a problem that they cannot deliver a water absorbing resin with necessary physical properties.
Specifically, water absorbing resin is required to exhibit good physical properties (centrifuge retention capacity, saline flow conductivity, absorbency against pressure, fixed height absorbency, mass-average particle diameter, liquid diffuaibility, etc.) in the actual use of the water absorbing resin. Conventional technology has so far failed to achieve sufficient values with these physical properties. One factor in the failure is the trade-off between centrifuge retention capacity and saline flow conductivity, both of which are important physical properties for water absorbing resin: if either of the physical properties improves, the other suffers. It is difficult to achieve good values with both of the physical properties.
In. addition, although the physical properties of the water absorbing resin improve through polymerization using an additive or by changing internal crosslinking agents, it is a different story whether these approaches would optimize the structure of the water absorbing resin in the first place, It is only through the optimal water absorbing resin structure that one can achieve fund amen tally improved physical properties and expect synergistic effects in combinations with
The present inveattoti, conceived in view- of these conventional issues, has an objective of improving the internal structure of the water absorbing resin and hence fundamentally improving its performance, to provide a water absorbing resin which e&ttibite high levels of multiple physical properties and a method of manufacturing such a water absorbing resin. Another objective of the present invention is to provide a water absorbent core with an excellent liquid acquisition rate per unit Lime,
The method of manufacturing a water absorbing resin of the present invention, to address the issues, is a method of manufacturing a water absorbing resin obtained by-polymerization of a water-soluble unsaturated monomer, the resin having an internal erosslinking structure, the method involving the steps of:
polymerizing a water-soluble unsaturated monomer; and
drying at 100 to 2SQ°C a water-containing gel which, has a thermally decomposing radical initiator content index of 40 to 100, the index being given by;
Thermally Decomposing Radical Initiator Content Index - {Ci/Mi)/(Cm/Mm) « 10* where:
Ci is the quantity in mass % of a thermally decomposing radical initiator extracted by stirring the water-containing gel
in a 5% aqueous solution of sodium chloride for 1 hour
Immediately prior to the drying step;
Mi is the mole-average molecular weight in mol/g of the extracted thermally decomposing radical initiator;
Cm is the solid content in mass % of the water-containing gel obtained by drying the water-containing gel at I80°C for 8 hours; and
Mm is the mole-average molecular weight in mol/g of a polymerized monomer.
The above regulation of the thermally decomposing radical initiator content index for the water-containing gel so that it falls within the specified range, and the drying at particular temperatures improve the internal structure of the water absorbing resin. The internal structure of the water absorbing resin is improved presumably because the thermally decomposing radical initiator contained in a particular quantity in the gel upon drying reacts with polymer chains in the water absorbing resin. The improved internal structure in turn improves gel strength and the physical properties listed above.
In addition, the method of manufacturing a water absorbing resin of the present invention is preferably such that the water-soluble unsaturated monomer contains an internal crogtslinking agent in an amount of 0.06 to 5 mol%„
The use of a crosslinking agent in polymerization within
a particular range of quantity and the drying at a particular range of temperatures of a water-containing gel which has a thermally decomposing radical initiator content index in the above range Improves the internal structure of the water absorbing resin. The internal structure of the water absorbing resin is improved presumably because the thermally decomposing radical initiator contained in a particular quantity in the gel upon drying reacts with polymer chains in the water absorbing resin. The improved internal structure in turn improves gel strength and the physical properties listed above.
The water absorbing resin of the present invention, to address the issue®, is a water absorbing resin obtained by polymerisation of a water-soluble unsaturated monomer, the resin having an internal crosslinking structure and exhibiting an intrinsic viscosity IV of 7,3 dL/g or lower at such a weight-average molecular weight Mw that Log (Mw) = 6.10, where the weight-average molecular weight Mw and the intrinsic viscosity IV are measured after 50 mg of the water absorbing resin is left in 10 grams of a 0.1 mol/L aqueous solution of sodium hydroxide at 80°C for 3 weeks.
A water absorbing resin with improved internal structure characteristically shows a reduced intrinsic viscosity in a particular range of molecular weight when the resin is decomposed into a polymer in the aqueous solution. This is
presumably because the thermally decomposing radical initiator contained in. a particular quantity in the gel upon drying reacts with polymer chains in the water absorbing resin, thereby improving the internal structure of the water absorbing renin* The improved internal structure in turn reduces the intrinsic viscosity in a particular range of molecular weight. This characteristic of the water absorbing resin imparts excellent gel strength and the physical properties listed above to the water absorbing resin.
The water absorbing resin of the present invention* to address the issues, is a water absorbing resin containing a water-soluble unsaturated monomer as a repeat unit for a major chain, 90 mol% of the monomer being composed of an acrylic acid and/or salt thereof, the resin having an internal crosslinking structure and exhibiting a weight-average molecular weight Mw of 360,000 to 1,000,000 daltons and an intrinsic viscosity IV of 2.1 to 6,0 dL/g where the weight-average molecular weight Mw and the intrinsic viscosity IV are measured after treatment under set 2 of hydrolysis conditions, in which treatment 20 mg of the water absorbing resin is left in 10 grams of a 0.1 mol/L aqueous solution of sodium hydroxide at 80aC for 3 weeks,
h water absorbing resin with a further improved internal structure is obtainable by setting the weight-average molecular weight Mw and the intrinsic viscosity IV after the
treatment under set 2 of hydrolysis condition® to the specified range®.
The present invention provides a water absorbing resin with improved internal structure and a manufacturing method therefor, In addition, preferably,, the present invention provides a water absorbing resin that ham an excellent centrifuge retention capacity CRC, which indicates the amount of absorption by the water absorbing rosin, and/or an excellent saline flow conductivity (SPC), which indicates liquid permeability. Thus, there are provided a water absorbing resin and a manufacturing method therefor which boasts an excellent liquid acquisition rate per unit time of the water absorbent core. In addition, preferably, the present indention provides a water absorbing resin that ha® an excellent absorbeocy against pressure of 4,83 kPa [MP). Thus, there are provided a water absorbing resin and a manufacturing method therefor with low liquid seeping, or "rewetting," when the water absorbent core is placed under pressure.
In addition, the present invention provides a water absorbing resin that exhibits an excellent liquid acquisition rate per unit time when used in a water absorbent core. In addition, the present invention provides a water absorbing resin that has a large weight-average molecular weight Mw after hydrolysis and thereby Is capable of preserving high
water absorption capability in some hydrolysis in actual uae.
Figure 1 is a schematic illustration of an Apparatus for measuring SFC in accordance with the present example of the invention.
Figure 2 is a CRC-SFC plot for water absorbing resins obtained in the present examples of the invention and for comparative water absorbing resins obtained in comparative examples.
Figure 3 is a schematic illustration of a measurement apparatus used to measure AAP,
31	Tank
32	Glass Tube
33- 0,69 Mass % Saline
34	Valved "1/ tube
35	Valve
40	Container
41	Cell
42	Stainless Steel Net
43	Stainless Steel Net
44	Swollen Gel
45	Glass Filter
46	Piston
47	Piston Hole
48	Collector
49	Balance
The following will describe the present invention in
detail. The scope of the present invention U however not limited by the description, Apart from the examples given below, the invention may be modified in other ways for implementation without departing from the spirit of the invention. Note that in the present invention, "weight* and "mass* arc synonyms of "wt%" and "mass %" respectively. Throughout the specification and claims, only 'mass" and "mass %" are- used.
Abbreviations which will be used in the following description are defined first.
CRC is an acronym of "centrifuge retention capacity.* SFC is an acronym of "saline flow conductivity,*" AAP refers to absorbency against a pressure of 4.83 kPa, FHA is an acronym of "fixed height absorbency,* LDV is an acronym of 'liquid distribution velocity." D50 {distribution) refers to a mass-average particle diameter, og is the logarithmic standard
deviation of a particle sise distribution. Saline is an aqueous solution of sodium chloride (0.9% to 0,6$%). 1 ppm is equal to 0.0001 iaaB»%.
An embodiment of the present invention i® now
The water absorbing resin of the present invention is a water absorbing resin, with art internal crosslink!tig structure, obtained by polymerization of a water-soluble unsaturated monomer (hereinafter, may be referred to simply as a "monomer*). The water absorbing resin used in the present embodiment is a water-insoluble, water-swelling, hydrogcl- forming polymer obtained by polymerization of a water-soluble unsaturated monomer (hereinafter, may be referred to as a "water absorbing resin"). In the present invention, a compound containing,, as the primary component, 50 to 100 wt%, preferably 70 to 100%, especially preferably 90 to 100% pf a water absorbing resin is also referred to as a water absorbing resin even if the compound contains a small quantity of additives or third components, provided that the additives or third components art part of resin particles, "Water insoluble" means that the cxtract&ble polymer content (hereinafter, may be referred to as the "water-soluble components"), or the water-soluble polymer, accounts for at
least 0 to 50% or less, preferably 25% or Ices, especially preferably 15% or less.
The "extractable polymer content" refers to the content, of the water absorbing renin, which is soluble in water. The content may be quantified, for example, by the methods outlined later wader the heading "Extr&ctable polymer content (Water-soluble Components)."
The content, of the water absorbing resin, which is soluble in water (saline water, preferably 0,9 mass % saline water) is, for example, a polymer content which extracts from water absorbing resin in water over 16 hours of stirring.
Concrete examples of the water-intoluble, water-swelling, hydragei»formi»g polymer include partially neutralised, croaalitLked polyacrylic acid polymers (Specification of U.S. Patent 4,625,001, Specification of U.S. Patent 4,654,039, Specification of U.S. Patent 5,250,640, Specification of U.S. Patent 5,275,773, Specification of European Patent 456136, etc.}; a partially neutralized, crosslinked starch-acrylic acid graft polymer (Specification of U.S. Patent 4,076,663); an isobutylene-maleic acid copolymer {Specification of U.S. Patent 4,389,513); a saponification product of a vinyl acetate-acrylic acid copolymer (Specification of U.S. Patent 4,124*74®}; a bydrolyaate of an acrylaniide (co)polymer (Specification of U.S, Patent 3,959,569); and a hydrolysate of an acrylonitrile polymer (Specification of U.S. Patent
3,935,099).
The water absorbing resin of the present embodiment ia
preferably a -water absorbing resin containing a polyacrylic acid/polyacrylatc-based crosslinked polymer obtained by polymerization of a monomer containing an acrylic acid and/or salt thereof. In the present embodiment, the polyaerylie acid/polyacryiate-based crosslinked polymer refers to the crosslinked polymer obtained by polymerization of a monomer containing an acrylic acid and/or salt thereof in at least 50 mol%, preferably at least 70 mol%» more preferably at least 90 mot%.
Acid groups in the crosslinked polymer are neutralized in a ratio preferably from 50 mol% to 90 mol% inclusive, more preferably from 60 mol% to 80 mol% inclusive. The polyacryl&te may be, for example, an alkali metal salt, such as sodium, potassium, or lithium; an ammonium salt; or an amine salt. A preferred example is a sodium salt. The neutralization in which salt is formed may be carried out before the polymerisation, that is, in the form of monomer, or during or after the polymerization, that is, in the form of polymer. Alternatively, any of the methods may be used together.
The polyacrylic acid/polyacrylate-based crosslinked polymer that is suited for use as the water absorbing resin of the present embodiment may be prepared by copolymcrising
another monomer, if necessary, in addition to the primary
component monomer (acrylic acid and/or salt thereof}.
Concrete examples of the other monomer include unsaturated
anionic monomers, such as methacryliei acid, maleie acid,
vinyl	sulfonic	acid,	styrcne	sulfonic	acid,
2-(methjacrylamide-2-methylpropanesulfonic	acid,
2~(meth)acryloylethancsulfonic	acid,	and
2-(meth)acryloylpropan«8ulfanic acid, and salts thereof;
non-ionic hydrophilic group-containing unsaturated
monomers, such as acrylamide, methacrylamide,
N~ethyl(meth)acry!amidc,	N-n-.propy](meth)acrylamide,
N-iftopropyUmcthJacrylamide, N.K-dimethylCmeihJaerylamidc,
2-hydroxyethyl(meth)acrylate, a-hydroxypropyl^methjacrylate,
roethoxypolyethylene glycol (methfacrylate, polyethylene glycol
mo»o{meth}acrylate,	vinylpyridine,	N-vinylpyrrolidonc,
N-acryloyl piperidine, N-aeryioyl pyrrolidine, and
N-vinylacetoamide; and unsaturated cationic monomers f such
as	N,N-dimethylaminoethyl{incth)acrylate,
NjN-diethylaminoethyHmethlacrylatc, N,N-dimcthy!aminopropyI(mcth)acrylate,
N,N-dimethylajninopropyl(meth|acrylaxmde, and quaternary &alt$ thereof. The monomers, other than the acrylic acid and/or salt thereof, may be used in an amount of preferably 0 mo!% to 30 mol% inclusive, more preferably 0 mol% to 10 moI% inclusive, to the total amount of the monomers.
The water absorbing resin used in the present embodiment is a crosslinleed polymer with an internal crosslinking structure. The internal crosslinking structure may be introduced to the water absorbing resin* for example, through self-crosslinking using no crosslinking agent or by copolymerizing or reacting an internal crosslinking agent containing two or more unsaturated polymerizing groups and/or two or more reactive groups per resin, molecule (the copolymerization or reaction of an internal crosslinking agent is preferred}.
Concrete examples of the internal crosslinking agent-
include polyhydric alcohols, such as N,N"-methylene
bistmethjacrylamide, (poly)ethyleoe glycol di(racth)acrylate,
(poly) propylene glycol di{meth)acryl&te, trimethylolpropane
tri(meth)acrylate,	trimethylolpropane di(meth)acrylatc,
glycerine tri(raeth)acrylater glycerine aerylatc meth aery late,
ethylene oxide denatured trimethylolpropane tri(meth)acrylate,
pentaerythritol	tetra(mcth)acrylatef	dipentaerythritol
hcxa(metfa)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, t rial ly lam ine, poly(rneth)allyloxyalkanea, (poly)ethylene glycol diglycidyl ether, glycerol diglycidyl ether, ethylene glycol, polyethylene glycol, 1,4-butanediol, propylene glycol, glycerine, and pentaerythritol; ethylenediaroinc; polyethyleneiminci and glycidyl(meth)acrylate.
Any one of the internal crosslinking agents may be used
alone; alternatively two or more of them may be used. In view of the water absorption property of the obtained water absorbing resin and other factor®, a preferred internal crosslinking agent has two or more unsaturated polymerizing groups; a more preferred one has a total of two or more (meth)acrylate groups, aliyl group**, or {methjacrylamide groups; and a still more preferred one has (meth)acrylate groups. The cross-linking agent is preferably soluble in water (solubility is 0.1 g or higher, preferably 1 g or higher; per 100 g of water at 25'aC). Furthermore, the cross linking agent includes EO structure units, especially, 2-100 EO ^ethylene oxide) units.
In the present invention, the internal croaglinking agent is used in an amount of 0,06 to S moi% relative to the entire monomer content before the polymerization step to improve the internal structure of the water absorbing resin. If less than or equal to 0.06 mol% is used, a large amount of uncrosslinked polymer occurs when a thermally decomposing radical initiator reacts during drying. That may cause increase in the extractable polymer content, which in turn reduces gel strength. Preferably, the amount of the internal erosslinking agent used is from 0.07 to 3 tnol%, more preferably from 0.08 to 1 mol%, and most preferably from 0.09 to 0,5 mol%.
In the polymerization step, a hydrophilic polymer, such
as starch-cellulose, a derivative of starch-cellulose, polyvinyl alcohol, polyacrylie acid (salt), or a crosslinked polymer of polyacrylie acid {salt}, may be added in, for example, 0 to 30 wt% (relative to the monomer). Also in the polymerization, a chain transfer agent, ®-uch as hypophosphorous acid (salt), may be added in, for example, 0 to I vrt% (relative to the monomer),
The monomer containing the above-mentioned acrylic acid and/or salt thereof as the primary companen.t{8) can be polymerized in the polymerization step by bulk polymerization* reverse suspension polymerization, or precipitation polymerisation* Nevertheless, solution polymerization, using the monomer dissolved or dispersed in water, is preferred in view of performance and eaae in controlling the polymerization. These polymerizations are described in, for example, the Specification of U.S. Patent 4,625,001, the Specification of U.S. Patent 4,769,427, the Specification of U.S. Patent 4,873,299, the Specification of U.S. Patent 4,093,776, the Specification of U.S. Patent 4,367,323, the Specification of U.S. Patent 4,446,261, the Specification of U.S. Patent 4,683,274, the Specification of U.S. Patent 4,690,996, the Specification of U.S. Patent 4,721,647, the Specification of U.S. Patent 4,738,867, the Specification of U.S. Patent 4,748,076., and the Specification of U.S. Published Patent Application 2002/4009S.
In the polymerization, step, a radical polymerization initiator, such as potassium persulfate, ammonium per sulfate, sodium persulfate, t-butylhydrepercxide, hydrogen peroxide, or 2,2'-a2ob£&(2-amidina propane} dihydrochloride, or an activation energy beam, such as an ultraviolet or electron beam, may be used.
In the case of using the radical polymerisation initiator, rcdoK polymerization may be carried out by using in combination with a reduction agent, such as sodium sulfite, sodium hydrogen, sulfite, ferrous sulfate, or L-ascorbic acid. Preferably, however, a thermally decomposing, water-soluble radical polymerization initiator {solubility is 1 g or higher, preferably 10 g or higher, per 100 g of water at 25BCK chosen from azo compounds and peroxides, i$ used.
The radical initiator is preferably added to a reaction system for the polymerisation step, The "reaction system for the polymerisation step" refers to a reaction system, capable of producing a water-containing gel,, in which the water-soluble unsaturated monomer could be polymerized. Therefore, the reaction system for the polymerization step is not limited in any particular manner so long as it includes a water-soluble unsaturated monomer, The system may include an internal crosslinking agent, a chain transfer agent, or a a-hydroxy carboxylie acid fsalt), to name a few examples.
The radical polymerisation initiator may be added before
and/or during the polymerization step, not after the polymerization step.
Throughout this specification, "before the polymerization step" refer® to the time before the water-soluble unsaturated monomer starts polymerization, "During the polymerization step* refers to the period from the time when the water-soluble unsaturated monomer starts polymerisation to the time when the polymerization terminates, "After the polymerisation step* refers to the time after the polymerization of the water-soluble unsaturated monomer terminates,
Whether or not the water-soluble unsaturated monomer has started polymerization is determined through a rise in temperature of the produced polymer. Specifically, it is determined that the water-soluble unsaturated monomer has started polymerisation when the rise in temperature has reached 3aC (preferably 5BC).
Whether or not the polymerization of the water-soluble unsaturated monomer has terminated is determined according to whether the rise in temperature in polymerization h has not reached a peak and whether the remaining monomer has or ha® not reduced to 5 mass % or less.
The addition of the radical polymerization initiator to the reaction system for the polymerisation step before the polymerization step and /or during the polymerization step
causes a particular amount of the radical initiator to remain inside the water-containing geL In addition,, when the water-containing gel is dried, the particular amount of the radical initiator works on polymer chains in the water absorbing resin, thereby improving the internal structure of the water aba orbing ressiru
The radical polymerization initiator (especially,, the thermally decomposing radical initiator) is uaed preferably in 0,051 to 1.000 mol% or less, more preferably in 0,054 to 0.2000 mol%f and most preferably in 0,058 to 0,1000 mol%, relative to the entire monomer content.
The polymerization is preferably performed in the presence of an a-hydroxy carboxylic acid (salt) in the present indention, which prevents the water absorbing resin from being colored- The hydroxy carboxylic acid is a carboxylic acid containing a hydroxy! group in a molecule, Examples of such acids include lactic acid, glycolic acid, malic acid, glyceric acid, tartaric acid, citric acid, isocitric add* salicylic acid, mandellc acid, gallic acid, mevalonic acid, quinic acid, sbikimic acid, and ji-hydroxy propionic acid.
Among the compounds, the a-hydr©xy carboxylic acid, usied in the present invention, refers to the e&rboxylic acid in which a hydroxy! group is bonded to the carbon at an a site in a molecule. The acid is preferably a non-polymer a-hydroxy carboxylic acid and has a weight-average molecular weight of
40 to 2000, more preferably 60 to 1000, and still more preferably J 00 to 500. Also, the acid is preferably water-nolubie. Examples of the a-hydroxy carboxyllc acid include lactic acid tsaltj, citric acid (salt), malic acid (salt), isocitric acid {salt), glyceric acid (salt), and polya-hydroxy acrylic acid (salt). Thotc a-hydroxy carboxyllc acids which are especially preferred among them are lactic acid and a-hydroxy polycarboxylic acids which contain two or more carboxyi groups, preferably 2 to 10, more preferably, 2 to 6, even more preferably 2 to 4, in a single molecule. Malic acid (salt) and citric acid (salt) arc most preferably used in view of water absorption and improvement in the coloring problem,
If the a-hydroxy carboxyllc acid is a salt in the present invention, the acid is preferably a monovalent salt of an alkali metal, such as lithium, potassium, and sodium, ammonia, or amine in view of solubility water, If the a-hydroxy polycarboxylic acid is used as a salt, either all or some of the carboxyl groups may be turned into salt.
The a-hydroxy carboxylic acid, preferably the a-hydroxy polycarboxylic acid, used in the present invention may be used normally in an amount of 0.01 to 10 mass %t preferably 0,05 to 5 mass %, more preferably 0,1 to 3 mass %t and most preferably 0.2 to 3 mass % relative to the water-soluble unsaturated monomer or the associated polymer, in view of water absorption and coloring prevention,
In the present invention, it takes preferably 20 minutes, or less, more preferably 15 miniates or less, for the polymer temperature to reach a maximum since the start of the polymerization (determined in terms of temperature rises, viscosity rises, and whitening).. Through these time range settings, the resultant thermally decomposing radical initiator content index readily falls in a preferred range.
In the present invention, the thermally decomposing radical initiator content index can be made to fall in the preferred range by adjusting, to a given value, the time taken by the polymer to become dried after its temperature has reached the maximum. The atmospheric temperature during that period of time is also adjustable to a given value to make the thermally decomposing radical initiator content index fall into the preferred range.
Water-containing Gel
In the present Invention, the thermally decomposing radical initiator content indess is regulated to 40 to 100, The index is given by the equation below from *Ci/ 'Mi,8 "Cm," and "Mm," Ci is the quantity in mass % of a thermally decomposing radical initiator extracted by stirring a water-containing gel in a 5% aqueous solution of sodium chloride for 1 hour immediately prior to the drying step. Mi is the mole-average molecular weight in mol/g of the extracted
thermally decomposing radical initiator, Cm is the solid content in mas® % of the water-containing gel obtained by drying the water-containing gel at 180*0 for 8 hours. Mm is the mole-average molecular weight in mol/g of a polymerized monomer. The thermally decomposing radical initiator content Index is preferably from 41 to 80 s and most preferably from 42 to 80.
Thermally Decomposing Radical Initiator Content Index - (Ci/Mi)/(Cm/Mm) * 10s5 where:
Ci is the quantity in mass % of a thermally decomposing radical initiator extracted by stirring a water-containing gel in a 5% aqueous solution of sodium chloride for 1 hour immediately prior to the drying step;
Cm is the «olid content in mass % of the water-coataining gel obtained by drying the water-containing gel at 180°C for 8 hours; and
We have found that the above regulation of the thermally decomposing radical initiator content index for the water-containing gel so that it falls within the specified range, and the drying at particular temperatures improve the
mcernai structure oi tne water absorbing resin, thereby greatly improving various physical properties, which has led to the completion of the invention. If the index is less than 40, the internal polymer chain of the water absorbing resin may experience little change, possibly failing to achieve sufficient improvement effects. That raises possibility that the physical properties may not be improved. If the indess is greater than 100, the internal polymer chain of the water absorbing resin may go under excess change and suffer damage. That can increase the extraetable polymer content, possibly failing to achieve improvement in the physical properties. The thermally decomposing radical initiator is preferably the above-mentioned radical initiator* most preferably a persulfate.
When samples are prepared of the water-containing gel immediately prior to the drying step, if necessary, the particle diameter should be adjusted to 5 mm,, preferably to shorter than or equal to 3 mm, and the samples then be immediately placed in an atmosphere at -25°G for rapid cooling before the measurement of the numeric values. These precautions prevents decomposition of the thermally decomposing radical initiator.
The water absorbing resin of the present invention changes its* solubility during the course of the 'treatment by preferably 10 to 100 wt%, more preferably 30 to 95 wt%, and
even more preferably 50 to 90 wt%. The solubility after the
treatment is preferably SO to 100 wt%, more preferably 70 to 100 wt%» and even more preferably 90 to 1Q0 wt%.
After the polymerization according to the present invention, the water-containing gel before the drying contains preferably 10 mass % or leas, more preferably 7 mass % or less, and most preferably 5 mass % less unreacted monomer. Accordingly, the improvement of the internal structure of the water absorbing resin,, which occurs during the drying,, is presumably less likely to be disrupted by the unreacted monomer. The ratio of the unreacted monomer does not need to be lowered further than about 0.01%* or more preferably 0.1%.
After the polymerization according to the present invention, the solid content {measured by the method which will be detailed later) in. the water-containing gel before the drying is preferably 10 to 80 mass %, more preferably 20 to 70 mass %, and most preferably 30 to 60 mass %, After the polymerization according to the present invention, the water-*containing gel before the drying preferably contains the aboYc-mentioned a-hydroxy c&rboxylic acid (salt),
In the	where the crosslinked polymer is obtained by
solution polymerisation and. is in the form of gel, in other
words, where the crosalinked polymer is a cros Blinked
polymer in the farm of a water- con tain in g gel (hereinafter may¬be referred to simply as "water-containing gel"}, the crosslinked polymer is dried and usually pulverized /crushed
before and/or after the drying, to produce the water absorbing resin. In the present invention, drying is an operation of increasing the solid content of a get-like substance until it becomes like powder* Typically, the content is increased up to 90% or higher, preferably 93%' or even higher, more preferably 95% or higher. There is no need to exceed about 99%. The drying may be performed simultaneously with the polymerization. Preferably* however, there is provided a drying step {drying device) after the polymerization.
In the present invention, the drying is performed at 100°C to 2$0°C at 50% or more, especially, substantially all. At temperatures below 10O*C, the internal polymer chain of the water absorbing resin may experience little change, possibly failing to achieve sufficient improvement effects. That raises possibility that the physical properties may not be improved. At temperatures above 2S0"C» the water absorbing resin may suffer damage. That can increase the extractable polymer content, possibly failing to achieve improvement in the physical properties. The drying temperature is specified in terms of the temperature of a heat medium. If the drying
temperature cannot be specified in terms of heat medium temperature as in the case of microwave drying, the drying temperature is specified in terms of material temperature, There is no particularly preferred drying method, so long as the parameters fall in the above-mentioned ranges. Possible examples would be windless drying, depre&surized drying, infrared drying> and microwave drying, Hot wind drying is preferred. The dry air flow rate is preferably from 0.01 to 10 m/scc, more preferably from 0.1 to 5 m/sec.
the drying temperature in more preferably from 130°C to 220°C> most preferably from ISO^C to 20QeC. The temperature may be either constant or varied. In any case, almost all the drying «tep{s) should be preferably performed at the above-mentioned temperature.
The drying time,, ■which may vary depending on the surface area of the polymer, water content, and the type of drier, is determined to achieve the target water content. The drying time is preferably 10 to 120 minutes, more preferably 20 to 90 minutes, most preferably 30 to 60 minutes. With a drying time shorter than 10 minutes, the internal polymer chain of the water absorbing rciin may experience little change, possibly failing to achieve sufficient improvement effects. That raise® possibility that the physical properties may not be improved, With a drying time in excess of 120 minutes, the water absorbing resin may suffer damage. That
can increase the extractable polymer content* possibly failing to achieve improvement in the physical properties.
In the present invention, the solid content (measured by the method which will be detailed later) in the water absorbing resin after the drying is preferably 90 mass % or higher, most preferably 95 mass % or higher. If the solid content £s low, fluidity falls, causing difficulty in manufacturing: the water absorbing resin may not be pulvcrizable, or a particular particle size distribution may not be achievable. In addition, the internal polymer chain of the water absorbing resin may experience little change, possibly failing to achieve sufficient improvement.
Pulverization & Classification
The dried substance obtained according to the above-mentioned method of manufacturing a water absorbing resin, is pulverised in a pulverizer. The pulveriser is not limited in any particular manner. Examples include a roll-using pulverizer like a roll mill; a hammer-using pulverizer like a hammer mill; an impact applying pulverizer, a cutter mill, a turbo grinder, a ball mill, and a flush mill. Among them, the roll mill is preferred for the control of a particle smc distribution- The pulverization may be performed successively twice or more times (preferably three or more times) for the control of a particle size distribution* If the
pulveriss&tion is performed twice or more, the same pulveriser or different pulverisers may be used. Different types of pulverizers may also be used in any combination.
The pulverized water absorbing resin may be subjected to classification using sieves with particular mesh, sizes to give the ream a particular particle size distribution. The classifier is not limited in any particular manner. Examples include a vibration sieve (unbalance weight drive type, resonance type, vibration motor type, electromagnetic type, . disc vibration type, etc.), an in-plane motion sieve {horizontal motion type, horizontal circular-straight line motion type, three-dimensional circular motion type, etc.J, a movable net type sieve, a forced stirring type sieve, a net surface vibration type sieve, a wind force sieve» and a sonic wave sieve. The vibration sieve and the in-plane motion sieve are preferred. The mesh is preferably from 1000 urn to 300 um, more preferably from 900 um to 400 pm, and most preferably from 710 urn to 450 pun. If the mesh is out ©f these ranges, the target particle mzc distribution may be unobtainable.
For the purpose of giving the resin a particular particle size distribution, the water absorbing resin of the present invention may be subjected to further classification to remove some or all of the particles smaller than a particular diameter. The classifier is not limited in any particular manner in the current step. Preferable example* include fine particle
classification devices (centrifugal force types, inertia force types, etc.), as well as those listed above. The current step removes some or all of the particles with diameters of preferably 200 pm or less, more preferably 150 pm or less, and most preferably 106 ytm or less.
The water absorbing resin obtained by the polymerisation explained above is typically granulated particles or primary particles (single particles) of which the shape w, for instance, Irregularly pulverized, spherical, fibrous, virgate, substantially spherical, or flat. It is preferred if the resin, has an irregularly pulverised shape because the • resin can be readily fixed when, for example, used in a water absorbent core.
Surface Crosslinking
The water absorbing resin according to the present embodiment preferably has its surface and nearby regions crossKnked by an organic surface crosslinking agent and/or a water-soluble inorganic surface crosslinking agent. In other words, the method of manufacturing a water absorbing resin according to the present invention preferably involves a step of surface crosalinking the dried water absorbing resin,
Having its surface and nearby regions erosslinked by the surface erosslinking agent, the water absorbing resin causes less liquid seeping when swollen and placed under pressure.
The resin hence shows greater AAP and SFC values. As a result, the water absorbing resin, when used in a water absorbent core, causes low liquid seeping, or "rcwetting," under pressure and provides a water absorbent core with an excellent liquid acquisition rate per unit time.
Examples of the surface crosslinking agent that can be used in the surface crosslinking Include organic surface crosslinking agents and /or water-soluble inorganic surface crosslinking agents with two or more functional groups which can react with the functional groups, especially, earboxyl groups, of the water absorbing resin. Water-soluble organic surface crosslinking agents arc preferred.
Examples include polyhydrie alcohols, such as ethylene
glycol, diethylene glycol, propylene glycol, triethylene glycol,
tetraethylene glycol, polyethylene glycol, 1,3-propanediol,
dipropylene	glycol,	2,2,4-trUnethyl-l>3-pentanedie»l,
polypropylene	glycol,	glycerine,	polyglycerine,
2-butene-l14-diol,	l,3-butaned*ol,	1,4-butanediol*
l,5«peatanediol, 1,6-hestanediol, l,2-cycloh«attc dimethanol, l,2-cyc1oh«anol, trimethylolpropane, diethanol amine, tricthanol amine, polyoxypropylene, OKyethylene-osEy propylene block copolymer, pentacrythritol, and sorbitol; epoxy compounds, such as ethylene glycol diglyeidyl ether, polyethylene glycol diglyeidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polygiycidyl ether,
propylene glycol diglycidyl ether, polypropylene glycol
diglycidyl ether, and glycidol; polyvalent amine compound*,
such	as	ethylen.ediam.itte,	diethylenetriawtoe,
triethylenetetraimne,	tetraethylencpeatantine,
pentaethylenchcxaminc, and polyethylcneiminc, and their
inorganic and organic salts (for example,, azetidiiiium salts J;
polyvalent	iaocyanate	compound®,	such	as
2t4-tolyIenediisocyanate and hex&methylenediisocyanate;
polyvalent	oxazoline	compounds,	such	as
1,2-ethylenebisoxazolinc; derivatives of carbonic acids, such
as urea, thiourea, guanidine, dicyandiamide, and
2-o^aa;oiidinon.e; alleylene carbonate compounds, such as
l,3-dioxoIanc-2-onc»	4-mcthyl-l»3-dioxolane-2~one,
4,5-dimethyl-1,3-diojcoiane-2»one, 4,4 -dimethyl-1,3-dioxolane-2»one,
4-ethyl-1,3-dioxolane-2-one,	4-hydroxy
methyl-1,3-dioxolanc-S-one,	l,3«dioxane-2-one,
4-methyl-l,3-dioxane-2HDne, 4J6-dimethyl-l,3-dioxane-2-one»
and l,3-dioxepane-2-o«e; baloepoxy compounds, such as
epichlorohydrin,	epibromohydrin,,	and
a-methylepiehlorohydfin, and their polyvalent amine adducts {for example, Kymeme fRegistered Trademark) manufactured by Hercules Incorporated; silane coupling agents, such as y-giycfdo&yprapyl trimethoxysilane and y-amlnopropyl triethoxysilane; and oxetame compounds, such as
3-s»ethyi-3-0«tane methanol, 3~ethyl«3~oxetane methanol,, 3-foutyl-3-oxctane methanol,, 3~methyl-3-oxetaric ethanal„ 3-ethyl-3-oxetane ethanoi, 3-butyl-3-oxetane eth&nol, 3-chloromethyi»3~methyl oxetane, 3-chlaromethyl-3-ethyl oxetane, and polyvalent oxetane compounds.
Any one of these surface crosalinking agents may be u»cd alone; alternatively two or more of them may be used together, Among them, poiyhydric alcohols are preferred because they are very safe and capable of improving the hydrophilielty of the water absorbing resin surface.
The surface crosslmking agent is used preferably in an amount of from 0.001 mass part& to 5 mass parts inclusive, relative to 100 mass parts of the solid content of the water absorbing resin.
Water may be used in mixing the surface crosslmking agent with the water absorbing resin, The water is used in an amount of preferably from 0,5 mass parts, exclusive, to 10 mass parts, inclusive, and more preferably from 1 mass part to S mass parts, both inclusive, relative to 100 mass parts of the solid content of the water absorbing resin.
A hydrophilic organic solvent or a third substance may be used as an auxiliary agent when mixing a surface crosslinking agent or its aqueous solution with the water absorbing resin. Examples of such hydrophilic organic solvents include lower alcohols, such as methyl alcohol, ethyl
alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
isobutyl alcohol, and t-butyl alcohol; ketones, such as
acetone; ethers, such as dioxane, tctrahydrofuran, and
mcthoxy (poly)ethylene glycol; amides, such as e-eaprolactam
and N,N-dimeth.yl formamide; sulfoxides, such as dimethyi
sulfoxide; and polyhydric alcohols, such as ethylene glycol,
diethylcnc glycol, propylene glycol, triethylene glycol,
dipropylene	glycol,	2,2,4-trixnetiiyM,3-pexitanediol,
polypropylene	glycol,	glycerine,	palyglycerinc,
2>butene-l,4-diolJ	1,3-butanediol,	1,4-butancdiol,
1,5-pentanediol, 1,6-hcxanediol, lt2-cyclohexa«e dimethanol, 1,2-cyclohexanol, trimethylolpropane, diethanol amine, triethanol amine* polyoxypropylene, oxyethylene-oxypropylcne block copolymer, pentaerythritol, and sorbitol.
The hydrophilic organic solvent may be used in an amount preferably 10 mass parts or less, and more preferably from 0 mass parts to 5 mass parts> both inclusive, relative to 100 mass parts of the solid content of the water absorbing resin. That amount however may vary depending on the type* particle diameter, and water content of the water absorbing resin, as well as other factors.
The third substance may be, for instance, the inorganic, organic, or polyamino acid described in the Specification of European Patent 0668080. The auxiliary mixed agent may act
as a surface crosslinking agent, but preferably should not adversely affect the water absorption capability of the water absorbing resin after the surface eras si inking. The water absorbing resin of the present embodiment is preferably croaslinked by mixing the resin with a surface crosslinking agent containing no bydrophilic organic solvent of which the boiling point is 100*C or below and then heating the mixture. If the water absorbing resin contains a hydrophilic organic solvent of which the boiling point is 100DC or below, the hydrophilic organic solvent may vaporizer changing the environment in which the surface crosslinking agent resides • on the surface of the water absorbing resin. One may not achieve sufficient SPC or other physical properties.
When the surface crosslinking agent is mixed with the water absorbing resin, preferably, a water-soluble inorganic salt (preferably a per#ulfate) is also present to obtain a more uniform mixture of the water absorbing resin and the surface crosslinking agent. The water-soluble inorganic salt is used in an amount of preferably from 0.01 mass parts to 1 mass, part inclusive, and more preferably from 0,05 mass parts to 0.5 mass parts inclusive, relative to 100 mass parts of the solid content of the water absorbing resin, The amount however may vary depending on the type and particle diameter of the water absorbing resin, a$ well as other factors, In other words, the water absorbing resin of the present embodiment is
preferably cro»»linked by mixing the resin with an organic surface crosslinking agent and/or a water-soluble inorganic surface crosslinking agent containing a water-soluble inorganic salt (preferably a pcrsulfate) in a ratio of 0.01 mass % to 1.0 mass %, inclusive, to the water absorbing resin and then heating the mixture.
The method for mixing the surface crosslinking agent with the water absorbing resin is not limited in any particular manner, ?or example, the water absorbing resin • may be immersed in a hydrophilic organic solvent and mixed with a surface crosslinking agent dissolved, as necessary, in water and/or a hydrophilic organic solvent. Another mixing method example may be to directly spray or add dropwfse to the water absorbing resin a surface crosslinking agent dissolved in water and /or a hydrophilic organic solvent,
After mixing the surface crosslinking agent with the water absorbing resin, heat is usually and preferably applied so that the crosslink reaction can proceed. The heat treatment temperature (heat medium temperature), although variable depending on the surface crosslinking agent being used, is preferably from 40rtC to 250°C inclusive, and more preferably from 150°C to 250°C inclusive. If the heat treatment temperature is lower than 40°C, the AAP, SFC, and other absorption properties may not be sufficiently improved. If the heat treatment temperature is higher than 250*0, the
excess heat may degrade the water absorbing resin and hence various physical properties; care should be taken, The heat treatment time is preferably from J minute to 2 hours inclusive, and more preferably from 5 minutes to I hour inclusive. Preferably, the surface crosslimking is performed in the presence of the a-hydroxy carbosylie acid {salt) mentioned above, in which case the water absorbing resin is prevented from being colored.
Salt of Polyvalent Metal and Other Additives
The method of manufacturing a water absorbing according to the present invention preferably involves a step of adding a polyvalent metal salt to the water absorbing resin (preferably to the particle surface), especially, in or after the surface croaalinking. The polyvalent metal salt Is added in an amount of preferably from 0.001 mass %' to 5 mass % inclusive, and more preferably from 0.01 mass % to 1 mass % inclusive, relative to the water absorbing resin.
Due to the addition of the polyvalent metal salt (preferably a water-soluble trivalent metal salt), the water absorbing resin of the present invention shows improved saline flow conductivity SPC while substantially preserving its absorbency under the pressure of 4.83 kPa AAP and fixed height absorbency FHA Concrete examples of the polyvalent metal salt that can
be U*cd in the present invention include a sulfate, nitrate, carbonate, phosphate, organic aeid salt, halide (e.g., chloride) of a metal selected from Zn, Be, Mg, Ca, Sr, Al, Fe, Mn, Ti, Zt, Ce, Ru, Y, and Cr as examples. Other examples are those polyvalent metal salts described in Japanese Unexamined Patent Publication (TokukaiJ 2005-U317.
Among the polyvalent metal salt*, water-soluble trivalent metal salts are the most preferred, Concrete examples of the water-soluble trivalent metal salts include aluminum chloride, aluminum, polychloride, aluminum sulfate, aluminum nitrate, aluminum potassium sulfate, aluminum sodium sulfate, potassium alum, ammonium alum, sodium alum, sodium aluminate, ironflll} chloride, cerium{lll} chloride, ruthenium(III) chloride, yttrium(III) chloride, and chromiumflll) chloride.
It is preferable to us© th	alts which contain crystal
water in view of the solubility of urine and other liquids absorbed. Preferred among them are aluminum compounds, especially, aluminum chloride, aluminum polychioridc, aluminum sulfate, aluminum nitrate, aluminum potassium sulfate, aluminum sodium sulfate, potassium alum, ammonium alum, sodium alum, and sodium aluminate. Aluminum sulfate is particularly preferred. The most preferred is an aqueous solution of aluminum sulfate (desirably, a solution of aluminum sulfate with a 90% or
higher concentration as based on saturation). Any one of these compounds may be used alone; alternatively two or more of them may be used together,
The method of manufacturing a water absorbing resin according to the present invention preferably involves a step of adding the a-hydroxy carboxylic acid (salt) named above, The addition prevents the water absorbing reain from being. colored. The a.-hydroxy carboxylic acid (salt) should be added to the water absorbing resin in an amount of 0.1 to 10 mass %, preferably 0.1 to 5 mass %, more preferably 0,15 to 3 mass) %, and most preferably 0.2 to 3 mass %, relative to the water absorbing resin. If the amount of the a-hydroxy carboxylic acid (salt) is out of the ranges, it becomes difficult to strike a good balance between water absorption properties (especially, SFC) and coloring prevention.
The polyvalent metal salt and/or the a»hydroxy carboxylic acid (salt), when mixed with the water absorbing resin, is/are preferably provided in the form of an aqueous solution, The concentration of the water-soluble polyvalent metal salt in an aqueous solution containing the polyvalent metal salt is preferably 50% or higher, more preferably 60% or higher, even more preferably 70% or higher, still more preferably 80% or higher, and further preferably 90% or higher, as based on saturation, to prevent the infiltration and diffusion into the water absorbing resin. The concentration
may equal the saturation concentration. Beside*, the aqueous solution which contain* at least the polyvalent metal salt may also contain an organic acid or salt thereof fpreferafcly the a-hydroxy earboxylic acid (salt}), such as the hydrophiiie organic solvent and lactic add (or salt thereof}. The addition of the organic acid or salt is preferable because at least the polyvalent metal salt is restrained from infiltrating or diffusing into the water absorbing resin, and the compounds are better misted.
The water absorbing resin of the present invention is a water absorbing resin obtained by polymerization of a water-soluble unsaturated monomer, the resin having an internal crosslitiking structure and exhibiting an intrinsic viscosity IV of 7.3 dL/g or lower, more preferably 7,25 dL/g or lower, and most preferably 7,2 dL/g or lower, at such a weight-average molecular weight Mw that Log (Mw) » 6.10, where the weight-average molecular weight Mw and the intrinsic viscosity IV are measured after leaving 50 mg of the water absorbing resin in 10 grams of a O.J mol/L aqueous solution of sodium hydroxide at 80°C for 3 weeks. The minimum intrinsic viscosity IV is preferably 4 dL/g or higher, more preferably 5 dL/g or higher, and most preferably 6 dL/g or higher- A measurement method will be described later in
The water absorbing resin of the present invention has a weight-average molecular weight in logarithm (Log (Mw)j of preferably 5.7 to 6.5, more preferably 5.8 to 6.3, and "most preferably 5.9 to 6,2, after the treatment. Out of the ranges, the feature represented by the intrinsic viscosity may not show up. In other wordsf The weight^average molecular weight in logarithm (Log (Htr)) falling in the above-mentioned ranges makes it easier to produce effective internal structure improvement with the water absorbing resin.
The water absorbing resin of the present invention is a water absorbing resin containing a water-soluble unsaturated monomer as a repeat unit for a major chain, 90 mol% of the monomer being composed of an acrylic acid and/or salt thereof, the resin having an internal cross-linking structure and exhibiting a weight-average molecular weight Mw of 360,000 to 1,000,000 doltons, preferably 370,000 to 700,000 dalions, most preferably 380,000 to 500,000 daltons, and an intrinsic viscosity IV of 2.1 to 6.0 dL/g, preferably 2.15 to 4,0 dL/g, more preferably 2.2 to 3.0 dL/g, most preferably 2.25 to 2.6 dL/g* where the weight-average molecular weight Mw and the intrinsic viscosity IV are measured after treatment under set 2 of hydrolysis conditions (will be described later).
The treatment under set 2 of hydrolysis conditions is a treatment in which 20 nag of the water absorbing resin is left
in 10 g of a 0,1 mol/L aqueous solution of sodium hydroxide at 8G*"C for 3 weeks. The weight-average molecular weight Mw and the intrinsic viscosity IV are measured after the treatment, A measurement method will be described later in
detail, A water absorbing resin with a further improved internal structure is obtainable by setting the weight-average molecular weight Mw and the intrinsic viscosity IV after the treatment under set 2 of hydrolysis conditions to the specified ranges.
The molecular weight distribution Mw/Mn after the treatment under set 2 of hydrolysis conditions of the present invention is preferably from 2,0 to 3.0, more preferably from 2.1 to 2,8, most preferably from 2,2 to 2,6, A water absorbing resin with a further improved internal structure is obtainable by setting the molecular weight distribution Mw/Mn after the treatment under set 2 of hydrolysis condition® to the specified range.
The water absorbing resin of the present invention has a CRC of preferably 5 g/g or greater, more preferably IS g/g or greater, even more preferably 25 g/g or greater, and still more preferably 28 g/g or greater. The maximum CRC, although not limited in any particular manner, m preferably 50 g/g or less, more preferably 45 g/g or less, and even more preferably 40 g/g or less, If the CRC is less than 5 g/g, the water absorbing resin, used in a water absorbent core* absorbs too small an
amount of liquid to be used as diaper® and -other
sanitary/hygienic materials. If the CRC Is greater than 50 g/g, the water absorbing resin, used in the water absorbent core, may not exhibit an excellent liquid acquisition rate to the water absorbent core per unit time.
The water absorbing resin of the present invention has a SFC of preferably 10 (lO-^cm^s'g-1) or greater, more preferably 30 {lO-^cun^s'g"1) or greater, wen more preferably 50 (10-?*cm3»s*g-4 or greater, still more preferably 70 (10,lf,cma*8*g,-1| or greater, and the most preferably 100 C10-y*cm3»s*g-^ or greater. If the SFC is less than 10 (lO-^cra^'g-1!, the liquid permeability is very low. The water absorbing resin, used in the water absorbent core, may not exhibit an excellent liquid acquisition rate per unit time.
The water absorbing resin of the present invention preferably has well-balanced CRC and SFC, Specifically, if the CRC is greater than or equal to 5 g/g and less than 25 g/g, the SPC is preferably 100 {lO-^cm^s'g"1) or greater, more preferably 150 (10-1'*cin**B*g'J) or greater, and the most preferably 300 (lO-^cm^s'g-*) or greater. If the CRC is greater than or equal to 25 g/g and less than 30 g/g, the SFC lit preferably 30 {10-**cni3*®,g"1) or greater, more preferably 70 {I0*7*cm3*s*g"11) or greater, and the most preferably 100 {10-**ctti3»8«g~l) or greater. If the CRC is more than or eqxaal to 30 g/g and less than SO g/g, the SFC is preferably 10
(I0-r*cm3*8*g"1} or greater, more preferably 30 (10-T#cmj,8*g,t) or greater* and the most preferably 50 (lO^'cm^s^g-1).
The water absorbing resin of the present invention preferably has a centrifuge retention capacity CRC of 26 g/g to 32 g/g, a mass-average particle diameter D50 of 300 to 500 urn, and such a saline flow conductivity SFC that satisfies a relationship with the centrifuge retention capacity CRC given by the following expressions
SPC i -20 x CRC + K,
where K is a constant, preferably 670, more preferably 680, most preferably 690.
If a good balance is struck between the CRC and the SFC, the water absorbing resin, used in the water absorbent core, shows a sufficiently high rate of absorption which makes up for a low liquid permeability. On the other hand, if the liquid permeability ia high, liquid diffuses in the water absorbing resin, enabling absorption across a wide area, even when the resin shows a low rate of absorption. Thus, the resulting water absorbing resin exhibits an excellent liquid acquisition rate per unit time whew used in the water absorbent core.
The water absorbing resin of the present invention has an AAP of 8 g/g or greater, preferably 16 g/g or greater, more preferably 20 g/g or greater* even more preferably 22 g/g or greater, and the most preferably 24 g/g or greater. The maximum AAP, although not limited In any particular manner,
is preferably 30 g/g or less. If the AAP is less than 20 g/g, the water absorbing resin, when used in the water absorbent core, may cause lot of liquid seeping* or "rewetting/ under pressure*
The extractable polymer content of the water absorbing resin of the present invention is preferably from 0 to 35 mass % incisive, more preferably from 0 to 23 mass % inclusive, and even more preferably from 0 to 15 mass % inclusive. If the extra.cta.ble polymer content is in excess of 35 mass %, the gel shows poor strength and liquid permeability. Besides, the water absorbing resin, when used in the water absorbent core, may cause lot of liquid seeping, or "rewefctmg," under pressure.
The water absorbing resin of the present invention preferably contains extractable polymer content which has a weight-average molecular weight Mw of 150,000 to 500,000 daitons. The weight-average molecular weight Mw is more preferably from 170,000 to 400,000 daitons and most preferably from 180,000 to 300,000 daitons,
The water absorbing resin of the present Invention preferably contains extractablc polymer content which has an intrinsic viscosity IV ©f 1.0 to 2.0 dL/g. The intrinsic viscosity IV is more preferably from 1,1 to 1.9 dL/g and most preferably from 1.2 to 1.8 dL/g.
The water absorbing resin of the present invention
preferably contains extractable polymer content which has a molecular weight distribution Mw/Mn of 2.0 to 3.0. The molecular weight distribution Mw/Mn is more preferably from 2.1 to 2.8 and most preferably from 2,2 to 2,7.
A water absorbing resin with, excellent AAP and S>FC is obtainable by setting the weight-average molecular weight Mw, intrinsic viscosity IV, and molecular weight distribution Mw/Mn of the extractable polymer content to the specified ranges. In addition, a water absorbent core is obtainable which has an excellent liquid acquisition rate per unit time when the water absorbing resin i» used in a water absorbent core.
The polymerisation initiator accounts for 0 to 5 ppm, and more preferably 0 to 2 ppm of the water absorbing resin. It is even more preferably if the initiator is ND {less than detection limit).
The water absorbing resin produces little dust. Dust, if present, is preferably from 0 to 300 ppm inclusive as measured with a Heubach dustmctcr (detailed later). So long as this condition is met* the fine particles in the water absorbing resin will not spread to the air, unlikely to raise safety/hygienic issues, during manufacture of the water absorbing resin. Also, the physical properties of the water absorbent core will not be adversely affected,
The water absorbing resin is characterised by a high
swelling pressure of gel layer,
The water absorbing resin of the present invention has a mass-average particle diameter D50 of, preferably, 200 to 600 um and more preferably 300 to 500 pm, If the water absorbing resin has a mass-average particle diameter DSQ out of the 200 to 600 pro range, the liquid permeability and diffusibillty may fall noticeably, or the absorption rate per unit time may fall by a large value. That water absorbing resin, if used in a diaper for example, may be leaky or otherwise defective.
The particle aise distribution of the water absorbing resin of the present invention has a logarithmic standard deviation 05 of preferably 0.20 to 0.50, and more preferably 0.30 to 0.40 inclusive. If the standard deviation is out of the ranges, the liquid permeability may so decrease that the water absorbent core has a very poor liquid acquisition rate per unit time.
Particles that can pass through a sieve of 150-|im mesh and particles with 850 pm or longer diameters preferably constitute 0 to 5 mas® % individually of the water absorbing resin of the present invention. The ratio is more preferably from 0 to 3 mass %, The exclusion of water absorbing resin less than 150 pm limits the amount of dust in the resulting water absorbing resin, Thus, the fine particles in the water absorbing resin will not spread in the air, unlikely to raise
safety/hygienic issues, during manufacture of the water absorbing resin. Also, the physical properties of the resultant water absorbing resin will not be adversely affected. If the ratio is in excess of 5 mass %» dust can occur during manufacture of the water absorbing resin, possibly raising safety/hygienic issues or degrading the physical properties of the water absorbent core, to name a few problems.
The water absorbing resin of the present invention has an absorption rate per unit time (FSR) of 0,2 g/g/s or greater, preferably 0.3 g/g/s or greater, more preferably 0,5 g/g/s or greater, even more preferably 0.7 g/g/s or greater, for • physiological saline diluted 20-fold* The maximum FSR, although not limited in any particular manner, is preferably 10 g/g/s or less, and more preferably 5 g/g/s or less. If the absorption rate per unit time (PSRJ ia less than 0,2 g/g/s, that water absorbing resin, used in a diaper for example, may not absorb a sufficient amount of urine, allowing it to leak.
The water absorbing resin of the present invention contains a polyvalent metal salt at least either on the surface or near the surface in a ratio of preferably 0.001 mass % to S mass % inclusive, and more preferably 0.01 mass % to 1 mass % inclusive, relative to the water absorbing resin. Owing to the inclusion of a polyvalent metal salt (preferably, a water-soluble trivalent metal salt), the water absorbing resin shows improved saline flow conductivity SFC while
subs tan ti ally preserving its absorbency tinder the pressure of 4,83 kPa AAP and fixed height absorbency FHA. Preferable concrete examples of the polyvalent metal salt are listed earlier.
The water absorbing resin of the present invention preferably contains the ot-hydroxy carboxylic acid (salt). The ratio of the a-hydroxy carboxylic acid (salt) contained in the water absorbing resin to the water absorbing resin is from 0.1 to 10 mass %, preferably from 0.1 to 5 mass %, more preferably 0.15 to 3 mass %„ and the most preferably 0,2 to 3 mas» %. If a particulate water absorbing resin contains the a-hydroxy carbewylie acid (salt) in a ratio out of these ranges, it becomes difficult to strike a good balance between water absorption properties (especially, SFCJ and coloring pretention.
water absorbent core
The water absorbent core of the present embodiment
contains the water absorbing resin described in the foregoing. The water absorbent core, when used in combination with an appropriate material, is suited for use as an absorbent layer in sanitary/hygienic materials* for example. The following will describe the water absorbent core.
The water absorbent core is a molded composition made of the water absorbing resin and other materials. The core is
used m disposable -diapers, sanitary napkins, incontinent pads, medical pads, and like sanitary/hygienic materials to absorb blood, body fluids, urine, etc. An example of the other materials, used in combination with the water absorbing re$in IM cellulose fiber. Concrete examples of cellulose fiber include mechanical pulp made from wood; wood pulp fibers, such as chemical pulp, semi-chemical pulp, and soluble pulp;, and artificial cellulose fibers, such as rayon and acetate. Preferred . cellulose fiber is the wood pulp fibers. The cellulose fiber may partially contain, nylon, polyester, or another synthetic fiber. When the water absorbing resin of the present embodiment is used as part of the water absorbent core, the mass of the water absorbing resin contained In the water absorbent core is preferably 20 mass % or -more, more preferably 30 mass % or more, even more preferably 40 ma«« % or more, still preferably 60 wt% or more, If the aws of the water absorbing resin of the present invention, contained in the water absorbent core is ]e»» than 20 mass %, sufficient effects may not be accomplished.
A publicly known, suitable method for producing a water absorbent core may be selected to produce the water abtorbeot core from the water absorbing resin of the present embodiment and the cellulose fiber. For example, the water absorbing resin may be sprayed onto sheets or mats made of the cellulose fiber and sandwiching more of the resin between
them if necessary. Alternatively, the cellulose fiber may be uniformly Wended with the water absorbing resin. A preferred method is to dry mix the cellulose fiber with the water absorbing resin and compress the mixture. This method is highly capable of restraining the water absorbing resin from falling off the cellulose fiber. The compression is preferably carried out on heating at, for example, 50° C to 200*C inclusive.
The water absorbing resin of the present embodiment, when vised in the water absorbent core, exhibits excellent physical properties; the resultant water absorbent core is of \rery excellent quality in that it can quickly absorb liquid, leaving only a little liquid on its surface.
The water absorbing resin of the present embodiment has an excellent water absorption property and hence is applicable to water absorbing/retaining agents for various purposes: for example, water absorbing/retaining agents for absorbent articles ^ such as disposable diapers, sanitary napkins, incontinent pads, and medical pad*; agriculture/horticulture water retaining agents, such as bog moss replacements, soil conditioners, water retaining agents, and agricultural chemical enhancers; water retaining agents for construction purposes, such as dew inhibitors for interior wall materials and cement additives; release controlling agents; cold insulators; disposable pocket stoves; sludge
coa.gula.ting agent; food freshness retaining agents; ton exchange column material®; sludge/oil dehydrate®; dcsi.ccan.ts; and humidity conditioning agents, in addition, the water absorbing resin of the present embodiment in especially suitable for use in disposable diapers, sanitary napkins, and like sanitary/hygienic materials for absorbing feces, urine, or blood.
Where the water absorbent core is used in sanitary/hygienic materials, such as disposable • diapers, sanitary napkins, incontinent pads, and medical pads, it is preferable if the core is placed between (a) a top sheet, permeable to liquid, provided next to the body of the user and (b) a back sheet, impermeable to liquid, provided next to the clothes of the user away from the body of the user, The water absorbent core may be multi-layered {two- or more layers). Further, the core may be used with a pulp layer as an example.
The following will more specifically describe the present invention by way of examples. The examples are by no means limiting the present invention. Throughout the following,, "mass parts" may be written simply as "parts" and "liter" as "1/ only for the sake of convenience. Also, "mass %H may be written as *wt%>"
The performance of the water absorbing resin was measured by the following methods. Unless otherwise specified, alt the measurements were conducted at room temperature |20 to 2S"C) and SO RH% humidity.
In the cases of the water absorbing resin being used in an end product, such a® a sanitary/hygienic material, the water absorbing renin had already absorbed moisture. The water absorbing resin was therefore separated appropriately from the end product and dried under reduced pressure and at low temperature (for example, under 1 mniHg or lower and at 60°C for 12 houfi} before measurements were made. All the water absorbing resins used in the examples and the comparative examples contained 94 mass % or more solid content.
Centrifuge Retention Capacity (CEC)
Centrifuge retention, capacity, or CRC, is absorption capacity for 0.9Q mass % saline under no load over 30
minutes. CRC may be referred to as "absorption capacity under no load,"
0.200 g of the water absorbing resin was placed evenly in a bag (85 mm x 60 mm) of non« woven fabric fHeatron Paper* GSP-22, manufactured by Nangoku Puip Kogyo Co,, Ltd,J, After heat scaling* the bag was immersed in a largely excessive amount (typically about 500 mL) of 0.90 mass %
saline (aqueous solution of sodium chloride) at room temperature. After 30 minutes, the bag was taken out of the ■ saline and eentrifuged for 3 minute® in a centrifugal separator ("Centrifuge H-122," manufactured by Kokusan Co.,. Ltd.) under centrifugal force described in edana ABSORBENCY II 441.1*99 (250 G). The mass, Wl (g), of the bag was then measured. The same process was carried out using no water aba-orbing resin, and the mass, WO (g), of the bag was measured. The centrifuge retention capacity CRC was calculated in grams per gram from Wl, WO as given by the following equations:
Centrifuge Retention Capacity CRC (g/g) - (Wl (gj - WO (g}} / (Mass (g) of Water Absorbing Resin) - 1
Absorbency Against Pressure of 4.83 kPa (AAP)
Absorbency against pressure, or AAP, is absorption capacity for 0.90 mass % saline under 4.83 kPa over 60 minutes. AAP may be referred to as absorption capacity under
4-83 kPa. Figure 3 is a cross-sectional view of an AAP measurement apparatus 10.
In the measurement apparatus 10 shown in Pigure 3, a 4QQ-mesh stainless steel net 101 (mesh size 38 um) was fused to the bottom of a plastic supporter cylinder 100 that had an internal diameter of 60 mm, 0.900 g of the water absorbing resin was sprayed evenly on the net 101 at room temperature
(from 20"C to 25*C inclusive) and 50 RH% humidity. A piston 103 and a weight 104 were placed in this order on the water absorbing resin, or the test sample 102. The piston 103 and weight 104 had an external diameter slightly less than 60 mm so that there occurred no gap between them and the supporter cylinder 100 and their up and down motion was not disturbed. The piston 103 and weight 104 were adjusted so that they could apply a 4,83 kPa (0,7 psi) load evenly, The mass, Wa (g), of the entire measurement apparatus 10 was measured.
A glass filter 106 measuring 90 mm in diameter (manufactured by Sogo Laboratory Glass Works Co., Ltd4 pore diameter 100 to 120 urn) was placed Inside a petri dish 105 measuring 150 mm. in diameter, 0.9O mass % saline 108 {from 20°C to 25°C inclusive) was poured until it sit level with the top face of the glass filter 106, A paper filter 107 'measuring 90 mm. in diameter (MIS P 3801, Ho. 2," Advantec Toyo Kaisha.,, Ltd*; thickness 0*26 mm, retainable particle diameter 5 urn) was placed on. the filter 106 so that the surface of the filter 107 could, 'be all wet. Excess solution was removed.
The whole measurement apparatus 10 was placed on the wet paper filter so that it could absorb the solution... under load. After I hour, the whole measurement apparatus 10 was lifted, and its mass Wb fg) was measured. The absorhency
under 4,83 kPa (AAP) was calculated in grama per gram from Wa, Wb as given by the following equation;
Absorbency under 4.83 kPa (AAP) « (Wb (g) - Wa (g)) / (Mass of Water Absorbing Resin (0,900 g))
Saline flow conductivity, or SFCr is a value indicating liquid permeability of the water absorbing resin when it has swollen. The greater the SFC, the higher liquid permeability the water absorbing resin has. SPC tests were conducted in the examples as described in the Specification of U.S. Patent 5,849,405. Figure I is a schematic illustration of an SFC measurement apparatus 30.
In the measurement apparatus 30 shown in Figure 1, a glass tube 32 was inserted into a tank 31. The lower end of the glass tube 32 was arranged so that 0.69 mass % saline 33 could be maintained 5 cm above the bottom of a gel 44 in a cell 41, The 0.69 mass % saline 33 in the tank 31 was fed to a cell 41 via an "L" tube 34 which has a valve 35. Under the cell 41 was provided a collector 48 which collected the solution that had passed through the cell 41. The collector 48 was placed on a balance 49. The cell 41 had an internal diameter of 6 cm and was provided with a Mo. 400 stainless steel net (mesh 38 umj 42 on the bottom. The piston 46 had, on its lower part, holes 47 through which the solution could
properly pass. Also, the piston 46 had a high permeability glass filter 45 attached to its bottom BO that the water absorbing resin, or their swollen gel could not enter the holes 47. The cell 41 was placed on a base. The face of the base at which it contacted the cell 41 was disposed on a stainless steel net 43 which did not disturb the passing solution.
Artificial mine (1) used here was a mixture of 0.25 g calcium chloride dihydrate, 2.0 g potassium chloride, O.50 g magnesium chloride hexahydrate, 2.0 g sodium sulfate, 0.85 g ammonium dihydrogenphosphate, 0,15 g diammonium hydrogenphosphate, arid 994,25 g pure water.
The water absorbing resin (0.900 g) placed evenly in the container 40 was let to swell, using the measurement apparatus 30 shown in Figure lt in artificial urine (1) under a load of 2.07 kPa {0,3 psi) for 60 minutes to prepare the gel 44. Thereafter, the height of the layer of the gel 44 was recorded. Next, the 0.69 mass % saline 33 was passed through the swollen gel layer from the tank 31 under a load of 2.07 kPa (0.3 psi) at a constant hydrostatic pressure. The SPC test was conducted at room temperature (from 20"C to 25*C inclusive). The amount of liquid having passed through the gel layer was recorded using a computer and a scale as a function of time at 20 second intervals for 10 minutes. The flow rate Fs(T) at which the solution passed through the swollen gel 44 (primarily between the gel's particles) was determined in units
of grams per second by dividing an increase in mass (g) by an increase in time {a). Flow rates were calculated only from the data obtained in the 10 minute period starting at time Ts at which a constant hydrostatic pressure and a stable flow rate were achieved. Fs{T»0}^ or the first flow rate at which the solution passed through the gel layera was calculated from the flaw rates obtained in the 10 minute period starting at Ts. Fs(T«0) was obtained by extrapolating, for T «■ 0, the result of least square approximation of Ps{T)f vs, time. Saline Flow Conductivity {SFC]
-	(F«(T-0) x LO) / {p x A x AP)
-	(Fs(T-O) * LO) / 139506
where Fs(TmO) was the flow rate in grams per second; LO waa the height of the gel layer in centimeters; p was the density of the NaCI solution {» 1,003 g/cms); A was the area of the top face of the gel layer in the cell 31 {= 28,27 cm2); and AP was the hydrostatic pressure exerted on the gel layer (= 4920 dyne/em2}. The SFC values were given in units of 10-7'cm**B"g-*.
Fixed Height Abaorbency {FHAJ
Fixed Height Abaorbency, or FHA, was measured in accordance with the method described in U.S. Published Patent Application 2005/0003191A1. The height upon measurement was set to 20 cm in the present invention.
Mass-average Particle Diameter D50 and Logarithmic Standard Deviation, o£„ of Particle Stee Distribution
These two parameters were measured based on the tests for the mass-average particle diameter, or D50, and the logarithmic standard deviation, at,, of a particle sia&e distribution described in International Application Published under PCT WO2004/69915.
Liquid Distribution Velocity (LDV)
Liquid distribution velocity, or LDV, was measured using a wieking index measurement apparatus described in Japanese Unexamined Patent Publication 5-200068/1993 fTokukaifaei 5-200068; equivalent to EP 532002). The trough sheet was prepared by SUS304, stainless steel, grade 2B finish for measurement.
First, 1.00 g ± 0,005 g of the water absorbing resin was sprayed evenly from the 0 to 20 cm marks in trough grooves on a trough sheet disposed at an angle of 2Q*C. The water absorbing resin was then more evenly spread using a spatula.
The liquid to be wicked away was 0.9 wt% saline (aqueous solution of sodium chloride) to which "*Blue No. 1 for Pood Testing* (available from Tokyo Chemical Industry Co., Ltd.) was added in a ratio of 0.01 g for every 1 L of the saline for coloring.
Adjustment was made so that the liquid surface in, a liquid storage vessel was 0-5 cm above the lowest point in the trough. After that, measurement of a liquid wicking time {WT) was started right when the stainless steel screen, mesh (400-mesh.) contacted the liquid. The liquid wicking time (WT) was the time in seconds it took for the liquid to be wicked up to the 10 cm mark. The velocity at which the liquid in the liquid storage vessel and the stainless steel screen mesh were immersed down to 0.S cm above the lowest point in the trough was From 1.35 to 1.40 mm/s in the direction perpendicular to the liquid surface. The liquid distribution velocity (LDV) was calculated from the following equation:
LDV (mm/s} - 100 (mm) / WT (s)
Ratio of Particles of Sl*e* which Pass through 150*)im Meshes of Sieve
The same classification process was performed as in the measurement of the mass-average particle diameter D50 and the logarithmic standard deviation, o£, of a particle size distribution. The ratio in mass % of the particles of sissea that could pass through a sieve with 150-pim meshes was calculated from the amount of the particles that had passed through that sieve with the 150-um meshes,
Extr&ctable polymer content {Water-soluble Components)
184,3 g of 0.90 mass % saline was prepared in, a lidded plastic container (capacity 250 ml), 1,00 g of the water absorbing resin was added to the aqueous solution, A stirrer was rotated for 16 hours to extract extractable polymer coatem of the resin by stirring the mixture. The liquid extract was filtered through a paper filter ("JIS P 3801, No, 2," Advantec Toyo Kaisha, Ltd.: thickness 0,26 mm, retainable particle diameter 5 vim). 50.0 g of the obtained filtrate was set aside for measurement as a sample solution.
First, a 0.1 N aqueous solution of NaOH was added to the 0,90 mass % saline alone, to pH 10. Then, a 0.1 N aqueous solution of HCl was added to pH 2.7 to determine a blank titer {[bNaOH] mL, [bHCl] mL|,
The same titration process was performed on the sample solution to determine a titer ([NaOH] mL, [HCl] ml).
In the case of a water absorbing resin made of known amounts of an acrylic acid and its sodium salt as an example, the cxtr&ctable polymer content of the water absorbing resin could be calculated according to the following equation from the weight-average molecular weight Mw of the monomer and the titer determined by the above-mentioned process If the water absorbing resin was made of unknown amounts of an acrylic acid and its sodium salt, the weight-average molecular weight ■ Mw of the monomer was calculated based on the neutralization ratio determined by the titration.
Ex-tractable polymer content {mass %) ■*
0.1 x Weight-Average Molecular Weight Mw x 184,3
x 100 x (IHC1] - [bHCl]) / 1000 / 1.0 / 50,0 Neutralization Ratio (mol%) - (1 - {[NaOHJ - fbNaOHj) / ([HCil - [bHCl])) * 100
Amount of Dust (Dust Related Properties)
The increase in mass of the dust absorbed and collected by a glass fiber filter over a predetermined period of time under the conditions detailed below was measured as the amount of dust in the water absorbing resin. The measurement was carried out on a Heubach Dustmeter manufactured by Heubach Engineering GmbH in Germany operating in measuring mode 1. The atmospheric conditions during the measurement were 2S*C (± 2*C) temperature, 20 to 40% relative humidity, and normal pressure. Specific procedures were as follows*
{1) 100.00 g of a sample (water absorbing resin) was placed in a rotation drum 200.
(2)	The mass of the glass fiber filter 50 mm in diameter (retainable particle diameter 0.5 um (JIS P3801}| was measured with 0.00001 gram accuracy ("Da" grams). The filter was prepared by fabricating, for example, Advantec's glass fiber, GC-90, or any equivalent to the 50 mm diameter.
(3)	A large-scale particle separator 201 was attached to
the rotation drum 200. A filter enclosure 202 loaded with a glass fiber filter 204 was Also attached.
(4)	Conditions were set as follows on the control section
203 of the dustmctcr. Measurement was made.
Rotation Rate of Drum * 30 R/min Volume of Absorbed Air = 20 L/min Time (Measurement Period) » 30 minutes
(5)	After the predetermined period, the mass of the glass
fiber filter 204 was measured with 0.00001 gram accuracy
fDb*).
The amount of dust was given by:
Amount of Dust (ppm) ■ (Db - Da| / 100.00 x 1,000,000
Faint Shaker Test
In a paint shaker test (F8), a glass container 6 cm in diameter and 11 cm in height was charged with 10 g of glass beads each 6 mm in diameter and 30 g of a water absorbing resin and loaded in a paint shaker (No. 488, Toyo Seiki Seisakusho Co., Ltd.) for shaking at 800 cycles per minute (CPM). See Japanese Unexamined Patent Publication 9-235378/1997 (Tokukaibei 9-235378) for details of the device,
Tests in which the shake time was set to 30 minutes and 10 minutes were designated paint shaker test 1 and paint shaker test 2 respectively.
After infiltration, the glass beads were removed using a JIS Standard sieve (mesh 2 mm), leaving behind damaged water absorbing resin.
Solid Content of Water Absorbing Resin
The value indicates the ratio in the water absorbing resin of components that do not volatilise at 180°C. The solid content is related with the water content as follows:
Solid Content {mass %) - 100 - Water Content (mass %)
The solid content was measured as in the following.
About 1 g of the water absorbing resin (actual mass Wi) was measured and placed in an aluminum cup (mass Wo) about 5 cm in bottom diameter. The cup was then placed in a windless drier at 180°C to sit there for 3 hours for drying. The combined mass, Wa, of the aluminum cup and the water absorbing resin after the drying was measured. The solid content was determined by the following equation;
Solid Content (mass %) - ((Wa - Wo) / WiJ x 100
Solid Content of Water-containing Gel
The solid content of a water-containing gel was measured by the same method as with th« solid content of a water absorbing resin, except that the water-containing gel weighed about S g and also that the cup sat in the drier for 8 hours for drying.
Intrinsic Viscosity IV and Weight-average Molecular Weight Mw at Log (Molecular Weight} = 6,10 Preparation of Samples
A polypropylene test tube (internal diameter 1,8 cm, length 15 to 18 cm) was charged with SO mg of the water absorbing resin and 10 g of a 0.1 mol/L aqueous solution of sodium hydroxide (for use in capacity analysis, manufactured by Wako Pure Chemical Ind.) and closed with a polypropylene seal. The test tube was shielded from light and left to sit at 80®C for 3 weeks. The solution thus obtained was diluted 6-fold with the solvent detailed below and passed through a filter (GL Chromatodisk, Aqueous 25A„ manufactured by GL Sciences Inc., pore diameter 0.2 )im), Measurement was done on the solution tinder the following conditions.
The measurement was carried out using a TDA302 (Registered Trademark) manufactured by Viscotek Corporation. The apparatus was configured from a size exclusion
chromatography device, a refractive index detector, an optical scatter detector, and a capillary viscosity meter. Details of the apparatus and its settings were as follows:
Pump Autosampler: GPCmax from Viteotek Corporation,
Guard Column; SHODEX GF-7B
Column: Two TOSOH OMFWXLs Connected in Series
Detector: TDA302 from Viscotek Corporation (system temperature maintained at 30°C)
Solvent: Aqueous Solution of 60 mM Sodium Dlhydrogenphosphate Dihydrate and 20 mM Disodium Hydrogenphosphate Dodeeahydrete
Flow Rat«: 0,5 mL/min
injections 100 »L
The apparatus was calibrated using pelyoacyethylene glycol (weight-average molecular weight Mw «• 22,396, differential refractive index dn/dc - 0.132, refractive index of solvent - 1.33) as a reference sample.
In the case of the water absorbing resin being obtained by polymerization of a monomer containing 99 mol% or more acrylic acid and/or its salt, the measurement was carried out presuming that the differential refractive index dn/dc of the target polymer for analysis was 0.12. In the case of the water absorbing resin being obtained by copolymerizing a monomer more than 1% of which is not an acrylic acid and/or its salt, the differential refractive index (dn/dc) may be measured in the foregoing solvent that is unique to that polymer, and its value be used.
Data on the refractive index, intensity of scattered light,: and viscosity were collected and analyzed using software, Vlftcotek Corporation OmsiSEC 3.1 (Registered Trademark)..
The weight-average molecular weight Mw was calculated from the data obtained from the refractive index and the intensity of scattered light. In addition, from the refractive index, the intensity of scattered light, and the data obtained from the viscosity meter, Mark-Houwink-Sakurada plotting was carried out with the X axis indicating Log (Mw) (molecular weight) and the Y axis indicating Log (IV) (intrinsic viscosity). The value of Log (IV) at Log (Mw) - 6,1 was read from the line drawn, and the intrinsic viscosity IV was calculated from that value. The intrinsic viscosity (IV) has the same meaning with the limiting viscosity (IV) throughout the specification.
Thermally Decomposing Radical Initiator Content Index
The thermally decomposing radical initiator content
index is a numeric value obtained from the mole ratio of a
thermally decomposing radical initiator and a the number of
monomer units in a polymer in a water-containing geL The
index is given by the following equation:
- (Ci/Mi)/(Cm/Mm) K 10B
Ci is the quantity in mass % of a thermally decomposing
radical initiator extracted by stirring a water-containing gel in
a 5% aqueous solution of sodium chloride for 1 hour
Mi is the mole»average molecular weight in mol/g of the extracted thermally decomposing radical initiator;
Cm is the solid content in mass % of the water-containing gel obtained by drying the water-containing gel at 180°C for 8 hours; and
Measurement of Quantity, CI (mass %), of Thermally Decomposing Radical Initiator for Water-containing Gel
A lidded polypropylene container (capacity 260 mL) was charged with 10 g of the water-containing gel immediately prior to the drying step and 170 g of a 5% aqueous solution of sodium chloride. If the gel has swollen and cannot be stirred, the concentration of the salt or the amount of the aqueous solution is adjusted properly. The solution was then stirred while the container was kept shielded from light and at room temperature. After 1 hour, the solution was removed from the container and passed through a filter (QL Chromatodisk, Aqueous 25A, manufactured by GL Sciences Inc. pore diameter 0.45 pm). 4,00 g of the filtered solution was put in a glass sample vial with a screw cap (capacity 50 mL, diameter 35 mm, height about SO ma), to which 6.00 g of a 5% aqueous solution of sodium chloride was added. Then, 1.00 g of a 44 mass % aqueous solution" of potassium iodide was
added immediately, and the mixture was stirred while the container was kept shielded from light and at room temperature. After 1 hour, the solution was transferred to a I-cra plastic cell. Absorption of 350 nm light was measured with a spectrophotometer {Hitachi Ratio Beam Spectrophotometer U-1100), taking the absorption of light by pure water to be 0. The quantity, Ci, of the thermally decomposing radical initiator in the water-containing gel was calculated in mass % from the light absorption value thus obtained.
An Inspection line was drawn from light absorption measurements obtained by the same process as above from 5% aqueous solutions of sodium chloride containing the thermally decomposing radical initiator in the respective ratios of 0.0005, 0.0010, 0.0015, and 0.0020 mass %. The quantity, Ci (mass %), of the thermally decomposing radical initiator in the water-containing gel was calculated from the inspection line and the light absorption.
Provided that the inspection line is given by a mathematically expression:
Quantity of Thermally Decomposing Radical Initiator (mass %) - a x (Absorption of Light) + b, where a and b are constants j
the quantity, Ci (mass %), of the thermally decomposing radical initiator in the water-containing gel is given by the
Quantity, Ci (mass %), of Thermally Decomposing Radical Initiator
- (a x (Absorption of Light) + b) x ((170 + 10)/ 10) x {(6 + 4)/4|
Solid Content, Cro, in Water*containing gel (mass %)
The solid content, Cm, in the water-containing gel was measured by the method described above.
Weight-average • Molecular Weight Mw, Number-average Molecular Weight Mn, and Molecular Weight Distribution Mw/Mn after Treatment of Set 2 of Hydrolysis Conditions Preparation of Samples
A polypropylene teat tube {internal diameter 1.8 cm, length IS to 18 cm) was charged with 20 mg of the water absorbing resin and 10 g of a 0.1 moi/L aqueous solution of sodium hydroxide (for use in capacity analysis, manufactured by Wako Pure Chemical Ind„) and closed with a polypropylene seal. The test tube was shielded from light and left to set at 80°C for 3 weeks. After the 3 weeks, the water absorbing resin was hydrolyzed and in a solution state. After the hydrolysis, insoluble content accounted for usually 50 mass % or leas, preferably 10 mats % ®t less, more preferably 0 mass %, of the water absorbing re sin.
The solution thus, obtained was diluted 4-fold with the solvent detailed below and passed through a filter (GL Chromatodisk, Aqueous 25A, manufactured by GL Sciences Inc., pore diameter 0,2 pm|, Measurement was done or* the solution under the following conditions.
Conditions for GPC Measurement
The measurement was carried out using a TDA302 (Registered Trademark) manufactured by Viscotek Corporation. The apparatus was configured from a siase exclusion chromatography device,, a refractive index detector, an light scattering detector, and a capillary viscosity meter, Details of the apparatus and its settings were as follow*:
Pump Autosampler; GPCmax from Viacotek Corporation
Guard Columns OHpak SB-G (manufactured by Showa Denko K.K.}
Column: Two OHpak SB-806 MHQs (manufactured by Showa Denko K.K,) Connected In Series
Solvent: Aqueous Solution (pH6.35 to 6.38) of 60 mM Sodium Dihydrogenphosphate Dihydratc, 20 mM Disodium Hydrogeaphosphate Dodecahydrate, and 400 ppm Sodium AtsMc
Flow Rate: 0*5 mh/min.
Injection: 100 pL
Impurities were removed sufficiently from the pure water used in the measurement. Before the measurement, a sufficient amount of solvent was passed through the device so as to gat a stable base line for detection values. Especially, the measurement was carried out while the light scattering detector shows no noise peaks.
The apparatus was calibrated using polyoxyethylcne glycol (weight-average molecular weight Mw - • 22,396, molecular weight distribution Mw/Mn = 1.0, differential refractive index dn/dc * 0.132, refractive index of solvent = 1,33) as a reference sample.
In the ease of the water absorbing resin being obtained by polymerization of a monomer containing 99 mol% or more acrylic acid and/or its salt, the measurement was carried out presuming that the differential refractive index dn/dc of the target polymer for analysis was 0,12 and also that the refractive index of the solvent was 1.33, In the case of the water absorbing resin being obtained by copolymeris&ing a monomer more than 1% of which is not an acrylic acid and/or its salt, the differential refractive index {dn/dc) may be measured in the foregoing solvent that is unique to that polymer, and it® value be used,
A chart drawn from the measurement was checked. If the peak obtained from the measurement of the intensity of
scattered light contains a lot of noise, the measurement was carried out again.
Data, on the refractive index, intensity of scattered light,. and viscosity were collected and analyzed using software, Viscotek Corporation OmniSEC 3.1 (Registered Trademark). The weight-average molecular weight Mw, number-average molecular weight Mn, molecular weight distribution Mw/Mn, and intrinsic viscosity IV were calculated from the data obtained from the refractive Index. RI and the intensity of scattered light LALS (angle 7*} as well as data from a viscosity meter (DP),
Weight-average Molecular Weight Mw, Number-average Molecular Weight Mn, and Molecular Weight Distribution Mw/Mn of Bxtractable polymer content Preparation of Samples
The solutions obtained as under the heading MIntractable polymer content (Water-soluble Components)" was used. If the sample concentration was too high, the sample was diluted with a suitable QPC solution so that the polymer content concentration could be about 0,5 mg/mL,
Measurement was carried out under the same conditions as the GFC measurement.
436.4 g of an acrylic acid, 4617.9 g of a 37 mass % aqueous solution, of sodium aery]ate, 373.8 g of pure water, and 11.40 g of polyethylene glycol diaerylate (weight-average molecular weight Mw 523] were dissolved in a reactor which was a lidded double-arm stainless steel kneader (internal volume 10 liters) equipped with two sigma-type blades a&d a jacket, to prepare a reaction solution. Next, the reaction solution was deaerated in a nitrogen gas atmosphere for 20 minutes, Subsequently, 36.33 g of a 10 mass % aqueous solution of sodium persulfate and 24.22 g of a 0.1 mass % aqueous solution of L-aacorbie acid were added to the reaction solution while stirring, about 25 seconds after which polymerization started. The polymerization was let to proceed at 25°C to 95°C inclusive, while crushing the produced gel. The water-containing gel-like crosslinked polymer was removed 30 minutes into the polymerization. After the polymerization started, it took not longer than 15 minutes to reach a maximum temperature. The resulting water-containing gel {water-containing gel-like crosslinked polymer) had betn comminuted to a diameter of about 5 mm or less.
The water-containrag gel contained 0,0547 mass % theraaliy decomposing radical initiator {** Ci mast %} and
40.9 mass % solid content («* Cm mass %). The thermally decomposing radical initiator content index was 49.7. These results are shown in Table I.
The comminuted water-containing gel-like crosslinked polymer was spread on a 50-mcsh metal net and dried in hot wind at 180°G for 45 minutes. The dried substance was pulverized in a roll mill and subjected to a classification using a JlS-standard sieve having a mesh opening size of 710 pm. Those particles which had passed through that sieve were then passed through a JlS-standard sieve having a mesh opening sisse of 175 um for further classification. The fine particles having passed through the sieve were removed to obtain water absorbing resin (1) which had an irregularly pulverized shape. Resin (1) had a mass-average particle diameter DSO of 341 urn. The logarithmic standard deviation, al, of the particle size distribution of resin (1) was 0.33. Water absorbing resin {1) had a centrifuge retention capacity CRC of 34.4 g/g and contained 7.6 mass % extractafolc polymer content. The particles of such sixes that they could pass through a sieve having a mesh opening size of 150 urn accounted for 1.7 mass % of resin flj* Table 3 show® »eatureme».ts by the aforementioned method of the intrinsic viscosity IV and the weight-average molecular weight Mw for water absorbing resin (1) at such a weight-average molecular weight Mw that Log (Mw) * 6.10.
100 mass parts of obtained water absorbing resin (1) was evenly mixed with a surface crosslinking agent that was a mixed solution of 0.38 mass part 1,4-butanediol, 0.63 mass part propylene glycol, and 2.74 mass part pure water. After the mixing, the mixture was heat treated at 212°'C. Sample mixtures were prepared with different heating time*: 25 minutes, 30 minutes, and 35 minutes. Thereafter, the resulting particle samples were disintegrated until they could pa»« through a JIS*standard sieve having a mesh opening size of 710 tim. Next, the disintegrated particle samples were subjected to paint shaker test 1, to obtain surfacc-crosslinked water absorbing resins: the one heated for 25 minutes was designated water absorbing resin (1-25), the one heated for 30 minutes water absorbing resin (1-30), and the one heated for 35 minutes water absorbing resin (1-35). Table 3 shows measurements by the aforementioned method of the intrinsic viscosity IV and the weight-average molecular weight Mw for water absorbing resins (1-30) and (1-35) at such a weight-average molecular weight Mw that Log (Mw) *» 6.10.
A mixed solution of 0,40 mass parts of a 27.5 mass % aqueous solution of aluminum sulfate (equivalent to 8 mass % aluminum oxide), 0-134 mass parts of a 60 mas* % aqueous solution of sodium lactate, and 0.002 mass part propylene glycol was added to the surface-crosslinked water absorbing resins (1-25), (1-30), and (1-35} each 100 mass parts. After
the addition „ the mixtures were dried in a windless
environment for 1 hour at 60°C. Following the drying, these particle samples were disintegrated until they could pass through a JI8-standard sieve having a mesh opening size of 710 pm. Next, the disintegrated particle samples were subjected to paint shaker test 2, to obtain water absorbing resins: the one obtained from water absorbing resin {1-25) was designated water absorbing resin (1-25A), the one obtained from water absorbing resin (1-30) water absorbing resin (1-30A), and the one obtained from water absorbing resin (i~35) water absorbing resin (1-35AJ.
Tabic 2 shows measurements of the CRC, AAP„ SPC, D50, and ratio of particles of such sizes that they could pass through a sieve having a mesh opening size of 150 pm for water absorbing resins {1-25A), (1-30A), and (1-35A)*
436*4 g of an acrylic acid, 4617,9 g of a 37 mass %
aqueous solution of sodium acrylafce, 377.S g of pure water, and 10,13 g of polyethylene glycol diacrylate (weight-average molecular weight Mw 523) were dissolved in a reactor which was a lidded double-arm stainless steel kneader {internal volume 10 liters) equipped with two sigma-type blades and a jacket, to prepare a reaction solution, Hext» the reaction solution was deaer&ted In a nitrogen gas atmosphere for 20
minutes. Subsequently, 33.91 g of a 10 mass % aqueous solution of sodium, peraulfatc and 24,22 g of a 0.1 mass % aqueous solution of L-ascorbic acid were added to the reaction solution while stirring, about 25 seconds after which polymerization started. The polymerization was let to proceed at 25°C to 95**C inclusive, while crushing the produced gel. The water-containing gel-like etosslinked polymer was removed 30 minutes into the polymerisation. After the polymerization started, it took not longer than IS minutes to reach a maximum temperature. The resulting water-containing gel (water-containing gel-like crosslinkcd polymer) had been comminuted to a diameter of about 5 mm or less.
The water-containing gel contained 0.0504 mass % thermally decomposing radical initiator (= Ci mass %| and 41.2 mass % solid content {» Cm mass %}. The thermally decomposing radical initiator content index was 45.5. These results arc shown to Table 1.
The comminuted water-containing gel-like crosslinked polymer was spread on a 50-mesh metal net and dried in hot wind at IS0°C for 45 minutes. The dried substance was pulverized in a roll mill and subjected to a classification using a JIS-standard sieve having a mesh opening size of 710 urn. Those particles which had passed through that sieve were then passed through a JlS-standard sieve having a mesh
opening size of 17S um for further classification. The fine particles having passed through the sieve were removed to obtain water absorbing resin (2) which had an irregularly pulverized shape. Resin (2) had a mass-average particle diameter DSO of 340 pin. The logarithmic standard deviation, aL of the particle size distribution of resin (2) was 0.33. Water absorbing resin. (2) had a centrifuge retention capacity CRC Of 34.7 g/g and contained 7.S mass % extractablc' polymer content. The particles of such sizes that they could pass through a sieve having a mesh opening siae of 150 pro accounted for 1.6 mass % of resin |2).
100 mass parts of obtained water absorbing resin |2) was evenly mixed with a surface erosslinking agent that was a mixed solution of 0.38 mass part 1,4-hutanedioI, 0.63 mass part propylene glycol, 3.39 mass part pure water, and 0,1 mass part -sodium per&ulfate. After the mixing, the mixture was heat treated at 212eC, Sample mixtures were prepared with different heating times: 35 minutes, 40 minutes, and 45 minutes. Thereafter* the resulting particle samples were disintegrated until they could pass through a JlS-standard sieve having a mesh opening nize of 710 pm, Next, the disintegrated particle samples were subjected to paint shaker test 1, to obtain surface-crossiinked water absorbing resins-the one heated for 35 minutes was designated water absorbing resin (2-3SJ, the one heated for 40 minutes water
absorbing resin (2-40), and the one heated for 45 minutes water absorbing resin (2-45),
A mixed solution of 0,40 mass parts of a 27,5 mass % aqueous solution of aluminum sulfate (equivalent to 8 mass % aluminum oxide), 0.134 mass parts of a 60 mass % aqueous solution of sodium lactate, and 0>002 mass part propylene glycol was added to the surface-cross linked water absorbing resins (2-35|u (2-40), and (2-45) each 100 mass parts. After the addition, the mixtures were dried in a windless environment for I hour at 60*C. Following the drying, these particle samples were disintegrated until they could pass through a JlS-standard sieve having a mesh opening size of 710 um. Next, the disintegrated particle samples were subjected to paint shaker test 2, to obtain water absorbing resins: the one obtained from water absorbing resin (2-35) was designated water absorbing resin (2«35A)f the one obtained from watcT absorbing resin (2-40) water absorbing resin (2-40A), and the one obtained from water absorbing resin (2-45) water absorbing resin (2-45A),
Table 2 showa measurements of the CRC, AAP, SFC„ D50, and ratio of particles of such sizes that they could pass through a sieve having a mesh opening size of 150 um for water absorbing resins (2-35A), (2-4QA), and (2-45A).
436,4 g of an acrylic acid, 4617.9 g of a 37 mats % aqueous solution of sodium, aery late t 372.6 g of pare water, and 10.13 g of polyethylene glycol diacrylate (weight-average molecular weight Mw 523} were dissolved in a reactor which was a lidded double-arm stainless steel kneader {internal volume 10 litersj equipped with two sigma-type blades and a jacket, to prepare a reaction solution, Next, the reaction solution was deaerated in a nitrogen gas atmosphere for 20 minutes. Subsequently, 38,76 g of a 10 mass % -aqueous solution of sodium persuifatc and 24.22 g of a 0.1 mass % aqueous solution of L«ascorbic acid were added to the reaction solution while stirring, about 25 seconds after which polymerization started. The polymerization was let to proceed at 25°C to 95DC inclusive, while crushing the produced geL The water-containing gel-like crosslinked polymer was removed 30 minutes into the polymerization, After the polymerisation started, it took not longer than 15 minutes to reach a maximum temperature. The resulting water-containing gel (water-containing gel-like crosslinked polymer) had been comminuted to a diameter of about S mm or less.
The water-containing gel contained 0.0591 mass % thermally decomposing radical initiator (» Ci mass %) and 41.4 mass % solid content (- Cm mass %)
The comminuted water-containing gel-like crossllnked polymer was spread on a 50-mesh metal net and dried in hot wind at 180DC for 45 minutes. The dried substance was pulverized in ft roll mill and subjected to a classification using a JlS-standard sieve having a mesh opening ssisse of 710 urn. Those particles which had passed through that sieve were then parsed through a JlS-standard sieve having a mesh opening sisse of 175 pm for further classification. The fine particles having passed through the sieve were removed to obtain water absorbing resin (3) which had an irregularly pulverised ahape. Resin (3) had a mass-average particle diameter D50 of 339 um. The logarithmic standard deviation, &l, of the particle size distribution of resin (3) was 0.33. Water absorbing resin (3) had a centrifuge retention capacity CRC of 34,8 g/g and contained 7.3 mass % extractablc polymer content. The particles of such sizes that they could pass through a sieve having a mesh opening size of 150 urn accounted for 1.7 mass % of resin (3).
100 m&m parts of obtained water absorbing resin (3} was evenly mixed with a surface crosslinking agent that was a mixed solution of 0.38 mass part l,4~butanediol, 0.63 mass part propylene glycol, $.39 mass part pure water, and 0,1 mass part sodium persulfate. After the mixing, the mixture was heat treated at 212*C, Sample mixtures were prepared
with different heating times: 40 minutes., 45 minutes, and 50 minutes. Thereafter, the resulting particle samples were disintegrated until they could pass through a JI8-standard sieve having a mesh, opening stee of 710 pra. Next, the disintegrated particle samples were subjected to paint shaker test 1, to obtain surface-crosslinked water absorbing resins: the one heated for 40 minutes was designated water absorbing resin (3-40), the one heated for 45 minutes water absorbing resin (3-45), and the one heated for 50 minutes water absorbing resin (3-50),
A mixed solution of 0,40 mass parts of a 27.5 mass % aqueous solution of aluminum sulfate (equivalent to 8 mass % aluminum oxide), 0.134 mass parts of a 60 mass % aqueous solution of sodium lactate, and 0,002 mass part propylene glycol was added to the surface-crosslinked water absorbing resins (3-40), (3-45), and {3-50) eaeh 100 mass parts. After the addition, the mixtures were dried in a windless environment for 1 hour at 60°C. Following the drying, these particle samples were disintegrated until they could pass through a JlS-standard sieve having a mesh opening si«e of 710 pm. Next, the disintegrated particle samples were subjected to paint shaker test 2, to obtain water absorbing resins: the one obtained from water absorbing resin (3-40) was designated water absorbing resin (3-40A), the one obtained from water absorbing resin (3-45) water absorbing
resin (3-45A), and the one obtained from water absorbing resin (S«50> water absorbing resin (3-SOA).
Table 2 shows measurements of the CRC, AAP, SFC, D50, and ratio of particles of such -sizes that they could pass through a sieve having a mesh opening size of 150 wm for water absorbing resins (3-40A), (3-45A), and. (3-5GA).
436.4 g of an acrylic acid, 4617.9 g of a 37 -111888 % aqueous solution of sodium acryiate, 362.9 g of pure water, and 10,13 g of polyethylene glycol diacrylate (weight-average molecular weight Mw 523} were dissolved in a reactor which was a lidded double-arm stainless steel kneader (internal volume 10 liters) equipped with two sigma-type blades and a jacket, to prepare a reaction solution, Next, the reaction solution was deaeratcd in a nitrogen gas atmosphere for 20 minutes. Subsequently, 48.45 g of a 10 mass % aqueous solution of sodium, persulfate and 24.22 g of a 0.1 mass % aqueous solution of L-ascorbic acid were added to the reaction solution while stirring, about 25 seconds after which polymerization started. The polymerization was let to proceed at 25°C to 9S°C inclusive, while crushing the produced gel. The water-containing gel-like crosslinked polymer was removed 30 minutes into the polymerisation. After the polymerisation started, it took not longer than IS minutes to
reach a maximum temperature. The resulting water-containing gel (water-containing gel-like eroasiittked polymer) had been comminuted to a diameter of about § mm or less.
The water-containing gel contained 0.0826 mass %
thermally decomposing radical initiator (- Ci mass %) and
'41.2 mass % solid content (- Cm mass %), The thermally
decomposing radical initiator content index was 74,6, These
results are shown in Table 1,
The comminuted water-containing gel-like crosslinked polymer was spread on a 50-mesh metal net and dried in hot wind at 180'C for 45 minutes, The dried substance was pulverized in a roll mill and subjected to a classification using a JlS-standard sieve having a mesh opening size of 710 um. Those particles which had passed through that sieve were then passed through a JlS-standard sieve having a mesh Opening size of 175 urn for further classification. The fine particles having passed through the sieve were removed to obtain water absorbing resin (4) which had an irregularly pulverized shape, Resin (4) had a mass-average particle diameter D50 of 341 um. The logarithmic standard deviation, a%, of the particle size distribution of resin (4) was 0.33, Water absorbing resin (4) had a centrifuge retention capacity CRC of 34.8 g/g and contained 7.8 mass % extractable polymer content. The particles of such sizes that they could
pass through a sieve having a mesh, opening size of 150 ptn accounted for 1.8 mass % of resin (4),
100 mass parts of obtained water absorbing resin. {4) was evenly mixed with a surface erosslinking agent that was a mixed solution of 0,38 mass part 1,4-butanediol, 0,63 mass part propylene glycol, 3.39 mass part pure water, and 0.1 mass part sodium persulfate. After the mixing, the mixture was heat treated at 212*0. Sample mixtures were prepared with different heating times: 35 minutes, 40 minutes, and 45 minutes. Thereafter, the resulting particle samples were disintegrated until they could pass through a JlS-standard sieve having a mesh opening size of 710 pm. Next, the disintegrated particle samples were subjected to paint shaker test 1, to obtain surface-crosslinkcd water absorbing resins: the one heated for 35 minutes was designated water absorbing resin (4-35), the one heated for 40 minutes water absorbing resin (4-40), and the one heated for 45 minutes water absorbing resin (4-45).
A mixed solution of 0,40 mass parts of a 27,5 mass % aqueous solution of aluminum sulfate {equivalent to S mass % aluminum oxide), 0.134 mass parts of a 60 mass % aqueous solution of sodium lactate, and 0,002 mass part propylene glycol was added to the surface-erosslinked water absorbing resins (4-35}, (4-40), and (4-45) each 100 mass parts. After the addition, the mixtures were dried in a windless
environment for 1 hour at 6CPC. Following the drying, these particle samples were disintegrated until they could pass through a Jl5~standard sieve having a mesh opening size of
?10 n». Next* the disintegrated particle samples were subjected to paint shaker test 2, to obtain water absorbing resins; the one obtained from water absorbing resin (4-35} was designated water absorbing resin (4-35A), the one obtained from water absorbing resin (4-40) water absorbing resin (4~40A)» and the one obtained from water absorbing resia (4-45) water absorbing resin (4-45A).
Table 2 shows measurements of the CRC, AAP, SFC, D50, and ratio of particles of such sizes that they could pass through a sieve having a mesh opening size of 150 urn for water absorbing resins {4-35A), (4-4QA), and (4-4SAJ.
436,4 g of an acrylic acid, 4617.9 g of a 37 mass % aqueous solution of sodium acrylate, 378.7 g of pure water, and 8.87 g of polyethylene glycol diacrylate (weight-average molecular weight Mw S23) were dissolved in a reactor which was a lidded double-arm stainless steel kneader (internal volttme 10 liters} equipped with two sigma-typc blades and a jacket, to prepare a reaction solution. Next, the reaction solution was deaerated in a nitrogen gas atmosphere for 20 minutes. Subsequently, 33.91 g of a 10 mass % aqueous
solution of sodium persuifate and 24.22 g of a O.i mass % aqueous solution of L-ascorbic acid were added to the reaction solution while stirring, about 2S seconds after wbieh polymerization started. The polymerization was let to proceed at 25*C to 95*>C inclusive, while crushing the produced gel. The water^co ntaining gel-like crosslinked polymer was removed 30 minutes into the polymerization. After ..the polymerisation started, it took not longer thaw 15 minutes to reach a maximum temperature. The resulting water-containing gel (water-containing gel-like crosslinked polymer) had been comminuted to a diameter of about 5 mm or less.
The water-containing gel contained 0.0510 mass % thermally decomposing radical initiator (= Ci mass %) and 40.7 mass % solid content (- Cm mass %). The thermally decomposing radical initiator content index was 46,6, These results are shown in Table 1.
The comminuted water-containing gel-like crosslinked polymer was spread on a 50-mesh metal net and dried in hot wind at 180*C for 45 minutes. The dried substance was pulverised in a roll mill and subjected to a classification using a JlS-standard sieve having a mesh opening size of 710 urn. Those particles which had passed through that sieve were then passed through & JlS-standard sieve having a mesh opening size of 175 um for further classification. The fine
particles having passed through the sieve were removed to
obtain water absorbing resin (S) which had an irregularly pulverized shape, Resin (5) had a ma&s-average particle diameter D50 of 340 urn. The logarithmic standard deviation, ol, of the particle size distribution of resin (Sji was 0,33, Water absorbing resin (SJ had a centrifuge retention capacity CRC of 36,9 g/g and contained 9.2 mass % extractable polymer content. The particles of such sizes that they could pass through a sieve having a mesh opening size of* ISO pis accounted for 1.7 mass % of resin (5),
100 mass parts of obtained water absorbing resin (5) was evenly mixed with a surface crosslinking agent that was a mixed solution of 0.38 mass part l,4-butanediol» 0.63 mass part propylene glycol,, and 2.74 mat* part pure water. After the mixing, the mixture was heat treated at 2i2**C. Sample mixtures were prepared with different heating times; 40 minutes and 45 minutes. Thereafter, the resulting particle samples were disintegrated until they could pass through a JIS-standard sieve hairing a mesh opening size of 710 urn. Next, the disintegrated particle sataples weft subjected to paint shaker test 1, to obtain surface-crosslinked water absorbing resins: the one heated for 40 minutes was designated water absorbing resin (5-40), and the one heated for 45 minutes water absorbing resin (5-45).
A mixed solution of 0.40 mass parts of a 27,5 mass %
aqueous solution of aluminum sulfate {equivalent to 8 mass % aluminum oxide), 0*134 mats parts of a &0 mass % aqueou» solution of sodium lactate,: and 0.002 mass part propylene glycol was added to the surface*eras8Baked water absorbing resins .(5-40) and (5-45) each 100 mass parts. After the addition, the mixtures were dried In a. windless environment for 1 hour at 60° C. Following the drying, these particle samples were disintegrated until they could pass through a J IS-standard sieve having a mesh opening size of 710 pm, Kext, the disintegrated particle samples were subjected to paint shaker test 2* to obtain water absorbing resins; the one obtained from water absorbing resin (5-40) was designated water absorbing resin (5-40A), and. the one obtained from water absorbing resin (S-45) water absorbing resin (5-45A).
Table 2 shows measurements of the CMC, AAP, SFC, D50, and ratio of particles of such sizes that they could pass through a sieve having; a mesh opening size of 150 pa for water absorbing resins (5~40A| and (5-4 5 A).
436,4 g of an acrylic acid* 4617.9 g of a 37 mass % aqueous solution of sodium aery late, 381*0 g of pure water, and 11.40 g of polyethylene glycol diacrylate (weight-average
molecular weight Mw 523) were dissolved in a reaotor which was a lidded double-arm stainless steel kaeader (internal
volume 10 liters) equipped with two sigma-type blades and a jacket, to prepare a reaction solution. Next, the reaction solution was de aerated in a nitrogen gas atmosphere for 20 minutes. Subsequently, 29.07 g of a 10 mass % aqueous solution of sodium persulfate and 24,22 g of a 0,1 mass % aqueous solution of L-ascorbic acid were added to the reaction solution while stirring, about 25 seconds after which polymerisation started, The polymerization was let to proceed at 25DC to 95°C inclusive, while crushing the produced gel. The water-containing gel-like crosslinked polymer was removed 30 minutes into the polymerization. After the polymerisation started, it took not longer than 15 minutes to reach a maximum temperature. The resulting water-containing gel (water-containing gel-like crosslinked polymer) had been comminuted to a diameter of about 5 mm or less.
The water-containing gel contained 0,0381 mass % thermally decomposing radical initiator (•* Ci mass %) and 40.9 mass % solid content (■ Cm mass %}. The thermally decomposing radical initiator content index was 34.6, These results are shown in Table 1 >
The comminuted water-containing gel*ltke crosslinked polymer was spread on a 50-mesh metal net and dried in hot wind at 180°C for 45 minutes- The dried substance was pulverised in a roll mill and subjected to a classification
using a JlS-standard sieve having a mesh opening size* of 710 pi, Those particles which had. passed through that sieve were then passed through a JI8-standard sieve having a mesh opening size of 175 pm for farther classification. The fine particles having passed through the sieve were removed to obtain comparative water absorbing resin (1) which had an irregularly pulverized shape. Comparative resin (I) had a mass-average particle diameter DSO of 342 pm. The logarithmic standard deviation, o%t of the particle size distribution of comparative resin {I) was 0.33, Comparative water absorbing resin fijl had a centrifuge retention capacity CRC of 33,3 g/g and contained 7,4 ma»$ % extractable polymer content. The particles of such sizes that they could pass through a sieve having a mesh opening size of 3 50 um accounted for 1.7 mass % of comparative resin (1). Table 3 shows measurements by the aforementioned method of the intrinsic viscosity IV and the weight-average molecular weight Mw for comparative water absorbing resin (1) at such a weight-average molecular weight Mw that Log |Mw) 100 mass parts of obtained comparative water absorbing resin (1) was evenly mixed with a surface crosslinking agent that was a misted solution of 0.38 mass part l,4-butancdiol> 0.63 mass part propylene glycol, and 2.74 mass part pure water. After the mixing, the mixture was heat treated at 212*C. Sample mixtures were prepared with different heating
times: 25 minutes, 30 minutes, and 35 minutes. Thereafter, the resulting particle samples were disintegrated until they could pass through a JlS-standard sieve having a mesh opening size of 710 «-». Next, the disintegrated particle sampler were subjected to paint shaker test 1, to obtain surface-croa&Hnked comparative water absorbing resins; the one heated for 25 minutes was designated comparative water absorbing resin (1-25), the one heated for 30 minutes comparative water absorbing resin (1-30), and the one heated for 35 minutes comparative water absorbing resin (1-35), Table 3 shows measurements by the aforementioned method of the intrinsic viscosity IV and the weight-average molecular weight Mw for comparative water absorbing resins {1-25) and (1-35) at such a weight-average molecular weight Mw that Log (Mw) • 6.10.
A mixed solution of 0.40 mass part® of a 27.5 mass % aqueous solution of aluminum sulfate (equivalent to 8 mass % aluminum oxide), 0*134 mass parts of a 60 mass % aqueous solution of sodium lactate, and 0.002 mass part propylene glycol was added to surface-crossiinked comparative water absorbing resins (1-25), (1-30), and (1-35) each 100 mass parts. After the addition, the mixtures were dried in a windless environment for 1 hour at eO^C. Following the drying, these particle samples were disintegrated until they could pass through a JlS-nt&ndard sieve having a mesh opening size
of 710 -vim. Next, the disintegrated particle samples were subjected to paint shaker test 2, to obtain water absorbing reslnst the one obtained from comparative water absorbing resin (1-25) was designated water absorbing resin (1-25A)» the one obtained from comparative water absorbing resin (1-30) water absorbing ream (1-30A), and the one obtained from comparative water absorbing resin (1-35) water absorbing resin (1-35A).
Table 2 shows measurements of the CRC, AAP, S-FC, D50, and ratio of particles of such sizes that they could pas® through a sieve having a mesh opening si»e of ISO pm for comparative water absorbing resins (1-25AJ, (i-30A)» and (1-35A).
436.4 g of an acrylic acid, 4617,9 g of a 37 mass % aqueous solution of sodium acryiate, 385.9 g of pure water, and 11.40 g of polyethylene glycol diacrylate (weight-average molecular weight Mw 523) were dissolved in a reactor which was a lidded double-arm stainless steel kneader (internal volume 10 liters) equipped with two slgma-type blades and a jacket, to prepare a reaction solution. Next, the reaction solution was deaerated in a nitrogen gas atmosphere for 20 minutes. Subsequently, 24,22 g of a 10 mas® % aqueous solution of sodium persuifate and 24,22 g of a 0,1 mass %
aqueous solution of L-ascorbic acid were added to the reaction solution while stirring, about 25 seconds after which polymerization started. The polymerization was let to proceed at 25*C to 95*C inclusive, while crushing the produced gel. The water-containing gel-like crosslinked polymer was removed 30 minutes into the polymerization. After the polymerization started, it took not longer than 15 minutes to reach a maximum temperature. The resulting water-containing gel (water-containing gel-like crosslinked polymer) had been comminuted to a diameter of about 5 mm or less.
The water-containing gel contained 0,0319 mass % thermally decomposing radical initiator (« Ci mass %) and 40.8 mass % solid content {= Cm mass %}. The thermally decomposing radical initiator content index was 29,1, These results are shown in Table 1.
The comminuted water-containing gel-like crosslinked polymer was spread on a 50-mesh metal net and dried in hot wind at 18G*C for 45 minutes. The dried substance was pulverised in a roll mill and subjected to a classification using a JlS-standard sieve having a mesh opening si2e of 710 p, Those particles which had passed through that sieve were then passed through a JIB-standard sieve having a mesh opening size of 175 iim for further classification. The fine particles having passed through the sieve were removed to
obtain comparative water absorbing resin (2) which had an irregularly pulverized shape, Comparative resin (2) had a mass-average particle diameter D50 of 340 urn. The logarithmic standard deviation, og, of the particle size distribution of comparative resin (2) was 0.33. Comparative water absorbing resin 12J had a centrifuge retention capacity CRC of 33.2 g/g and contained 7.4 mass % extractable polymer content. The particles of such siases that they could pass through a sieve having a mesh opening sise of- 150 um accounted for 1.6 mass % of comparative resin (2). Table 3 shows measurements by the aforementioned method of the intrinsic viscosity IV and the weight-average molecular weight Mw for comparative water absorbing resin (2} at such a weight-average molecular weight Mw that Log (Mw) • 6,10.
100 mass parts of obtained comparative water absorbing resin (2) was evenly mixed with a surface crosslink!ng agent that was a mixed solution of 0.38 mass part 1,4-butancdiol, 0,63 mass part propylene glycol, and 2.74 mass part pure water. After the mixing, the mixture was heat treated at 212°C. Sample mixtures were prepared with different heating times: 30 minutes, 40 minutes, and 45 minutes. Thereafter, the resulting particle samples were disintegrated until they could pass through a J IS-Standard sieve having a mesh Opening sisse of 710 pm. Next, the disintegrated particle samples were subjected to paint'shaker test I, to obtain
surface-crosslinked comparative water absorbing resins; the one heated for 30 minutes was designated comparative water absorbing resin (2-30), the one heated for 40 minutes
comparative water absorbing resin (2-40), and the one heated for 35 minutes comparative water absorbing resin (2-45),
A mixed solution of 0.40 mass parts of a 27,5 mass % aqueous solution of aluminum sulfate (equivalent to 8 mass % aluminum oxide), 0,134 mass parts of a 60 mass % aqueous solution of sodium lactate, and 0.002 mass part propylene glycol was added to surface-crosslinked comparative water absorbing resins (2*30), (2-40), and (2-45) each 100 mass parts. After the addition, the mixtures were dried in a windless environment for 1 hour at ©O^C Following the drying, these particle samples were disintegrated until they could pass through a J1S-standard sieve having a mesh opening stee of 710 um. Next, the disintegrated particle samples were subjected to paint shaker test 2, to obtain water absorbing resins: the one obtained from comparative water absorbing resin (2-30) was designated water absorbing resin (2-30A), the one obtained from comparative water absorbing resin (2-40) water absorbing resin (2-40A), and the one obtained from comparative water absorbing resin (2-45) water absorbing resin (2-45A),
Table 2 shows measurements of the CRC, AAP, SFC, DS0, and ratio of particles of such sizes that they could pass
through a sieve having a mesh opening nlze of 150 um for comparative water absorbing resins {2-30AJ, (2-40A), and (2-45A).
436.4 g of an acrylic acid, 4617.9 g of a 37 mass % aqueous solution of sodium aeryl&te, 382,3 g of pure water, and 10.13 g of polyethylene glycol diacrylate (weight-average molecular weight Mw 523) were dissolved in a reactor which was a lidded double-arm stainless steel knesder (internal volume 10 liters) equipped with two sigma-type blade® and a jacket, to prepare a reaction solution, Next, the reaction solution, was deaerated in a nitrogen gas atmosphere for 20 minutes. Subsequently, 29,07 g of a 10 mass % aqueous solution of sodium persulfate and 24,22 g of a 0.1 mass % aqueous solution of L-ascorbic acid were added to the reaction solution while stirring, about 25 seconds after which polymerization started. The polymerization was let to proceed at 25**C to 95°C inclusive, while crushing the produced gel. The water-containing gel-like crosslinked polymer was removed 30 minutes into the polymerisation. After the polymerisation started, it took not longer than 15 minutes to reach a maximum temperature, The resulting water*containing gel (water-containing gel-like crosslinked polymer) had been comminuted to a diameter of about 5 mm
•The water-containing gel contained 0.0403 mass % thermally decomposing radical initiator (- Ci mass %) and 41.4 mass % solid content (■ Cm mass %), The thermally decomposing radical initiator content index was 36,2. These results are shown in Table 1.
The comminuted water-containing gel-like crosslinked polymer was spread on a 50-raesh metal net and dried in hot wind at 180*C for 4S minutes. The dried substance was pulverised in a roll mill and subjected to a classification using a JlS-ttandard sieve having a mesh opening size of 710 um
100 mass parts of obtained comparative water absorbing resin (3) was evenly mixed with a surface Crosslinking agent that was a mixed solution of 0.38 mass part 1,4-butanediol, 0.63 mass part propylene glycol, 3,39 mass part pure water, and 0.1 mass part sodium persulfat*. After the mixing, the mixture was heat treated at 212°C, Sample mixtures were prepared with, different heating times: 35 minutes, 40 minute®, and 45 minutes. Thereafter, the resulting particle samples were disintegrated until they could pass through a JlS-standard sieve having a mesh opening sisse of 710 pm, Hejet, the disintegrated particle samples were subjected to paint shaker test I, to obtain surface-crosslinked comparative water absorbing resins: the one heated for 35 minutes was designated comparative water absorbing resin (3-35), the one heated for 40 minutes comparative water absorbing resin (3-40), and the one heated for 35 minutes comparative water absorbing resin (3-45).
A mixed solution of 0,40 mass parts of a 27,5 mass % aqueous solution of aluminum sulfate (equivalent to 8 mass % aluminum oxide), 0,134 mass parts of a 60 mass % aqueous solution of sodium lactate> and 0.002 mass part propylene glycol was added to surface-crosslinked comparative water absorbing resins (3-35), (3-40), and (3-4S) each 100 mass parts. After the addition, the mixtures were dried in a windless environment for 1 hour at 60°C. Following the drying,
these particle aamplea were disintegrated until they could pass through a JlS-standard sieve having a mesh opening si*e of 710 pm. Next, the disintegrated particle sampler were subjected to paint shaker test 2, to obtain water absorbing resins: the erne obtained from comparative water absorbing resin (3-35) was designated water absorbing resin (3-35A), the one obtained from comparative water absorbing resin (3-40) water absorbing resin (3-40A), and the one obtained from comparative water absorbing resin (3-45} water absorbing resin (3-45A),
Table 2 shows measurements of the CRC, AAP, SFC, D50, and ratio of particles of such sizes that they could pass through a sieve having a mesh opening size of 150 pm for comparative water absorbing resins (3-35A), (3-40A), and (3*45A).
436.4 g of an acrylic acid, 4617,9 g of a 37 matt % aqueous solution of sodium acrylate, 384.8 g of pure water, and 7.60 g of polyethylene glycol diacrylate (weight-average molecular weight Mw 523) were dissolved in a reactor which was a lidded double-arm stainless steel kneadcr {internal volume 10 liters) equipped with two sigma-type blades and a jacket, to prepare a reaction solution. Next, the reaction solution was deacrated in a nitrogen gas atmosphere for 20
minute®. Subsequently* 29.07 g of a 10 mass % aqueous solution of sodium peraulfate and 24,22 g of a 0.1 mass % aqueous solution, of L-ascorbic acid were added to the reaction solution while stirring, about 25 seconds after which polymerization started. The polymerization was let to proceed at 2SeC to 95*C inclusive, while crushing the produced gel. The water-containing gel-like crasslin&ed polymer was removed 30 minute® into the polymerisation. After the polymerization started, it took not longer than IS minutes to reach a maximum temperature. The resulting water-containing gel (water-containing gel-like crosslinked polymer) had been comminuted to a diameter of about 5 mm or less.
The water-containing gel contained 0.0384 mass % thermally decomposing radical initiator {- CI mass %) and 41.1 mass % solid content (,- Cm mas® %J. The thermally decomposing radical initiator content index, was 34.7. These results are shown in Table 1.
The comminuted water-containing gel-like crossiinked polymer was spread on a 50-mesh metal net and dried in hot wind at 180°C for 45 minutes. The dried substance was pulverized in a roll mill and subjected to a classification using a JlS-standard sieve having a mesh opening size of 710 urn. Those particles which had passed through that sieve were then passed through a JlS-standard sieve having a mesh
opening sisse of 175 um for further classification. The fine particles having passed through the sieve were removed to obtain comparative water absorbing resin {4| which had an irregularly puiveriated shape. Comparative resin (4) had a mass-average particle diameter DSO of 341 \im. The logarithmic standard deviation, ot, of the particle size distribution of comparative re sin (4 J was 0.33, Comparative water absorbing resin {4) had a centrifuge retention capacity CRC of 39.5 g/g and contained 12,1 mass % extractable polymer content. The particles of such sizes that they could pass through a sieve having a mesh opening size of ISO urn accounted for 1,6 mass % of comparative resin (4).
100 mass parts of obtained comparative water absorbing resin (4) was evenly mixed with a surface crosslinklng agent that was a mixed solution of 0.38 mass part 1,4-butancdiol, 0.63 mass part propylene glycol, and 2.74 mass part pure water. After the mixing* the mixture was heat treated at 212"C. Sample mixtures were prepared with different heating times: 45 minutes and SO minutes. Thereafter, the resulting particle samples were disintegrated until they could pass through a JlS-standard sieve having a mesh opening sise of 710 urn. Next, the disintegrated particle samples were subjected to paint shaker test 1, to obtain surface-crosslmked comparative water absorbing resins: the one heated for 45 minutes was designated comparative water absorbing resin
{4-45J, and the one heated for 5-0 minutes comparative water absorbing resin (4-50) ►
A mixed solution of 0.40 mass parts of a 27.5 mass % aqueous solution of aluminum sulfate (equivalent to 8 mass % aluminum oxide}, 0.134 mass parts of a 60 mass % aqueous solution of sodium lactate, and 0,002 mass part propylene glycol was added to surf&ce-crossKnked comparative water absorbing resins (4-4S) and (4-50) each 100 mass parts. After the addition, the mixtures were dried in a windless environment for I hour at 60°C. Following the drying, these particle samples were disintegrated until they could pass through a JlS-standard sieve having a mesh opening size of 710 pniu Next* the disintegrated particle samples were subjected to paint shaker test 2, to obtain water absorbing resins: the one obtained from comparative water absorbing resin {4-45) was designated water absorbing resin (4-45A), and the one obtained from comparative water absorbing resin (4-50) water absorbing resin (4-5GA).
Table 2 shows measurements of the CRC, AAP, SFC, 050, and ratio of particles of such sizes that they could pass through a sieve having a mesh opening siase of 150 um for comparative water absorbing resins (4-4SA) and (4-50A),
From Table 1* the thermally decomposing radical initiator content indices of the water-containing gels obtained in the examples of the indention ranged from 40 to 100. In contrast, those of the water-containing gels obtained in the comparative examples ranged from 29.1 to 36.2, which was out of the range of the present invention. In other words, the adoption of the step of polymerizing a water-soluble unsaturated monomer 0.06 to 5 mol% of which is composed of an internal erosslinking agent and the step of drying at 100 to 25G*C a water-containing gel which has a thermally decomposing radical initiator content index of 40 to 100 enables the proiiision of a water absorbing resin with excellent physical properties. Accordingly, the water absorbing resin of the present invention, if used, in a water absorbent core, forma a water absorbent core with excellent liquid acquisition rate per unit time and high performance.
From Tabic 2, the water absorbing resins obtained in the
examples ©f the invention had very well-balanced CRCs and SPCs when compared to the comparative water absorbing resins obtained in the comparative examples. This was also evident from the graph in Figure 2, Accordingly, the water
absorbing resin of the present invention, if used in a water absorbent core, forms a water absorbent core with excellent liquid acquisition rate per unit time and high performance,
From Table 3, the intrinsic viscosities, IV, of the water absorbing resins obtained in the examples of the invention after the treatment at such a weight-average molecular weight Mw that Log (Mw-J - fi.10 were 7.3 dL/g or lower. Meanwhile, those of the comparative water Absorbing resins obtained in the comparative examples were all 7.3 dL/g or higher. These differences appear to indicate improvement of the internal structure of the water absorbing resins. In other words, the use of a water absorbing resin of which the intrinsic -viscosity IV is 7,3 dL/g or lower after the treatment at such a weight-average molecular weight Mw that Log (Mw) - 6JO enables the previaion of a water absorbing resin with excellent physical properties, as can be seen from the results shown in Table 2 and Table 3. Accordingly, the water absorbing resin of the present invention, if used in a water absorbent core, forms a water absorbent core with excellent liquid acquisition rate per unit time and high performance.
258,8 g of an acrylic acid, 1.78 (0,0095 mol%) g of polyethylene glycol diacryl&te {weight-average molecular
weight Mw 523), and 1.58 g of a 1.0 mass % aqueous solution of pentasodium diethyienetriamincpentaacetatc were mixed in a polypropylene container (internal diameter 80 mm, capacity 1 liter) to prepare solution (A),
210.6 g of a 48.5 mass % aqueous solution of sodium hydroxide and 212,8 g of ion-exchanged water of which the temperature was adjusted to 32*C were mixed to prepare solution (BJ, Thereafter, solution (B) was quickly added to and mixed with solution fAJ in an open system while stirring with a magnetic stirrer, to prepare a monomer aqueous solution. Neutralization heat and dissolution heat were produced during the course of the mixture; the temperature of the monomer aqueous solution rose to about 102'eC>
14.37 g of a 3,75 mass % aqueous solution of sodium persulfate was added when the temperature of the resultant monomer aqueous solution fell from 102WC to 95°C. After stirring for several seconds, the solution was poured Into a tray-type stainless steel container in an open system. The inside of the container was coated with Teflon (Registered Trademark}. The tray-type stainless steel container had been heated in advance on a hot plate (Neo Hotplate HI-1000, manufactured by As One Corporation) so that the surface temperature reached 100°C.
The tray-type stainless steel container had a bottom {250 mm x 250 mm) &»d a top {640 mm x 640 sua). Its height was SO mm. The cross-section of the mid-section of the tray-type stainless steel container was trapezoidal. Its top was open.
Soon after the monomer aqueous solution was poured
into the tray-type stainless steel container, polymerisation started. The polymerisation proceeded producing water vapor and expanding in every direction. Thereafter, the content shrank to a size a little larger than the bottom. The expansion and shrink finished in about 1 minute. After being left in the polymerization container for 3 minutes, the water-containing gel-like crossimked polymer was removed.
The obtained water-containing gel" like crosslinked polymer was crushed using a meat chopper with- a dice diameter of 9,5 mm (Royal Meat Chopper VR40Q K, manufactured by lidsswka Industries Co., Ltd.} to obtain a comminuted water-containing gel-like crosslihked'polymer. In the crushing, the gel was fed at a rate of about 340 g/min, and at the same time deionized water was also added at 48 g/min.
The amount, Ci, of the thermally decomposing radical initiator of the water-containing gel in ma«i % wa® 0.0698 mass %. The solid content. Cm, of the water-containing gel in mass % was 50.75 mass %. The thermally decomposing radical initiator content index was 50.7, These results are shown in Table 4,
The comminuted water-containing gel-like erosslinkcd polymer was spread on a 60-mesh metal net and dried in hot wind at 180*C for 35 minutes. The dried product was then pulverised in a roll mill and then subjected to a classification
using a JIS«st&ndard sieve having a mesh opening size of 710 urn. Those particles that were passed through the sieve were
further classified using a JIS-standard sieve having a mesh opening size of 175 um to filter out fine particles. The result was water absorbing resin (61 which was irregularly pulverised. Resin {6\ was had a mass-average particle diameter D50 of 342 urn. The logarithm standard deviation, The water absorbing resin (6) had a centrifuge retention capacity CRC of 31.1 g/g and contained a 6.3 mass % extractable polymer content. Resin {6) contained 1.5 mass % particles which could pass through a sieve having a mesh opening size of 150 pm»
100 mass parts of water absorbing resin {6} obtained was evenly mixed with a surface erosslinking agent that was a mixed solution of 0-31 mass parts of 1,4-butanediol, 0.49 m&$s parts of propylene glycol, and 2,4 mass parts of pure water. The mixture was then heat treated at 212*C for 35 minutes. Thereafter, obtained particles were subjected to paint shaker test I, to obtain surface-crosslinked water absorbing resin (6-35},,
A solution was added to 100 mass parts of surface-crosslinked water absorbing resin {6-35). The solution was a mixture of 0.80 mass parts of a 27 mass % aqueous solution of aluminum sulfate (equivalent to an S mass %
aqueous solution of aluminum oxide), 0.134 mass parts of a 60 mass % aqueous solution of sodium lactate, and 0.016 mass parts of propylene glycol. After the addition, the obtained particles were disintegrated until they could pass through a JlS-standard sieve having a mesh opening sise of 710 urn. Next, the disintegrated particles were subjected to paint shaker test 2, to obtain water absorbing resin (6-35A).
The same process was carried out as in example 6P except that the concentration of the aqueous solution of sodium persuifate was changed from. 3,75 mass % to 4,50 mass %.
The amount, Ci, of the thermally decomposing radical initiator of the obtained water-containing gel in mass % was 0.OS51 ma»*i %- The solid content, Cm, of the water-containing gel in mass % was 51.02 mass %, The thermally decomposing radical initiator content index was 61,4, These results are shown in Tabic 4.
The obtained water-containing gel was further processed as in example 6 to obtain irregularly pulverised water absorbing resin (7) which had a mass-average particle diameter BfSO of 342 urn, The logarithm standard deviation, al, of the particle swse distribution of resin (7) was 0,32.
Water absorbing resin (71 had a centrifuge retention
capacity CRC of 30.0 g/g and contained a 5.6 mass % extract&ble polymer content. Resin (7) contained 1.4 mass % particles which could pass through a sieve having a mesh
opening si»c of 150 urn.
Water absorbing resin {7) was further processed as in example 6 to obtain water absorbing resin {7-35A}.
The same process was carried out as in example 6, except that the concentration of the aqueous solution of sodium per&ulfate was changed from 3,75 mass % to 3.00 mass %.
The amount, Ci» of the thermally decomposing radical initiator of the obtained water-containing gel in mass % was 0.0495 mass %. The aolid content, Cm, of the water-containing gel in mass % was 50.35 mass %. The thermally decomposing radical initiator content index was 36.2. These results are shown in Table 4,
The obtained water-containing gel was further processed as in example 6 to obtain irregularly pulverized comparative water absorbing resin (5) which had a mass-average particle diameter D50 of 342 pun. The logarithm standard deviation, o£, of the particle sisse distribution of resin (5) was 0.32.
Comparative water absorbing resin {5} had a centrifuge retention capacity CRC of 30,6 g/g and contained a 5.6 mass % extractable polymer content. Comparative resin (5} contained 1.6 mass % particles which could pass through a sieve hairing a mesh opening size of 150 pm,
Comparative water absorbing resin (5) was further processed as i» example 6 to obtain water absorbing resin (5-35A).
Table 5 shows measurements Of the CRC> AAP, 8FC, D50, and ratio of particles of such sizes that they could pass through a sieve having a mesh opening size of 150 \xta for water absorbing reams (6-35A) and {7-35A} and comparative water absorbing resin (5"35A),
Water absorbing resin was taken out from the lower
layer (close to the back sheet) of "Refte Wearable Shorts* {thin type; for long time usei size LLj lot no. 40623} obtained in December 2004. The water absorbing resin was used as comparative water absorbing resin (6).
Water absorbing resin was taken out from a *GO0. NM {First Underwear; stew J*; lot no, 7026281519) obtained in April 2006. The water absorbing resin was dried under reduced pressure {i mmHg or lower) at 60°C for 12 hours, to prepare comparative water absorbing resin {7),
Water absorbing resin was taken out from a "HUGOIES Ultra Comfort- (sizt h; lot no. 2005.11.26, TJ0430541128) obtained in June 2006, The water absorbing resin was dried under reduced pressure (i mmHg or lower) at 60*C for 12 hours, to prepare comparative water absorbing resin (8).
Water absorbing resin was taken out from "Pampers Let's go* (size 4 maxi; lot no. FOL02/02/O6 6033 4518 09 22:15) obtained in Ju»e 2006. The'water absorbing resin was
dried under reduced pressure (1 mmHg or lower) at 6Q°C for 12 hours, to prepare comparative water absorbing resist (9).
Table 6 shows measurements of the weight-average molecular weight Mw, number-average molecular weight Ma, and molecular weight distribution Mw/Mn of water absorbing resins (1-40A), (2-45A), (3-50AJ, ?4~4SA), (5-45A), (6-35A), and (7-35A}, comparative water absorbing resin (1-30A), (2-40A), (3-40A), (4-50A), (5-35AJ, (6), (7), and (8}, and comparative water absorbing resin (9) obtained above were measured under set 2 of hydrolysis conditions,
Tabic 7 shows measurements of the weight-average molecular weight Mw„ number-average molecular weight Mn, and molecular weight distribution Mw/Mn of the water-soluble components of water absorbing resins {1-40A}, {2-45A), (3-50A), (4-45A), (5-45A)> (6-35A), and (7-35A) obtained above.
Water absorbing resins (1-40AJ, (2-45A}, (3-5GA), (4-45A), (5-45A), (6-35A}, and (7-35A) were processed as below.
50 weight parts of the water absorbing resin was dry-mixed with 50 weight parts of wood-crushed pulp in a mixer. Next, the obtained mixture was molded into a web 120 mm * 350 mm. The web was pressed under a pressure of 2 kg/ cm2 for 5 seconds, to obtain a water absorbent core the basic weight of which was about 500 g/ro3«
Subsequently, a back sheet {liquid impermeable sheet), the water absorbent core, and a top sheet (liquid permeable sheetj were attached together in this order using double-sided adhesive tape. The back sheet was made of polypropylene which was impermeable to liquid and had •'leg gathers." The top sheet waa made of polypropylene which was permeable to liquid. The assembly was then provided with two "tape zippers" to make am absorbing article (that is, a disposable diaper). The absorbing article weighed 44 grams.
The absorbing article was fixed flat on a table- On top of the article were placed a 20-mesh metal net (12 x 40 cm), an acrylic plate of the eame siae (equipped at the center with a cylinder 70 mm in diameter for liquid injection), and a load, so that the water absorbent core, is under a total load of 20 g/cm2.
75 tnL of a 0.9 mass % aqueous solution of sodium
chloride, the temperature of which was adjusted to 37°C, was quickly poured into the cylinder. Time (AT) was counted until the liquid was absorbed. The same operation was repeated every 60 minutes (a total of four tiroes).
The times ATI to AT4 which it took for the liquid to be absorbed in the first to fourth observations respectively were summed to obtain a value AT (sec). From this value, a liquid acquisition rate per unit time (AR) was calculated as in the equation foeiow:
AR (mL/sec) - 300/AT
Table 8 shows measurements of the AT (sec) and liquid acquisition rate per unit time (AR) of each, of the absorbing articles prepared using the above water absorbing resins.
The same process was carried out as in example % on each of comparative water absorbing resins {1-30A), (2-40A), (3-40A), (4-50A), (5-35A), (6), (?}, (8), and (9). Table 8 shows measurements of the AT (sec) and liquid acquisition rate per unit time (AR) of each of the absorbing articles prepared using the comparative water absorbing resins,
It is understood from Table 8 that the water absorbing resins of the example of the present application, when used as water absorbent seres, exhibit excellent liquid acquisition rates per unit time.
The water absorbing resin and water absorbent core in accordance with the present Invention, as well as the water absorbing resin obtained by the method of manufacturing a water absorbing resin in accordance with the present invention* are applicable as water absorbing/retaining agents for various uses because they have excellent water absorption and other properties and produce little dust.
Specific	applications	may	include	water
absorbing/retaining agents for absorbent articles, such as disposable diapers, sanitary napkins* incontinent pads, and medical pads; agriculture/horticulture water retaining agents, such as bog moss replacements, soil conditionera, water retaining agents, and agricultural chemical enhancers; water retaining agents for construction purposes, such as dew inhibitors for interior wall materials and cement additives; release controlling agent; cold insulators; disposable pocket stoves; sludge coagulating agents; food freuhness retaining agents; ion exchange column materials; sludge/oil dehydrates: desiccants; and humidity conditioning agents.
In addition the water absorbing resin of the present invention ia especially suitable for use in disposable diapers, sanitary napkins, and like sanitary/hygienic materials for absorbing feces, urine, or blood.
1. A method of manufacturing a water absorbing resin obtained by polymerization of a water-soluble unsaturated monomer 90 mol% or more of which i* composed of an acrylic acid and/or salt thereof, the resin having an internal crosslinking structure, the method comprising the steps of:
fa) polymerizing cither an aqueous solution or a water dispersed solution of the water-soluble unsaturated monomer; and
(b) drying at, 100 to 250*C a water-containing gel which has a thermally decomposing radical initiator content index of 40 to iO0» step (b) being implemented simultaneously with or after step (a), the index being given by:
Thermally Decomposing Radical Initiator Content Index - (Ci/Mi)/(Cm/Mm) x 10s where:
Ci is a quantity in mas® % of a thermally decomposing radical initiator extracted by stirring the water-containing gel in a 5% aqueous solution of sodium chloride for 1 hour immediately prior to step (b);
Mi is a mole-average molecular weight in mol/g of the extracted thermally decomposing radical initiator;
Cm is a solid content in mass % of the water-containing gel obtained by drying the water-containing gel at ISO^C for 8
Mm is a mole-average molecular weight in mol/g of a polymerized monomer.
2,	The method of claim 1, wherein the water-soluble
unsaturated monomer contains an internal cross! in king agent
in an amount 0,06 to 5 moi%.
3,	The method of either one of claims 1 and 2, wherein the thermally decomposing radical initiator is added to a reaction system of step {a) before and/or during step (a),
4,	The method of any one of claims 1 and 3, wherein the thermally decomposing radical initiator is a persulfate.
5,	The method of any one of claims 1 to 4, wherein the water-containing gel contains 10 mass % or less unreaeted monomer.
6,	The method of any one of claims 1 to 5, wnerein the water-containing gel contains 10 to 80 mass % solid content and after the drying, 90 mass % or more solid content,
7,	The method of any one of claims 1 to 6f further comprising the step of surface crosslinking the dried water absorbing
8,	The method of any one of claims I to 7„ further comprising
the step of adding a polyvalent metal salt to the water
absorbing resin,
9.	A water absorbing resin, comprising a water-soluble
unsaturated monomer as a repeat unit for a major chain, 90
mol% or more of the monomer being composed of an acrylic
acid and/or salt thereof, the resin having an internal
cro&slinking structure and exhibiting an intrinsic viscosity IV
of 7.3 dL/g or lower at such a weight-average molecular
weight M« that Log (Mw) - 6,10, where the molecular weight
Mw and the intrinsic viscosity IV are measured after treating
SO rog of the water absorbing resin in 10 grams of a 0.1 mel/L
aqueous solution of sodium hydroxide at 80°C for 3 weeks.
10,	The water absorbing resin of claim 9, wherein the water
absorbing resin has a weight-average molecular weight in
logarithm {Log (Mw)) of 5,7 to 6.5 after the treatment.
11.	The water absorbing resin of either one of claims 9 and 10,
the water absorbing resin has a solubility which differs
by 10 to 100 wt% before and after the treatment; and
the water absorbing resin lias a solubility of 50 to 100 wt% after the treatment.
12,	The water absorbing resin of any one of claims 9 to 11, further comprising a polyvalent metal salt at least either on a surface of the water absorbing resin or near the surface in a ratio of 0.001 mass % to 5 mats %a inclusive, to the water absorbing resin,
13,	The water absorbing resin of any one of claims 9 to 12, wherein:
the water absorbing resin has a centrifuge retention capacity CRC of more than or equal to 5 g/g and less than 25
g/gJ and
the water absorbing resin has a saline flow conductivity SFC of more than or equal 100 (10-7«cm3#s»g*lJ,
14,	The water absorbing resin of any one of claims 9 to 12,
the water absorbing resin has a centrifuge retention capacity CRC of more than or equal to 25 g/g and less than 30 g/g; and
the water absorbing resin has a saline flow conductivity SPC of more than or equal to 30 (l0-»«caa»*B»g-»).
15.	The water absorbing resin of any one of claims 9 to 12,
the water absorbing resin has a centrifuge retention capacity CRC of HIOTC than, or equal to 30 g/g and less than
SO g/g: aad
the water absorbing resin has a saline flow conductivity SFC of more than or equal to 10 (10-7cm3s*G-1),
16.	The water absorbing resin of any one of claims -9 to 15,
wherein the water absorbing resin had an absorbency under a
4,83 kPa load AAP of more than or equal to 20 g/g and less than or equal to 30 g/g,
17.	The water absorbing resin of any one of claims 9 to 16,
the water absorbing resin has a mass-average particle diameter D50 of 200 to 600 urn;
the water absorbing resin contains 0 to 5 mass % particles of such sizes that the particles can pass through a sieve having a mesh opening size of 150 µm; and
the water absorbing resin has such a particle size distribution with a logarithmic standard deviation o£ of 0.20 to 0,50,
IS. The water absorbing resin of any one of claims 9 to 17,
wherein the water absorbing resin contains dust in an amount of less than or equal to 300 ppm to a mass of water absorbing resin.
19.	A water absorbing resin, comprising a water-soluble
mol% of the monomer being composed of an acrylic acid
and/or salt thereof, the resin having an interna] crosslinking
structure and exhibiting a weight-average molecular weight
Mw of 360,000 to 1,000,000 daltons and an intrinsic viscosity
IV of 2.1 to 6,0 dL/g where the weight-average molecular
weight Mw and the intrinsic viscosity IV are measured after
treatment under set 2 of hydrolysis conditions, in which
treatment 20 mg of the water absorbing resin is left in 10
grama- of a 0,1 mol/L aqueous solution of sodium hydroxide at
80*0 for 3 weeks,
20.	The water absorbing resin of claim 19, wherein the resin shows a molecular weight distribution Mw/Mn after the treatment of 2.0 to 3.0.
21.	The water absorbing resin of either one of claims 19 and 20, wherein the resin contains extractable polymer content which has a weight-average molecular weight Mw of 150,000 to 500,000 daltona.
22,	The water absorbing resin of any one of claims 19 to 21, wherein the resin contains extractable polymer content which ha an intrinsic viscosity IV of 1.0 to 2.0 dL/g.
23,	The water absorbing resin of any one of claims 19 to 22, wherein the resin contains extractable polymer content which has a molecular weight distribution Mw/Mn of 2.0 to 3.0,
24,	The water absorbing resin of any one of claims 19 to 23,
the water absorbing resin has a mass-average particle diameter D50 of 200 to 600 pm;
• the water absorbing resin has such a particle size distribution with a logarithm standard deviation of of 0,20 to 0.50.
5042-CHENP-2008 AMENDED PAGES OF SPECIFICATION 05-01-2012.pdf
5042-CHENP-2008 AMENDED PAGES OF SPECIFICATION 1 05-01-2012.pdf
5042-CHENP-2008 AMENDED CLAIMS 05-01-2012.pdf
5042-CHENP-2008 AMENDED PAGES OF SPECIFICATION 25-09-2013.pdf
5042-CHENP-2008 AMENDED CLAIMS 25-09-2013.pdf
5042-CHENP-2008 CORRESPONDENCE OTHERS 05-01-2012.pdf
5042-CHENP-2008 EXAMINATION REPORT REPLY RECEIVED. 25-09-2013.pdf
5042-CHENP-2008 FORM-13 05-01-2012.pdf
5042-CHENP-2008 FORM-3 25-09-2013.pdf
5042-CHENP-2008 FORM-5 25-09-2013.pdf
5042-CHENP-2008 OTHERS 25-09-2013.pdf
5042-CHENP-2008 CORRESPONDENCE OTHERS 27-12-2013.pdf
5042-CHENP-2008 CORRESPONDENCE OTHERS 18-12-2013.pdf
5042-chenp-2008 description (complete) 2.pdf
5042-chenp-2008 description (complete).pdf
5042-CHENP-2008 FORM-3 27-12-2013.pdf
5042-CHENP-2008 FORM-3 18-12-2013.pdf
5042-chenp-2008 abstract.pdf
5042-chenp-2008 claims.pdf
5042-chenp-2008 correspondence-others.pdf
5042-chenp-2008 drawings.pdf
5042-chenp-2008 form-1.pdf
5042-chenp-2008 form-18.pdf
5042-chenp-2008 form-3.pdf
5042-chenp-2008 form-5.pdf
5042/CHENP/2008
1-1, KORAIBASHI 4-CHOME, CHUO-KU OSAKA-SHI, OSAKA 541-0043
1 KAZUSHI TORII 931-11-F-202, HAMADA ABOSHI-KU HIMEJI - SHI HYOGO 671-1242
2 HIROFUMI SHIBATA 931-11-F-301 HAMADA ABOSHI-KU HIMEJI - SHI HYOGO 671-1242
C08F20/06
PCT/JP2007/056528
1 85652/2006 2006-03-27 Japan
2 239474/2006 2006-09-04 Japan
3 188668/2006 2006-07-07 Japan