Organic binder for shaping ceramic, its production method and product employing the same

A multilayer ceramic substrate comprising at least one ceramic layer made by laminating at least one ceramic green sheet layer and conductor layers formed on surfaces of the at least one ceramic green sheet layer into laminates and by sintering the resulting laminates. Each ceramic green sheet layer comprises a ceramic precursor composition comprising (I) 100 parts by weight of ceramic fine powder having an average particle diameter of 10 microns or less as component (C) and (II) 5 to 30 parts by weight, based on 100 parts by weight of the ceramic fine powder, of an organic binder for bonding the ceramic fine powder. The organic binder comprises (i) 100 parts by weight of a water insoluble polymer of at least one vinyl monomer as a major component of the organic binder, as component (A), and (ii) 1 to 9.5 parts by weight, based on 100 parts by weight of the component (A), of water soluble polymer as component (B). In the binder particles of the component (A) being dispersed by the component (B) in an aqueous medium resulting from suspension polymerization of the at least one vinyl monomer in water containing the water soluble polymer as a dispersion stabilizer.

BACKGROUND OF THE INVENTION 
The present invention relates to an organic binder for shaping ceramic used 
to produce the shaped product, namely green sheet consisting of ceramic 
precursor when shaping so called ceramic including alumina from the 
viewpoint of low pollution, resource saving and safety; it related 
especially to the organic binder for shaping ceramic of water system 
excellent in removability of binder, its production method and product 
employing the same. 
(i) Conventionally, such an organic binder as butylal resin and acrylic 
acid ester is generally used as ceramic binder. This binder is dissolved 
or dispersed in such organic solvent as alcohol, ketone, chloride system 
solvent, aromatic solvent, is mixed with fine ceramic powder, and is 
kneaded by the ball mill or similar means for a long time to be made into 
a slip form. After being degassed, this is cast into sheets having a 
specified thickness by the doctor blade method or reverse quarter method, 
and heated and dried on such a material as polyester film to be made into 
green sheets. 
(ii) Regarding the ceramic water-soluble binder, the watersoluble polyvinyl 
acetal having an acetalization degree of 10 mol percent or less is 
disclosed in the Japanese Patent Application Laid-open NO. 56-76405, and 
the cold water soluble polyvinyl acetal having an acetalization degree of 
10 to 30 mol percent or less is disclosed in the Japanese Patent 
Application Laid-open NO. 1-29408-1989, while the denaturated polyvinyl 
alcohol (PVA) having the side chain of hydrophobic group or specific ionic 
hydrophilic group uses as water system organic binder is disclosed in the 
Japanese Patent Application Laid-open NO. 59-156959. 
(iii) The water soluble acrylic acid ester system binder is disclosed in 
the Japanese Official Patent Gazette 1-53233, the Japanese Official Patent 
Gazette 1-44668 and the Japanese Patent Application Laid-open NO. 
1-286955. Ammonia, trialkylamine such as trimethylamine, and amine such as 
dimethylamine alcohol, monoethanolamine are added to the methacrylic acid 
ester or acrylic acid ester copolymer having the carboxyl group 
(hereinafter referred to as "(meth)acrylic acid copolymer") -the 
(meth)acrylic acid ester copolymer consisting of copolymerized 
(meth)acrylic acid--thereby achieving neutralization (pH adjustment). 
(iv) Emulsion binders which are produced by emulsification and 
polymerization of vinyl monomer by the surfactant and which are 
neutralized (pH-adjusted) by ammonia using the (meth)acrylic acid are 
disclosed in Japanese Patent Application Laid-open NO. 60-180955, Japanese 
Patent Application Laid-open NO. 60-180956, Japanese Patent Application 
Laid-open NO. 61-151060 and Japanese Patent Application Laid-open NO. 
1-286955, while those having crosslinking structure are disclosed in the 
Japanese Patent Application Laid-open NO. 63-260855. 
(v) The Japanese Patent Application Laid-open NO. 3-131604 discloses the 
swollen substance comprising (a) alpha-olefin polymer, (b) single 
(meth)acrylic acid or (meth)acrylic acid monomer and stylene monomer, and 
(c) polymerization initiator is dispersed, for example, in the water 
system medium containing such a polymerization dispersant as water soluble 
high polymer polyvinyl alcohol and is subjected to suspension 
polymerization to be formed into the binder. 
(vi) The Japanese Patent Application Laid-open NO. 59-128266 discloses the 
complex organic binder for shaping ceramic containing 1 to 1,000 parts by 
weight of hydrophobic high polymer (a) for 100 parts by weight of the 
water soluble high polymer. 
On the other hand, (vii) the Japanese Patent Application Laidopen NO. 
59-995 and Japanese Patent Application Laid-open NO. 60-254697 disclose 
the ceramic circuit board production method, where polymethyl methacrylate 
resin and polymethacrylic acid ester resin as the binding including the 
pyrolytic polymer type resin are disclosed. 
For the binder mentioned in said (i), however, butyl alcohol, isopropyl 
alcohol, trichloroethylene, toluene, etc. are used as organic solvent. 
However, they have problems in explosiveness by ignition, hazard of 
causing fire, and offensive odor in molding and drying--especially, the 
halogen system solvent involving such pollution problems as environmental 
pollution by evaporative gas and hazards to human bodies; solution of 
these problems requires installation of an explosion proof device, exhaust 
treatment equipment and solvent recovery equipment. 
The cases of said (ii) and (iii) have the disadvantage that characteristics 
of the ceramic green sheet are subjected to variation because water 
soluble has a great hygroscopicity. The case of said (iv) has the 
disadvantage that the ceramic green sheet using emulsion having carboxyl 
group features a weak tensile strength and is inferior in glossiness and 
flatness. 
Furthermore, all binders involve such problems as inferior removability of 
binders and inferior strength of the ceramic sheet and ceramic circuit 
board after firing. 
The case of said (v) features poor mutual solubility between components (a) 
and (b) is poor and inferior mechanical characteristics of the ceramic 
precursor composition. Use of polymers featuring poor thermal 
decomposition such as alphaolefin polymer and polyvinyl alcohol involves 
such problems as inferior removability of binders and inferior strength of 
the ceramic, ceramic sheet and ceramic circuit board after firing. 
The case of said (vi) provides a method by which hydrophobic high polymer 
latex produced as water system dispersion substance by emulsification and 
polymerization is dissolved in water soluble high polymer solution. Since 
the water soluble high polymer contains a great deal of high polymers 
featuring poor thermal decomposition, it is important to minimize the 
amount to be added if the water soluble high polymer is to be used as 
binder. Presence of a great deal of water soluble high polymers will cause 
the green sheet to absorb moisture, resulting in increased variations of 
mechanical characteristics. Furthermore, hydrophobic high polymer latex 
generated by emulsification and polymerization contains much surfactant; 
this means a poor workability since it may cause coagulation depending on 
the type of ceramic powder, and cause foams to be produced during 
degassing. 
On the other hand, when the polymethylmethacrylate resin and 
polymethacrylic acid ester resin used in (vii) are to be used as organic 
binder for shaping ceramic, it provides a method of producing the green 
sheet having a uniform thickness from the slip composed, for example, of 
ketone solution such as methylethylketone, alcohol solvent such as butyl 
alcohol, plasticizer, and ceramic powder by the doctor blade method. In 
this case, all solvents have high steam pressure, and safety against fire 
is inferior. To ensure safety against fire, conventional techniques have 
depended on a combined use of halogen solvent, involving environmental 
pollution problems. 
SUMMARY OF THE INVENTION 
The object of the present invention is to provided an organic binder for 
shaping ceramic which will solve these problems involved in the 
conventional techniques, will improve such characteristics of the green 
sheet as flexibility, shapability, dispersive power, surface states, 
mechanical strength by the application of the present invention, will 
improve such characteristics as compactness, surface flatness, laminated 
pressure bondability and mechanical strength of the multilayer ceramic 
substrate gained by lamination and firing of said green sheet, and will 
ensure a low pollution and resource saving; another object of the present 
invention is to provide a method of producing said organic binder; and a 
still another object is to provide the ceramic precursor, ceramic, ceramic 
green sheet, ceramic sheet, multilayer ceramic substrate which have 
excellent characteristics and are obtained by using said organic binder. 
In an attempt to achieve said objects, the present inventors have made 
strenuous efforts to find out that the organic binder for shaping ceramic 
obtained by suspension polymerization using the water soluble high polymer 
as dispersion stabilizer for polymerization has an excellent removability 
of binders and is effective as a water system organic binder for shaping 
ceramic, thereby completing the present invention. 
The present invention achieves said objects by means of the organic binder 
for shaping ceramic characterized in that component (A) is subjected to 
suspension polymerization in the presence of the polymerization initiator 
in the water containing 100 parts by weight of dissolved component (A) 
comprising of one or more types of methacrylic acid esters (the alkyl 
group having 1 to 18 carbons or the ring alkyl group or aryl group ester 
having 1 to 12 carbons) and 1 to 9.5 parts by weight of dissolved 
component (B) comprising water soluble high polymer for 100 parts by 
weight of component (A)!, or in the mixture between water and water 
soluble organic solvent. 
The ceramic powder as component (C) is not specifically limited, but the 
average particle size of the ceramic powder, when turned into green sheet, 
should preferably be 50.0 microns or less. The specified shaped product is 
obtained from the ceramic precursor composition slurry comprising the 100 
parts by weight of ceramic powder as component C, 5 to 30 parts by weight 
of said organic binder for shaping ceramic as component (D) and, whenever 
required, the dispersant and plasticizer as component (E). 
The green sheet is obtained by coating on the substrate a thin film of the 
ceramic precursor composition slurry comprising the 100 parts by weight of 
ceramic powder as component (C) having an average particle size of 50.0 
microns or less, 5 to 30 parts by weight of said organic binder for 
shaping ceramic as component (D) and, whenever required, the dispersant 
and plasticizer as component (E), thereby achieving said object. 
The ceramic green sheet layer is composed of the ceramic precursor 
composition slurry comprising the 100 parts by weight of ceramic powder as 
component (C) having an average particle size of 50.0 microns or less, 5 
to 30 parts by weight of said organic binder for shaping ceramic as 
component (D) and, whenever required, the dispersant and plasticizer as 
component (E); on which conductor layers are formed patternlike and the 
5-60 green sheet layers with conductor layers are laminated and bonded, 
and sintered (in the binder removing process, then in the residual carbon 
reducing process), thereby producing multilayer ceramic substrates. 
Furthermore, the green sheet layer is composed of the ceramic precursor 
composition slurry comprising the 100 parts by weight of ceramic powder as 
component (C) having an average particle size of 10.0 microns or less, 5 
to 30 parts by weight of said organic binder for shaping ceramic as 
component (D) and, whenever required, the dispersant and plasticizer as 
component (E); and said object can be achieved by the method of producing 
the multilayer wiring ceramic substrate formed by sintering the laminate 
having conductor layers through two or more of said green sheet layers. 
When used as such IC substrates, the average particle size of the ceramic 
powder is more preferably 10 microns or less.

DETAILED DESCRIPTION OF THE INVENTION 
The following describes the details of the present invention: 
The present invention relates to the organic binder for shaping ceramic and 
its production method characterized in that component (A) is subjected to 
suspension (co)polymerization in the presence of the polymerization 
initiator in the water or in the mixture between water and water soluble 
organic solvent, containing 100 parts by weight of dissolved component (A) 
comprising one or more types of (meth)acrylic acid esters (the alkyl group 
having 1 to 18 carbons or the ring alkyl group or aryl group ester having 
1 to 12 carbons), and 1 to 9.5 parts by weight of dissolved component (B) 
comprising water soluble high polymer for 100 parts by weight of 
component (A)!. 
The component (A) used in the present invention is the major component of 
the organic binder for shaping ceramic, and serves to bind between ceramic 
powder and ceramic powder. As the component (A) there can be employed 
methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth)acrylate, 
isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 
n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 
n-octyl (meth)acrylate, isooctyl (meth)acrylate, desyl (meth)acrylate, 
dodesyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 
cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, phenyl 
(meth)acrylate, benzyl (meth)acrylate or the like. 
Of these components, methacrylic acid ester system, and n-butyl 
methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl 
methacrylate, n-octyl methacrylate and methyl methacrylate are suitable 
from the viewpoint of thermal decomposition. 
The component (B) used in the present invention is a water soluble high 
polymer used as a dispersion stabilizer for polymerization when said 
component (A) is polymerized in the presence of the polymerization 
initiator. For example, polyethylene oxide, polyvinyl-2-pyrolidone, 
polyvinyl-2-pyrolidone copolymer, poly(2-oxazoline) system or the like are 
used. From the viewpoint of thermal decomposition, polyethylene oxide is 
more preferred. When used as organic binder for ceramic, the average 
particle size of the polymer (the particle size at the center of the 
particle size distribution) should be 5 microns or less and more 
preferably 3.0 microns or less. 
To produce the polymer particle size, the polyethylene oxide for the 
dispersion stabilizer for polymerization should have the viscometric 
molecular weight from 100,000 to 1,000,000, preferably from 250,000 to 
500,000. The amount of component (B) to be used should be 1 to 9.5 parts 
by weight for 100 parts by weight as the total volume of the monomer. When 
the amount used is less than 1 part by weight, there is no dispersion. The 
polymer size will increase, resulting in particle sedimentation. When 9.5 
parts by weight are exceeded, the sintered product will have mall strength 
because of inferior removability of binder if this water soluble high 
polymer is used as binder. In this case, moreover, the dielectric constant 
is high beyond practical use. Since component (B) comprises polymer, the 
external appearance of the green sheet prepared will much flat than the 
low molecular surfactant is used. In this case, ceramic powder is less 
likely to drop from the surface and foams are not easily formed in the 
degassing process, exhibiting excellent workability. When the water 
soluble high polymer is used, humidity will cause the variation of the 
mechanical characteristics of the green sheet, resulting in reduced 
drilling accuracy. 
However, the water soluble high polymer having crystallinity like the 
polyethylene oxide (melting point: over 60.degree. C. to 67.degree. C., 
viscometric molecular weight: 100,000 to 1,000,000) has a low 
hygroscopicity; it has been found out that, even if it is mixed with the 
polymer of component (A) to be used as binder, it is not affected very 
much by humidity. It has also been found out that the performance of the 
water system organic binder according to the present invention is equal to 
or greater than that of the green sheet produced from the organic solvent 
comprising said component. 
It is also possible to use by adding a combination of one or more of 
hydroxyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate and 
2-hydroxypropyl (meth)acrylate to component (A) in the range of 30 weight 
percent or less, if so required. If 30 weight percent is exceeded, 
coagulation will occur among polymer particles dispersed in the suspension 
during suspension polymerization, resulting in failure in obtaining stable 
suspension; hence practical use is not possible. In the same way, it is 
also possible to use by adding a combination of one or more of such 
ethylene monomer as ethyrene, isobutylene and methacrylonitrile, such 
styrene monomer as styrene, alphamethylstyrene and such unsaturated 
diester monomer as maleic acid diester, fumaric acid diester, itaconic 
acid diester and citraconic diester in the range of 50 weight percent or 
less, if so required. If 50 weight percent is exceeded, the sintered 
product is less strong because of poor removability of binder when the 
ceramic sintered product is produced by using this copolymer as a binder, 
resulting in higher dielectric constant; hence practical use is not 
possible. The purpose of copolymerizing said vinyl monomer such as 
ethylene to component (A) is to ensure improved thermal decomposition and 
enhanced mechanical properties. 
The plasticizer used with the binder is basically not likely to azeotrope 
wit water or water system solvent, and has an excellent solubility with 
the polymer gained from vinyl monomer. Examples are phthalic acid ester 
such as dibutyl phthalate (hereinafter referred to as "DBP"), 
di-2-ethylhexyl phthalate (DOP), diisonyl phthalate (DINP), diisodesyl 
phthalate (DIDP), dihexyl phthalate (DHP), di-n-octyl-phthalate (N-DOP), 
butylbenzyl phthalate (BBP) and ethyl phthalyl ethyl glycolate, such 
aliphatic ester as di-2-ethylhexyl adipate (DOA) and dibutyl glycol 
adipate (BXA), such propylene glycol ether as tripropylene glycol methyl 
ether (TPM), dipropylene glycol-n-butyl ether (DPnB), tripropylene 
glycol-nbutyl ether (TPnB) and propylene glycol hexyl ether (PPh); of 
these, DOP, DINP, DIDP, DHP and N-DOP are preferred. The said plasticizer 
may be added according to each form, and is not placed under particular 
restriction, so long as the mechanical characteristics of the ceramic 
precursor composition formed by the use of the organic binder for shaping 
ceramic are maintained and good handling properties are ensured. Namely, 
the mechanical properties of the green sheet obtained by changing the 
amount of the plasticizer to be added can be adjusted by the plasticizer. 
As a guideline, elongation of about 5 to 25% is required in order to 
ensure the good handling properties of the green sheet and drilling 
accuracy. The plasticizer may be added either during the suspension 
polymerization of vinyl monomer or after polymerization. It is more 
preferred to add it during polymerization to prevent the polymer particles 
from bonding with each other. 
The solid content of the organic binder should be at most 50 wt %, and at 
least 15 wt %. When it exceeds 50 wt %, the particle diameter of component 
(A) becomes too large, and when it is less than 15 wt %, the efficiency of 
work lowers. 
To produce the organic binder for shaping ceramic used in the present 
invention is, 1 to 9.5 parts by weight of component (B) for the total 100 
parts by weight of component (A) comprising the monomer is dissolved in 
water or or in the mixture between water and water soluble organic 
solvent. Component (A) is added in this solution in the presence of the 
polymerization catalyst while being heated and violently agitated; hence 
polymerization or copolymerization. 
Typical solvents used in the present invention are water soluble solvents 
such as alcohol including water, methanol, ethanol, propanol and 
isopropanol, ethylene glycol derivatives including ethylene glycol methyl 
ether, ethylene glycol ethyl ether, and ethylene glycol butyl ether, 
diethylene glycol derivatives including diethylene glycol methyl ether, 
diethylene glycol ethyl ether, and diethylene glycol butyl ether, 
propylene glycol derivatives including propylene glycol methyl ether, 
propylene glycol ethyl ether, and propylene glycol butyl ether, acetic 
ether derivatives including methyl acetate and ethyl acetate, lactic ester 
derivatives including methyl lactate and ethyl lactate. Selection is made 
from at least one type of water or in the mixture between water and water 
soluble solvent. It is also possible to add some of the alcohol solvent 
which is not water soluble. 
When water and water soluble solvent are used, the mixing ratio should be 
100 to 50 weight percent of water and 0 to 50 weight percent of water 
soluble solvent, or more preferably 95 to 50 weight percent of water and 5 
to 50 weight percent of water soluble solvent. 
As polymerization initiator, such azo-compounds as 2, 
2'-azobis(isobutyronitrile), and 2, 2'-azobis(isobutyl) baleronitrile, 
such peroxides as t-butyl hydroperoxide, benzoyl peroxide and t-butyl 
peroxide, such persulfates as ammonium persulfide and potassium 
persulfide--these water soluble polymerization initiators can be used 
without restriction. The preferred amount to be used should be 0.05 to 5 
parts by weight for the total amount of monomer, 100 parts by weight. The 
molecular weight of the binder can be controlled by addition of such chain 
transfer agents as tertiary-dodecyl mercaptan and thioglycol as required. 
This reaction can be performed normally at the temperature of 40 to 
90.degree. C., even if it may depend on the type of the polymerization 
catalyst. High molecular products will be generated at a lower 
temperature, and low molecular products will be produced at a higher 
temperature. 
The weight average molecular weight of the polymer of the vinyl monomer 
which is said binder used for the present invention should be 100,000 to 
1,000,000, or more preferably, 200,000 to 550,000. Mechanical properties 
of the green sheet will be insufficient below 100,000, and the fluidity of 
the binder resin will be reduced over 1,000,000, resulting in insufficient 
mechanical properties of the green sheet. 
The particle diameter of the polymer obtained from the present invention 
can be measured by an electronic microscope and microtrack technique. 
As ceramic powder having an average particle diameter of 50.0 microns or 
less used in the present invention, at least one type has been selected 
from among the following; Al.sub.2 O.sub.3, SiO.sub.2, 3Al.sub.2 
O.sub.3.SiO.sub.2, PbO, Al.sub.2 O.sub.3.MgO, B.sub.2 O.sub.3, CaO, BaO, 
ZrO.sub.2, ZrO, Na.sub.2 O, P.sub.2 O.sub.3, K.sub.2 O, Li.sub.2 O and so 
on. To give more concrete examples, it is selected from at least one type 
of ceramic powder of alumina (Al.sub.2 O.sub.3), mullite (3Al.sub.2 
O.sub.3.2SiO.sub.2) and cordierite (2MgO.2Al.sub.2 O.sub.3.5SiO.sub.2) and 
from at least one type of glass ceramic powder of the borosilicate glasses 
SiO.sub.2 -B.sub.2 O.sub.3 -Na.sub.2 O system, SiO.sub.2 -B.sub.2 O.sub.3 
-K.sub.2 O system, SiO.sub.2 - B.sub.2 O.sub.3 -ZnO system, and SiO.sub.2 
-B.sub.2 O.sub.3 -Li.sub.2 O system. These glasses should preferably be 
the non-crystalline or crystalline glass ceramics which can be fired at 
the temperature lower than the melting point of the copper or should 
preferably have the components where cristobalite are difficult to 
generate after sintering. The fine particle of this ceramic is used in 
spherical or pulverized form. When fine through hole drilling is required, 
the average particle diameter of the ceramic powder for the green sheet 
should generally be 10 microns or less, or more preferably, 5 microns or 
less. 
Such high dielectric substances as BaTiO.sub.3 and highly resistant 
materials can be listed as ceramic materials used for the present 
invention; they are not placed under any particular restriction. The 
examples of the dispersant aid for ceramic include such polyacrylates as 
ammonium polyacrylate, phosphate ester, polyethylene glycol, 
polyvinyl-2-pyrolidone and copolymer, glycerol trioleaste (Advances in 
ceramics, Vol. 21 Ceramic Powder Science PP. 537 to 547, 1987). 
The ceramic dispersant aid serves to make mutual coagulation of ceramic 
power difficult and to facilitate slurry flow. The ceramic dispersant aid 
is used by adding the ceramic powder to the solution dissolved or 
dispersed in the solvent (water, water and water soluble solvent). Before 
it is used, a ball mill is utilized to perform wet mixing for 1 to 5 
hours, then a specified amount of the organic binder for shaping ceramic 
is added. Again the ball mill is used to wet mix this ceramic precursor 
composition for at least 10 hours. 
To produce the ceramic precursor composition used in according to the 
present invention, ceramic precursor composition comprising the 100 parts 
by weight of ceramic powder as component (C), 5 to 30 parts by weight of 
(meth)acryl resin suspension liquid as the binder which is component (D), 
and, if required, the dispersant as component (E) selected from among many 
ceramic dispersant aids is wet mixed by the ball mill for at least five 
hours, to be made into ceramic precursor composition slurry. After passing 
through the degassing process, it is subjected to extrusion molding, 
injection molding, doctor blade method, calender roll method and other 
methods, to be formed into the ceramic precursor composition. Production 
method is not restricted. 
According to the ceramic production method adopted in the present 
invention, the product is obtained by fired the ceramic precursor 
composition obtained from said procedure at the temperature of 350 to 
1800.degree. C. in the air or non-reducible atmosphere for at least 5 
hours. 
The following introduces the method of producing the multilayer ceramic 
substrate used for the present invention: 
The ceramic precursor composition comprising the 100 parts by weight of 
ceramic powder as component (C) having an average particle size of 50.0 
microns or less, 5 to 30 parts by weight of (meth)acryl resin suspension 
liquid as the binder as component (D) and, if required, the dispersant as 
component (E) selected from among many ceramic dispersants is wet mixed by 
the ball mill for 5 to 50 hours, to be made the ceramic precursor 
composition slurry. After passing through the degassing process, it is 
formed into the green sheet by the doctor blade method or the like at the 
room temperature or cast temperature. To improve the mechanical properties 
of the green sheet, it may be dried at 100 to 120.degree. C. for 90 
minutes if required. The resulting green sheet of 0.05 to 2 mm thickness 
is cut off to a specified size (e.g. 10 to 200 mm .times.10 to 200 mm 
square), and through-holes are drilled at the specified positions on the 
required layer. The through hole diameter is not placed under restriction, 
but may be as small as 40 microns. 
The conductor paste comprising the major component made of one or more of 
the conductors W (melting point 3410.degree. C.), Mo (melting point 
2620.degree. C.), Ag (melting point 961.9.degree. C.). Au (melting point 
1064.degree. C.), Pt (melting point 1769.degree. C.), Pd (melting point 
1554.degree. C.), Cu (melting point 1083.4.degree. C.), Ni (melting point 
1453.degree. C.), etc. is printed at the specified position of the green 
sheet provided with said holes by means of screen printing. In this way, a 
specific circuit is formed on the green sheet via the screen mask. Five to 
sixty of the green sheets provided with circuits are laminated, and are 
hot pressed and pressure bonded at the temperature of 80 to 150.degree. C. 
with the pressure of 0.98 MPa to to 29.4 MPa (10 to 300 kg/cm.sup.2). The 
resultant laminate is cut off to get the specified shape and dimensions. 
Firing temperature differs depending on the type of the said conductor 
(generally to be fired below the melting point of the conductor); however, 
the ceramic substrate can be obtained by firing at the temperature of 350 
to 1800.degree. C. in the air or non-reducible atmosphere for at least 5 
hours. 
To produce the multilayer glass ceramic circuit substrate, during the 
firing process, firing is conducted at the temperature of 350 to 
450.degree. C. in the process of temperature rise in the air or 
nonreducible atmosphere, and further firing is performed at the 
temperature of 600 to 900.degree. C. for removing the binder. After that, 
in order to scatter the residual carbon, firing is performed, if required, 
at the temperature from 900.degree. C. to the temperature below the 
melting point of the said conductor under the atmosphere of hydrogen 
(H.sub.2) and water vapor (H.sub.2 O) at the volume ratio of 10.sup.-7 to 
10.sup.-4 or the water vapor (inert atmosphere controled the water vapor 
pressure in the range of 0.005 to 0.5 atm.); then the multilayer glass 
ceramic substrate can be obtained. 
The organic binder for shaping ceramic obtained from the present invention 
has the solvent composed of water alone or water and water soluble organic 
solvent. It makes it possible produce the ceramic green sheet featuring 
excellent ceramic dispersion, surface flatness, density, elongation, and 
strength, completely or almost without using the non-water soluble organic 
solvent or without having to use it. This provides a great advantage in 
meeting the low pollution and resource saving requirements. Furthermore, 
laminating and firing said green sheet provide the more dense multilayer 
ceramic substrate featuring excellent surface flatness and strength. 
The organic binder for shaping ceramic according to the present invention 
is very effective as the organic binder for water system ceramic, and said 
organic binder for shaping ceramic exhibits its function for bondage among 
ceramic fine powders, to provide the characteristics of flexibility, 
shapability, dispersive power and surface properties required from the 
green sheet. It also provides characteristics such as lamination pressure 
bonding and mechanical strength required from the laminate of the green 
sheet provided with circuit patterns. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The following describes the preferred embodiments of the present invention; 
however, it should not be understood that the present invention is limited 
only to the following description. 
Notice that symbol "%" appearing in the following description stands for 
"weight percentage." 
The ceramic precursor composition was obtained by adding the 100 parts by 
weight of ceramic powder to 5 to 30 parts by weight of organic binder for 
shaping ceramic, and was kneaded by the ball mill. After making the 
ceramic precursor composition slurry, this slurry was degassed by pressure 
reduction. After adjustment of the viscosity of the uniform slurry mixture 
liquid prepared in this way, it was coated on the polyester film, using 
the doctor blade casting device. Then the film was dried and the green 
sheet was manufactured, and characteristics of the sheet were evaluated 
for shapability, flexibility and dispersive power. 
Shapability 
Shapability was evaluated by visual observation by coating the green sheet 
on the polyester film and drying it. 
o: The green sheet can be removed smoothly from the polyester film without 
being cracked. 
.DELTA.: Green sheets were a little cracked. 
x: Excessive cracks without forming green sheets 
Flexibility 
The center of the green sheet was held by each of five types of glass rods 
having different diameters, and a 180.degree. C. bending test around that 
position was conducted. Flexibility was indicated by the rod diameters 
(mm) immediately before the sheet was cracked. Rod diameters used were 2, 
3, 4, 6 and 8 mm. 
Dispersive power 
o: Little secondary coagulation for dispersion of ceramic fine particles in 
the green sheet 
.DELTA.: Slightly excessive secondary coagulation for dispersion of ceramic 
fine particles in the green sheet 
x: Much secondary coagulation for dispersion of ceramic fine particles in 
the green sheet 
EXAMPLE 1 
Synthesis of Organic Binder for Shaping Ceramic 
There were added 742.7 g of ion-exchanged water and 28.5 g of polyethylene 
oxide (hereinafter referred to as "PEO", average molecular weight: 250,000 
to 300,000) in the 2-liter flask provided with the agitator, thermometer, 
reflux condenser, dropping funnel and nitrogen gas feed tube downstream of 
the nitrogen gas, while being agitated, so that uniform dissolution would 
be ensured, and nitrogen gas exchange was conducted for 30 minutes. During 
agitation, 300 g of n-butyl methacrylate, 31.5 g of diisonyl phthalate 
(DINP) as plasticizer, and 9 g of water solution of ammonium persulfate of 
5 wt % (solid concentration 0.45 g) as polymerization initiator were added 
to it, and the nitrogen gas was replaced for 30 minutes to 1 hour. It was 
heated at the polymerization temperature of 60.degree. C. for 4 hours, and 
polymerization was further conducted at 80.degree. C. for 2 hours, to 
complete the reaction. It was cooled down to the room temperature to get 
the organic binder for shaping ceramic having a solid concentration of 32% 
(polymer particle diameter: 3.0 microns (50% average particle diameter), 
suspension liquid viscosity: 7 Pa.s, average weight molecular weight : 
500,000). 
Green Sheet Production 
There were mixed 100 parts by weight of the ceramic powder having the 
particle diameter of 5 microns or less composed of alumina powder as major 
component and the total composition being 91% Al.sub.2 O.sub.3, 6% 
SiO.sub.2 and 3% MgO, 40 parts by weight of the ion exchanged water, and 
0.1 parts by weight of the ceramic dispersant aid A6114 (trade name of 
Toagosei Chemical Industry Co., Ltd. in Japan, solid content; 40%) and the 
mixture was kneaded in the ball mill using the vessel lined with alumina 
and alumina-made ball for two hours. Then, there was added 20 pars by 
weight of the organic binder for shaping ceramic, to get the ceramic 
precursor composition. This was kneaded in the ball mill using the vessel 
lined with alumina and alumina-made ball for 24 hours. After producing the 
ceramic precursor composition slurry, this slurry was degassed at the 
reduced pressure of 133.3 Pa to 6665 Pa (1 mm Hg to 50 mm Hg). The 
viscosity of uniform slurry mixture liquid prepared in this way was 
adjusted again under the reduced pressure by scattering water to be 3 Pa.s 
to 10 Pa.s., and the slurry was coated on the polyester film, using the 
doctor blade type casting device. Then it was dried to produce the 0.2 mm 
thick green sheet. The characteristics of the sheet were highly evaluated 
for shapability, flexibility and dispersive power. 
Multilayer Ceramic Substrate Production 
The resulting green sheet was cut off into the squares of 200 mm .times.200 
mm, using a punching die, and guide holes were drilled. After that, the 
green sheet was fixed using these guide holes, and through-holes having a 
diameter of 0.1 mm were punched at specified positions by the punching 
method. The conductor paste of tungsten powder having a particle diameter 
of 5 microns, cellulose nitrate, ethyl cellulose, 
alpha-terepineol=100:4:2:23 (by weight ratio) is coated on the 
through-holes on the green sheet, and specified circuit patterns were 
printed on the surface of the green sheet by screen printing. There are 
laminated 40 of these green sheets provided with circuit patterns printed 
with conductor according to the position of the guide hole, and they were 
hot pressed and pressure bonded at the temperature of 120.degree. C. with 
the pressure of 9.80 MPa (100 kgf/cm.sup.2). The resulting laminates were 
cut off into specified shapes to get 150 mm square green sheet alminates, 
which were fired at 1600.degree. C. in the firing furnace having the 
atmosphere with the mixture of nitrogen, hydrogen and water vapor for 2 
hours. During the firing process, binders were removed when the 
temperature was rising. Multilayer ceramic substrates having 120 mm square 
and 7 mm thickness were produced by this green sheet lamination method. 
EXAMPLES 2 to 11 
Table 1 illustrates the binder composition, amount to be used, and results 
of evaluating the green sheet characteristics with reference to said 
Example 1 and Examples 2 to 11. 
Synthesis of Organic Binder for Shaping Ceramic 
In Examples 2 to 4, the mixing ratio between component (A) and component 
(B) was determined so that, for 300 g of component (A), the PEOs as 
components (B) were 24 g, 21 g and 15 g in weight respectively, and the 
weight of ion-exchanged water was set to 733.1 g, 726.8 g and 718.0 g, 
respectively. In Examples 5 to 7, the type of the vinyl monomer as 
component (A) (at the fixed mixing ratio) and the type of the viscometric 
molecular weight and amount to be used of component (B) were changed; in 
Examples 8 to 11, the mixing ratio between water and water soluble solvent 
was changed. Except these, conditions were the same as those of Example 1, 
thereby gaining the organic binder for shaping ceramic having the solid 
concentration of 32 weight percent. 
Green Sheet Production 
The same conditions as those of Example 1 were used, except that the 
organic binder for shaping ceramic and its amount to be added were 
changed, and the green sheet was produced. Table 1 illustrates the 
characteristics of the green sheet. 
The same experiment as that in Example 1 was conducted to produce a 
multilayer wiring ceramic substrate from the green sheet. 
Embodiments 12 to 28 
Table 2 shows the type of the component (A) which is the binder 
composition, the type of the plasticizer, the type of the polymerization 
initiator and its amount used, and various dispersants for polymerization 
of component (B), as well as the resultant valuation of the properties of 
the green sheet. 
Organic Binder for Shaping Ceramic Synthesis 
The organic binder for shaping ceramic having a solid content concentration 
of 32 weight percent was obtained under the same condition as those in 
Example 1, except that the type of component (A), the type of the 
plasticizer and its amount used, the type of the polymerization initiator, 
and the type of the water-soluble solvent and its amount used were changed 
as shown in Table 2. 
Green Sheet Production 
The 0.1 parts by weight of said A6114 and 40 parts by weight of 
ionexchanged water were added to 100 parts by weight of ceramic powder 
having a particle diameter of 5. micros or less comprising of the 
components of 65 vol % of borosilicate glasses (SiO.sub.2 : 79%, B.sub.2 
O.sub.3 : 19% and K.sub.2 O: 2%), 15 vol % of alumina and 20 vol % of 
cordierite as glass ceramic. Then they were kneaded by the ball mill for 
two hours; then 10 to 30 parts by weight of the organic binders for 
shaping ceramic shown in Table 2 were added to them, thereby obtaining the 
ceramic precursor composition. This ceramic precursor composition was put 
to experiment in the same way as Example 1, and the green sheet was 
produced. Table 2 illustrates the properties thereof. 
Multilayer Ceramic Substrate Production 
The resulting green sheet was cut off into the squares of 200 mm .times.200 
mm, using a punching die, and guide holes were drilled. After that, the 
green sheet was fixed using these guide holes, and through-holes having a 
diameter of 0.1 mm were punched at specified positions by the punching 
method. The conductor paste comprising the 89 weight percent of copper 
powder having a particle diameter of 3 microns, and 11 weight percent of 
vehicle (solvent: 90 to 95 weight percent of n-butyl carbitol acetate, 
binder: ethyl cellulose, 5 to 10 weight percent) is filled into the green 
sheet provided with through holes. The specified circuit patterns were 
printed on the surface of the green sheet by screen printing. These fourty 
green sheets provided with circuit patterns printed with conductor are 
laminated according to the position of the guide hole, and were hot 
pressed and pressure bonded at the temperature of 120.degree. C. with the 
pressure of 9.80 MPa (100 kgf/cm.sup.2). The resulting laminates were cut 
off into specified shapes to get 150 mm square green sheet alminates, 
which were fired at 950.degree. C. in the nitrogen atmosphere for 2 hours 
after binders had been removed at 350 to 850.degree. C. under the 
nitrogen-hydrogen-water vapor atmosphere for 20 hours. During the firing 
process, binders were removed sufficiently when the temperature was 
rising. There were produced 120 mm square, 7 mm-thick multilayer ceramic 
substrates by this green sheet lamination method. 
Reference Example 1 
Binder Resin 
The binder used was the denaturated PVA which was the polyvinyl acetate 
copolymer containing 0.4 mol percent of octyl acrylamide and 2.0 mol 
percent of trimethyl-3-(1-methacrylamide propyl) ammonium chloride, where 
88.7 mol percent of the vinyl acetate component was saponified and 4 
percent water solution viscosity at 20.degree. C. was 34 centipoises. 
Green Sheet Production 
The 100 parts by weight of the ceramic powder having the particle diameter 
of 5 microns or less composed of alumina powder as major component and the 
total composition being 33% Al.sub.2 O.sub.3, 33% SiO.sub.2 and 43% 
borosilicate glasses, 6 parts of the said binder, one part of 
polyoxyethylene nonyl phenol as dispersant, and 50 parts of ion exchanged 
water were added to get the ceramic precursor composition. This was 
kneaded in the ball mill using the vessel lined with alumina and 
alumina-made ball for 24 hours. Experiment was then continued in the same 
way as Example 1, to get the green sheet. Table 4 illustrates the 
characteristics thereof. 
Reference Example 2 
Binder Resin 
Using 20 g of monoethanolamine salt as a dispersant, for obtaining 
copolymer having the weight average molecular weight of about 100,000 
comprising the acrylic acid, butyl acrylate and ethyl acrylate (at the 
weight ratio of 50 to 25 to 25) using 0.4 g of ammonium persulfate as 
polymerization initiator, ethyl acrylate is emulsified and polymerized in 
80 g of mixed solvent of water and methanol at the ratio of 5 to 5 by 
weight, thereby obtaining latex of 50% solid content. 
Green Sheet Production 
Except that 24 parts of said latex and 18 parts of ion exchanged water were 
used, experiment was conducted in the same way as Reference Example 1 and 
the green sheet was produced. Table 4 illustrates the characteristics 
thereof. 
Reference Example 3 
Binder Resin 
Using non-ionic surfactant as dispersant, the latex comprising butyl 
acrylate, acrylic acid and methacrylic acid (at the polymerization ratio 
of 70 to 15 to 15) as emulsifier was obtained. 
Green Sheet Production 
Except that 10 parts of said latex (solid contents) and 25 parts of 
monoethanolamine and ion exchanged water as neutralizer were used, 
experiment was conducted in the same way as Reference Example 1 and the 
green sheet was produced. Table 4 illustrates the characteristics thereof. 
Reference Example 4 
Binder Resin 
The latex having the composition of 75 parts by weight of ethyl acrylate, 
75 parts by weight of methyl methacrylate, and 4.5 parts by weight of 
N-methylol acryl acid amide was obtained, using 4 parts by weight of the 
glycine betaine chloride ester of the polyoxyethylene octyl phenyl ether 
and 4 parts by weight of dimethacylic acid ester of polyoxy propylene 
polyoxyethylene glycol as emulsifier, and using 2, 2'-azobis (N, 
N'-dimethylene isobutylamidine) hydrochloride as polymerization initiator. 
Green Sheet Production 
Except that 10 parts of said latex (solid contents), 3 parts of 
polyethylene glycol (molecular weight 200) as plasticizer, 2 parts of 
ethyl carbitol and 25 parts of ion exchanged water were used, experiment 
was conducted in the same way as Reference Example 1 and the green sheet 
was produced. Table 4 illustrates the characteristics thereof. 
Reference Example 5 
Binder Resin 
The emulsion of hydrophobic high polymer water system 
dispersant/methacrylic acid ester (MMA/n-BMA/LMA/CHMA =10/60/10/20, solid 
content 48%) and 10% water soluble high polymer PVA (polymerization 500, 
saponification degree 88.5 mol percent) as component (A) were mixed at the 
weight ratio of 1 to 1 to get the organic binder for green sheet 
(composite binder). 
Green Sheet Production 
Experiment was conducted in the same way as Reference Example 1 and the 
green sheet was produced, except that 100 parts by weight of the ceramic 
powder having the particle diameter of 5 microns or less composed of 
alumina powder as major component and the total composition being 33% 
Al.sub.2 O.sub.3, 33% SiO.sub.2 and 43% borosilicate glasses, 16 parts by 
weight of said latex (solid content), 50 parts by weight of water, and 0.3 
parts by weight of dispersant aid of ammonium salt polyacrylate were 
kneaded by the ball mill for two hours; then 10 parts of the composite 
binder (solid content) were added to be mixed uniformed with the powder. 
Table 4 illustrates the characteristics of the obtained green sheet. 
The following defines the abbreviations appearing in Tables 1, 2, 3 and 4: 
PEO: polyethylene oxide 
PEtOZO: poly(2-oxazoline) 
PVP: polyvinyl-2-pyrolidone 
n-BMA: n-butyl methacrylate 
i-BMA: isobutyl methacrylate 
n-BAA: n-butyl acrylate 
MAA: methyl acrylate 
HEMA: 2-hydroxyethyl methacrylate 
St: s tyrene 
EAA: ethyl acrylate 
EMA: ethyl methacrylate 
HEA: hydroxyethyl acrylate 
i-Bt: isobutylene 
i-BMA: isobutyl methacrylate 
BZMA: benzyl methacrylate 
MMA: methyl methacrylate 
HPMA: hydroxy propyl methacrylate 
.alpha.-St: .alpha.-methyl styrene 
MEAA: methoxy ethyl acrylate 
MAA: methyl acrylate 
LMA: lauryl methacrylate 
CHMA: cyclohexyl methacrylate 
PGM: propylene glycol monomethyl ether 
PGE: propylene glycol monomethyl ether 
ML: methyl lactate 
IPA: isopropyl alcohol 
AIBN: 2, 2'-azobis(isobutyronitrile) 
APS: ammonium persulfate 
KPS: potassium persulfate 
t-BHPO: tertiary butyl hydroperoxide 
Then the organic binder obtained in Embodiments 1, 5, 8, 13, 14, 17, 18, 
20, 23 and 26 and Reference Examples 1 to 5 was put into the platinum 
crucible and was incinerated in the 600.degree. C. electric furnace under 
the nitrogen atmosphere for three hours to measure the weight. Five green 
sheets obtained in Embodiments 1, 5 and 8 were hot pressed and pressure 
bonded at 120.degree. C. with the pressure of 100 kg f/cm.sup.2 ; the 
number of the sheets peeled at this time was checked by visual 
observation. Furthermore, it was fired at 1600.degree. C. under the 
nitrogen-hydrogen-water vapor atmosphere for two hours to get the ceramic 
sheet. Five green sheets obtained in Examples 13, 14, 17, 18, 20, 23 and 
26, and Reference Examples 1 to 5 were hot pressed and pressure bonded at 
120.degree. C. with the pressure of 100 kg f/cm.sup.2 the number of the 
sheets peeled at this time was checked by visual observation. Furthermore, 
this laminates ware fired at 950.degree. C. in the nitrogen atmosphere for 
2 hours after binders had been removed at 350 to 850.degree. C. in the 
nitrogen-hydrogen-water vapor atmosphere for 20 hours. The density of 
these sheets was measured and surface conditions were checked by visual 
observation. Table 5 illustrates the results. 
As is clear from the said Embodiments, the organic binder for shaping 
ceramic according to the present invention makes it possible to produce 
the ceramic green sheet featuring excellent dispersion of the produced 
ceramic, surface flatness, density, mechanical strength, completely or 
almost without using the nonwater soluble organic solvent or without 
having to use it. This provides a great advantage in meeting the low 
pollution and resource saving requirements. Especially in the doctor blade 
method, it permits transfer from the organic solvent system to safe and 
hygienic water system, and provides such excellent properties as improved 
mechanical properties, ensuring an efficient use as ceramic binder. 
TABLE 1 
__________________________________________________________________________ 
Binder 
Component (B) 
dispersant for 
polymerization 
Component (A) 
(g) Polymerization 
Green sheet characteristics 
Exam- 
vinyl monomer 
(molecular 
Plasticizer 
Solvent 
initiator 
Binder 
Shapabi- 
Flexibility 
Dispersive 
ple (g) weight) 
(g) (g) (g) (part) 
lity (mm)* 
power 
__________________________________________________________________________ 
1 n-BMA PEO DINP 
Water APS 20 .largecircle. 
2 .largecircle. 
300 28.5 31.5 
742.7 0.45 
(300,000) 
2 n-BMA PEO DINP 
Water APS 20 " " " 
300 24 31.5 
733.1 0.45 
(300,000) 
3 n-BMA PEO DINP 
Water APS 20 " " " 
300 21 31.5 
726.8 0.45 
(300,000) 
4 n-BMA PEO DINP 
Water APS 20 " " " 
300 15 31.5 
718.0 0.45 
(300,000) 
5 n-BMA 
n-BAA 
PEO None 
Water AIBN 20 " " " 
210 90 27 694.9 0.5 
(250,000) 
6 n-BMA 
n-BAA 
PEO None 
Water AIBN 20 " " " 
210 90 21 682.1 0.5 
(500,000) 
7 n-BMA 
n-BAA 
PEO None 
Water AIBN 20 " " " 
210 90 15 984.4 0.5 
(800,000) 
8 n-BMA 
EMA PEO DINP 
Water 
IPA 
KPS 9 " " " 
210 90 21 50.7 
394.9 
394.9 
0.5 
(300,000) 
9 n-BMA 
EMA PEO DINP 
Water 
IPA 
KPS 14 " " " 
210 90 21 50.7 
473.9 
315.9 
0.5 
(300,000) 
10 n-BMA 
EMA PEO DINP 
Water 
IPA 
KPS 16 " " " 
210 90 21 50.7 
552.9 
236.9 
0.5 
(300,000) 
11 n-BMA 
EMA PEO DIDP 
Water 
IPA 
KPS 20 " " " 
210 90 21 50.7 
631.9 
158.0 
0.5 
(300.000) 
__________________________________________________________________________ 
*Used glass rod diameter 
TABLE 2 
__________________________________________________________________________ 
Binder 
Component 
(B) 
dispersant 
for poly- 
merization Polymeri- 
Green sheet characteristics 
Component (A) 
(g) Plasti- zation Flexibi- 
Disper- 
Exam- 
vinyl monomer 
(molecular 
cizer 
Solvent 
initiator 
Binder 
Shapabi- 
lity 
sive 
ple (g) weight) 
(g) (g) (g) (part) 
lity (mm)* 
power 
__________________________________________________________________________ 
12 n-BMA EMA PED DINP 
Water 
IPA 
KPS 25 .largecircle. 
2 .largecircle. 
210 90 21 50.7 
710.9 
79.0 
0.5 
(300,000) 
13 i-BMA EMA PED DOP Water APS 20 " " " 
270 30 21 28.5 
742.7 0.45 
(300,000) 
14 i-BMA n-BMA PEO DOP Water APS 15 " " " 
180 120 21 20.5 
725.7 0.45 
(300,000) 
15 i-BMA n-BAA PED DOP Water APS 30 " " " 
255 45 21 16.1 
703.4 0.45 
(300,000) 
16 i-BMA n-BAA PEO DOP Water 
EGM 
APS 20 " " " 
228 72 21 10.0 
347.4 
347.4 
0.45 
(300,000) 
17 n-BMA n-BAA PEO DOP Water APS 20 " " " 
210 90 21 6.0 694.9 0.45 
(300,000) 
18 n-BMA NEMA PEO DOP Water APS 5 " " " 
210 90 21 15.2 
714.4 0.45 
(1,000,000) 
19 n-BMA HEMA PEO DOP Water APS 30 " " " 
240 60 21 13.9 
711.7 0.5 
(300,000) 
20 n-BMA St PED DIDP 
Water AIBN 20 " " " 
150 150 15 17.4 
706.4 0.5 
(1,100,000) 
21 MMA EAA 
HEMA PED DIDP 
Water 
IPA 
AIBN 5 " " " 
150 90 60 21 24.D 
513.2 
219.9 
0.5 
(300,000) 
22 EMA n- HEA i- 
PEtOZO 
None 
Water 
ML t-BNPO 
15 " " " 
15B BAA 
75 Bt 
21 477 205 
0.5 
60 15 
(500,000) 
__________________________________________________________________________ 
*: Used glass rod diameter 
TABLE 3 
__________________________________________________________________________ 
Binder 
Component 
(B) 
dispersant 
for poly- 
merization Polymeri- 
Green sheet characteristics 
Component (A) 
(g) Plasti- zation Flexibi- 
Disper- 
Exam- 
vinyl monomer 
(molecular 
cizer 
Solvent 
initiator 
Binder 
Shapabi- 
lity 
sive 
ple (g) weight) 
(g) (g) (g) (part) 
lity (mm)* 
power 
__________________________________________________________________________ 
23 EMA i-BMA 
BzMA 
PEO DHP 
Water 
PGE 
BPO 20 .largecircle. 
2 .largecircle. 
120 120 60 21 4D 537.D 
230.1 
(300,000) 
24 n-BMA 
n-BAA 
MAA PEtDZO 
None 
Water APS 20 " " " 
210 60 30 21 767.125 
0.5 
(500,000) 
25 MMA HEMA 
HPMA 
PEO DBP Water 
ML AIBH 20 " " " 
210 45 45 18 43.5 
537.7 
230.5 
0.5 
(600,000) 
26 i-BMA 
.alpha.-St 
MEAA 
PEO DBP Water APS 20 " " " 
150 90 60 18 9.4 695.7 0.5 
(500,000) 
27 EMA EAA HEAA 
PEO DHP Water 
IPA 
AIBH 20 " " " 
150 90 60 21 29.6 
512.9 
219.5 
0.5 
(300,000) 
28 EMA 
MAA 
HEA 
i-Bt 
PEtOzD 
None 
Water 
PGM 
APS 20 " " " 
30 60 180 
30 21 341.1 
341.1 
0.5 
(500,000) 
__________________________________________________________________________ 
TABLE 4 
__________________________________________________________________________ 
Green sheet properties 
Flexibi- 
Binder 
Shapabi- 
lity 
Dispersive 
Binder composition (part) 
lity (mm)* 
power 
__________________________________________________________________________ 
Reference 
Acetic vinyl copolymer containing 4 mol % 
6 x 8 .DELTA. 
Example 1 
Octyl acryl amide, and 2 mol % trimethyl- 
3-(1-methacrylamide propyl) ammonium 
chloride (saponification degree of acetic 
vinyl component 88.7%), solvent: water 3880 
Reference 
Emulsified polymer of ethyl 
Solvent 
24 x 6 .DELTA. 
Example 2 
acrylate, using monoethanol- 
Water MeOH 
amine salt of acrylic acid/ 
480 120 
ethyl acrylate/butyl acrylate 
(weight ratio: 50/25/25) 
as dispersant 
Reference 
Emulsified polymer of acrylic acid/ethyl 
10 x 6 .DELTA. 
Example 3 
acrylate/butyl acrylate (weight ratio: 15/ 
15/70), using nonionic surfactant as 
emulsifier 
Reference 
4 parts by weight of polyoxyethylene octyl 
10 .DELTA. 
6 .DELTA. 
Example 4 
phenyl ether glycine betaine ester chloride, 
4 parts by weight of methacrylic acid ester 
of polyoxyethylene propylene polyocyl 
ethylene glycol, 75 parts by weight of ethyl 
acrylate, 75 parts by weight of ethyl 
methacrylate, 4.5 parts by weight of 
N-methyrolacrylamide 
Reference 
(B) Water system dispersant of hydrophobic 
5 .DELTA. 
6 .DELTA. 
Example 5 
high polymer: emulsion of methacryl 
acid ester (MMA/n-BNA/LMA/CHMA = 
10/60/10/20) (solid content 48%), 
(A) 10% water soluble high polymer PVA 
(polymerization 500, saponification 
degree 86.5 mol %) 
(B)/(A) = 1/1 
__________________________________________________________________________ 
*Used glass rod diameter 
TABLE 5 
______________________________________ 
Hot pressing and 
pressure bonding 
Density 
Surface 
Example 
Binder ash (%/solid) 
(number of peels) 
(g/cm.sup.3) 
conditions 
______________________________________ 
1 0.0007 0 3.13 Good 
5 0.0075 0 3.12 " 
8 0.0005 0 2.69 " 
13 0.0007 0 2.63 " 
14 0.0011 0 2.68 " 
17 0.0064 0 2.67 " 
18 0.0045 0 2.68 " 
20 0.0162 0 2.69 " 
23 0.0071 0 2.67 " 
26 0.0221 0 2.68 " 
Reference 
2.5664 2 2.32 Rough 
Example 1 
Reference 
1.7230 2 2.55 Rough 
Example 2 
Reference 
3.2410 5 -- Split 
Example 3 
Reference 
0.9451 5 2.52 Cracked 
Example 4 
Reference 
3.1251 5 -- Split 
Example 5 
______________________________________