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Patent US5338815 - Used in thickeners, dispersion stabilizers and lubricants - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA fine particulate crosslinked type N-vinylcarboxylic acid amide resin having an average particle size of 10 μm or less comprising backbone chains of a homopolymer or copolymer comprising repeating units (A) or (A) and (B) of the formulae: ##STR1## wherein R1, R2 and R3 each independently represent...http://www.google.com/patents/US5338815?utm_source=gb-gplus-sharePatent US5338815 - Used in thickeners, dispersion stabilizers and lubricantsAdvanced Patent SearchPublication numberUS5338815 APublication typeGrantApplication numberUS 08/159,242Publication dateAug 16, 1994Filing dateNov 30, 1993Priority dateApr 23, 1991Fee statusPaidAlso published asDE69122377D1, DE69122377T2, EP0510246A1, EP0510246B1, US5280095Publication number08159242, 159242, US 5338815 A, US 5338815A, US-A-5338815, US5338815 A, US5338815AInventorsToshiyuki Aizawa, Hitoshi Nakamura, Tetsuhiko YamaguchiOriginal AssigneeShowa Denko K.K.Export CitationBiBTeX, EndNote, RefManPatent Citations (7), Referenced by (14), Classifications (66), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetUsed in thickeners, dispersion stabilizers and lubricantsUS 5338815 AAbstract A fine particulate crosslinked type N-vinylcarboxylic acid amide resin having an average particle size of 10 μm or less comprising backbone chains of a homopolymer or copolymer comprising repeating units (A) or (A) and (B) of the formulae: ##STR1## wherein R1, R2 and R3 each independently represent a hydrogen atom or methyl group; X represents a group --COOY, wherein Y represents a hydrogen atom, an alkali metal, a C1 -C18 alkyl group or a lower alkyl group substituted with hydroxyl group, a dialkylamino group or a quaternary ammonium group; a group --CONHZ, wherein Z represents a hydrogen atom or a lower alkyl group substituted with a dialkylamino group, a quaternary ammonium group, a sulfonic acid or an alkali metal salt thereof; a cyano group, a 2-ketopyrroridinyl group, a lower alkoxy group, a lower acyl group, a lower alkoxycarbonyl group or a lower alkyl group substituted with sulfonic acid or an alkali metal salt thereof; M represents a hydrogen atom, an alkali metal or an ammonium group, with proviso that when R3 is a methyl group, X is not a cyano group, a 2 -ketopyrrolidinyl group, a lower alkoxy group, a lower acyl group, a lower alkoxycarbonyl group and a lower alkyl group substituted with sulfonic acid or an alkali metal salt thereof, p represents 0 or 1, and the molar ratio of m:n represents 30-100:70-0.
We claim: 1. A microgel of a crosslinked N-vinylcarboxylic acid amide resin comprising a fine particle crosslinked N-vinylcarboxylic acid amide resin gelled with water or an organic solvent, said fine particle crosslinked N-vinylcarboxylic acid amide resin having an average particle size of 10 μm or less comprising backbone chains of a homopolymer comprising repeating units (A) or copolymer comprising repeating units (A) and (B) of the formulae: ##STR3## wherein R1, R2 and R3 each independently represents a hydrogen atom or a methyl group; X represents a group --COOY, wherein Y represents a hydrogen atom, an alkali metal atom, a C1 -C18 alkyl group or a lower alkyl group substituted with a hydroxyl group, a dialkylamino group or a quaternary ammonium group; a group CONHZ, wherein Z represents a hydrogen group or a lower alkyl group substituted with a dialkylamino group, a quaternary ammonium group, a sulfonic acid group or an alkali metal salt thereof; a cyano group, a 2-ketopyrrolidinyl group, a lower alkoxy group, a lower acyl group, a lower alkoxycarbonyl group or a lower alkyl group substituted with a sulfonic acid group or an alkali metal salt thereof: M represents a hydrogen atom, an alkali metal atom, or an ammonium group, with the proviso that when R3 is a methyl group, X is not a cyano group, a 2-ketopyrrolidinyl group, a lower alkoxy group, a lower acyl group, a lower alkoxycarbonyl group or a lower alkyl group substitutes with a sulfonic acid group or an alkali metal salt thereof, p represents 0 to 1, and the molar ratio of m:n represents 30-100:70-0, said resin being produced by the steps of:precipitation (co)polymerizing 30 to 100 mol % of (A) a compound having the formula (I): CH2 ═CHNR1 COR2, wherein R1 and R2 are the same as defined above and 0 to 70 mol % of (B) at least one of fumaric acid, maleic acid or itaconic acid or anhydrides thereof, N-vinyl-2-pyrrolidone or compounds having the formula (II): CH2 ═CR3 X, wherein R3 and X are the same as defined above, in the presence of at least one crosslinking agent selected from the group consisting of:N,N'-1,4-butylenebis(N-vinylacetamide), N,N'-1,6-hexylenebis(N-vinylacetamide), N,N'-1,10-decylenebis(N-vinylacetamide), N,N'-3,6-dioxa-1,5-pentylenebis(N-vinylacetamide), N,N'-xylenebis(N-vinylacetamide), and N,N'-diacetyl-N,N'-divinyl-1,4-bisaminomethylcyclohexane, in a non-aqueous solvent which uniformly dissolves the reaction components upon initiation of the reaction and converting the carboxyl groups or sulfonic acid groups in the molecules with an alkali metal or ammonium hydroxide, if necessary. 2. A microgel as claimed in claim 1, wherein the organic solvent is at least one member selected from the group consisting of a single solvent having a solvent polarity parameter ET of 45 or more and a mixed liquid having a solvent polarity parameter ET of 43 or more.
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to eliminate the defects possessed by a thickener by using a water absorptive resin as represented by the sodium polyacrylate crosslinked product, particularly a low thickening ability in a liquid wherein inorganic or organic ions coexist (electrolyte solution) or a low chemical stability which is a drawback of natural polymeric compounds or chemically modified products thereof, and further, develop a substance having an affinity not only for aqueous systems but also for other organic solvents such as alcohols, and also exhibiting a thixotropic and free flowing thickening property instead of a sticky thickening ability (fiber forming property) with a tacky substance.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Representative specific examples of the respective monomer components of the crosslinked type N-vinylcarboxylic acid amide resin of the above formula are shown below.
EXAMPLES The present invention is described in more detail with reference to Examples, which in no way limit the scope of the present invention.
EXAMPLE 1 A solution of 99 g of N-vinylacetamide and 1.0 g of N,N'-methylenebis(acrylamide) as the crosslinkig agent dissolved in 900 g of benzene was boiled, 0.1 g of azobis(isobutyronitirile) was added as the initiator thereto and the boiling state was maintained. With the progress the polymerization, the polymer formed was precipitated into benzene, which was filtered and vacuum dried at 40� C. for 24 hours and macerated, to obtain a white fine powder with an average particle size of 2 μm.
EXAMPLE 2 The reaction was carried out by the same procedure as in Example 1, except that N-vinylformamide was used in place of N-vinylacetamide, to obtain a white fine powder with an average particle size of 4 μm.
EXAMPLE 3 The reaction was carried out by the same procedure as in Example 1, except that ethyl acetate was used as the polymerization solvent in place of benzene, to obtain a white fine powder with an average particle size of 2 μm.
EXAMPLE 4 A solution of 70 g of N-vinylacetamine, 30 g of acrylic acid, and 2.0 g of divinylbenzene as the crosslinking agent dissolved in 900 g of ethyl acetate was boiled, 0.4 g of azobisisobutyronitrile was added as the initiator, and the boiling state was maintained. With the progress of the polymerization, the polymer formed was precipitated into ethyl acetate. Then, the same procedure as in Example 1 was carried out to obtain a white fine powder with an average particle size of 2 μm. The tests of the thickening ability and salt resistance performance were conduct in the same manner as in Example 1, and the results are shown in Table 1 and able 2.
EXAMPLE 5 The reaction was carried out in the same way as in Example 4 except that 55 g of N-vinylacetamide and 45 g of acrylic acid was used in place of 70 g of N-vinylacetamide and 30 g of acrylic acid, to obtain a white powder with an average particle size of 2.5 μm. The tests of thickening ability and salt resistance were conducted in the same manner as in Example 4, and the results are shown in Table 1 and Table 2.
EXAMPLE 6 A solution of 90 g of N-vinylacetamide, 10 g of methacrylic acid and 1.5 g of tetraallytloxyethane as the crosslinking agent dissolved in 500 g of ethyl acetate was boiled, 0.3 g of benzoyl peroxide was added as the initiator, and the boiling state was maintained. With the progress of polymerization the formed polymer was precidpitated into ethyl acetate, and then the same procedure as in Example 1 was carried out to obtain a white fine powder with an average particle size of 2 μm.
EXAMPLE 7 A solution of 70 g of N-vinylacetamide, 29 g of acrylic acid, 2.0 g of tetraallyloxy-ethane as the crosslinking agent dissolved in 600 g of ethyl acetate was boiled, 0.3 g of benzoyl peroxide was added as the initiator, and the boiling state was maintained. With the progress of the polymerization, the formed polymer was precipitated into ethyl acetate, and then the same procedure as in Example 1 was carried out to obtain a white fine powder with an average particle size of 2 μm.
EXAMPLE 8 A solution of 90 g of N-vinylacetamide, 9 g of methacrylic acid, 1 g of stearyl methacrylate and 1.0 g of pentaerythritol triacrylate as the crosslinking agent dissolved in 900 g of acetone was boiled, 0.3 g of cumyl peroxide was added as the initiator, and the boiling state was maintained. With the progress of the polymerization, the formed polymer was precipitated into ethyl acetate, and then the same procedure as in Example 1 was carried out to obtain a white fine powder with an average particle size of 1.5 μm.
EXAMPLE 9 A solution of 80 g of N-vinylacetamide, 20 g of 2-acrylaide-2-methylpropanesulfonic acid and 0.8 g of N,N'-butylenebis(N-vinyl;acetamide) as the crosslinking agent dissolved in 900 g of acetone was boiled, 0.3 g of cumyl peroxide was added as the initiator, and the boiling state was maintained. With the progress of the polymerization, the polymer formed was precipitated into ethyl acetate, and then the same procedure as in Example 1 was carried out to obtain a white fine powder.
EXAMPLE 10 A solution of 90 g of N-vinylacetamide, 10 g of methyl vinyl ether and 3.0 g of divinyl ether as the crosslinking agent dissolved in 900 g of acetone was boiled, 1.0 g of t-butyl hydroperoxide was added as the initiator, and the boiling state was maintained. With the progress of the polymerization, the formed polymer was precipitated into ethyl acetate, and then the same procedure as in Example 1 was carried out to obtain a white fine powder with an average particle size of 3 μm.
EXAMPLE 11 A solution of 60 g of N-vinylacetamide, 40 g of acrylamide and 3.0 g of N,N'-methylenebisacrylamide as the crosslinking agent dissolved in 900 g of acetone was boiled, 0.4 g of azobisisobutyronitrile was added as the initiator, and the boiling state was maintained. With the progress of the polymerization, the formed polymer was precipitatyed into ethyl acetate, and then the same procedure as in Example 1 was carried out to obtain a white fine powder with an average particle size of 3 μm.
EXAMPLE 12 The reaction was carried out according to entirely the same procedure as in Example 11 except that ethyl vinyl ether was used in place of acrylamide to obtain a white fine powder with an average particle size of 3 μm.
EXAMPLE 13 A solution of 85 g of N-vinylacetamide, 15 g of vinyl acetate and 3.0 g of N,N'-butylenebis(N-vinylacetamide) as the crosslinking agent dissolved in 900 g of acetone was boiled, 0.3 g of azobisisobutyronitrile was added as the initiator, and the boiling state was maintained. With the progress of the polymerization, the formed polymer was precipitated into ethyl acetate, and then the same procedure as in Example 1 was carried out to obtain a white fine powder with an average particle size of 3 μm.
EXAMPLE 14 A solution of 70 g of N-vinylacetamide, 30 g of acrylic acid and 2.5 g of trimethylolpropane trimethacrylate as the crosslinking agent dissolved in 700 g of benzoyl peroxide was boiled, 0.3 g of azobisisobutyronitrile was added as the initiator, and the boiling state was maintained. With the progress of the polymerization, the formed polymer was precipitatyed into ethyl acetate, and then the same procedure as in Example 1 was carried out to obtain a white fine powder with an average particle size of 2 μm.
EXAMPLE 15 The reaction was carried out by the same procedure as in Example 4, except that 40 g of N-vinylacetamide, 30 g of 2-acrylamide-2-methylpropanesulfonic acid and 30 g of acrylic acid to obtain a white fine powder with an average article size of 4 μm.
EXAMPLE 16 The reaction was carried out by the same procedure as in Example 14 except that triallyl phosphate was used in place of trimethylolpropane trimethacrylate to obtain a white fine powder with an average particle size of 4 μm.
EXAMPLE 17 The reaction was carried out by the same procedure as in Example 4, except that trimethylolpropane diallyl ether was used in place of divinylbenzene to obtain a white fine powder with an average particle size of 2 μm.
EXAMPLE 18 The reaction was carried out by the same procedure as in Example 4, except that N,N'hexylenebis(N-vinylacetamide) was used in place of divinylbenzene to obtain a white fine powder with an average particle size of 2 μm.
EXAMPLE 19 The reaction was carried out by the same procedure as in Example 1 except N,N'-(diacetyl)-N,N'-(divinyl)-1,3-bis(aminomethyl)cyclohexane was used in place of N,N'-methylenebis acrylamide to obtain a white fine powder with an average article size of 1 μm.
EXAMPLE 20 The reaction was carried out by the same procedure as in Example 4, except that N,N'-butylenebis(N-vinylacetamide) was used in place of divinylbenzene to obtain a white fine powder with an average article size of 1 μm.
EXAMPLE 21 The reaction was carried out by the same procedure as in Example 4 except methyl ethyl ketone was used in place of ethyl acetate as the solvent to obtain a white fine powder with an average article size of 5 μm.
EXAMPLE 22 The reaction was carried out by the same procedure as in Example 4 except that toluene was used in place of ethyl acetate as the solvent to obtain a white fine powder with an average article size of 1 μm.
EXAMPLE 23 The reaction was carried out by the same procedure as in Example 1 except that isopropyl acetate was used in place of benzene as the solvent to obtain a white fine powder with an average article size of 1 μm.
EXAMPLE 24 Into a solution of 70 g of N-vinylacetamide, 30 g of acrylic acid, 1.5 g of N,N'-butylenebis(N-vinylacetamide) as the crosslinking agent dissolved in 900 g of ethyl acetate was bubbled nitrogen at 1 (liter/min.) for 30 minutes, and the solution then elevated to a temperature of 70� C. As the initiator, 0.3 g of azobisisobutyronitrile was added, and this state was maintained at 80� C. in a nitrogen atmosphere. With the progress of the polymerization, the formed polymer was precipitated into ethyl acetate, and then the same procedure as in Example 1 was carried out to obtain a white fine powder with an average particle size of 1 μm. The tests of the thickening ability and salt resistance were conducted in the same manner as in Example 1, and the results are shown in Table 1 and Table 2.
EXAMPLE 25 The reaction was carried out by the same procedure as in Example 24 except that 100 g of N-vinyl acetamide was used in place of ethyl acetate as the solvent, to obtain a white fine powder with an average article size of 1 μm.
EXAMPLE 26 The reaction was carried out by the same procedure as in Example 25 except that the polymerization temperature was changed from 70� C. to 90� C. to obtain a white fine powder with an average article size of 2.1 μm.
EXAMPLE 27 Into a solution of 70 g of N-vinylacetamide, 29 g of acrylic acid, 1 g of stearyl methacrylate, 2.0 g of pentaerythritol triacrylate as the crosslinking agent dissolved in 900 g of acetone was bubbled nitrogen at 1 (liter/min.)liter/min.) for 30 minutes, and the solution then elevated to a temperature of 50� C. As the initiator, 0.3 g of azobisisobutyronitrile was added, and this state was maintained at 50� C. in a nitrogen atmosphere. With the progress of the polymerization, the formed polymer was precipitated into ethyl acetate, and then the same procedure as in Example 1 was carried out to obtain a white fine powder with an average particle size of 1 μm. The tests of the thickening ability, salt resistance were conducted in the same manner as in Example 1 was carried out to obtain a white fine powder with an average particle size of 1.5 μm.
EXAMPLE 28 The reaction was carried out by the same procedure as in Example 27 except that 95 g of N-vinyl acetamide, 5 g of vinyl acetate, in place of 70 g of N-vinylacetamide, 29 g of acrylic acid, 1 g of stearyl methacrylate, and 2.0 g of trimethylolpropane diallyl ether were used in place of pentaerythritol triacrylate as the crosslinking agent to obtain a white fine powder with an average particle size of 0.2 μ.
EXAMPLE 29 The reaction was carried out by the same procedure as in Example 26 except that 90 g of N-vinylacetamide and 10 g of maleic anhydride was used in place of 70 g of N-vinylacetamide and 30 g of acrylic acid to obtain a white fine with an average article size of 2.0 μm.
EVALUATION TESTS 1) Thickening ability.
Method of Measuring viscosity of Pure water Dispersion Into a tall 200 ml beaker was charged 198 g of deionized water, and 2 g of the fine powder obtained in Example was dispersed therein so that no mass was formed. The viscosity of the 1% aqueous dispersion thus obtained was measured by using a BL type viscometer under the conditions of a No. 4 rotor, 30 rpm, and 320� C. In the Example wherein the monomers containing carboxylic acids such as acrylic acid, methacrylic acid, etc, and anhydride are copolymerized, the viscosity was measured after neutralizing with 10% aqueous NaOH to a pH of 6.0-8.0.
SALT RESISTANCE TEST In the 1% aqueous dispersion prepared according to the deionized water dispersion viscosity measuring method, NaCl wa added and dissolved to the solid concentrations in the liquid as shown in Table 2, and the viscosities were measured.
TABLE 3__________________________________________________________________________  Example              Comparative Example  1     4    7    8    1    2    4__________________________________________________________________________Solubility in  Dissolved        Swelled             Swelled                  Swelled                       Insoluble                            Insoluble                                 Swelledethyl alcoholDispersibility  +     +    +    +    � -    -of talcLubricity  +     +    +    +    +    +    -__________________________________________________________________________ Dispersibility of talc +: no precipitation observed, and stable dispersion state maintained �: slight precipitation observed. -: mostly precipitated. Lubricity +: friction coefficient: less than 0.01 (high lubricity) �: friction coefficient: 0.01 to 0.3 -: friction coefficient: more than 0.3 (low lubricity).   6) Dissolution in organic solvent
TABLE 4______________________________________Solvent            Solubility                       ET______________________________________HFIP               ++       65.3water              ++       63.1phenol             ++       61.4p-cresol           ++       60.8glycerol           ++       57formamide          ++       56.6glycol             ++       56.3methanol           ++       55.5trimethyleneglycol ++       54.9propylene glycol   ++       54.11,4-butandiol      ++       53.5triethleneglycol   ++       53.51,3-butandiol      ++       52.82-methoxyethanol   ++       52.3allyl alcohol      ++       52.1N-methylacetamide  +        52ethanol            ++       51.92-aminoethanol     ++       51.82,3-butandiol      ++       51.8acetic acid        ++       51.22-ethoxyethanol    ++       511-propanol         ++       50.71-butanol          +        50.22-butoxyethanol    ++       50.2ethyl acetoacetate -        49.4amyl alcohol       -        49.1______________________________________
TABLE 5______________________________________Solvent            Solubility                       ET______________________________________isoamyl alcoho     ++       491-hexanol          +        48.8isopropyl alcohol  +        48.6isobuthyl alcohol  ++       48.62-pyrolidinone     ++       48.31-octanol          -        48.32-butanol          ++       47.1cyclopentanol      ++       47acetonitrile       +        46DMSO               -        45NMP                -        44.1DMF                -        43.8DMAc               -        43.7acetone            -        42.2nitroenzene        -        42metylene chloride  -        41.1pyridine           -        40.2chloroform         -        39.1ethylacetate       -        38.1THF                -        37.4chlorobenzene      -        36.81,4-dixane         -        36.3diethylamine       -        35.4benzene            -        34.5triethylamine      -        33.3cyclohexane        -        32.1______________________________________
TABLE 6______________________________________         Composition ofSolvent mixture         solvent       Solubility                                ET______________________________________water-dioxane  0:100        -        36         10:90         -        46         30:70         ++       51         50:50         ++       54         100:0         ++       63ethanol-acetone          0:100        -        42         10:90         -        47         50:50         ++       51         100:0         ++       52chloroform-ethanol          0:100        ++       52         12:88         ++       51         50:50         ++       48         60:40         ++       47         70:30         ++       46         80:20         ++       46         90:10         ++       44         100:0         -        39methanol-methylene          0:100        -        41chloride       4:96         -        46          9:91         ++       48         39:61         ++       51         100:0         ++       56water-acetone  0:100        -        42         20:80         -        48         40:60         -        51         50:50         -        52         60:40         ++       53         100:0         ++       63water-THF      0:100        -        37         40:60         -        48         80:20         ++       51         100:0         ++       63______________________________________
COMPARATIVE EXAMPLE 1 A 1% deionized water dispersion was prepared by using a crosslinked type polyacrylic acid (Carbopol 940: B. F. Goodrich) in place of the polymer in Example 1, and the thickening ability and the salt resistance were measured in the same manner as in Example 1. The results are shown in Table 1 and Table 2. Also, evaluations of the ethyl alcohol solubility, dispersion stability of talc, and lubricity were conducted in the same manner as in Example 1. The results are shown in Table 3.
COMPARATIVE EXAMPLE 2 By using a commercially available sodium polyacrylate type water absorbent resin, a 1% aqueous dispersion was prepared and thickening ability and salt resistance were measured in the same manner as in Example 1. The results are shown in Table 1 and Table 2. Also, evaluations of the ethyl alcohol solubility, dispersion stability of talc, and lubricity were evaluated in the same manner as in Example 1. The results are shown in Table 3.
COMPARATIVE EXAMPLE A solution of 70 g of N-vinylacetamide, 30 g of acrylic acid, 20.0 g divinylbenzene as the crosslinking agent dissolved in in 900 g of ethyl acetate was boiled, 0.4 g of azobisisobutyronitrile was added as the initiator and the boiling state was maintained. With the progress of the polymerization, the formed polymer was precipitated into ethyl acetate, and then the same procedure as in Example 1, a white fine powder was obtained. The tests of the thickening ability and salt resistance were conducted in the same manner as in Example 1, and the results are shown in Table 1 and Table 2.
COMPARATIVE EXAMPLE 4 The reaction was carried out by the same procedure as in Comparative Example 3, to obtain a white fine powder. The 1% dispersion exhibited no thixotropic liquid property. The tests of the thickening ability and salt resistance were conducted in the same manner as in Comparative Example 3, and the results are shown in Table 1 and 2. Also, evaluations of the ethyl alcohol solubility, dispersion stability of talc, and lubricity, were made in the same manner as in Example 1. The results are shown in Table 3.
COMPARATIVE EXAMPLE 5 The reaction was carried out in the same manner as in Comparative Example 3, except that the 20.0 g of divinylbenzene of the crosslinking agent was changed to 2.0 g, and the amount of azobisisobutyronitrile of the initiator added was changed 0.4 g to 11.0 g, to obtain a white fine powder. The tests of thickening ability and salt resistance were conducted in the same manner as in Comparative Example 3, and the results are shown in Table 1 and Table 2.
COMPARATIVE EXAMPLE 6 The reaction was carried out in the same manner as in Comparative Example 3 except that the 20.0 g of divinylbenzene was changed to 2.0 g, and the amount of azobisisobutyronitrile of the initiator added was changed 0.4 g to 0.01 g to obtain a white fine powder. The 1% dispersion exhibited no thixotropic liquid property. The tests of the thickening ability and salt resistance were conducted in the same manner as in Comparative Example 3, and the results are shown in Table 1 and Table 2.
COMPARATIVE EXAMPLE 7 The reaction was carried out in the same manner as in Comparative Example 3, except that 20.0 g of the divinylbenzene of the crosslinking agent was changed to 2.0 g, and 30 g of acrylic acid was changed to 109 g of N-vinylacetamide and 90 g of acrylic acid to obtain a white fine powder. The tests of the thickening ability and salt resistance were conducted in the same manner as in Comparative example 3, and the results are shown in Table 1 and Table 2.
COMPARATIVE EXAMPLE 8 A solution of 70 g of N-vinylacetamide, 30 g of sodium acrylate and 0.3 g of N,N'-butylenebis(N-vinylacetamide) dissolved in 400 g of water was adjusted to a temperature of 40� C. As the initiator, 0.4 g of 2,2'-azobis(2-amizinopropane) dihydrochloride was added, and the state of 40� C. was maintained. With the progress of the polymerization, the viscosity of reaction mixture became increased, until it finally became a gelatin-like transparent solid mass. The mass was macerated, dehydrated to remove the water contained in acetone, vacuum dried at 40� C. for 24 hours, and then crushed to obtain a white powder. The 1% dispersion exhibited no thixotropic liquid property. The tests of the thickening ability and salt resistance were conducted in the same manner as in Comparative Example 1, and the results are shown in Table 1 and Table 2.
APPLICATION EXAMPLE 1: WARP GLUE Using an aqueous glue solution having the following composition;
APPLICATION EXAMPLE 2: MOISTURIZING HAND LOTION ______________________________________A     deionized water      85     wt. parts glycerine            5      wt. parts propylene glycol     1      wt. parts methyl p-hydroxybenzoate                      0.2    wt. parts propyl p-hydroxybenzoate                      0.1    wt. partsB     mineral oil          5      wt. parts paraffin wax         1      wt. parts glycol stearate      1      wt. parts acetylated lanoline alcohol                      0.6    wt. parts dimethicone          0.5    wt. parts polymer obtained in Example 7                      0.2    wt. partsC     triethanolamine      0.2    wt. parts PEG-15-cocamine      0.2    wt. partsD     fragrance            q.s.______________________________________
The components A were mixed with stirring at 70� C., the oil components, excluding the polymer of Example 7, were mixed, and then the polymer of Example 7 was added and mixed at 70� C. To the components A were added the components B, and the mixture was vigorously agitated for 30 minutes, followed by an addition of the components C to neutralize the mixture, and the fragrance was added with stirring and the mixture cooled. Thus, a hand lotion having a good dispersibility of the oil components and a stable product viscosity with a lapse of time was obtained.
APPLICATION EXAMPLE 3; FACIAL CLEANSING CREAM ______________________________________A      deionized water     78    wt. parts  polymer of Example 8                      0.2   wt. parts  glycerine           5     wt. parts  PEG-8               0.5   wt. parts  methyl p-hydroxybenzoate                      0.1   wt. parts  imidazolidinyl urea 0.3   wt. partsB      paraffin wax        0.5   wt. parts  capric acid triglyceride                      2     wt. parts  mineral oil         13    wt. partsC      triethanolamine     0.2   wt. parts  PEG-15-cocamine     0.2   wt. parts______________________________________
APPLICATION EXAMPLE 4: SUN SCREEN LOTION ______________________________________A      deionized water    81.2   wt. parts  polymer of Example 8                     0.2    wt. parts  methyl p-hydroxybenzoate                     0.2    wt. parts  propyl p-hydroxylbenzoate                     0.2    wt. partsB      coconut oil        5      wt. partsC      triethanolamine    0.2    wt. partsD      octyldimethyl PABA 5      wt. parts  benzophenone       3      wt. parts  octyl salicylate   5      wt. partsE      fragrance          q.s.______________________________________
APPLICATION EXAMPLE 5: PRINTING GLUE A polymer dispersion was obtained by adding 20 parts by weight of the polymer obtained in Example 11 to 70 parts by weight of mineral spirit (isoparaffin mixture having a boiling point of 207�-254� C.), followed by stirring for 20 minutes. Then, 10 parts by weight of sodium carbonate was mixed, while stirring, with the dispersion, followed by stirring for 20 minutes to prepare a 20% polymer mixture.
______________________________________        Composition A                  Composition B______________________________________cold water     38.5   wt. parts                          32.3 wt. partssilicone antifoamer          0.25   wt. parts                          0.25 wt. partssurfactant*1          0.25   wt. parts                          0.25 wt. partsreactive red 24*2          4.0    wt. parts                          --reactive black 8*2          --              8.0  wt. partsurea           10     wt. parts                          10   wt. partssodium m-nitrobenzene          0.5    wt. parts                          0.5  wt. partssulfonatehot water      37.5   wt. parts                          37.5 wt. parts20% polymer mixture          6.0    wt. parts                          7.5  wt. partsKHCO3     3.0    wt. parts                          2.5  wt. partsNa2 CO3          --              1.2  wt. parts______________________________________ *1 hexaoxyethylene nonylphenyl ether *2 monochlorotriazine dye (Chiba Geigy)
APPLICATION EXAMPLE 6: ZINC ALKALI BATTERY A zinc alkali battery provided with an anode cell containing an arrode agent mainly composed of manganese dioxide, a separator and a zinc cathode was prepared according to a conventional manner.
APPLICATION EXAMPLE 7: LIQUID CLEANSER Liquid cleansers having the following formulations were prepared.
______________________________________          Formulation A                    Formulation B______________________________________Silicon dioxide (size 2-100 &#956;m)            7      wt. parts                            --Bentonite (size 2-150 &#956;m)            --              10   wt. partsPolymer of Example 14            0.3    wt. parts                            0.3  wt. partsHexaoxyethylene lauryl ether            3      wt. parts                            3    wt. parts(HLB 12)Ethanol          3      wt. parts                            3    wt. partsWater            86.7   wt. parts                            83.7 wt. partsTriethanolamine  q.s. (adjusting to pH 7)Viscosity of composition (cps)            1500            1800BL type viscosimeter 30 rpm______________________________________
APPLICATION EXAMPLE 8: LIQUID SHAMPOO Liquid shampoo compositions having the following formulations were prepared.
APPLICATION EXAMPLE 9: GELLED NAIL LACQUER REMOVER A gelled Nail Lacquer remover having the following formulation was prepared.
APPLICATION EXAMPLE 10: LIQUID DETERGENT (FOR SOIL ADHERED TO WALLS AND CEILINGS OF, FOR EXAMPLE, KITCHENS) Liquid detergents having the following formulations were prepared.
APPLICATION EXAMPLE 11: LIQUID DETERGENT (FOR FUNGUS SOIL ATTACHED TO TILE JOINT PORTIONS AND WALLS OF, FOR EXAMPLE, BATH ROOMS) Liquid detergents having the following formulations were prepared.
APPLICATION EXAMPLE 12: SUSTAINED RELEASE PREPARATION FOR ORAL CAVITY (PREPARATION COMPRISING AN ADHESIVE LAYER AND A MEDICINE LAYER APPLIED BY ATTACHING TO TUNICA MUCOSA ORIS) Oral preparations having the following preparations were prepared.
______________________________________         Preparation                   Preparation         A         B______________________________________(A)  Composition foradhesive layerPolymer of Example 4               5      wt. part                             5    wt. partEthylcellulose 1      wt. part                             0.2  wt. partGlycerol fatty acid ester               1      wt. part                             --Titanium dioxide               0.4    wt. part                             --Caster oil     --            0.5  wt. partEthanol        60     wt. part                             60   wt. part(B)  Composition formedicine layerVinyl acetate resin               10     wt. part                             10   wt. partHydroxypropylmethyl               1      wt. part                             1    wt. partcelluloseacetate succinateTriethyl citrate               0.5    wt. part                             0.5  wt. partAcetone        10     wt. part                             10   wt. partMethanol       2      wt. part                             2    wt. partProstaglandin E2               0.1           --Prostaglandin E1               --            0.1  wt. part______________________________________
APPLICATION EXAMPLE 13: POULTICE A poultice having the following formulation was prepared.
APPLICATION EXAMPLE 14: GELLED OINTMENT (TRANSPARENT) A 3 g amount of the polymer obtained in Example 5 was swollen in 25 g of distilled water. On the other hand, 3 g of ketoprofene and 2 g of hydroxypropyl cellulose (HPC-M available from Nippon Soda K.K.) were dissolved in a mixed solvent of 39 of ethanol and 10 g of isopropanol and the resultant solution was added to the above-prepared polymer, followed by thoroughly stirring. To the resultant mixture, 0.4 g of diisopropanol amine dissolved in 17.6 g of distilled water was added and stirring was effected until the mixture became totally uniform, to thus obtain the desired translucent gelled ointment composition.
APPLICATION EXAMPLE 15: GELLED OINTMENT (CREAMY) A 2 g amount of the polymer obtained in Example 5 was swollen in 66 g of distilled water. On the other hand, 3 g of ketoprofen and 1 g of polyethleneglycol monostearate (MYB-40 available from Nikko Chemicals K. K.) were dissolved in a mixed solvent of 39 g of ethanol and 10 g isopropanol and the resultant solution was added to the above polymer, followed by thoroughly stirring. To this mixture, 0.4 g of diisopropanol amine dissolved in 17.6 g of distilled water was added, followed by thoroughly stirring until the mixture became totally uniform, to obtain the desired white creamy ointment composition.
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