JPWO2010113566A1 - Dispersion stabilizer for aqueous emulsion and aqueous emulsion - Google Patents
Dispersion stabilizer for aqueous emulsion and aqueous emulsion Download PDFInfo
- Publication number
- JPWO2010113566A1 JPWO2010113566A1 JP2011507056A JP2011507056A JPWO2010113566A1 JP WO2010113566 A1 JPWO2010113566 A1 JP WO2010113566A1 JP 2011507056 A JP2011507056 A JP 2011507056A JP 2011507056 A JP2011507056 A JP 2011507056A JP WO2010113566 A1 JPWO2010113566 A1 JP WO2010113566A1
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- hydrogen atom
- aqueous emulsion
- polymerization
- polyoxyalkylene
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- 239000000839 emulsion Substances 0.000 title claims abstract description 73
- 239000006185 dispersion Substances 0.000 title claims abstract description 36
- 239000003381 stabilizer Substances 0.000 title claims abstract description 36
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 57
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 55
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 34
- 238000007127 saponification reaction Methods 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 10
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- 238000007334 copolymerization reaction Methods 0.000 claims description 11
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- 150000001993 dienes Chemical class 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
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- 239000000853 adhesive Substances 0.000 abstract description 22
- 230000001070 adhesive effect Effects 0.000 abstract description 22
- 239000011230 binding agent Substances 0.000 abstract description 7
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 69
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- 238000000034 method Methods 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 19
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 5
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- 238000000576 coating method Methods 0.000 description 4
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
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- 238000010992 reflux Methods 0.000 description 4
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- 229920002554 vinyl polymer Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
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- 150000002505 iron Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
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- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
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- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- YMDZGJOTVBKZQK-UHFFFAOYSA-N n,n-dimethylpropan-1-amine;2-methylprop-2-enamide Chemical compound CCCN(C)C.CC(=C)C(N)=O YMDZGJOTVBKZQK-UHFFFAOYSA-N 0.000 description 1
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- NYUSKIVSFXNJTN-UHFFFAOYSA-N n-(hydroxymethyl)prop-2-enamide;prop-2-enamide Chemical class NC(=O)C=C.OCNC(=O)C=C NYUSKIVSFXNJTN-UHFFFAOYSA-N 0.000 description 1
- ADTJPOBHAXXXFS-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]prop-2-enamide Chemical compound CN(C)CCCNC(=O)C=C ADTJPOBHAXXXFS-UHFFFAOYSA-N 0.000 description 1
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- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QJWFJOSRSZOLKK-UHFFFAOYSA-N prop-2-enamide Chemical compound NC(=O)C=C.NC(=O)C=C QJWFJOSRSZOLKK-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 210000002435 tendon Anatomy 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- WKEWCYHGACEYTR-UHFFFAOYSA-N tert-butyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(C)(C)C WKEWCYHGACEYTR-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
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- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
下記一般式（Ｉ）で示されるポリオキシアルキレン基を側鎖に含有するポリビニルアルコール系重合体であり、粘度平均重合度が２００〜３０００であり、けん化度が８０〜９９．９９モル％であり、ポリオキシアルキレン基変性量が０．１〜１０モル％であり、ポリビニルアルコール系重合体の主鎖１００重量部に対するポリオキシアルキレン基含有量が６〜５０重量部であるポリオキシアルキレン変性ポリビニルアルコール系重合体を含有する水性エマルジョン用分散安定剤とする。それによって、接着剤や各種バインダーとして使用する場合に重要な性能の一つである初期接着性が高く、高速生産が可能な水性エマルジョンが提供される。式中、Ｒ１は水素原子またはメチル基、Ｒ２は水素原子または炭素数１〜８のアルキル基を表す。ｍとｎはそれぞれのオキシアルキレンユニットの繰り返し単位数を表し、１≦ｍ≦１０、５≦ｎ≦２０である。It is a polyvinyl alcohol polymer containing a polyoxyalkylene group represented by the following general formula (I) in the side chain, has a viscosity average polymerization degree of 200 to 3000, and a saponification degree of 80 to 99.99 mol%. The polyoxyalkylene group-modified polyvinyl alcohol has a polyoxyalkylene group modification amount of 0.1 to 10 mol% and a polyoxyalkylene group content of 6 to 50 parts by weight with respect to 100 parts by weight of the main chain of the polyvinyl alcohol polymer. A dispersion stabilizer for an aqueous emulsion containing a polymer is used. Thereby, an aqueous emulsion that has high initial adhesiveness, which is one of important performances when used as an adhesive or various binders, and can be produced at high speed is provided. In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. m and n represent the number of repeating units of each oxyalkylene unit, and 1 ≦ m ≦ 10 and 5 ≦ n ≦ 20.
Description
本発明は、特定の官能基を有するビニルアルコール系重合体を含有する水性エマルジョン用分散安定剤および水性エマルジョンに関する。 The present invention relates to a dispersion stabilizer for an aqueous emulsion and an aqueous emulsion containing a vinyl alcohol polymer having a specific functional group.
従来、ビニルアルコール系重合体（以下、ＰＶＡと略記することがある）を分散安定剤とした水性エマルジョンは、乳化作用を有する界面活性剤だけを乳化重合用分散安定剤に用いてモノマーを乳化重合して得られる水性エマルジョンに比べて、エマルジョンの安定性が良好で、無機物などとの混和性にも優れ、しかも、各種用途に合った流動特性を比較的容易に付与できるといった多くの利点を有することから、接着剤および塗料をはじめとした多岐にわたる用途で幅広く使用されている。しかしながら、従来公知のＰＶＡを分散安定剤とした場合、得られる水性エマルジョンには幾つかの問題点があり、水性エマルジョンの用途の拡大および高性能化を図る上で性能が不十分な点があった。 Conventionally, an aqueous emulsion using a vinyl alcohol polymer (hereinafter sometimes abbreviated as PVA) as a dispersion stabilizer is an emulsion polymerization of monomers using only a surfactant having an emulsifying action as a dispersion stabilizer for emulsion polymerization. Compared to the aqueous emulsion obtained in this way, the emulsion has better stability, better miscibility with inorganic materials, etc., and has many advantages such as being able to impart flow characteristics suitable for various applications relatively easily. Therefore, it is widely used in various applications including adhesives and paints. However, when a conventionally known PVA is used as a dispersion stabilizer, the obtained aqueous emulsion has several problems, and the performance is insufficient for expanding the use and performance of the aqueous emulsion. It was.
ＰＶＡを分散安定剤とする水性エマルジョンに対する更なる要求性能としては、主として耐水性と初期接着性の改善が挙げられる。耐水性の改善策としては、各種架橋系や高耐水性ＰＶＡを分散安定剤に使用するなどの提案が数多くなされており、用途や要求性能に応じた様々な手法が確立しつつある。一方、初期接着性は、水性エマルジョンを接着剤や各種バインダーとして使用する場合に非常に重要な性能の一つである。特に、水性エマルジョンに対して高速生産を志向する昨今の流れの中では、より一層の改善要求が強く、古典的な手法を含めたいくつかの手法が提案されているものの、環境にやさしく、安全性が高く、高い初期接着性を実現できる手法はないのが実情であった。 Further required performances for aqueous emulsions using PVA as a dispersion stabilizer mainly include improvements in water resistance and initial adhesion. As measures for improving water resistance, various proposals such as the use of various cross-linking systems and high water-resistant PVA as dispersion stabilizers have been made, and various methods according to applications and required performance are being established. On the other hand, initial adhesiveness is one of the very important performances when an aqueous emulsion is used as an adhesive or various binders. In particular, in the current trend toward high-speed production for aqueous emulsions, there is a strong demand for further improvement, and several methods including the classical method have been proposed, but they are environmentally friendly and safe. The reality is that there is no method that can achieve high initial adhesiveness.
従来公知の初期接着性改善策としては、例えば、特許文献１には、ポリマー分散質に対して平均重合度３５００以上のＰＶＡを０．１〜５０重量％含有する水性エマルジョンが開示されている。この場合、水性エマルジョンの乾燥により系の粘度が上昇しやすいため初期接着力が発現しやすいが、使用時の粘度調整が困難な上、作業性に問題があるのが実情であった。 As a conventionally known initial adhesiveness improvement measure, for example, Patent Document 1 discloses an aqueous emulsion containing 0.1 to 50% by weight of PVA having an average degree of polymerization of 3500 or more with respect to the polymer dispersoid. In this case, the viscosity of the system is likely to increase due to the drying of the aqueous emulsion, so that the initial adhesive force is likely to be developed. However, it is difficult to adjust the viscosity during use and there is a problem in workability.
また、特許文献２には、分散剤として粘度平均重合度が２００以上で、重量平均重合度（Ｐｗ）と数平均重合度（Ｐｎ）の比Ｐｗ／Ｐｎが４以上であり、かつＧＰＣ測定による分子量分布の最大の分子量のピーク位置が重合度３５００以上であるＰＶＡを含む水性エマルジョンが開示されている。この場合も、乾燥による系の増粘が大きく、初期接着力の発現には効果があるが、依然として作業性などが問題になることがあった。 Patent Document 2 discloses that the dispersant has a viscosity average polymerization degree of 200 or more, a ratio Pw / Pn of weight average polymerization degree (Pw) to number average polymerization degree (Pn) of 4 or more, and GPC measurement. An aqueous emulsion containing PVA having a maximum molecular weight peak position in the molecular weight distribution having a degree of polymerization of 3500 or more is disclosed. Also in this case, the thickening of the system due to drying is large and effective in developing the initial adhesive force, but workability and the like may still be a problem.
特許文献３に記載のＰＶＡを含有する水性エマルジョンに特定量の界面活性剤とポリアルキレングリコール類を添加してなる紙用高速接着剤や、特許文献４あるいは非特許文献１などに記載のＰＶＡを保護コロイドとする水性エマルジョンにほう酸などの電解質を添加してなる接着剤も知られている。しかしながら、これらのものは界面活性剤やポリアルキレングリコール、ほう酸などの添加剤の安全性、環境に対する影響などの問題があった上、初期接着性も昨今の要求レベルを満たせない場合が多かった。 A high-speed adhesive for paper formed by adding a specific amount of a surfactant and a polyalkylene glycol to an aqueous emulsion containing PVA described in Patent Document 3, or PVA described in Patent Document 4 or Non-Patent Document 1 There is also known an adhesive obtained by adding an electrolyte such as boric acid to an aqueous emulsion as a protective colloid. However, these products have problems such as safety of additives such as surfactants, polyalkylene glycols, and boric acid, and influence on the environment, and initial adhesiveness often fails to meet the current required level.
また、特許文献５には、カルボキシル基および炭素数が５〜１５のアルキル基を有するＰＶＡを保護コロイドとした酢酸ビニル樹脂系エマルジョンと可塑剤からなる接着剤組成物が開示されている。さらに、特許文献６には、ＰＶＡを保護コロイドとする酢酸ビニル樹脂系エマルジョンに芳香族スルホン酸アルカリ金属ホルムアルデヒド縮合物と可塑剤を配合した接着剤組成物が開示されている。しかしながら、これらの方法では初期接着性のレベルが必ずしも十分ではなかった。また、特許文献６に記載の接着剤組成物の場合にはホルムアルデヒドの遊離の問題もあり好ましくなかった。 Patent Document 5 discloses an adhesive composition comprising a vinyl acetate resin emulsion using a PVA having a carboxyl group and an alkyl group having 5 to 15 carbon atoms as a protective colloid and a plasticizer. Further, Patent Document 6 discloses an adhesive composition in which an aromatic sulfonic acid alkali metal formaldehyde condensate and a plasticizer are blended with a vinyl acetate resin emulsion using PVA as a protective colloid. However, these methods do not always have a sufficient initial adhesion level. In the case of the adhesive composition described in Patent Document 6, there is a problem of liberation of formaldehyde, which is not preferable.
特許文献７には、カルボキシル基変性ＰＶＡもしくはα−オレフィンと不飽和カルボン酸との共重合体またはその誘導体を保護コロイドとした酢酸ビニル樹脂系エマルジョンに尿素を含有し、可塑剤を含有する接着剤組成物が開示されている。また、特許文献８には、イソブチレン−無水マレイン酸共重合体のイミド化物を保護コロイドとして、酢酸ビニルモノマーを乳化重合してなる酢酸ビニル系エマルジョンと、グリセリン脂肪酸エステルを含有することを特徴とする高速接着剤組成物が開示されている。これらＰＶＡ以外の水溶性高分子を使用することで初期接着性等を改善しようとする試みはあるものの、工業的にはこれらを保護コロイドとする水性エマルジョンは製造時の安定性が問題になる場合があった。また、初期接着性のレベルをさらに上げたいという要求も依然としてあった。 Patent Document 7 discloses an adhesive containing urea in a vinyl acetate resin emulsion in which a copolymer of a carboxyl group-modified PVA or α-olefin and an unsaturated carboxylic acid or a derivative thereof is used as a protective colloid, and a plasticizer. A composition is disclosed. Patent Document 8 is characterized by containing a vinyl acetate emulsion obtained by emulsion polymerization of a vinyl acetate monomer using an imidized isobutylene-maleic anhydride copolymer as a protective colloid, and a glycerin fatty acid ester. A high speed adhesive composition is disclosed. Although there are attempts to improve initial adhesiveness etc. by using water-soluble polymers other than these PVA, industrially, aqueous emulsions using these as protective colloids are problematic in terms of stability during production was there. There was also a need to further increase the level of initial adhesion.
特許文献９には、オキシアルキレン基を含有する不飽和単量体と酢酸ビニルとの共重合体をケン化することを特徴とする変性ＰＶＡの製造方法が開示されている。該変性ＰＶＡの製造に用いる不飽和単量体中のオキシアルキレン基としては、繰り返し単位数が１〜５０程度のポリオキシエチレン基、ポリオキシプロピレン基、ポリオキシブチレン基等が例示されている。また、該変性ＰＶＡの用途として多数例示されているものなかに、乳化重合用乳化剤が記載されている。 Patent Document 9 discloses a method for producing a modified PVA characterized by saponifying a copolymer of an unsaturated monomer containing an oxyalkylene group and vinyl acetate. Examples of the oxyalkylene group in the unsaturated monomer used for the production of the modified PVA include polyoxyethylene groups, polyoxypropylene groups, polyoxybutylene groups having about 1 to 50 repeating units. Moreover, emulsifiers for emulsion polymerization are described in many examples of uses of the modified PVA.
本発明は、上記従来の技術における問題点を解消し、接着剤や各種バインダーとして使用する場合に重要な性能の一つである初期接着性が高く、高速生産が可能な水性エマルジョンを製造するのに適した水性エマルジョン用分散安定剤、および、それを分散安定剤とする水性エマルジョンを提供するものである。 The present invention eliminates the above-mentioned problems in the prior art and produces an aqueous emulsion that has high initial adhesiveness and is capable of high-speed production, which is one of the important performances when used as an adhesive or various binders. A dispersion stabilizer for aqueous emulsions suitable for use in water and an aqueous emulsion using the dispersion stabilizer as a dispersion stabilizer are provided.
本発明者らは、従来のＰＶＡを保護コロイドに用いて製造された水性エマルジョンが有する種々の特徴（すなわち機械的安定性、化学的安定性、凍結融解安定性、無機物との混和性などの特徴）を損なうことなく、接着剤や各種バインダーとして使用する場合に重要な性能の一つである初期接着性が優れた水性エマルジョンを工業的な規模で容易に得ることのできる水性エマルジョン用分散安定剤について鋭意検討した。 The inventors of the present invention have various characteristics (namely, mechanical stability, chemical stability, freeze-thaw stability, miscibility with inorganic substances, etc.) that aqueous emulsions produced using conventional PVA as a protective colloid have. Dispersion stabilizer for aqueous emulsion that can easily obtain an aqueous emulsion with excellent initial adhesion, which is one of the important performances when used as an adhesive or various binders, on the industrial scale. We studied earnestly.
その結果、下記一般式（Ｉ）で示されるポリオキシアルキレン（以下、ＰＯＡと略すことがある）基を側鎖に含有するビニルアルコール系重合体であり、ビニルアルコール系重合体の粘度平均重合度が２００〜３０００であり、けん化度が８０〜９９．９９モル％であり、ポリオキシアルキレン基変性量が０．１〜１０モル％であり、ビニルアルコール系重合体の主鎖１００重量部に対するポリオキシアルキレン基含有量が６〜５０重量部であるポリオキシアルキレン変性ビニルアルコール系重合体（以下、ＰＯＡ変性ＰＶＡと略すことがある）を含有する水性エマルジョン用分散安定剤が、目的の水性エマルジョン用分散安定剤として適していることを見出し、本発明を完成するに至った。 As a result, it is a vinyl alcohol polymer containing a polyoxyalkylene (hereinafter abbreviated as POA) group represented by the following general formula (I) in the side chain, and the viscosity average degree of polymerization of the vinyl alcohol polymer. Is 200 to 3000, the saponification degree is 80 to 99.99 mol%, the polyoxyalkylene group modification amount is 0.1 to 10 mol%, and the polyalcohol with respect to 100 parts by weight of the main chain of the vinyl alcohol polymer. A dispersion stabilizer for an aqueous emulsion containing a polyoxyalkylene-modified vinyl alcohol polymer (hereinafter sometimes abbreviated as POA-modified PVA) having an oxyalkylene group content of 6 to 50 parts by weight is provided for the intended aqueous emulsion. The present inventors have found it suitable as a dispersion stabilizer and have completed the present invention.
式中、Ｒ１は水素原子またはメチル基、Ｒ２は水素原子または炭素数１〜８のアルキル基を表す。ｍとｎはそれぞれのオキシアルキレンユニットの繰り返し単位数を表し、１≦ｍ≦１０、５≦ｎ≦２０である。ここで、繰り返し単位数ｍで表されるユニットをユニット１と呼び、繰り返し単位数ｎで表されるユニットをユニット２と呼ぶことにする。ユニット１とユニット２の配置は、ランダム状、ブロック状のどちらの形態になっても良い。 In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. m and n represent the number of repeating units of each oxyalkylene unit, and 1 ≦ m ≦ 10 and 5 ≦ n ≦ 20. Here, a unit represented by the number m of repeating units is referred to as unit 1, and a unit represented by the number of repeating units n is referred to as unit 2. The arrangement of the unit 1 and the unit 2 may be random or block.
このとき、前記ポリオキシアルキレン変性ビニルアルコール系重合体が、下記一般式（II）で示されるポリオキシアルキレン基を有するマクロモノマーとビニルエステルとを共重合した後、けん化することによって得られたものであることが好ましい。
式中、Ｒ１は水素原子またはメチル基、Ｒ２は水素原子または炭素数１〜８のアルキル基を表す。ｍとｎはそれぞれのオキシアルキレンユニットの繰り返し単位数を表し、１≦ｍ≦１０、５≦ｎ≦２０である。Ｒ３は水素原子または−ＣＯＯＭ基を表し、ここでＭは水素原子、アルカリ金属またはアンモニウム基を表す。Ｒ４は水素原子、メチル基または−ＣＨ２−ＣＯＯＭ基を示し、ここでＭは前記定義どおりである。Ｘは−Ｏ−、−ＣＨ２−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−または−ＣＯ−ＮＲ５−を表す。ここでＲ５は水素原子または炭素数１〜４の飽和アルキル基を表す。In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. m and n represent the number of repeating units of each oxyalkylene unit, and 1 ≦ m ≦ 10 and 5 ≦ n ≦ 20. R3 represents a hydrogen atom or a -COOM group, where M represents a hydrogen atom, an alkali metal or an ammonium group. R4 represents a hydrogen atom, a methyl group or a —CH 2 —COOM group, where M is as defined above. X represents —O—, —CH 2 —O—, —CO—, —CO—O— or —CO—NR 5 —. Here, R5 represents a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms.
前記ポリオキシアルキレン変性ビニルアルコール系重合体が、下記一般式（III）で示されるポリオキシアルキレン基を有するマクロモノマーとビニルエステルとを共重合した後、けん化することによって得られたものであることがより好ましい。 The polyoxyalkylene-modified vinyl alcohol polymer is obtained by copolymerization of a macromonomer having a polyoxyalkylene group represented by the following general formula (III) and a vinyl ester and then saponifying. Is more preferable.
式中、Ｒ１は水素原子またはメチル基、Ｒ２は水素原子または炭素数１〜８のアルキル基を表す。ｍとｎはそれぞれのオキシアルキレンユニットの繰り返し単位数を表し、１≦ｍ≦１０、５≦ｎ≦２０である。Ｒ４は水素原子、メチル基または−ＣＨ２−ＣＯＯＭ基を示し、ここでＭは水素原子、アルカリ金属またはアンモニウム基を表す。Ｒ５は水素原子または炭素数１〜４の飽和アルキル基を表す。In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. m and n represent the number of repeating units of each oxyalkylene unit, and 1 ≦ m ≦ 10 and 5 ≦ n ≦ 20. R4 represents a hydrogen atom, a methyl group or a —CH 2 —COOM group, where M represents a hydrogen atom, an alkali metal or an ammonium group. R5 represents a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms.
また、本発明の分散安定剤とエチレン性不飽和単量体およびジエン系単量体から選ばれる一種以上の不飽和単量体からなる重合体の分散質とを含有する水性エマルジョンが本発明の好適な実施態様である。 An aqueous emulsion containing the dispersion stabilizer of the present invention and a polymer dispersoid composed of one or more unsaturated monomers selected from ethylenically unsaturated monomers and diene monomers is also included in the present invention. This is a preferred embodiment.
本発明の水性エマルジョン用分散安定剤を用いて乳化重合して得られたエマルジョンは、従来の分散剤を用いた場合に比べて、初期接着性に優れる。 An emulsion obtained by emulsion polymerization using the dispersion stabilizer for aqueous emulsions of the present invention is excellent in initial adhesiveness as compared with the case of using a conventional dispersant.
以下、本発明について詳しく説明する。本発明は、上記の一般式（Ｉ）で示されるＰＯＡ基を側鎖に含有するＰＶＡであり、該ＰＶＡの粘度平均重合度が２００〜３０００であり、けん化度が８０〜９９．９９モル％であり、ＰＯＡ基変性量が０．１〜１０モル％であり、該ＰＶＡの主鎖１００重量部に対するポリオキシアルキレン基含有量が６〜５０重量部であるＰＯＡ変性ＰＶＡを含有する水性エマルジョン用分散安定剤である。 The present invention will be described in detail below. The present invention is a PVA containing a POA group represented by the above general formula (I) in the side chain, the PVA has a viscosity average polymerization degree of 200 to 3000, and a saponification degree of 80 to 99.99 mol%. For aqueous emulsion containing POA-modified PVA having a POA group modification amount of 0.1 to 10 mol% and a polyoxyalkylene group content of 6 to 50 parts by weight based on 100 parts by weight of the main chain of the PVA Dispersion stabilizer.
本発明において、水性エマルジョン用分散安定剤に使用されるＰＯＡ変性ＰＶＡの側鎖に存在するＰＯＡ基は、ユニット１の繰り返し単位数ｍは１≦ｍ≦１０であり、ユニット２の繰り返し単位数ｎは５≦ｎ≦２０である必要がある。ｍ及びｎがこのような範囲であることで該ＰＯＡ変性ＰＶＡを分散剤とする水性エマルジョンの優れた接着性、特に初期接着性が発現する。ｍは２以上であることが好ましい。ｍは５以下であることが好ましく、３以下であることがより好ましい。ｎは８以上であることが好ましい。ｎは１８以下であることが好ましく、１５以下であることがより好ましい。 In the present invention, the POA group present in the side chain of the POA-modified PVA used in the dispersion stabilizer for aqueous emulsions has a unit 1 repeating unit number m of 1 ≦ m ≦ 10 and a unit 2 repeating unit number n. Needs to be 5 ≦ n ≦ 20. When m and n are within such ranges, excellent adhesiveness, particularly initial adhesiveness, of the aqueous emulsion using the POA-modified PVA as a dispersant is developed. m is preferably 2 or more. m is preferably 5 or less, and more preferably 3 or less. n is preferably 8 or more. n is preferably 18 or less, and more preferably 15 or less.
上記の一般式（Ｉ）で示されるＰＯＡ基を側鎖に含有するＰＶＡにおいて、ＰＯＡ基変性量Ｓは０．１〜１０モル％であることが必要であり、好ましくは０．１５〜８モル％、より好ましくは０．２〜６モル％である。ＰＯＡ基の変性量が０．１モル％よりも小さい場合には、本発明の目的である該ＰＶＡを分散安定剤とする水性エマルジョンの初期接着性が発現しない。一方、１０モル％を超える場合には、該ＰＶＡの疎水性が増加し、水溶性の低下が起こることがあるため不適である。 In the PVA containing the POA group represented by the general formula (I) in the side chain, the POA group modification amount S needs to be 0.1 to 10 mol%, preferably 0.15 to 8 mol. %, More preferably 0.2 to 6 mol%. When the modification amount of the POA group is smaller than 0.1 mol%, the initial adhesiveness of the aqueous emulsion using the PVA as a dispersion stabilizer, which is the object of the present invention, is not expressed. On the other hand, if it exceeds 10 mol%, the hydrophobicity of the PVA increases and water solubility may be lowered, which is not suitable.
ＰＯＡ基変性量は、ＰＶＡの主鎖メチレン基に対するＰＯＡ基のモル分率で表される。ＰＯＡ変性ＰＶＡのＰＯＡ基変性量は、例えば、該ＰＶＡの前駆体であるＰＯＡ変性ポリビニルエステル、具体的には、ＰＯＡ変性ポリ酢酸ビニル（以下、ポリ酢酸ビニルをＰＶＡｃと略記することがある）のプロトンＮＭＲから求めることができる。具体的には、ｎ−ヘキサン／アセトンでＰＯＡ変性ＰＶＡｃの再沈精製を３回以上十分に行った後、５０℃の減圧下で乾燥を２日間行い、分析用のＰＯＡ変性ＰＶＡｃを作成する。該ＰＶＡｃをＣＤＣｌ３に溶解させ、５００ＭＨｚのプロトンＮＭＲ（ＪＥＯＬ ＧＸ−５００）を室温で測定する。ビニルエステルの主鎖メチンに由来するピークα（４．７〜５．２ｐｐｍ）とユニット２の末端メチル基に由来するピークβ（０．８〜１．０ｐｐｍ）から下記式を用いてＰＯＡ基変性量Ｓを算出する。
Ｓ（モル％）＝｛（βのプロトン数／３ｎ）／（αのプロトン数＋（βのプロトン数／３ｎ））｝×１００
ｎはユニット２の繰り返し単位数を表す。The amount of POA group modification is represented by the molar fraction of the POA group with respect to the main chain methylene group of PVA. The POA group modification amount of the POA-modified PVA is, for example, the POA-modified polyvinyl ester that is the precursor of the PVA, specifically, POA-modified polyvinyl acetate (hereinafter, polyvinyl acetate may be abbreviated as PVAc). It can be determined from proton NMR. Specifically, after re-precipitation purification of POA-modified PVAc with n-hexane / acetone three times or more sufficiently, drying is performed under reduced pressure at 50 ° C. for 2 days to prepare POA-modified PVAc for analysis. The PVAc is dissolved in CDCl 3 and 500 MHz proton NMR (JEOL GX-500) is measured at room temperature. POA group modification from the peak α derived from the main chain methine of vinyl ester (4.7 to 5.2 ppm) and the peak β derived from the terminal methyl group of unit 2 (0.8 to 1.0 ppm) using the following formula The quantity S is calculated.
S (mol%) = {(number of protons of β / 3n) / (number of protons of α + (number of protons of β / 3n))} × 100
n represents the number of repeating units of unit 2.
また、本発明において、ＰＯＡ変性ＰＶＡ中のＰＯＡ基の含有量は、６〜５０重量部であることが必要であり、この範囲内において、本発明の効果であるＰＯＡ変性ＰＶＡを分散安定剤とする水性エマルジョンの初期接着性が発現する。ここで、ＰＯＡ基の含有量とは、ＰＶＡの主鎖１００重量部に対するＰＯＡ基の重量部（重量分率）で表される。ＰＯＡ基の含有量はＰＯＡ基変性量Ｓ、ユニット１の繰り返し単位数ｍ、ユニット２の繰り返し単位数ｎ、ＰＯＡ変性ＰＶＡのけん化度を用いて計算される値である。前述のＰＯＡ基変性量Ｓが同等であっても、けん化度が高くなるにつれ、あるいはｍ又はｎが大きくなるにつれ、ＰＯＡ変性ＰＶＡ中のＰＯＡ基の含有量は大きくなる。 In the present invention, the content of the POA group in the POA-modified PVA needs to be 6 to 50 parts by weight. Within this range, the POA-modified PVA which is the effect of the present invention is used as a dispersion stabilizer. The initial adhesiveness of the aqueous emulsion is developed. Here, the content of the POA group is represented by the weight part (weight fraction) of the POA group with respect to 100 parts by weight of the main chain of PVA. The content of the POA group is a value calculated using the POA group modification amount S, the number of repeating units m of unit 1, the number of repeating units n of unit 2, and the degree of saponification of POA modified PVA. Even if the above-mentioned POA group modification amount S is equivalent, the POA group content in the POA-modified PVA increases as the degree of saponification increases or as m or n increases.
上記の一般式（Ｉ）で示されるＰＯＡ基を側鎖に含有するＰＶＡの粘度平均重合度は、２００〜３０００であることが必要であり、２５０〜２８００が好ましく、３００〜２６００がより好ましい。ここで、粘度平均重合度Ｐは、ＪＩＳ−Ｋ６７２６に準じて測定される。すなわち、該ＰＶＡを再けん化し、精製した後、３０℃の水中で測定した極限粘度[η]から次式により求められる。
Ｐ＝（[η]×１０３／８．２９）（１／０．６２）
なお、粘度平均重合度は、単に重合度と呼ぶことがある。The viscosity average degree of polymerization of the PVA containing the POA group represented by the general formula (I) in the side chain needs to be 200 to 3000, preferably 250 to 2800, and more preferably 300 to 2600. Here, the viscosity average polymerization degree P is measured according to JIS-K6726. That is, after re-saponifying and purifying the PVA, it is obtained from the intrinsic viscosity [η] measured in water at 30 ° C. by the following equation.
P = ([η] × 10 3 /8.29) (1 / 0.62)
The viscosity average degree of polymerization may be simply referred to as the degree of polymerization.
重合度が２００より小さい場合には、水性エマルジョン用分散安定剤として十分な安定化能力を有さないために水性エマルジョンの安定性が不足するため不適である。３０００よりも大きい場合には、エマルジョンの粘度をコントロールするのが困難となるため不適である。 When the degree of polymerization is less than 200, it is not suitable because it does not have sufficient stabilizing ability as a dispersion stabilizer for an aqueous emulsion, and the stability of the aqueous emulsion is insufficient. When it is larger than 3000, it is difficult to control the viscosity of the emulsion, which is not suitable.
上記の一般式（Ｉ）で示されるＰＯＡ基を側鎖に含有するＰＶＡのけん化度は８０〜９９．９９モル％であることが必要であり、８３〜９９．５モル％が好ましく、８５〜９９モル％がより好ましい。けん化度が８０モル％よりも小さい場合にはＰＯＡ変性ＰＶＡの水溶性が失われるために分散安定剤として機能せず、水性エマルジョンが不安定化する。一方、けん化度が９９．９９モル％を超える場合には、水性エマルジョン用分散安定剤として十分な安定化能力を有さないために水性エマルジョンの安定性が不足する。なお、該ＰＶＡのけん化度は、ＪＩＳ−Ｋ６７２６に準じて測定し得られる値である。 The saponification degree of the PVA containing the POA group represented by the general formula (I) in the side chain needs to be 80 to 99.99 mol%, preferably 83 to 99.5 mol%, 99 mol% is more preferable. If the degree of saponification is less than 80 mol%, the water solubility of the POA-modified PVA is lost, so that it does not function as a dispersion stabilizer and the aqueous emulsion becomes unstable. On the other hand, when the degree of saponification exceeds 99.99 mol%, the aqueous emulsion lacks stability because it does not have sufficient stabilizing ability as a dispersion stabilizer for aqueous emulsions. The degree of saponification of the PVA is a value that can be measured according to JIS-K6726.
上記一般式（Ｉ）で示されるＰＯＡ基を側鎖に含有するＰＶＡは、各種の方法により製造される。一般式（Ｉ）で表されるＰＯＡ基とＰＶＡの水酸基などと反応しうる官能基（カルボキシル基、イソシアネート基など）とを有する化合物とＰＶＡとを反応させることにより得ることも可能であるが、一般的および工業的には、一般式（Ｉ）で示されるＰＯＡ基を含有する不飽和単量体（マクロモノマー）とビニルエステルとを共重合した後、けん化することにより得られる。ここで、ＰＯＡ基を有するマクロモノマーとしては、上記の一般式（II）で示されるものが好ましい。 PVA containing the POA group represented by the general formula (I) in the side chain is produced by various methods. Although it is also possible to obtain by reacting a compound having a functional group (carboxyl group, isocyanate group, etc.) capable of reacting with the POA group represented by the general formula (I) and the hydroxyl group of PVA with PVA, In general and industrially, it is obtained by copolymerizing an unsaturated monomer (macromonomer) containing a POA group represented by the general formula (I) with a vinyl ester and then saponifying it. Here, as a macromonomer which has POA group, what is shown by said general formula (II) is preferable.
例えば、一般式（II）のＲ１が水素原子、Ｒ２が水素原子、Ｒ３が水素原子の場合、一般式（II）で示されるマクロモノマーとして具体的には、ポリオキシエチレンポリオキシブチレンモノアクリレート、ポリオキシエチレンポリオキシブチレンモノメタクリレート、ポリオキシエチレンポリオキシブチレンモノアクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノアリルエーテル、ポリオキシエチレンポリオキシブチレンモノメタアリルエーテル、ポリオキシエチレンポリオキシブチレンモノビニルエーテルなどが挙げられる。なかでも、ポリオキシエチレンポリオキシブチレンモノアクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノビニルエーテルが好適に用いられ、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノビニルエーテルが特に好適に用いられる。 For example, when R1 in the general formula (II) is a hydrogen atom, R2 is a hydrogen atom, and R3 is a hydrogen atom, specifically, as a macromonomer represented by the general formula (II), polyoxyethylene polyoxybutylene monoacrylate, Polyoxyethylene polyoxybutylene monomethacrylate, polyoxyethylene polyoxybutylene monoacrylic amide, polyoxyethylene polyoxybutylene monomethacrylamide, polyoxyethylene polyoxybutylene monoallyl ether, polyoxyethylene polyoxybutylene monomethallyl Examples include ether and polyoxyethylene polyoxybutylene monovinyl ether. Among them, polyoxyethylene polyoxybutylene monoacrylic acid amide, polyoxyethylene polyoxybutylene monomethacrylic acid amide, polyoxyethylene polyoxybutylene monovinyl ether are preferably used, polyoxyethylene polyoxybutylene monomethacrylic acid amide, Polyoxyethylene polyoxybutylene monovinyl ether is particularly preferably used.
一般式（II）のＲ２が炭素数１〜８のアルキル基の場合、具体的には、一般式（II）のＲ１が水素原子、Ｒ２が水素原子、Ｒ３が水素原子の場合の例として上記に例示したマクロモノマーの末端のＯＨ基が炭素数１〜８のアルコキシ基に置換されたものが挙げられる。なかでも、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミド、ポリオキシエチレンポリオキシブチレンモノビニルエーテルの末端のＯＨ基がメトキシ基に置換されたマクロモノマーが好適に用いられ、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミドの末端のＯＨ基がメトキシ基に置換されたマクロモノマーが特に好適に用いられる。 When R2 in the general formula (II) is an alkyl group having 1 to 8 carbon atoms, specifically, as an example in which R1 in the general formula (II) is a hydrogen atom, R2 is a hydrogen atom, and R3 is a hydrogen atom, In which the OH group at the end of the macromonomer exemplified in the above is substituted with an alkoxy group having 1 to 8 carbon atoms. Of these, a macromonomer in which the OH group at the terminal of polyoxyethylene polyoxybutylene monomethacrylamide or polyoxyethylene polyoxybutylene monovinyl ether is substituted with a methoxy group is preferably used. A macromonomer in which the OH group at the terminal of the acid amide is substituted with a methoxy group is particularly preferably used.
また、本発明の水性エマルジョン用分散安定剤を構成するＰＯＡ変性ＰＶＡを、上記の一般式（II）で示されるマクロモノマーとビニルエステルとの共重合体をけん化して得る場合には、共重合性を考慮して、Ｘが−ＣＯ−ＮＲ５−である上記の一般式（III）で示されるマクロモノマーを用いることがさらに好適である。 When the POA-modified PVA constituting the dispersion stabilizer for an aqueous emulsion of the present invention is obtained by saponifying a copolymer of a macromonomer and a vinyl ester represented by the general formula (II), In view of the properties, it is more preferable to use a macromonomer represented by the above general formula (III) in which X is —CO—NR 5 —.
上記の一般式（III）で示されるマクロモノマーとしては、ポリオキシエチレンポリオキシブチレンモノアクリル酸アミド、およびその末端のＯＨ基がメトキシ基に置換された不飽和単量体、ポリオキシエチレンポリオキシブチレンモノメタクリル酸アミド、およびその末端のＯＨ基がメトキシ基に置換された不飽和単量体が代表的である。 Examples of the macromonomer represented by the general formula (III) include polyoxyethylene polyoxybutylene monoacrylic acid amide, an unsaturated monomer in which the terminal OH group is substituted with a methoxy group, polyoxyethylene polyoxy Typical are butylene monomethacrylamide and unsaturated monomers in which the terminal OH group is substituted with a methoxy group.
本発明で使用するＰＯＡ変性ＰＶＡを製造するには、ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合をアルコール系溶媒中または無溶媒で行い、得られたＰＯＡ変性ビニルエステル系共重合体をけん化する方法が好ましい。ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合を行う際に採用される温度は０〜２００℃が好ましく、３０〜１４０℃がより好ましい。共重合を行う温度が０℃より低い場合は、十分な重合速度が得られにくい。また、重合を行う温度が２００℃より高い場合、本発明で規定するＰＯＡ基変性量を有するＰＯＡ変性ＰＶＡを得られにくい。共重合を行う際に採用される温度を０〜２００℃に制御する方法としては、例えば、重合速度を制御することで、重合により生成する発熱と反応器の表面からの放熱とのバランスをとる方法や、適当な熱媒を用いた外部ジャケットにより制御する方法等があげられるが、安全性の面からは後者の方法が好ましい。 In order to produce the POA-modified PVA used in the present invention, copolymerization of a macromonomer having a POA group and a vinyl ester monomer is carried out in an alcohol solvent or without solvent, and the resulting POA modified vinyl ester system is obtained. A method of saponifying the copolymer is preferred. The temperature employed when copolymerizing the macromonomer having a POA group and the vinyl ester monomer is preferably 0 to 200 ° C, more preferably 30 to 140 ° C. When the copolymerization temperature is lower than 0 ° C., it is difficult to obtain a sufficient polymerization rate. Moreover, when the temperature which superposes | polymerizes is higher than 200 degreeC, it is difficult to obtain POA modified PVA which has the POA group modification amount prescribed | regulated by this invention. As a method for controlling the temperature employed in the copolymerization to 0 to 200 ° C., for example, by controlling the polymerization rate, the heat generated by the polymerization is balanced with the heat released from the surface of the reactor. Examples thereof include a method and a method of controlling by an external jacket using an appropriate heating medium, but the latter method is preferable from the viewpoint of safety.
ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合を行うのに用いられる重合方式としては、回分重合、半回分重合、連続重合、半連続重合のいずれでもよい。重合方法としては、塊状重合法、溶液重合法、懸濁重合法、乳化重合法など公知の任意の方法を用いることができる。その中でも、無溶媒またはアルコール系溶媒中で重合を行う塊状重合法や溶液重合法が好適に採用され、高重合度の共重合体の製造を目的とする場合は乳化重合法が採用される。アルコール系溶媒としては、メチルアルコール、エチルアルコール、プロピルアルコールなどを用いることができるが、これらに限定されるものではない。またこれらの溶媒は２種類またはそれ以上の種類を混合して用いることができる。 As a polymerization method used for copolymerization of a macromonomer having a POA group and a vinyl ester monomer, any of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization may be used. As the polymerization method, any known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method can be used. Among them, a bulk polymerization method or a solution polymerization method in which polymerization is performed in the absence of a solvent or an alcohol solvent is preferably employed, and an emulsion polymerization method is employed for the purpose of producing a copolymer having a high degree of polymerization. As the alcohol solvent, methyl alcohol, ethyl alcohol, propyl alcohol, and the like can be used, but are not limited thereto. These solvents can be used in combination of two or more.
共重合に使用される開始剤としては、重合方法に応じて従来公知のアゾ系開始剤、過酸化物系開始剤、レドックス系開始剤などが適宜選ばれる。アゾ系開始剤としては、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）などが挙げられ、過酸化物系開始剤としては、ジイソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネートなどのパーカーボネート化合物；ｔ−ブチルパーオキシネオデカネート、α−クミルパーオキシネオデカネート、ｔ−ブチルパーオキシデカネートなどのパーエステル化合物；アセチルシクロヘキシルスルホニルパーオキシド；２，４，４−トリメチルペンチル−２−パーオキシフェノキシアセテートなどが挙げられる。さらには、上記開始剤に過硫酸カリウム、過硫酸アンモニウム、過酸化水素などを組み合わせて開始剤とすることもできる。また、レドックス系開始剤としては、上記の過酸化物と亜硫酸水素ナトリウム、炭酸水素ナトリウム、酒石酸、Ｌ−アスコルビン酸、ロンガリットなどの還元剤とを組み合わせたものが挙げられる。 As the initiator used for copolymerization, conventionally known azo initiators, peroxide initiators, redox initiators and the like are appropriately selected according to the polymerization method. As the azo initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethyl valeronitrile) and the like. Peroxide compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl Perester compounds such as peroxyneodecanate, α-cumylperoxyneodecanate, t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, etc. Is mentioned. Furthermore, the initiator can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator. Examples of the redox initiator include a combination of the above-described peroxide and a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.
また、ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合を高い温度で行った場合、ビニルエステル系単量体の分解に起因するＰＶＡの着色等が見られることがあるため、その場合には着色防止の目的で重合系に酒石酸のような酸化防止剤を１〜１００ｐｐｍ（ビニルエステル系単量体に対して）程度添加することはなんら差し支えない。 In addition, when copolymerization of a macromonomer having a POA group and a vinyl ester monomer is carried out at a high temperature, coloring of PVA due to decomposition of the vinyl ester monomer may be seen. In that case, an antioxidant such as tartaric acid may be added to the polymerization system in an amount of 1 to 100 ppm (relative to the vinyl ester monomer) for the purpose of preventing coloring.
ビニルエステル系単量体としては、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル、カプロン酸ビニル、カプリル酸ビニル、ラウリル酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、オレイン酸ビニル、安息香酸ビニルなどが挙げられるが、中でも酢酸ビニルが最も好ましい。 Examples of vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, Examples include vinyl stearate, vinyl oleate, and vinyl benzoate. Among them, vinyl acetate is most preferable.
ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合に際して、本発明の主旨を損なわない範囲で他の単量体を共重合しても差し支えない。使用しうる単量体として、例えば、エチレン、プロピレン、ｎ−ブテン、イソブチレンなどのα−オレフィン；アクリル酸およびその塩；アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸ｉ−プロピル、アクリル酸ｎ−ブチル、アクリル酸ｉ−ブチル、アクリル酸ｔ−ブチル、アクリル酸２−エチルヘキシル、アクリル酸ドデシル、アクリル酸オクタデシルなどのアクリル酸エステル類；メタクリル酸およびその塩；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸ｉ−プロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｉ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸２−エチルヘキシル、メタクリル酸ドデシル、メタクリル酸オクタデシルなどのメタクリル酸エステル類；アクリルアミド；Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、ジアセトンアクリルアミド、アクリルアミドプロパンスルホン酸およびその塩、アクリルアミドプロピルジメチルアミンおよびその塩またはその４級塩、Ｎ−メチロールアクリルアミドおよびその誘導体などのアクリルアミド誘導体；メタクリルアミド；Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド、メタクリルアミドプロパンスルホン酸およびその塩、メタクリルアミドプロピルジメチルアミンおよびその塩またはその４級塩、Ｎ−メチロールメタクリルアミドおよびその誘導体などのメタクリルアミド誘導体；メチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、ｉ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル、ｉ−ブチルビニルエーテル、ｔ−ブチルビニルエーテル、ドデシルビニルエーテル、ステアリルビニルエーテルなどのビニルエーテル類；アクリロニトリル、メタクリロニトリルなどのニトリル類；塩化ビニル、フッ化ビニルなどのハロゲン化ビニル類；塩化ビニリデン、フッ化ビニリデンなどのハロゲン化ビニリデン類；酢酸アリル、塩化アリルなどのアリル化合物；マレイン酸、イタコン酸、フマル酸などの不飽和ジカルボン酸およびその塩またはそのエステル；ビニルトリメトキシシランなどのビニルシリル化合物；酢酸イソプロペニルなどが挙げられる。 When the macromonomer having a POA group and the vinyl ester monomer are copolymerized, other monomers may be copolymerized within a range not impairing the gist of the present invention. Examples of monomers that can be used include α-olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, and i-propyl acrylate. Acrylates such as n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and salts thereof; methyl methacrylate, methacryl Methacrylic acid such as ethyl acetate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate Beauty treatment Acrylamide; N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide, acrylamide propane sulfonic acid and its salt, acrylamidopropyldimethylamine and its salt or quaternary salt thereof, N-methylol acrylamide Acrylamide derivatives such as and derivatives thereof; methacrylamide; N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propane sulfonic acid and salts thereof, methacrylamide propyldimethylamine and salts thereof or quaternary salts thereof, N-methylol methacryl Methacrylamide derivatives such as amides and derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl Vinyl ethers such as nyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; Vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid, and salts or esters thereof; vinyltrimethoxysilane, etc. Vinylsilyl compounds; isopropenyl acetate and the like.
また、ＰＯＡ基を有するマクロモノマーとビニルエステル系単量体との共重合に際し、得られる共重合体の重合度を調節することなどを目的として、本発明の主旨を損なわない範囲で連鎖移動剤の存在下で共重合を行っても差し支えない。連鎖移動剤としては、アセトアルデヒド、プロピオンアルデヒド、などのアルデヒド類；アセトン、メチルエチルケトンなどのケトン類；２−ヒドロキシエタンチオールなどのメルカプタン類；トリクロロエチレン、パークロロエチレンなどのハロゲン化炭化水素類が挙げられ、中でもアルデヒド類およびケトン類が好適に用いられる。連鎖移動剤の添加量は、添加する連鎖移動剤の連鎖移動定数および目的とするビニルエステル系重合体の重合度に応じて決定されるが、一般にビニルエステル系単量体に対して０．１〜１０重量％が望ましい。 In addition, in the copolymerization of a macromonomer having a POA group and a vinyl ester monomer, a chain transfer agent is used within the range not impairing the gist of the present invention for the purpose of adjusting the degree of polymerization of the resulting copolymer. Copolymerization may be carried out in the presence of. Examples of chain transfer agents include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; and halogenated hydrocarbons such as trichloroethylene and perchloroethylene. Of these, aldehydes and ketones are preferably used. The addition amount of the chain transfer agent is determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target vinyl ester polymer, but is generally 0.1% relative to the vinyl ester monomer. -10 wt% is desirable.
ＰＯＡ変性ビニルエステル系共重合体のけん化反応には、従来公知の水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシドなどの塩基性触媒またはＰ−トルエンスルホン酸などの酸性触媒を用いた加アルコール分解反応ないし加水分解反応を適用することができる。この反応に使用しうる溶媒としては、メタノール、エタノールなどのアルコール類；酢酸メチル、酢酸エチルなどのエステル類；アセトン、メチルエチルケトンなどのケトン類；ベンゼン、トルエンなどの芳香族炭化水素などが挙げられ、これらは単独で、または２種以上を組み合わせて用いることができる。中でもメタノールまたはメタノール／酢酸メチル混合溶液を溶媒とし、水酸化ナトリウムを触媒に用いてけん化反応を行うのが簡便であり好ましい。 In the saponification reaction of the POA-modified vinyl ester copolymer, an alcoholysis reaction using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as P-toluenesulfonic acid. Alternatively, a hydrolysis reaction can be applied. Examples of the solvent that can be used for this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene; These can be used alone or in combination of two or more. Among them, it is convenient and preferable to perform the saponification reaction using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst.
本発明の好適な実施態様は、上記のＰＯＡ変性ＰＶＡを分散安定剤とし、エチレン性不飽和単量体あるいはジエン系単量体から選ばれる一種以上の不飽和単量体からなる重合体を分散質とする水性エマルジョンである。該水性エマルジョンは、分散安定剤として該ＰＯＡ変性ＰＶＡ、分散質として該重合体を含有するものであれば特に制限はない。本発明の水性エマルジョンを接着剤や各種バインダーとして使用する場合に、本発明の重要な性能の一つである初期接着性を十分に発現させる意味では、水性媒体中でＰＯＡ変性ＰＶＡ存在下にエチレン性不飽和単量体あるいはジエン系単量体から選ばれる一種以上の不飽和単量体を乳化重合して得られる水性エマルジョンが好ましい。この乳化重合を実施するにあたっては、水、分散安定剤および重合開始剤の存在下に該不飽和単量体を一時または連続的に添加して、加熱、撹拌するような通常の乳化重合法がいずれも実施しうる。また、不飽和単量体を予め分散安定剤と混合して乳化させたものを連続的に添加する方法も実施しうる。 In a preferred embodiment of the present invention, the above POA-modified PVA is used as a dispersion stabilizer, and a polymer comprising one or more unsaturated monomers selected from ethylenically unsaturated monomers or diene monomers is dispersed. It is an aqueous emulsion to make. The aqueous emulsion is not particularly limited as long as it contains the POA-modified PVA as a dispersion stabilizer and the polymer as a dispersoid. When the aqueous emulsion of the present invention is used as an adhesive or various binders, ethylene in the presence of POA-modified PVA is present in an aqueous medium in the sense that the initial adhesiveness, which is one of the important performances of the present invention, is fully expressed. An aqueous emulsion obtained by emulsion polymerization of one or more unsaturated monomers selected from a polymerizable unsaturated monomer or a diene monomer is preferred. In carrying out this emulsion polymerization, an ordinary emulsion polymerization method in which the unsaturated monomer is added temporarily or continuously in the presence of water, a dispersion stabilizer and a polymerization initiator, and heated and stirred is used. Either can be implemented. Also, a method of continuously adding an unsaturated monomer previously mixed with a dispersion stabilizer and emulsified can be carried out.
本発明の水性エマルジョン用分散安定剤を用いた乳化重合において、上記ＰＯＡ変性ＰＶＡの使用量は、ＰＯＡ変性ＰＶＡの重合度や、要求される水性エマルジョンの樹脂濃度等によって多少異なるが、通常、分散質の重合体の合成に用いられる不飽和単量体１００重量部に対して１〜２０重量部、好ましくは２〜１０重量部である。ＰＯＡ変性ＰＶＡの使用量が１重量部よりも少ない場合には乳化重合の安定性が確保しにくく、また、２０重量部を超えると得られる水性エマルジョンの粘度が高くなりすぎ重合のコントロールが困難になると同時に、水性エマルジョンの耐水性等の物性に悪影響を及ぼすことがある。重合開始剤としては、通常の乳化重合に用いられる、例えば、過酸化水素、過硫酸塩類、過炭酸塩類、過酸化物等を単独で用いたり、これらと酒石酸、クエン酸、アスコルビン酸などのオキシカルボン酸、シュウ酸、スルフィン酸およびこれらの塩類、ロンガリット、水溶性鉄塩などとの組み合わせによるレドックス系重合開始剤などを用いることができる。 In the emulsion polymerization using the dispersion stabilizer for aqueous emulsions of the present invention, the amount of the POA-modified PVA used is somewhat different depending on the polymerization degree of the POA-modified PVA, the required resin concentration of the aqueous emulsion, etc. 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the unsaturated monomer used for the synthesis of the polymer. When the amount of POA-modified PVA used is less than 1 part by weight, it is difficult to ensure the stability of emulsion polymerization, and when it exceeds 20 parts by weight, the viscosity of the resulting aqueous emulsion becomes too high, making it difficult to control the polymerization. At the same time, physical properties such as water resistance of the aqueous emulsion may be adversely affected. As the polymerization initiator, used in ordinary emulsion polymerization, for example, hydrogen peroxide, persulfates, percarbonates, peroxides, etc. can be used alone, and these can be used together with oxyacids such as tartaric acid, citric acid and ascorbic acid. Redox polymerization initiators in combination with carboxylic acid, oxalic acid, sulfinic acid and salts thereof, Rongalite, water-soluble iron salt and the like can be used.
本発明の水性エマルジョンの分散質を構成する重合体の合成に用いるエチレン性不飽和単量体及びジエン系単量体としては、以下のものが挙げられる。エチレン、プロピレン、イソブチレン等のオレフィン；塩化ビニル、フッ化ビニル、ビニリデンクロリド、ビニリデンフルオライドなどのハロゲン化オレフィン；ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル等のビニルエステル；アクリル酸、メタクリル酸およびそのエステルである（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸α−エチルヘキシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸ジメチルアミノエチル及びこれらの四級化物；（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、（メタ）アクリルアミド−２−メチルプロバン、スルホン酸及びそのナトリウム塩のアクリルアミド系単量体；スチレン、α−メチルスチレン、Ｐ−スチレンスルホン酸及びそのナトリウム塩等のスチレン系単量体；ブタジエン、イソプレン、クロロプレン等のジエン系単量体；その他Ｎ−ビニルピロリドン等があげられ、これらの単独重合もしくは共重合が実施しうる。 Examples of the ethylenically unsaturated monomer and diene monomer used for the synthesis of the polymer constituting the dispersoid of the aqueous emulsion of the present invention include the following. Olefins such as ethylene, propylene and isobutylene; Halogenated olefins such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride; Vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and vinyl versatate; Acrylic acid, methacrylic acid and its esters methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, α-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, dimethylaminoethyl (meth) acrylate and quaternized products thereof; (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylamide- -Acrylamide monomers such as methylpropan, sulfonic acid and sodium salt thereof; Styrene monomers such as styrene, α-methylstyrene, P-styrenesulfonic acid and sodium salt thereof; Diene types such as butadiene, isoprene and chloroprene Monomer; other examples include N-vinylpyrrolidone, and homopolymerization or copolymerization thereof can be carried out.
なお、本発明の水性エマルジョン用分散安定剤を用いた水性エマルジョンは、得られる水性エマルジョンの性能を損なわない範囲で、他の保護コロイドを重合時もしくは重合後に添加して、水性エマルジョンに望まれる特性を付与することも有効である。このような保護コロイドとしては、例えば、従来のポリビニルアルコール、ポリアクリル酸またはポリメタクリル酸およびその塩類、ポリビニルアルキルエーテル、酢酸ビニルとアクリル酸、メタクリル酸又は無水マレイン酸との共重合物およびそのけん化物、低級アルキルビニルエーテル−無水マレイン酸共重合物、アルキルセルロース、ヒドロキシアルキルセルロース、アルキルヒドロキシアルキルセルロース、カルボキシメチルセルロースなどのセルロース誘導体、アルキル澱粉、カルボンキシメチル澱粉、酸化澱粉などの澱粉誘導体、アラビアゴム、トラガントゴム、ポリアルキレングリコールなどが挙げられる。この他、水性エマルジョンの性能を損なわない範囲であれば、乳化重合の際に従来用いられている液性調節剤、１価または多価のアルコール類、可塑剤、消泡剤などの助剤を重合時または重合後に添加することは何ら差し支えない。また、水性エマルジョンの性能を損なわない範囲であれば、従来公知のアニオン性、ノニオン性、カチオン性の界面活性剤やＰＶＡ、ヒドロキシエチルセルロース等の水溶性高分子を添加することもできる。 In addition, the aqueous emulsion using the dispersion stabilizer for aqueous emulsion of the present invention has characteristics desired for the aqueous emulsion by adding other protective colloids during or after the polymerization within a range not impairing the performance of the obtained aqueous emulsion. Is also effective. Examples of such protective colloids include conventional polyvinyl alcohol, polyacrylic acid or polymethacrylic acid and salts thereof, polyvinyl alkyl ether, copolymers of vinyl acetate and acrylic acid, methacrylic acid or maleic anhydride, and tendons thereof. , Lower alkyl vinyl ether-maleic anhydride copolymer, cellulose derivatives such as alkyl cellulose, hydroxyalkyl cellulose, alkyl hydroxyalkyl cellulose, carboxymethyl cellulose, starch derivatives such as alkyl starch, carboxoxymethyl starch, oxidized starch, gum arabic, Examples include tragacanth rubber and polyalkylene glycol. In addition, as long as the performance of the aqueous emulsion is not impaired, auxiliary agents such as liquid modifiers, monovalent or polyhydric alcohols, plasticizers, antifoaming agents and the like conventionally used in emulsion polymerization are added. It may be added at the time of polymerization or after polymerization. Further, conventionally known anionic, nonionic, and cationic surfactants and water-soluble polymers such as PVA and hydroxyethyl cellulose can be added as long as the performance of the aqueous emulsion is not impaired.
このようにして得られる水性エマルジョンは、接着剤や各種バインダーとして使用する場合に重要な性能の一つである初期接着性が高く、高速生産が可能である。これは、実用に際して乾燥の工程での濃縮により分散剤に含まれる特定のＰＯＡ基間の相互作用が強まり、粘度上昇が大きくなるためと考えられる。その特徴を利用してそのままあるいは従来公知の添加剤を添加して各種用途に利用される。例えば、初期接着性を生かした接着剤や各種バインダーはもちろん、塗料、繊維加工剤、紙加工剤、セメント混和剤、モルタルプライマー等広範に利用される。 The aqueous emulsion thus obtained has high initial adhesiveness, which is one of the important performances when used as an adhesive or various binders, and can be produced at high speed. This is considered to be because, in practical use, the interaction between specific POA groups contained in the dispersant is strengthened by concentration in the drying step, and the increase in viscosity is increased. Utilizing its characteristics, it can be used in various applications as it is or by adding conventionally known additives. For example, not only adhesives and various binders that make use of initial adhesiveness, but also paints, fiber processing agents, paper processing agents, cement admixtures, mortar primers, etc. are widely used.
以下、実施例を挙げて本発明をより具体的に説明するが本発明はこれらによって何ら制限されるものではない。なお、実施例中の「％」および「部」は特に断りのない限り、それぞれ「重量％」および「重量部」を表す。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “%” and “parts” represent “% by weight” and “parts by weight”, respectively, unless otherwise specified.
［ＰＯＡ変性ＰＶＡの製造］
製造例１（ＰＶＡ１の製造）
撹拌機、還流冷却管、窒素導入管、コモノマー滴下口および開始剤の添加口を備えた３Ｌの反応器に、酢酸ビニル７５０ｇ、メタノール２５０ｇ、ＰＯＡ基を有する不飽和単量体（単量体Ａ）１７．６ｇを仕込み、窒素バブリングをしながら３０分間系内を窒素置換した。また、ディレー溶液としてＰＯＡ基を有する不飽和単量体（単量体Ａ）をメタノールに溶解して濃度２０％としたコモノマー溶液を調製し、窒素ガスのバブリングにより窒素置換した。反応器の昇温を開始し、内温が６０℃となったところで、２，２’−アゾビスイソブチロニトリル（ＡＩＢＮ）０．２５ｇを添加し重合を開始した。ディレー溶液を滴下して重合溶液中のモノマー組成（酢酸ビニルと単量体Ａの比率）が一定となるようにしながら、６０℃で３時間重合した後冷却して重合を停止した。重合を停止するまで加えたコモノマー溶液の総量は７５ｍｌであった。また重合停止時の固形分濃度は２４．４％であった。続いて３０℃、減圧下でメタノールを時々添加しながら未反応の酢酸ビニルモノマーの除去を行い、ＰＯＡ変性ＰＶＡｃのメタノール溶液（濃度３５％）を得た。さらに、これにメタノールを加えて調製したＰＯＡ変性ＰＶＡｃのメタノール溶液４５３．４ｇ（溶液中のＰＯＡ変性ＰＶＡｃ１００．０ｇ）に、５５．６ｇのアルカリ溶液（水酸化ナトリウムの１０％メタノール溶液）を添加してけん化を行った（けん化溶液のＰＯＡ変性ＰＶＡｃ濃度２０％、ＰＯＡ変性ＰＶＡｃ中の酢酸ビニルユニットに対する水酸化ナトリウムのモル比０．１モル％）。アルカリ溶液を添加後約１分でゲル状物が生成したので、これを粉砕器にて粉砕し、４０℃で１時間放置してけん化を進行させた後、酢酸メチル５００ｇを加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノール２０００ｇを加えて室温で３時間放置洗浄した。上記の洗浄操作を３回繰り返した後、遠心脱液して得られた白色固体を乾燥機中６５℃で２日間放置してＰＯＡ変性ＰＶＡ（ＰＶＡ１）を得た。ＰＶＡ１の重合度は１７６０、けん化度は９８．７モル％、ＰＯＡ基変性量（Ｓ）は０．４モル％、ＰＯＡ基含有量は１０重量部であった。[Production of POA-modified PVA]
Production Example 1 (Production of PVA1)
In a 3 L reactor equipped with a stirrer, reflux condenser, nitrogen inlet, comonomer dropping port and initiator addition port, 750 g of vinyl acetate, 250 g of methanol, unsaturated monomer having POA group (monomer A ) 17.6 g was charged, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen. Further, a comonomer solution having a concentration of 20% was prepared by dissolving an unsaturated monomer having a POA group (monomer A) in methanol as a delay solution, and nitrogen substitution was performed by bubbling nitrogen gas. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. While the delay solution was added dropwise so that the monomer composition (ratio of vinyl acetate and monomer A) in the polymerization solution was constant, polymerization was performed at 60 ° C. for 3 hours and then cooled to stop the polymerization. The total amount of comonomer solution added until the polymerization was stopped was 75 ml. The solid content concentration when the polymerization was stopped was 24.4%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol under reduced pressure at 30 ° C. to obtain a methanol solution (concentration 35%) of POA-modified PVAc. Furthermore, 55.6 g of an alkali solution (10% methanol solution of sodium hydroxide) was added to 453.4 g of POA-modified PVAc methanol solution prepared by adding methanol to this (100.0 g of POA-modified PVAc in the solution). Saponification was carried out (POA-modified PVAc concentration of saponified solution 20%, molar ratio of sodium hydroxide to vinyl acetate unit in POA-modified PVAc 0.1 mol%). A gel-like product was formed in about 1 minute after the addition of the alkaline solution. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to proceed with saponification, and then 500 g of methyl acetate was added to leave the remaining alkali. Neutralized. After confirming that the neutralization was completed using a phenolphthalein indicator, a white solid was obtained by filtration, 2000 g of methanol was added thereto, and the mixture was allowed to stand and washed at room temperature for 3 hours. After the above washing operation was repeated three times, the white solid obtained by centrifugal drainage was left in a dryer at 65 ° C. for 2 days to obtain POA-modified PVA (PVA1). PVA1 had a polymerization degree of 1760, a saponification degree of 98.7 mol%, a POA group modification amount (S) of 0.4 mol%, and a POA group content of 10 parts by weight.
製造例２〜２２（ＰＶＡ２〜２２の製造）
酢酸ビニルおよびメタノールの仕込み量、重合時に使用するＰＯＡ基を有する不飽和単量体の種類（表２）や添加量等の重合条件、けん化時におけるＰＯＡ変性ＰＶＡｃの濃度、酢酸ビニルユニットに対する水酸化ナトリウムのモル比等のけん化条件を表１および表２に示すように変更した以外は、製造例１と同様の方法により各種のＰＯＡ変性ＰＶＡ（ＰＶＡ２〜２２）を製造した。Production Examples 2 to 22 (Production of PVA 2 to 22)
Charge amount of vinyl acetate and methanol, type of unsaturated monomer having POA group used during polymerization (Table 2), polymerization conditions such as addition amount, concentration of POA-modified PVAc during saponification, hydroxylation to vinyl acetate unit Various POA-modified PVAs (PVA2-22) were produced in the same manner as in Production Example 1 except that the saponification conditions such as the molar ratio of sodium were changed as shown in Tables 1 and 2.
製造例２３（ＰＶＡ２３の製造）
撹拌機、還流冷却管、窒素導入管、開始剤の添加口を備えた３Ｌの反応器に、酢酸ビニル７００ｇ、メタノール３００ｇを仕込み、窒素バブリングをしながら３０分間系内を窒素置換した。反応器の昇温を開始し、内温が６０℃となったところで、２，２’−アゾビスイソブチロニトリル（ＡＩＢＮ）０．２５ｇを添加し重合を開始し、６０℃で３時間重合した後冷却して重合を停止した。重合停止時の固形分濃度は１７．０％であった。続いて３０℃、減圧下でメタノールを時々添加しながら未反応の酢酸ビニルモノマーの除去を行い、ポリ酢酸ビニル（ＰＶＡｃ）のメタノール溶液（濃度３０％）を得た。さらに、これにメタノールを加えて調製したＰＶＡｃのメタノール溶液５４４．１ｇ（溶液中のＰＶＡｃ１２０．０ｇ）に、５５．８ｇのアルカリ溶液（水酸化ナトリウムの１０％メタノール溶液）を添加してけん化を行った（けん化溶液のＰＶＡｃ濃度２０％、ＰＶＡｃ中の酢酸ビニルユニットに対する水酸化ナトリウムのモル比０．１）。アルカリ溶液を添加後約１分でゲル状物が生成したので、これを粉砕器にて粉砕し、４０℃で１時間放置してけん化を進行させた後、酢酸メチル５００ｇを加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノール２０００ｇを加えて室温で３時間放置洗浄した。上記の洗浄操作を３回繰り返した後、遠心脱液して得られた白色固体を乾燥機中６５℃で２日間放置して無変性ＰＶＡ（ＰＶＡ２３）を得た。ＰＶＡ２３の重合度は１７００、けん化度は９８．５モル％であった。Production Example 23 (Production of PVA23)
700 g of vinyl acetate and 300 g of methanol were charged into a 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, and an initiator addition port, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to start polymerization, and polymerization was performed at 60 ° C. for 3 hours. After cooling, the polymerization was stopped. The solid content concentration when the polymerization was stopped was 17.0%. Subsequently, unreacted vinyl acetate monomer was removed while sometimes adding methanol under reduced pressure at 30 ° C. to obtain a methanol solution (concentration 30%) of polyvinyl acetate (PVAc). Furthermore, saponification was performed by adding 55.8 g of an alkaline solution (sodium hydroxide in 10% methanol) to 544.1 g of PVAc methanol solution prepared by adding methanol thereto (120.0 g of PVAc in the solution). (PVAc concentration of saponification solution 20%, molar ratio of sodium hydroxide to vinyl acetate unit in PVAc 0.1). A gel-like product was formed in about 1 minute after the addition of the alkaline solution. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to proceed with saponification, and then 500 g of methyl acetate was added to leave the remaining alkali. Neutralized. After confirming that the neutralization was completed using a phenolphthalein indicator, a white solid was obtained by filtration, 2000 g of methanol was added thereto, and the mixture was allowed to stand and washed at room temperature for 3 hours. After repeating the above washing operation three times, the white solid obtained by centrifugal drainage was allowed to stand in a dryer at 65 ° C. for 2 days to obtain unmodified PVA (PVA23). The polymerization degree of PVA23 was 1700, and the saponification degree was 98.5 mol%.
製造例２４〜２６（ＰＶＡ２４〜２６の製造）
酢酸ビニルおよびメタノールの仕込み量、けん化時におけるＰＶＡｃの濃度、酢酸ビニルユニットに対する水酸化ナトリウムのモル比等のけん化条件を表１に示すように変更した以外は、製造例２３と同様の方法により各種の無変性ＰＶＡ（ＰＶＡ２４〜２６）を製造した。Production Examples 24-26 (Production of PVA 24-26)
Various methods were used in the same manner as in Production Example 23 except that the saponification conditions such as the amount of vinyl acetate and methanol, the concentration of PVAc during saponification, and the molar ratio of sodium hydroxide to vinyl acetate unit were changed as shown in Table 1. Of unmodified PVA (PVA 24-26).
実施例１
還流冷却器、滴下ロート、温度計、窒素吹込口、イカリ型攪拌翼を備えた１リットルガラス製重合容器に、イオン交換水４５０ｇと製造例１で得られたＰＶＡ１を２４ｇ仕込み、９５℃で溶解した。次に、このＰＶＡ水溶液を冷却、窒素置換後、１４０ｒｐｍで撹拌しながら酢酸ビニル４０ｇを仕込み、６０℃に昇温した後、過酸化水素／酒石酸のレドックス系開始剤の存在下で重合を開始した。重合開始１５分後から酢酸ビニル３６０ｇを３時間にわたって連続的に添加し、重合を完結させた。使用した開始剤は、１％過酸化水素水３０ｇ、５％酒石酸水溶液１０ｇであった。得られたポリ酢酸ビニルエマルジョン（ＰＶＡｃ−１）は、固形分濃度４６．１％、粘度５０００ｍＰａ・ｓ（ＢＨ型粘度計、３０℃、２０ｒｐｍ（ローター７））であった。ＰＶＡｃ−１を用いて、以下に示す初期接着力を評価した。結果を表３に示す。Example 1
A 1 liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet, and a squid stirring blade was charged with 450 g of ion-exchanged water and 24 g of PVA1 obtained in Production Example 1 and dissolved at 95 ° C. did. Next, the PVA aqueous solution was cooled, purged with nitrogen, charged with 40 g of vinyl acetate while stirring at 140 rpm, heated to 60 ° C., and then polymerization was initiated in the presence of a redox initiator of hydrogen peroxide / tartaric acid. . From 15 minutes after the start of the polymerization, 360 g of vinyl acetate was continuously added over 3 hours to complete the polymerization. The initiator used was 30 g of 1% hydrogen peroxide solution and 10 g of 5% aqueous tartaric acid solution. The obtained polyvinyl acetate emulsion (PVAc-1) had a solid content concentration of 46.1% and a viscosity of 5000 mPa · s (BH viscometer, 30 ° C., 20 rpm (rotor 7)). The initial adhesive force shown below was evaluated using PVAc-1. The results are shown in Table 3.
［初期接着力試験］
接着力試験機ＡＳＭ−０１（日本たばこ産業株式会社製）を用いて、次の測定条件により測定した。
原紙 ：ライナー紙（コブサイズ度１９ｇ／ｍ２／２分）
測定環境 ：２０℃、６５％ＲＨ
接着剤塗工量 ：６０ｇ／ｍ２（ｗｅｔ塗工量）
接着剤温度 ：４０℃
塗工速度 ：０．５ｍ／秒
塗工後の放置時間 ：１秒
プレス圧 ：３ｋｇ
圧着時間 ：１秒、３秒、５秒、１０秒
圧着後の放置時間 ：１秒
剥離速度 ：２００ｍｍ／秒[Initial adhesion test]
Using an adhesive strength tester ASM-01 (manufactured by Japan Tobacco Inc.), the measurement was performed under the following measurement conditions.
Paper: liner paper (Kobusaizu of 19g / m 2/2 minutes)
Measurement environment: 20 ° C, 65% RH
Adhesive coating amount: 60 g / m 2 (wet coating amount)
Adhesive temperature: 40 ° C
Coating speed: 0.5 m / sec. Standing time after coating: 1 sec. Press pressure: 3 kg
Crimping time: 1 second, 3 seconds, 5 seconds, 10 seconds standing time after crimping: 1 second Peeling speed: 200 mm / second
実施例２〜６、比較例１〜２０
実施例１のＰＶＡ１に代えて製造例２〜２６で得られたＰＶＡ２〜２６を用いる以外は実施例１と同様にしてポリ酢酸ビニルエマルジョン（ＰＶＡｃ−２〜ＰＶＡｃ−２６）を得た。結果を表３に示す。Examples 2-6, Comparative Examples 1-20
Polyvinyl acetate emulsions (PVAc-2 to PVAc-26) were obtained in the same manner as in Example 1 except that PVA2 to 26 obtained in Production Examples 2 to 26 were used in place of PVA1 of Example 1. The results are shown in Table 3.
実施例７
実施例１において、ＰＶＡ１を３６ｇ用いる以外は実施例１と同様にしてポリ酢酸ビニルエマルジョン（ＰＶＡｃ−２７）を得た。結果を表３に示す。Example 7
A polyvinyl acetate emulsion (PVAc-27) was obtained in the same manner as in Example 1 except that 36 g of PVA1 was used in Example 1. The results are shown in Table 3.
実施例８
還流冷却器、滴下ロート、温度計、窒素吹込口を備えた１リットルガラス製重合容器に、イオン交換水５００ｇ、製造例２で得られたＰＶＡ２を２８ｇ仕込み、９５℃で溶解した。次に、メタクリル酸メチル２０ｇとアクリル酸ｎ−ブチル２０ｇを添加し、窒素置換後６５℃まで昇温し、１％過硫酸カリウム水溶液１２ｇを添加して重合を開始し、さらに２時間かけてメタクリル酸メチル１８０ｇ、アクリル酸ｎ−ブチル１８０ｇを連続的に添加した。重合は４時間で完結し、固形分濃度４５．１％、粘度３０００ｍＰａ．ｓのメタクリル酸メチル／アクリル酸ｎ−ブチル共重合体エマルジョン（ＡＣＲ−１）を得た。結果を表３に示す。Example 8
In a 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen blowing port, 500 g of ion-exchanged water and 28 g of PVA2 obtained in Production Example 2 were charged and dissolved at 95 ° C. Next, 20 g of methyl methacrylate and 20 g of n-butyl acrylate were added, the temperature was raised to 65 ° C. after nitrogen substitution, and 12 g of 1% potassium persulfate aqueous solution was added to initiate polymerization. 180 g of methyl acid and 180 g of n-butyl acrylate were continuously added. The polymerization was completed in 4 hours, the solid content concentration was 45.1%, and the viscosity was 3000 mPa.s. s methyl methacrylate / n-butyl acrylate copolymer emulsion (ACR-1) was obtained. The results are shown in Table 3.
実施例において示されているように、本発明の水性エマルジョン用分散安定剤を用いて乳化重合して得られたエマルジョンは、従来の分散剤を用いた場合に比べて、初期接着性に優れる。本発明の水性エマルジョン用分散安定剤を用いて得られた水性エマルジョンは、上記の特徴を生かして、各種接着剤、塗料、紙、繊維加工剤などに好適に用いることができ、工業上の利用価値が極めて大きい。 As shown in the examples, the emulsion obtained by emulsion polymerization using the dispersion stabilizer for aqueous emulsions of the present invention is excellent in initial adhesiveness as compared with the case of using a conventional dispersant. The aqueous emulsion obtained by using the dispersion stabilizer for aqueous emulsions of the present invention can be suitably used for various adhesives, paints, papers, fiber processing agents, etc. by taking advantage of the above characteristics, and is industrially utilized. The value is extremely great.
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| JPS6058402A (en) * | 1983-09-07 | 1985-04-04 | Nippon Synthetic Chem Ind Co Ltd:The | Dispersion stabilizer |
| JPH111505A (en) * | 1997-06-11 | 1999-01-06 | Nippon Synthetic Chem Ind Co Ltd:The | Disperse stabilizer |
| JP2004075870A (en) * | 2002-08-20 | 2004-03-11 | Nippon Synthetic Chem Ind Co Ltd:The | Dispersion stabilizer |
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| JPS6058402A (en) * | 1983-09-07 | 1985-04-04 | Nippon Synthetic Chem Ind Co Ltd:The | Dispersion stabilizer |
| JPH111505A (en) * | 1997-06-11 | 1999-01-06 | Nippon Synthetic Chem Ind Co Ltd:The | Disperse stabilizer |
| JP2004075870A (en) * | 2002-08-20 | 2004-03-11 | Nippon Synthetic Chem Ind Co Ltd:The | Dispersion stabilizer |
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