JP2006328269A - Aqueous emulsion composition of thermal crosslinking synthetic resin and paper or fiber treatment agent using the same - Google Patents
Aqueous emulsion composition of thermal crosslinking synthetic resin and paper or fiber treatment agent using the same Download PDFInfo
- Publication number
- JP2006328269A JP2006328269A JP2005155613A JP2005155613A JP2006328269A JP 2006328269 A JP2006328269 A JP 2006328269A JP 2005155613 A JP2005155613 A JP 2005155613A JP 2005155613 A JP2005155613 A JP 2005155613A JP 2006328269 A JP2006328269 A JP 2006328269A
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- Prior art keywords
- synthetic resin
- aqueous emulsion
- resin aqueous
- acid
- emulsion composition
- Prior art date
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- Granted
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- 239000000839 emulsion Substances 0.000 title claims abstract description 69
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 58
- 239000000057 synthetic resin Substances 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000004132 cross linking Methods 0.000 title claims abstract description 29
- 239000000835 fiber Substances 0.000 title claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 24
- 239000000123 paper Substances 0.000 title description 26
- 239000002253 acid Substances 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 125000000524 functional group Chemical group 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- -1 methyl glycidyl Chemical group 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 12
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 10
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 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
- 125000003700 epoxy group Chemical group 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GTZCVFVGUGFEME-HNQUOIGGSA-N trans-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C/C(O)=O GTZCVFVGUGFEME-HNQUOIGGSA-N 0.000 description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- SASYRHXVHLPMQD-UHFFFAOYSA-N 2-(1,2-dicarboxyethylsulfanyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)SC(C(O)=O)CC(O)=O SASYRHXVHLPMQD-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical compound C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 description 1
- DPTGFYXXFXSRIR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl prop-2-enoate Chemical compound C1C(COC(=O)C=C)CCC2OC21 DPTGFYXXFXSRIR-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
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- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
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- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
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- 235000002906 tartaric acid Nutrition 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paper (AREA)
Abstract
Description
本発明は、塗料、接着剤、粘着剤、紙処理剤及び繊維処理剤等に利用できる熱架橋型合成樹脂水性エマルジョン組成物に関する。 The present invention relates to a thermally crosslinkable synthetic resin aqueous emulsion composition that can be used in paints, adhesives, pressure-sensitive adhesives, paper treatment agents, fiber treatment agents, and the like.
近年、省資源及び環境保全の見地から有機溶剤を含まない水性樹脂に関心が向けられている。特にポリマーエマルジョンは、乾燥性に優れ、不揮発分を高くしても低粘度化が可能であるため、水性樹脂として、塗料、接着剤、粘着剤、紙処理剤及び繊維処理剤等に広く使用されている。しかしながらポリマーエマルジョンには、エマルジョン粒子を安定に分散させるために、比較的多量の分散安定剤が用いられており、そのため乾燥皮膜は耐水性が劣り、性能が不十分になる傾向がある。この傾向は、塗料、接着剤、粘着剤、紙処理剤及び繊維処理剤として用いた場合に特に問題となる。この問題を解決するために、エマルジョンのポリマー分子中に官能基を導入し、該官能基を利用して熱架橋反応を行なうことにより耐水性等を改善した熱架橋型合成樹脂水性エマルジョンを得る方法が多数提案されている。 In recent years, interest has been directed to water-based resins that do not contain organic solvents from the viewpoint of resource saving and environmental conservation. In particular, polymer emulsions are excellent in drying properties and can be reduced in viscosity even when the non-volatile content is increased. Therefore, they are widely used as paints, adhesives, pressure-sensitive adhesives, paper treatment agents and fiber treatment agents as aqueous resins. ing. However, a relatively large amount of a dispersion stabilizer is used in the polymer emulsion in order to stably disperse the emulsion particles, so that the dry film tends to have poor water resistance and insufficient performance. This tendency becomes a problem particularly when used as a paint, an adhesive, a pressure-sensitive adhesive, a paper treatment agent, and a fiber treatment agent. In order to solve this problem, a method for obtaining a thermally crosslinked synthetic resin aqueous emulsion having improved water resistance and the like by introducing a functional group into the polymer molecule of the emulsion and performing a thermal crosslinking reaction using the functional group Many have been proposed.
熱架橋型合成樹脂水性エマルジョンとしては、公知の技術として、例えばＮ−メチロール（メタ）アクリルアミド等の加熱縮合反応性官能基を有する重合性単量体を用いたものがある。この熱架橋型合成樹脂水性エマルジョンを紙処理剤及び繊維処理剤として使用すると、得られた紙は耐水性に優れ、また得られた繊維は非常に柔らかくなる。 As a heat-crosslinking synthetic resin aqueous emulsion, there is a known technique using a polymerizable monomer having a heat condensation reactive functional group such as N-methylol (meth) acrylamide. When this heat-crosslinking type synthetic resin aqueous emulsion is used as a paper treatment agent and a fiber treatment agent, the obtained paper is excellent in water resistance, and the obtained fiber becomes very soft.
しかしながら、これらの加熱縮合反応性官能基は、熱エネルギーを与えると、ホルムアルデヒドを放出することでさらに架橋が進行することが知られており、これが問題となる。すなわち、ホルムアルデヒドは刺激臭のある無色の気体であるだけでなく、発ガン性物質として知られており、例えば、繊維処理工程での作業環境だけでなく、製品として使用時に消費者にまで影響が及ぶことを考慮して、近年、安全性指向の高まりと共に、発ガン性のホルムアルデヒドを発生する物質の使用に対する規制や自粛が強化される傾向にある。 However, these heat-condensation reactive functional groups are known to undergo further crosslinking by releasing formaldehyde when heat energy is applied, which is a problem. In other words, formaldehyde is not only a colorless gas with an irritating odor, but also known as a carcinogenic substance. For example, it affects not only the working environment in the fiber treatment process but also the consumer when used as a product. In recent years, with the increase in safety orientation, regulations and self-restraint on the use of substances that generate carcinogenic formaldehyde tend to be strengthened.
これらの問題から、前記のＮ−メチロール化合物による熱架橋型エマルジョンに代えて、水酸基を有する水溶性高分子とその架橋剤として、ポリカルボン酸とリンのオキソ酸の塩を用いた架橋性組成物が提案されている（特許文献１参照）。
この架橋性組成物によれば、水酸基を有する水溶性高分子として、例えばポリビニルアルコール（ＰＶＡ）等を用いた場合、ホルムアルデヒドを放出せずに架橋が進行する。しかしながら、水溶性高分子水溶液を高不揮発分化すると、水溶液粘度が著しく上昇し、作業性が低下することとなり、利用分野によっては、大きな障害となる。
According to this crosslinkable composition, for example, when polyvinyl alcohol (PVA) or the like is used as the water-soluble polymer having a hydroxyl group, crosslinking proceeds without releasing formaldehyde. However, when the water-soluble polymer aqueous solution is highly non-volatilely differentiated, the viscosity of the aqueous solution is remarkably increased, and the workability is lowered.
本発明はこのような状況に鑑み、ホルムアルデヒドを放出せず、熱架橋性を有し、紙処理剤及び繊維処理剤として使用すると、得られた紙は優れた耐水性を有し、また得られた繊維は柔軟性に富む熱架橋型合成樹脂水性エマルジョン組成物、および紙又は繊維処理剤の提供を目的とする。 In view of such circumstances, the present invention does not release formaldehyde, has thermal crosslinkability, and when used as a paper treating agent and a fiber treating agent, the obtained paper has excellent water resistance and is obtained. It is an object of the present invention to provide a thermally crosslinkable synthetic resin aqueous emulsion composition rich in flexibility and a paper or fiber treatment agent.
上記目的を達成すべく、本発明者らは鋭意研究した結果、従来のＮ−メチロール（メタ）アクリルアミド等のＮ−メチロール化合物の熱架橋剤に代えて、カルボキシル基と熱架橋反応し得る官能基を含有する合成樹脂水性エマルジョンに、ポリカルボン酸を配合することで上記課題を解決できることを見出した。
すなわち、本発明は、
（１）カルボキシル基と熱架橋反応し得る官能基を有する合成樹脂水性エマルジョンとポリカルボン酸とを含有してなる熱架橋型合成樹脂水性エマルジョン組成物、
（２）前記合成樹脂水性エマルジョンが、カルボキシル基と熱架橋反応し得る官能基を有する不飽和単量体（Ａ）を、単独で、または該不飽和単量体（Ａ）と共重合可能な不飽和単量体（Ｂ）と共に、界面活性剤の存在下に乳化重合させた重合体のエマルジョンである上記（１）に記載の熱架橋型合成樹脂水性エマルジョン組成物、
（３）（Ａ）成分と（Ｂ）成分との合計量中の（Ａ）成分の量が、０．１〜１００質量％である（２）に記載の熱架橋型合成樹脂水性エマルジョン組成物、
（４）ポリカルボン酸の含有量が、合成樹脂水性エマルジョン中の合成樹脂成分１００質量に対し１〜１００質量部である上記（１）〜（３）いずれかに記載の熱架橋型合成樹脂水性エマルジョン組成物、及び
（５）上記（１）〜（４）のいずれかに記載の熱架橋型合成樹脂水性エマルジョン組成物を用いた紙又は繊維処理剤
を提供するものである。
In order to achieve the above object, the present inventors have intensively studied, and as a result, a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group in place of a conventional thermal crosslinking agent of an N-methylol compound such as N-methylol (meth) acrylamide. It has been found that the above-mentioned problems can be solved by blending a polycarboxylic acid with a synthetic resin aqueous emulsion containing a polycarboxylic acid.
That is, the present invention
(1) A thermally crosslinked synthetic resin aqueous emulsion composition comprising a synthetic resin aqueous emulsion having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group and a polycarboxylic acid,
(2) The synthetic resin aqueous emulsion can copolymerize the unsaturated monomer (A) having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group alone or with the unsaturated monomer (A). Thermally crosslinkable synthetic resin aqueous emulsion composition according to (1) above, which is an emulsion of a polymer emulsion-polymerized in the presence of a surfactant together with the unsaturated monomer (B),
(3) Thermally crosslinkable synthetic resin aqueous emulsion composition according to (2), wherein the amount of component (A) in the total amount of component (A) and component (B) is 0.1 to 100% by mass. ,
(4) The heat-crosslinking type synthetic resin aqueous solution according to any one of the above (1) to (3), wherein the content of the polycarboxylic acid is 1 to 100 parts by mass with respect to 100 mass of the synthetic resin component in the synthetic resin aqueous emulsion. An emulsion composition and (5) a paper or fiber treatment agent using the thermally crosslinked synthetic resin aqueous emulsion composition according to any one of (1) to (4) above are provided.
本発明によれば、カルボキシル基と熱架橋反応し得る官能基を有する水性分散液とポリカルボン酸とを含有した熱架橋型合成樹脂水性エマルジョン組成物としているので、環境、健康への悪影響が懸念される有害物質の発生の問題がなく、これを紙処理剤及び繊維処理剤として使用すると、耐水性に優れた紙が得られ、かつ柔らかい繊維を得ることができる。
なお、繊維処理剤は、処理後の繊維に耐水性、柔軟性、易乾燥性、ノーアイロン性、防しわ性を発現させる為のものであるが、本発明によれば柔軟性を更に向上させることができる。
According to the present invention, since it is a thermally crosslinked synthetic resin aqueous emulsion composition containing an aqueous dispersion having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group and a polycarboxylic acid, there is a concern about adverse effects on the environment and health. There is no problem of generation of harmful substances, and when this is used as a paper treatment agent and a fiber treatment agent, paper having excellent water resistance can be obtained and soft fibers can be obtained.
The fiber treatment agent is for causing the treated fiber to exhibit water resistance, flexibility, easy drying, no ironing, and wrinkle resistance, but according to the present invention, the flexibility is further improved. be able to.
以下、本発明を詳細に説明する。
本発明の熱架橋型合成樹脂水性エマルジョン組成物ではカルボキシル基と熱架橋反応し得る官能基を有する合成樹脂水性エマルジョンを用いるが、この合成樹脂水性エマルジョンはカルボキシル基と熱架橋反応し得る官能基を有する不飽和単量体（Ａ）を、単独で、または該不飽和単量体（Ａ）と共重合可能な不飽和単量体（Ｂ）と共に、界面活性剤の存在下に乳化重合させた重合体のエマルジョンであるのが好ましい。
ここで、カルボキシル基と熱架橋反応し得る官能基としては、エポキシ基、水酸基、カルボジイミド基、アジリジン基、オキサゾリン基、シクロカーボネート基が挙げられる。好ましくはエポキシ基あるいは水酸基である。カルボキシル基と熱架橋反応し得る官能基を有する不飽和単量体（Ａ）は、これらの基を１分子中に少なくとも１個有する不飽和単量体
１分子中に少なくとも１個のエポキシ基を有する不飽和単量体として、例えば、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル、メチルグリシジルアクリレート、メチルグリシジルメタクリレート、３，４−エポキシシクロヘキシルメチルアクリレート、３，４−エポキシシクロヘキシルメチルメタクリレートなどが挙げられる。好ましくはグリシジルメタクリレートである。
また、１分子中に少なくとも１個の水酸基を有する不飽和単量体として、ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、ヒドロキシブチルアクリレート、ポリエチレングリコールモノアクリレート、ポリプロピレングリコールモノアクリレート、ポリテトラメチレングリコールモノアクリレート、ポリエチレングリコールポリテトラメチレングリコールモノアクリレート、ポリプロピレングリコールポリテトラメチレングリコールモノアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルメタクリレート、ポリエチレングリコールモノメタクリレート、ポリプロピレングリコールモノメタクリレート、ポリテトラメチレングリコールモノメタクリレート、ポリエチレングリコールポリテトラメチレングリコールモノメタクリレート、ポリプロピレングリコールポリテトラメチレングリコールモノメタクリレート等が挙げられる。好ましくはヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレートである。
これらのカルボキシル基と熱架橋反応し得る官能基を有する不飽和単量体（Ａ）は単独であるいは二種以上を組み合わせて使用することができる。
Hereinafter, the present invention will be described in detail.
In the thermally crosslinkable synthetic resin aqueous emulsion composition of the present invention, a synthetic resin aqueous emulsion having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group is used. This synthetic resin aqueous emulsion has a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group. The unsaturated monomer (A) having the above component was emulsion-polymerized in the presence of a surfactant alone or together with the unsaturated monomer (B) copolymerizable with the unsaturated monomer (A). A polymer emulsion is preferred.
Here, examples of the functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group include an epoxy group, a hydroxyl group, a carbodiimide group, an aziridine group, an oxazoline group, and a cyclocarbonate group. An epoxy group or a hydroxyl group is preferable. The unsaturated monomer (A) having a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group comprises an unsaturated monomer having at least one of these groups in one molecule and at least one epoxy group in one molecule. Examples of the unsaturated monomer include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexyl methyl acrylate, 3,4-epoxycyclohexyl methyl methacrylate, and the like. Glycidyl methacrylate is preferred.
Further, as unsaturated monomers having at least one hydroxyl group in one molecule, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polytetramethylene glycol monoacrylate, polyethylene Glycol polytetramethylene glycol monoacrylate, polypropylene glycol polytetramethylene glycol monoacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol monomethacrylate, polyethylene Glycol polytetramethylene glycol monomethacrylate, polypropylene glycol polytetramethylene glycol monomethacrylate, and the like. Preferred are hydroxyethyl acrylate and hydroxyethyl methacrylate.
The unsaturated monomer (A) having a functional group capable of undergoing a thermal crosslinking reaction with these carboxyl groups can be used alone or in combination of two or more.
（Ａ）成分と共重合可能な不飽和単量体（Ｂ）としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、アリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、アクリロニトリル、スチレン、スチレン誘導体、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、塩化ビニリデン、ジビニルベンゼン、エチレン、プロピレン、ブチレン、イソブチレン等を使用することができる。これら不飽和単量体は、単独であるいは組み合わせて使用することができる。本発明の水性エマルジョンのガラス転移温度は、特に制限されない。 As unsaturated monomer (B) copolymerizable with component (A), methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, allyl (meth) Acrylate, ethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, acrylonitrile, styrene, styrene derivatives, vinyl acetate, propion Vinyl acid, vinyl chloride, vinylidene chloride, divinylbenzene, ethylene, propylene, butylene, isobutylene, and the like can be used. These unsaturated monomers can be used alone or in combination. The glass transition temperature of the aqueous emulsion of the present invention is not particularly limited.
合成樹脂水性エマルジョンを製造する際のカルボキシル基と熱架橋反応し得る官能基を含有する不飽和単量体（Ａ）の配合量は、（Ａ）成分と（Ｂ）成分との合計量中、０．１〜１００質量％の範囲が好ましく、特に０．５〜５０質量％の範囲が好ましい。
配合量が０．１質量％未満の場合には熱架橋型合成樹脂水性エマルジョン組成物の架橋反応性（硬化性）が低下して、紙処理剤に用いた場合、紙の耐水性が不十分となるおそれがある。
The blending amount of the unsaturated monomer (A) containing a functional group capable of undergoing a thermal crosslinking reaction with a carboxyl group in producing the synthetic resin aqueous emulsion is the total amount of the component (A) and the component (B). The range of 0.1-100 mass% is preferable, and the range of 0.5-50 mass% is especially preferable.
When the blending amount is less than 0.1% by mass, the crosslinking reactivity (curability) of the thermally crosslinkable synthetic resin aqueous emulsion composition decreases, and when used as a paper treatment agent, the water resistance of the paper is insufficient. There is a risk of becoming.
合成樹脂水性エマルジョンは、（Ａ）成分と（Ｂ）成分とを界面活性剤の存在下で乳化重合して得られる。界面活性剤としては、一般に市販されているアニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤及び共重合性乳化剤が使用できる。また、これらの界面活性剤は、単独であるいは二種以上を組み合わせて使用することができる。本発明の水性エマルジョンの界面活性剤量は、特に制限されない。 The synthetic resin aqueous emulsion is obtained by emulsion polymerization of the component (A) and the component (B) in the presence of a surfactant. As the surfactant, commercially available anionic surfactants, nonionic surfactants, cationic surfactants and copolymerizable emulsifiers can be used. These surfactants can be used alone or in combination of two or more. The amount of the surfactant in the aqueous emulsion of the present invention is not particularly limited.
乳化重合においては、重合開始剤を使用するのが好ましく、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素、アゾ系化合物等が使用される。また、これらと還元剤の併用によるレドックス系開始剤を使用することもできる。 In the emulsion polymerization, a polymerization initiator is preferably used, and persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, azo compounds and the like are used. Moreover, the redox initiator by using these together with a reducing agent can also be used.
乳化重合法としては、一括して仕込み重合する方法、各成分を連続供給しながら重合する方法などが適用できる。重合は通常３０〜８５℃の温度で攪拌下に行われる。 As the emulsion polymerization method, a method of batch polymerization and a method of polymerization while continuously supplying each component can be applied. The polymerization is usually carried out at a temperature of 30 to 85 ° C. with stirring.
本発明の熱架橋型合成樹脂水性エマルジョン組成物において使用されるポリカルボン酸は、１分子中に２個以上のカルボキシル基を有する有機化合物である。そのようなポリカルボン酸としては、例えば、各種の直鎖状脂肪族ポリカルボン酸、分岐状脂肪族ポリカルボン酸、脂環族ポリカルボン酸、芳香族ポリカルボン酸等が使用できる。それらのポリカルボン酸は水酸基、ハロゲン基、カルボニル基、炭素−炭素二重結合等を有していてもよく、またアミノ酸であってもよい。
なお、ポリカルボン酸に代えて、１分子中に１個のカルボキシル基を有する不飽和単量体のホモポリマー、例えば（メタ）アクリル酸ホモポリマー等を使用し、繊維処理剤に用いた場合、得られた繊維は非常に硬くなり、風合いに不具合が発生するため、使用できない。即ち、このようなポリマーは、本発明でいうポリカルボン酸に該当しないものである。
さらにポリカルボン酸は水溶性であっても、水不溶あるいは難溶性であってもよいが、反応性および作業性の点で水溶性のものがより好ましい。
The polycarboxylic acid used in the thermally crosslinkable synthetic resin aqueous emulsion composition of the present invention is an organic compound having two or more carboxyl groups in one molecule. Examples of such polycarboxylic acids include various linear aliphatic polycarboxylic acids, branched aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, aromatic polycarboxylic acids, and the like. These polycarboxylic acids may have a hydroxyl group, a halogen group, a carbonyl group, a carbon-carbon double bond, or the like, or may be an amino acid.
In place of polycarboxylic acid, when using a homopolymer of an unsaturated monomer having one carboxyl group in one molecule, for example, (meth) acrylic acid homopolymer, etc. The obtained fiber becomes very hard and has a problem with the texture, so it cannot be used. That is, such a polymer does not correspond to the polycarboxylic acid referred to in the present invention.
Furthermore, the polycarboxylic acid may be water-soluble, water-insoluble or hardly soluble, but water-soluble ones are more preferable in terms of reactivity and workability.
ポリカルボン酸の例としては、具体的には、蓚酸、マロン酸、コハク酸、グルタル酸、アジピン酸、スベリン酸、アゼライン酸、セバチン酸等の直鎖状脂肪族ポリカルボン酸、これらの酸の分岐状脂肪族ポリカルボン酸；イタコン酸、マレイン酸、フマル酸等の不飽和二塩基酸、ヘキサヒドロフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸、テトラヒドロフタル酸、ナジック酸等の脂環族二塩基酸；トリカルバリル酸、アコニチン酸、メチルシクロヘキセントリカルボン酸等の三塩基酸、１，２，３，４−ブタンテトラカルボン酸、全シス−１，２，３，４−シクロペンタンテトラカルボン酸、テトラヒドロフランテトラカルボン酸、メチルテトラヒドロフタル酸とマレイン酸の塩付加物等の四塩基酸、リンゴ酸、酒石酸、クエン酸等のヒドロキシ脂肪酸、ｏ−、ｍ−またはｐ−フタル酸、トリメリット酸、ピロメリット酸、ビフェニルテトラカルボン酸、ベンゾフェノンテトラカルボン酸、ジフェニルスルホンテトラカルボン酸等の芳香族ポリカルボン酸、シトラコン酸、トランス−アコニット酸、オキシジコハク酸及びチオジコハク酸等が例示できる。これらのうち好ましいポリカルボン酸は１，２，３，４−ブタンテトラカルボン酸、イタコン酸である。 Specific examples of the polycarboxylic acid include linear aliphatic polycarboxylic acids such as succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and the like. Branched aliphatic polycarboxylic acids; unsaturated dibasic acids such as itaconic acid, maleic acid and fumaric acid; alicyclics such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, tetrahydrophthalic acid and nadic acid Dibasic acid; tribasic acid such as tricarbaric acid, aconitic acid, methylcyclohexytricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, all cis-1,2,3,4-cyclopentanetetracarboxylic acid Tetrabasic acids such as tetrahydrofuran tetracarboxylic acid, methyl tetrahydrophthalic acid and maleic acid salt adducts, malic acid, tartaric acid Hydroxy fatty acids such as citric acid, o-, m- or p-phthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, aromatic polycarboxylic acid such as diphenylsulfonetetracarboxylic acid, citracone Examples thereof include acid, trans-aconitic acid, oxydisuccinic acid, and thiodisuccinic acid. Of these, preferred polycarboxylic acids are 1,2,3,4-butanetetracarboxylic acid and itaconic acid.
本発明の熱架橋型合成樹脂水性エマルジョン組成物中のポリカルボン酸の含有量としては、合成樹脂水性エマルジョン中の合成樹脂成分、例えば、前記の（Ａ）成分と（Ｂ）成分とから得られた合成樹脂水性エマルジョンである場合は（Ａ）成分と（Ｂ）成分との合計量、１００質量部に対し、１〜１００質量部の範囲が好ましく、特に１０〜５０質量部の範囲が好ましい。含有量が１質量部未満の場合には熱架橋型合成樹脂水性エマルジョン組成物の架橋反応性（硬化性）が低下し、紙処理剤に用いた場合、紙の耐水性が不十分となるおそれがある。一方１００質量部を越える場合にはポリマーエマルジョンの貯蔵安定性が悪くなり、短期間で硬化が進み使用不可能となるおそれがある。 The content of the polycarboxylic acid in the heat-crosslinking type synthetic resin aqueous emulsion composition of the present invention is obtained from the synthetic resin component in the synthetic resin aqueous emulsion, for example, the component (A) and the component (B). In the case of a synthetic resin aqueous emulsion, the total amount of the component (A) and the component (B) is preferably 100 to 100 parts by mass, and more preferably 10 to 50 parts by mass. When the content is less than 1 part by mass, the crosslinking reactivity (curability) of the thermally crosslinkable synthetic resin aqueous emulsion composition is lowered, and when used as a paper treatment agent, the water resistance of the paper may be insufficient. There is. On the other hand, when the amount exceeds 100 parts by mass, the storage stability of the polymer emulsion is deteriorated, and there is a possibility that the curing progresses in a short period and cannot be used.
本発明の熱架橋型合成樹脂水性エマルジョン組成物を処理剤として使用するのに好適な紙又は繊維は、紙はパルプセルロースからなる汎用の紙類、繊維は
綿、亜麻、黄麻、大麻、ラミー及び再生繊維セルロース、レーヨン等のセルロース繊維、ポリビニルアルコール系合成繊維等を３０％程度以上含むものである。
また、繊維処理剤として使用する場合、繊維の形態は、短繊維（ファイバー）、リンター、ロービング、スライバー、ヤーン、織物、編物、不織布等何れの形態であっても適用することができる。
Papers or fibers suitable for using the heat-crosslinking type synthetic resin aqueous emulsion composition of the present invention as a treating agent are: general-purpose papers made of pulp cellulose, fibers made of cotton, flax, jute, cannabis, ramie and It contains about 30% or more of cellulose fibers such as regenerated fiber cellulose and rayon, and polyvinyl alcohol synthetic fibers.
Moreover, when using as a fiber processing agent, the form of a fiber is applicable even if it is any form, such as a short fiber (fiber), a linter, a roving, a sliver, a yarn, a woven fabric, a knitted fabric, a nonwoven fabric.
以下実施例によって本発明を更に説明するが、本発明はそれに限定されるものではない。なお、例中の「部」は質量部を示す。 EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In addition, "part" in an example shows a mass part.
なお、実施例、比較例及び参考例で得られた熱架橋型合成樹脂水性エマルジョン組成物の物性試験及び評価は以下の通りに行った。 In addition, the physical-property test and evaluation of the heat-crosslinking type synthetic resin aqueous emulsion composition obtained by the Example, the comparative example, and the reference example were performed as follows.
濾紙強度
得られた合成樹脂水性エマルジョン組成物を１０質量％に希釈し、濾紙（東洋濾紙社製：分析用定性濾紙No．２）に２５ｇ／ｍ2（固形分含浸量）含浸させ、１１０℃にて１０分間乾燥した。こうして、得られた濾紙をオーブンにて１５０℃で５分間熱処理した。その処理後の濾紙の引張り強度を常態濾紙強度とし、２３℃の水中に１０分間浸漬した後の濾紙の引張り強度を湿潤濾紙強度として測定した。（引張り速度；２００ｍｍ／分、試験片サイズ；２５×１００ｍｍ、チャック間距離；５０ｍｍ）
Filter paper strength The resulting synthetic resin aqueous emulsion composition was diluted to 10% by mass, impregnated with filter paper (Toyo Roshi Kaisha, Ltd .: qualitative filter paper for analysis No. 2) and impregnated with 25 g / m 2 (solid content impregnation amount), 110 ° C. For 10 minutes. Thus, the obtained filter paper was heat-treated in an oven at 150 ° C. for 5 minutes. The tensile strength of the filter paper after the treatment was measured as normal filter paper strength, and the tensile strength of the filter paper after being immersed in water at 23 ° C. for 10 minutes was measured as wet filter paper strength. (Tensile speed: 200 mm / min, test piece size: 25 × 100 mm, distance between chucks: 50 mm)
剛軟性
得られた合成樹脂水性エマルジョン組成物を１０質量％に希釈し、綿試験布（綿金巾３号）に２０〜３０ｇ／ｍ2（固形分含浸量）含浸させ、ピンテンターにて１３０℃で５分間処理した後、ＪＩＳ Ｌ１０９６ ６．１９剛軟性 Ｅ法（ハンドルオメーター法）に準じて、剛軟性を測定した。
Stiffness The resulting synthetic resin aqueous emulsion composition was diluted to 10% by mass and impregnated with a cotton test cloth (cotton gold width 3) at 20 to 30 g / m 2 (solid content impregnation amount) at 130 ° C. with a pin tenter. After the treatment for 5 minutes, the bending resistance was measured according to JIS L1096 6.19 bending resistance E method (handle ohmmeter method).
実施例１
撹拌機、温度計、窒素導入管、還流冷却器、滴下ロートを取り付けた五つ口セパラブルフラスコに、イオン交換水を１００部およびアニオン性界面活性剤ニューレックスＲ（商品名：日本油脂社製 ノルマルドデシルベンゼンスルホン酸ナトリウム）を１部仕込み５５℃まで昇温した。
一方、１リットルビーカーにイオン交換水１５０部およびニューレックスＲ２部、（Ａ）成分としてグリシジルメタクリレート６部（（Ａ）および（Ｂ）成分の合計量中２．３質量％）、（Ｂ）成分として、エチルアクリレート１９３部およびブチルアクリレート６２部を仕込み、ホモミキサーで乳化し、混合乳化液をつくった。
上記のフラスコに、過硫酸カリウムを０．３部および重亜硫酸ナトリウム０．３部を仕込んだ後、上記の混合乳化液と３質量％過硫酸カリウム水溶液１８部および３質量％重亜硫酸ナトリウム２０部をそれぞれ３時間かけてロートから滴下して乳化重合を行った。この間容器内は６５℃に保った。滴下終了後、１時間、６５℃に保ち、熟成を行った。その後冷却を開始し、３０℃まで冷却後、ポリカルボン酸類として、１，２，３，４，−ブタンテトラカルボン酸（以下単に「ブタンテトラカルボン酸」と表記する場合がある。）の１０質量％水溶液を５３０部（ブタンテトラカルボン酸として５３部、（Ａ）および（Ｂ）成分の合計量１００部に対し２０．３部）を添加した。得られた熱架橋型合成樹脂水性エマルジョン組成物の不揮発分（固形分）は３０質量％であった。
Example 1
In a five-neck separable flask equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser, and dropping funnel, 100 parts of ion-exchanged water and anionic surfactant Newlex R (trade name: manufactured by NOF Corporation) 1 part of normal sodium dodecylbenzenesulfonate) was added and the temperature was raised to 55 ° C.
On the other hand, 150 parts of ion exchange water and 2 parts of Newlex R in a 1 liter beaker, 6 parts of glycidyl methacrylate as component (A) (2.3% by mass in the total amount of components (A) and (B)), component (B) As above, 193 parts of ethyl acrylate and 62 parts of butyl acrylate were charged and emulsified with a homomixer to prepare a mixed emulsion.
After charging 0.3 part of potassium persulfate and 0.3 part of sodium bisulfite into the flask, the mixed emulsion, 18 parts of 3% by weight aqueous potassium persulfate and 20 parts of 3% by weight sodium bisulfite were added. Were respectively added dropwise from a funnel over 3 hours to carry out emulsion polymerization. During this time, the inside of the container was kept at 65 ° C. After completion of the dropwise addition, the mixture was kept at 65 ° C. for 1 hour for aging. Thereafter, cooling was started, and after cooling to 30 ° C., 10 masses of 1,2,3,4, -butanetetracarboxylic acid (hereinafter sometimes simply referred to as “butanetetracarboxylic acid”) as polycarboxylic acids. 530 parts of an aqueous solution (53 parts as butanetetracarboxylic acid, 20.3 parts with respect to 100 parts of the total amount of components (A) and (B)) were added. The obtained thermally crosslinked synthetic resin aqueous emulsion composition had a non-volatile content (solid content) of 30% by mass.
実施例２
ポリカルボン酸としてのブタンテトラカルボン酸１０％水溶液の量を２１２０部（ブタンテトラカルボン酸として２１２部、（Ａ）および（Ｂ）成分の合計量１００部に対し８１．２部）に変更した以外は、実施例１と同様に実施し、得られた熱架橋型合成樹脂水性エマルジョン組成物のテストを行い、表１の結果を得た。
Example 2
Except for changing the amount of 10% aqueous solution of butanetetracarboxylic acid as polycarboxylic acid to 2120 parts (212 parts as butanetetracarboxylic acid, 81.2 parts with respect to 100 parts of the total amount of components (A) and (B)) Were carried out in the same manner as in Example 1, and the obtained thermally crosslinked synthetic resin aqueous emulsion composition was tested. The results shown in Table 1 were obtained.
実施例３
（Ａ）成分としてのグリシジルメタクリレートの量を１２０部（（Ａ）および（Ｂ）成分の合計中３２．０質量％）に変更した以外は、実施例１と同様に実施し、得られた熱架橋型合成樹脂水性エマルジョン組成物のテストを行い、表１の結果を得た。
Example 3
(A) Except having changed the quantity of the glycidyl methacrylate as a component into 120 parts (32.0 mass% in the sum total of (A) and (B) component), it carried out similarly to Example 1 and obtained heat The cross-linked synthetic resin aqueous emulsion composition was tested and the results shown in Table 1 were obtained.
実施例４
（Ａ）成分としてのグリシジルメタクリレートの量を１９２部（（Ａ）および（Ｂ）成分の合計量中４３．０質量％）に変更した以外は、実施例１と同様に実施し、得られた熱架橋型合成樹脂水性エマルジョン組成物のテストを行い、表１の結果を得た。
Example 4
(A) Except having changed the quantity of the glycidyl methacrylate as a component into 192 parts (43.0 mass% in the total amount of (A) and (B) component), it carried out similarly to Example 1, and was obtained. The test of the thermally crosslinked synthetic resin aqueous emulsion composition was conducted, and the results shown in Table 1 were obtained.
実施例５
（Ａ）成分として、ヒドロキシエチルメタクリレートを用い、ヒドロキシエチルメタクリレートの量を１２部（（Ａ）および（Ｂ）成分の合計量中５質量％）とし、さらにポリカルボン酸としてのブタンテトラカルボン酸１０％水溶液の量を１０６０部（質量％ブタンテトラカルボン酸として１０６部、（Ａ）および（Ｂ）成分の合計１００部に対し４０部）に変更した以外は、実施例１と同様に実施し、得られた熱架橋型合成樹脂水性エマルジョン組成物のテストを行い、表１の結果を得た。
Example 5
As component (A), hydroxyethyl methacrylate is used, the amount of hydroxyethyl methacrylate is 12 parts (5% by mass in the total amount of components (A) and (B)), and butanetetracarboxylic acid 10 as a polycarboxylic acid. The same as in Example 1 except that the amount of the aqueous solution was changed to 1060 parts (106 parts as mass% butanetetracarboxylic acid, 40 parts with respect to 100 parts in total of the components (A) and (B)), The obtained thermally crosslinked synthetic resin aqueous emulsion composition was tested, and the results shown in Table 1 were obtained.
実施例６
（Ａ）成分として、グリシジルメタクリレートおよびヒドロキシエチルメタクリレートを用い、グリシジルメタクリレートの量を３部（（Ａ）および（Ｂ）成分の合計量中１．１質量％）およびヒドロキシエチルメタクリレートの量を６部（（Ａ）および（Ｂ）成分の合計量中２．３質量％）とし、さらにポリカルボン酸としてのブタンテトラカルボン酸１０％水溶液の量を５３０部（ブタンテトラカルボン酸として５３部、（Ａ）および（Ｂ）成分の合計量１００部に対し２０部）に変更した以外は、実施例１と同様に実施し、得られた熱架橋型合成樹脂水性エマルジョン組成物のテストを行い、表１の結果を得た。
Example 6
As component (A), glycidyl methacrylate and hydroxyethyl methacrylate are used, the amount of glycidyl methacrylate is 3 parts (1.1% by mass in the total amount of components (A) and (B)), and the amount of hydroxyethyl methacrylate is 6 parts. (2.3% by mass in the total amount of the components (A) and (B)), and further the amount of 10% aqueous solution of butanetetracarboxylic acid as polycarboxylic acid is 530 parts (53 parts as butanetetracarboxylic acid, (A ) And (B) except that the total amount of the components is changed to 20 parts), the test was performed on the obtained heat-crosslinkable synthetic resin aqueous emulsion composition. Table 1 The result was obtained.
実施例７
ポリカルボン酸として、ブタンテトラカルボン酸１０％水溶液に変えて、イタコン酸１０％水溶液を使用した以外は、実施例１と同様に実施し、得られた熱架橋型合成樹脂水性エマルジョン組成物のテストを行い、表１の結果を得た。
Example 7
Test of the obtained thermally crosslinkable synthetic resin aqueous emulsion composition in the same manner as in Example 1 except that a 10% aqueous solution of itaconic acid was used instead of the 10% aqueous solution of butanetetracarboxylic acid as the polycarboxylic acid. And the results shown in Table 1 were obtained.
実施例８
（Ａ）成分としてのグリシジルメタクリレートの量を２６１部、（Ｂ）成分を０部（（Ａ）および（Ｂ）成分の合計中１００質量％）に変更した以外は、実施例１と同様に実施し、得られた熱架橋型合成樹脂水性エマルジョン組成物のテストを行い、表１の結果を得た。
Example 8
The same procedure as in Example 1 was conducted except that the amount of glycidyl methacrylate as the component (A) was changed to 261 parts and the component (B) was changed to 0 part (100% by mass in the total of the components (A) and (B)). Then, the obtained thermal crosslinkable synthetic resin aqueous emulsion composition was tested, and the results shown in Table 1 were obtained.
比較例１
（Ａ）成分を使用しない以外は、実施例１と同様に実施し、得られた合成樹脂水性エマルジョン組成物のテストを行い、表２の結果を得た。
Comparative Example 1
(A) Except not using a component, it implemented similarly to Example 1, the test of the obtained synthetic resin aqueous emulsion composition was performed, and the result of Table 2 was obtained.
比較例２
（Ａ）成分として、グリシジルメタクリレートを１９２部（（Ａ）および（Ｂ）成分の合計量中８０質量％）使用し、さらにポリカルボン酸を使用しない以外は、実施例１と同様に実施し、得られた合成樹脂水性エマルジョン組成物のテストを行い、表２の結果を得た。
Comparative Example 2
As the component (A), 192 parts of glycidyl methacrylate (80% by mass in the total amount of the components (A) and (B)) was used, and a polycarboxylic acid was not used. The obtained synthetic resin aqueous emulsion composition was tested, and the results shown in Table 2 were obtained.
比較例３
（Ａ）成分として、ヒドロキシエチルメタクリレートを１２部（（Ａ）および（Ｂ）成分の合計量中５質量％）使用し、さらにポリカルボン酸を使用しない以外は、実施例１と同様に実施し、得られた合成樹脂水性エマルジョン組成物のテストを行い、表２の結果を得た。
Comparative Example 3
As component (A), 12 parts of hydroxyethyl methacrylate (5% by mass in the total amount of components (A) and (B)) was used, and further, polycarboxylic acid was not used. The obtained synthetic resin aqueous emulsion composition was tested, and the results shown in Table 2 were obtained.
比較例４
ポリカルボン酸として、ブタンテトラカルボン酸に変えてポリゾールＧＸ−１０（昭和高分子社製、アクリル酸ホモポリマー１０％水溶液、重量平均分子量２１００００、粘度１００ｍＰａ・ｓ）を使用した以外は、実施例１と同様に実施し、得られた合成樹脂水性エマルジョン組成物のテストを行い、表２の結果を得た。
Comparative Example 4
Example 1 except that polysol GX-10 (manufactured by Showa Polymer Co., Ltd., 10% aqueous solution of acrylic acid homopolymer, weight average molecular weight 210000, viscosity 100 mPa · s) was used as the polycarboxylic acid instead of butanetetracarboxylic acid. The obtained synthetic resin aqueous emulsion composition was tested, and the results shown in Table 2 were obtained.
比較例５
（Ａ）成分として、Ｎ−メチロールアクリルアミドを６部（（Ａ）および（Ｂ）成分の合計量中５質量％）使用し、ポリカルボン酸を使用しない以外は、実施例１と同様に実施し、得られた合成樹脂水性エマルジョン組成物のテストを行い、表２の結果を得た。
Comparative Example 5
As component (A), N-methylolacrylamide was used in the same manner as in Example 1 except that 6 parts (5% by mass in the total amount of components (A) and (B)) was used and no polycarboxylic acid was used. The obtained synthetic resin aqueous emulsion composition was tested, and the results shown in Table 2 were obtained.
Claims (5)
Paper or fiber processing agent using the heat-crosslinking type synthetic resin aqueous emulsion composition in any one of Claims 1-4.
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Cited By (2)
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| JP2010126638A (en) * | 2008-11-27 | 2010-06-10 | Showa Highpolymer Co Ltd | Aqueous emulsion composition of thermally crosslinkable polymer, method for producing the same, and fiber treatment agent |
| JP2013076095A (en) * | 2013-01-29 | 2013-04-25 | Showa Denko Kk | Production method of aqueous emulsion composition of thermal crosslinking polymer, production method of treated paper, and production method of treated fiber |
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| JP2010126638A (en) * | 2008-11-27 | 2010-06-10 | Showa Highpolymer Co Ltd | Aqueous emulsion composition of thermally crosslinkable polymer, method for producing the same, and fiber treatment agent |
| JP2013076095A (en) * | 2013-01-29 | 2013-04-25 | Showa Denko Kk | Production method of aqueous emulsion composition of thermal crosslinking polymer, production method of treated paper, and production method of treated fiber |
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| JP4703264B2 (en) | 2011-06-15 |
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