JPH0374416A - Water dispersible resin composition for nonwoven fabric or paper impregnation - Google Patents
Water dispersible resin composition for nonwoven fabric or paper impregnationInfo
- Publication number
- JPH0374416A JPH0374416A JP1209444A JP20944489A JPH0374416A JP H0374416 A JPH0374416 A JP H0374416A JP 1209444 A JP1209444 A JP 1209444A JP 20944489 A JP20944489 A JP 20944489A JP H0374416 A JPH0374416 A JP H0374416A
- Authority
- JP
- Japan
- Prior art keywords
- water
- resin composition
- dispersible resin
- tensile strength
- unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 26
- 239000011342 resin composition Substances 0.000 title claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 19
- 238000005470 impregnation Methods 0.000 title description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 unsaturated glycidyl compound Chemical class 0.000 claims abstract description 25
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 11
- 230000009477 glass transition Effects 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 29
- 239000011230 binding agent Substances 0.000 abstract description 18
- 239000003513 alkali Substances 0.000 abstract description 16
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract description 6
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004078 waterproofing Methods 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- PUANAIYYEZIDDG-NSCUHMNNSA-N (e)-n-(hydroxymethyl)but-2-enamide Chemical compound C\C=C\C(=O)NCO PUANAIYYEZIDDG-NSCUHMNNSA-N 0.000 description 1
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- FKOZPUORKCHONH-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid Chemical compound CC(C)CS(O)(=O)=O FKOZPUORKCHONH-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- HVGIUNGSUCQGDX-UHFFFAOYSA-N 3-amino-2-methylpropane-1-sulfonic acid Chemical compound NCC(C)CS(O)(=O)=O HVGIUNGSUCQGDX-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
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- BSCJIBOZTKGXQP-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCCO BSCJIBOZTKGXQP-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- OKPYIWASQZGASP-UHFFFAOYSA-N n-(2-hydroxypropyl)-2-methylprop-2-enamide Chemical compound CC(O)CNC(=O)C(C)=C OKPYIWASQZGASP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Nonwoven Fabrics (AREA)
- Paper (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は建築用に使用される不繊布または紙の結合剤と
して好適な含浸用水分散性樹脂組成物に関する。更に詳
しくは屋根及び浴室等の建築物防水用として使用される
アスファルト含浸用不織布に優れた常態抗張力、引裂抗
張力、熱時抗張力、耐水・耐アルカリ性及び柔軟性等を
付与する水分散性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a water-dispersible resin composition for impregnation, which is suitable as a binder for nonwoven fabrics or papers used in construction. More specifically, a water-dispersible resin composition that imparts excellent normal tensile strength, tear tensile strength, hot tensile strength, water resistance, alkali resistance, flexibility, etc. to asphalt-impregnated nonwoven fabrics used for waterproofing buildings such as roofs and bathrooms. Regarding.
現在ポリエステル不織布は屋根及び浴室等防水用のアス
ファルト含浸不織布として広く使用されているが、アス
ファルト含浸加工時に、同時に各種水分散性樹脂組成物
を不織布の結合剤として含浸させ、不織布に防水シーh
としての常態抗張力、引裂抗張力、熱時抗張力、耐水・
耐アルカリ性及び柔軟性を付与することが通常行われて
いる。しかしながら、これら従来型水分散性樹脂組成物
では、不織布結合剤として十分な常態抗張力、引裂抗張
力、熱時抗張力、耐水・耐アルカリ性及び柔軟性付与効
果を兼備していないのが現状である。Currently, polyester nonwoven fabrics are widely used as asphalt-impregnated nonwoven fabrics for waterproofing roofs, bathrooms, etc. During the asphalt impregnation process, various water-dispersible resin compositions are simultaneously impregnated as binders for the nonwoven fabrics, and the nonwoven fabrics are coated with waterproof seals.
normal tensile strength, tear tensile strength, hot tensile strength, water resistance and
It is common practice to impart alkali resistance and flexibility. However, the current situation is that these conventional water-dispersible resin compositions do not have sufficient normal tensile strength, tear tensile strength, hot tensile strength, water resistance/alkali resistance, and flexibility imparting effect as nonwoven fabric binders.
その解決策として、従来型水分散性樹脂組成物に結合剤
として部分メチル化メチロールメラミン樹脂を併用する
方法が提案されているが(繊維加工技術、日本繊維機械
学会幅、昭和48年9月25臼発刊、800頁参照)、
それでも尚これら物性を同時に満足することには不十分
であった。As a solution to this problem, a method has been proposed in which a partially methylated methylolmelamine resin is used as a binder in combination with a conventional water-dispersible resin composition (Textile Processing Technology, Textile Machinery Society of Japan, September 25, 1972). Published by Usu, see page 800),
Even so, it was still insufficient to simultaneously satisfy these physical properties.
例えば、特公昭80−44421号では疎水性不飽和単
量体を用いた水分散性樹脂組成物とメラミン樹脂を併用
して不織布結合剤を得ているが、該水分散性樹脂組成物
皮膜の耐水・耐アルカリ性は優れていても耐熱性を兼ね
備えたものではなかった。For example, in Japanese Patent Publication No. 80-44421, a nonwoven fabric binder is obtained by using a water-dispersible resin composition using a hydrophobic unsaturated monomer in combination with a melamine resin. Although it had excellent water resistance and alkali resistance, it did not have heat resistance.
また、特開昭8!3−270850号には粒子間及び粒
子内に架橋構造を有し、強靭な機械的強度を有すると共
に耐水性及び耐溶剤性に優れた不織布結合剤が、反応性
官能基を有する不飽和単量体を含むアクリル酸エステル
を乳化重合することによって得られた官記されているが
、10℃〜40℃のような比較的低いガラス転移点(以
下Tgという)を有する結合剤では強力な熱時抗張力を
有していない。In addition, JP-A-83-270850 describes a nonwoven fabric binder that has a crosslinked structure between and within particles, has strong mechanical strength, and has excellent water resistance and solvent resistance. It is obtained by emulsion polymerization of acrylic ester containing an unsaturated monomer having a group, and has a relatively low glass transition point (hereinafter referred to as Tg) of 10°C to 40°C. The binder does not have strong tensile strength when heated.
本発明は前記従来技術の有する欠点を克服し、不織布ま
たは紙に含浸し、常態抗張力、引裂抗張力、熱時抗張力
、耐水・耐アルカリ性及び柔軟性を兼備する優れた結合
剤として好適な水分散性樹脂組成物を提供せんとするも
のである。The present invention overcomes the drawbacks of the prior art, and provides water dispersibility suitable for impregnating nonwoven fabric or paper as an excellent binder that has normal tensile strength, tear tensile strength, hot tensile strength, water resistance, alkali resistance, and flexibility. The present invention aims to provide a resin composition.
本発明者等は、前記課題を解決すべく、鋭意研究を重ね
た結果、スチレンと(メタ)アクリル酸アルキルエステ
ルとを、不飽和グリシジル化合物、不飽和メチロール化
合物及び不飽和ジカルボン酸それぞれの0.2〜10重
量%の存在下に乳化重合させて得られる、スチレン−(
メタ)アクリル酸アルキルエステル系共重合体の水分散
性樹脂組成物からなり、且つ前記共重合体のガラス転移
点が10〜40℃である水分散性樹脂組成物が、常態抗
張力、引裂抗張力、熱時抗張力、耐水・耐アルカリ性及
び柔軟性が極めて優れていることを見出し、本発明に到
った。In order to solve the above problem, the present inventors have conducted intensive research and found that styrene and (meth)acrylic acid alkyl ester are combined with 0.00% of each of an unsaturated glycidyl compound, an unsaturated methylol compound, and an unsaturated dicarboxylic acid. Styrene (obtained by emulsion polymerization in the presence of 2 to 10% by weight)
The water-dispersible resin composition is composed of a water-dispersible resin composition of a meth)acrylic acid alkyl ester copolymer, and the copolymer has a glass transition point of 10 to 40°C, and has a normal tensile strength, a tear tensile strength, It was discovered that the tensile strength under heat, water resistance, alkali resistance, and flexibility are extremely excellent, leading to the present invention.
本発明において、抗張力及び耐水・耐アルカリ性を付与
するスチレンをポリマー中に含み他に(メタ)アクリル
酸エステル類の併用により、Tgを自由に設定し、乳化
重合によって水分散性樹脂組成物の粒子内にグリシジル
基等の親油性官能基を持ちまた粒子表面にメチロール基
等の親水性官能基を存在させた水分散性樹脂組成物を得
た。In the present invention, the polymer contains styrene, which imparts tensile strength and water/alkali resistance, and in addition, (meth)acrylic acid esters are used in combination to freely set the Tg, and particles of the water-dispersible resin composition are formed by emulsion polymerization. A water-dispersible resin composition was obtained which had a lipophilic functional group such as a glycidyl group therein and a hydrophilic functional group such as a methylol group present on the particle surface.
該水分散性樹脂組成物は、乾燥及び熱処理によって粒子
内及び粒子間の架橋を完結させることにより、強靭で柔
軟な皮膜特性を得た。The water-dispersible resin composition achieved tough and flexible film characteristics by completing intraparticle and interparticle crosslinking through drying and heat treatment.
また、公知技術で不織布結合剤として水分散性樹脂組成
物とメラミン樹脂を併用し、不織布に常態抗張力、熱時
抗張力を付与するものがあるが、該技術では柔軟性に欠
けるため引裂抗張力が劣っていた。In addition, there is a known technique that uses a water-dispersible resin composition and a melamine resin together as a nonwoven fabric binder to impart normal tensile strength and hot tensile strength to the nonwoven fabric, but this technique lacks flexibility and has poor tear tensile strength. was.
かかる点についても本発明者等が鋭意工夫を重ねた結果
、上記水分散性樹脂組成物はその粒子内及び粒子間で同
時に架橋構造を有する特徴を付与きせることに成功した
。As a result of intensive efforts by the present inventors regarding this point, the above-mentioned water-dispersible resin composition has succeeded in imparting the characteristic of having a crosslinked structure both within the particles and between the particles.
即ち、本発明に係わる水分散性樹脂組成物は前記の如く
粒子内及び粒子間で不飽和単量体の架橋性官能基と不飽
和ジカルボン酸との縮合反応等によって架橋化されてい
るため強靭な機械的強度、高熱時抗張力及び耐水・耐ア
ルカリ性を不織布に付与する。That is, the water-dispersible resin composition according to the present invention is strong because it is crosslinked within the particles and between the particles by a condensation reaction between the crosslinkable functional group of the unsaturated monomer and the unsaturated dicarboxylic acid as described above. It provides nonwoven fabric with excellent mechanical strength, tensile strength at high temperatures, and water and alkali resistance.
更1;、本発明における第二の特徴は、ポリマーのTg
を10℃〜40℃と比較的低く設定することにより上記
物性の他に柔軟性と同時に強力な引裂抗張力を不織布に
付与することである。Furthermore, the second feature of the present invention is that the Tg of the polymer
By setting the temperature at a relatively low temperature of 10° C. to 40° C., in addition to the above-mentioned physical properties, the nonwoven fabric is provided with flexibility and strong tear tensile strength.
また、本発明における第三の特徴は水分散性樹脂組成物
の粒子に存在するカルボン酸が粒子表面の親水性官能基
と架橋するだけでなく架橋剤として後添加により使用す
る部分メチル化メチロールメラミン樹脂との架橋にも寄
与することである。In addition, the third feature of the present invention is that the carboxylic acid present in the particles of the water-dispersible resin composition not only crosslinks with the hydrophilic functional groups on the particle surface, but also partially methylated methylolmelamine, which is used as a crosslinking agent by post-addition. It also contributes to crosslinking with the resin.
即ち、本発明で用いる水分散性樹脂組成物は、架橋構造
を有するにもかかわらず前記のように比較的低いTgの
ポリマーにより柔軟な皮膜を形成する。そのため柔軟で
ありながら、強靭な引張抗張力、熱時抗張力、耐水・耐
アルカリ性及び柔軟性機能を不織布に付与できる。That is, although the water-dispersible resin composition used in the present invention has a crosslinked structure, it forms a flexible film due to the relatively low Tg polymer as described above. Therefore, while being flexible, it is possible to impart strong tensile strength, hot tensile strength, water resistance, alkali resistance, and flexibility functions to the nonwoven fabric.
本発明の重要部分であるポリマーの架橋の機構について
考察すれば、水分散性樹脂組成物に用いられる親油性官
能基を有する不飽和単量体は粒子内部に存在し易く、粒
子内部の架橋に貢献する。Considering the mechanism of polymer crosslinking, which is an important part of the present invention, it is found that unsaturated monomers having lipophilic functional groups used in water-dispersible resin compositions tend to exist inside the particles, resulting in crosslinking inside the particles. To contribute.
そのためポリマーのTgを低く設定してもポリマーの架
橋が強靭であるため、ポリマーが柔軟であっでも常態抗
張力、熱時抗張力及び耐水・耐アルカリ性が保持できる
。また、親水性官能基を有する不飽和単量体は、その親
水性のために比較的粒子表面に存在するためその官能基
が粒子間架橋に貢献すると推測される。そのため粒子間
で架橋が十分に行われれば柔軟であっても強靭な皮膜が
形成される。また、この水分散性樹脂組成物に部分メチ
ル化メチロールメラミン樹脂を併用することで更に強力
な粒子間架橋を形成することができ、より強靭な皮膜を
形成することができるε推定される。Therefore, even if the Tg of the polymer is set low, the crosslinking of the polymer is strong, so even if the polymer is flexible, it can maintain normal tensile strength, tensile strength at heat, and water and alkali resistance. Moreover, since the unsaturated monomer having a hydrophilic functional group is relatively present on the particle surface due to its hydrophilic property, it is assumed that the functional group contributes to interparticle crosslinking. Therefore, if sufficient crosslinking occurs between particles, a tough film will be formed even if it is flexible. Furthermore, it is estimated that by using a partially methylated methylolmelamine resin in combination with this water-dispersible resin composition, even stronger interparticle crosslinking can be formed, and a stronger film can be formed.
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明の水分散性樹脂組成物は、スチレン、(メタ)ア
クリル酸アルキルエステル、不飽和グリシジル化合物、
不飽和メチロール化合物及び不飽和ジカルボン酸からな
る不飽和単量体を常法に従って乳化剤の存在下で乳化重
合することによって得るここができる。The water-dispersible resin composition of the present invention comprises styrene, (meth)acrylic acid alkyl ester, unsaturated glycidyl compound,
It can be obtained by emulsion polymerization of an unsaturated monomer consisting of an unsaturated methylol compound and an unsaturated dicarboxylic acid in the presence of an emulsifier according to a conventional method.
本発明で使用される(メタ)アクリル酸アルキルエステ
ル類としては下記−数式(1)で示きれる。The (meth)acrylic acid alkyl esters used in the present invention are represented by the following formula (1).
(式中Rは水素原子またはメチル基、R2は炭素数2〜
8のアルキル基を表す。)
その中で、アクリル酸またはメタクリル酸のエチル、プ
ロピル、ブチル、2−エチルヘキシルのエステル類の1
種以上が好適に使用される。(In the formula, R is a hydrogen atom or a methyl group, and R2 has 2 to 2 carbon atoms.
8 represents an alkyl group. ) Among them, one of the esters of ethyl, propyl, butyl, and 2-ethylhexyl of acrylic acid or methacrylic acid.
More than one species is preferably used.
また、本発明においては生成する水分散性樹脂組成物に
粒子内及び粒子間の強固な架橋構造を付与するために、
反応性官能基を有する不飽和単量体が必須成分として用
いられる。このような反応性官能基を有する不飽和単量
体としては、下記(II)〜(IV)で示される化合物
があげられ、これらの反応性官能基を有する不飽和単量
体(■)。In addition, in the present invention, in order to impart a strong crosslinked structure within and between particles to the water-dispersible resin composition to be produced,
Unsaturated monomers with reactive functional groups are used as essential components. Examples of unsaturated monomers having such reactive functional groups include compounds shown in (II) to (IV) below, and unsaturated monomers (■) having these reactive functional groups.
(m)、 (IV)はそれぞれ1種または2種以上用
いることができる。Each of (m) and (IV) can be used alone or in combination.
1 は−C−0−または一〇−を表す)。1 represents -C-0- or 10-).
(II)の例としてはグリシジルアクリレート、グリシ
ジルメタクリレート、グリシジルクロトネート、アリル
グリシジルエーテル等が挙げられこれらの中でもグリシ
ジルメタクリレートが好ましい。Examples of (II) include glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, allyl glycidyl ether, and among these, glycidyl methacrylate is preferred.
匿
NH(m)
R,−0H
(式中、R5、R8は水素原子またはメチル基、R7は
炭素数2〜4のアルキレン基を表す)。NH(m) R, -0H (in the formula, R5 and R8 represent a hydrogen atom or a methyl group, and R7 represents an alkylene group having 2 to 4 carbon atoms).
−数式(m)の例としてはN−メチロールアクリルアミ
ド、N−メチロールメタクリルアミド、N−メチロール
クロトンアミド、N−(2−ヒドロキシエチル)アクリ
ルアミド、N−(2−ヒドロキシエチル)メタクリルア
ミド、N−(2−ヒドロキシプロピル)アクリルアミド
、N−(2−ヒドロキシプロピル)メタクリルアミド等
が挙げられるが、これらの中でもN−メチロールアクリ
ルアミドもしくはN−メチロールメタクリルアミドが好
ましい。- Examples of formula (m) include N-methylolacrylamide, N-methylolmethacrylamide, N-methylolcrotonamide, N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)methacrylamide, N-( Examples thereof include 2-hydroxypropyl)acrylamide, N-(2-hydroxypropyl)methacrylamide, and among these, N-methylolacrylamide and N-methylolmethacrylamide are preferred.
(式中、R8は水素原子、またはメチル基、カルボキシ
ル基、R9は水素原子、炭素数1〜3のアルキル基また
は−CHC0OHを表す、但しR8まま
たはR9の少くとも一方はカルボキシル基である)。(In the formula, R8 represents a hydrogen atom, a methyl group, or a carboxyl group; R9 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or -CHCOOH, provided that at least one of R8 or R9 is a carboxyl group) .
−数式(IV)の例としては、イタコン酸、マレイン酸
、フマル酸等が挙げられる。- Examples of formula (IV) include itaconic acid, maleic acid, fumaric acid, etc.
以上は、すべて必須成分であるが、これらの他に次の一
般式(V)で示される化合物も、ヒドロキシル基を共重
合体中に導入して物性を向上させる必要がある場合には
、共重合成分として用いられる。All of the above are essential components, but in addition to these, a compound represented by the following general formula (V) may also be used in the copolymer when it is necessary to introduce a hydroxyl group into the copolymer to improve its physical properties. Used as a polymerization component.
(式中’ R10’ R11は水素原子またはメチル基
、Bは−CH20−または−coo−1R12は炭素数
2〜4のアルキレン基もしくは一〇(CH2+2〜4、
nは1〜20の実数を表す)。(In the formula, 'R10' R11 is a hydrogen atom or a methyl group, B is -CH20- or -coo-1R12 is an alkylene group having 2 to 4 carbon atoms or 10 (CH2+2 to 4,
n represents a real number from 1 to 20).
一般式(V)の例としては、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、ヒドロキシプ
ロピルアクリレート、ヒドロキシプロピルメタクリレー
ト、ヒドロキシポリオキシエチレンアクリレート、ヒド
ロキシポリオキシエチレンメタクリレート、ヒドロキシ
ポリオキシプロピレンアクリレート、ヒドロキシポリオ
キシプロピレンメタクリレート、ヒドロキシポリオキシ
ブチレンモノアクリレート、ヒドロキシポリオキシブチ
レンメタクリレート、ヒドロキシブチルアクリレート、
ヒドロキシブチルメタクリレート、ヒドロキシエチルア
リルエーテル、ヒドロキシプロピルアリルエーテル、ヒ
ドロキシブチルアリルエーテル、ヒドロキシエチルクロ
トネート、ヒドロキシプロピルクロトネート、ヒドロキ
シブチルクロトネート等が挙げられ、これらの中でもヒ
ドロキシエチルメタクリレートもしくはヒドロキシプロ
ピルメタクリレートが好ましい。Examples of general formula (V) include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxypolyoxyethylene acrylate, hydroxypolyoxyethylene methacrylate, hydroxypolyoxypropylene acrylate, hydroxypolyoxypropylene methacrylate, Hydroxypolyoxybutylene monoacrylate, hydroxypolyoxybutylene methacrylate, hydroxybutyl acrylate,
Examples include hydroxybutyl methacrylate, hydroxyethyl allyl ether, hydroxypropyl allyl ether, hydroxybutyl allyl ether, hydroxyethyl crotonate, hydroxypropyl crotonate, hydroxybutyl crotonate, and among these, hydroxyethyl methacrylate or hydroxypropyl methacrylate is preferred. .
その他アクリルアミド、メタクリルアミド等も共重合に
より用いられる。In addition, acrylamide, methacrylamide, etc. can also be used by copolymerization.
さらに、これらモノマーの他に酢酸ビニル、プロピオン
酸ビニル、酪酸ビニル等の低級脂肪酸ビニルエステル類
、アクリロニトリル、メタクリロニトリル等のニトリル
類、α−メチルスチレン、クロルスチレン等のスチレン
類、塩化ビニル、臭化ビニル等のビニル類、塩化ビニリ
デン、臭化ビニリデン等のビニリデン類、ブタジェン、
クロロプレンイソプレン等のジエン類及びビニルピリジ
ン等が用いられる。In addition to these monomers, lower fatty acid vinyl esters such as vinyl acetate, vinyl propionate, and vinyl butyrate, nitriles such as acrylonitrile and methacrylonitrile, styrenes such as α-methylstyrene and chlorstyrene, vinyl chloride, and Vinyls such as vinyl chloride, vinylidenes such as vinylidene chloride and vinylidene bromide, butadiene,
Dienes such as chloroprene isoprene, vinylpyridine, etc. are used.
上記スチレン及び不飽和単量体(1)と反応性官能基を
有する不飽和単量体(II)〜(IV)の使用割合は9
971〜7G/30 (重量)である。The usage ratio of the unsaturated monomers (II) to (IV) having reactive functional groups with the styrene and unsaturated monomer (1) is 9
971-7G/30 (weight).
本発明においてスチレンは水分散性樹脂組成物に常態抗
張力、熱時抗張力及び耐水・耐アルカリ性を付与するた
めに必要であり、また不飽和単量体(1)は、本発明の
水分散性樹脂組成物のポリマー7gを10℃〜40℃に
設定するために必要で結合剤に常態抗張力、引裂抗張力
、及び柔軟性を付与し同時に耐水・耐アルカリ性を付与
することができる。尚、本発明の水分散性樹脂組成物に
用いるスチレンと不飽和単量体(1)の組成比はポリマ
ーのTgが10℃〜40℃の範囲内に設定される場合に
限って任意であるが、好適にはスチレン/不飽和単量体
(りは60/40〜γ5/25である。In the present invention, styrene is necessary for imparting normal tensile strength, hot tensile strength, and water/alkali resistance to the water-dispersible resin composition, and the unsaturated monomer (1) is It is necessary to set the temperature of 7 g of the polymer in the composition to 10°C to 40°C, and can impart normal tensile strength, tear tensile strength, and flexibility to the binder, as well as water resistance and alkali resistance. In addition, the composition ratio of styrene and unsaturated monomer (1) used in the water-dispersible resin composition of the present invention is arbitrary only when the Tg of the polymer is set within the range of 10 ° C. to 40 ° C. However, preferably styrene/unsaturated monomer (the ratio is 60/40 to γ5/25).
また、本発明においてスチレン、及び不飽和単量体(I
)の使用割合が99を超えると生成する水分散性樹脂組
成物の粒子内及び粒子間の架橋密度が小さくなり目的と
した加工物性が得られず、またスチレン、及び不飽和単
量体(1)の使用割合が70より低いと、乳化共重合す
る場合の重合安定性に欠は重合中のゲル化物生成等や乳
化共重合により得られた水分散性樹脂組成物の保存中に
おけるゲル化等が発生したりする。In addition, in the present invention, styrene and unsaturated monomer (I
) If the usage ratio of ) is lower than 70, the polymerization stability during emulsion copolymerization will be poor, resulting in formation of gelled products during polymerization and gelation during storage of the water-dispersible resin composition obtained by emulsion copolymerization. may occur.
さらに、本発明においては不飽和グリシジル化合物(不
飽和単量体(n)’) 、不飽和メチロール化合物(不
飽和単量体(■))及び不飽和ジカルボン酸(不飽和単
量体(■))はそれぞれ0.2〜lG重量%の範囲で使
用されるが、不飽和グリシジル化合物と不飽和メチロー
ル化合物の両者を多量、に使用すると重合中にゲル化し
、また両者が少いと目的とする物性が得られない゛。ま
た前者が多く後者が少ないと加工物の引張り伸び、引裂
強度が低下し、その逆では引張り強度、熱時抗張力が低
下する。不飽和ジカルボン酸は、不飽和メチロール化合
物と共に粒子間架橋に貢献するが、その使用量が多いと
重合中にゲル化が発生する。また少量では粒子間架橋密
度が低くなり、加工物の物性が低下する。Furthermore, in the present invention, unsaturated glycidyl compounds (unsaturated monomers (n)'), unsaturated methylol compounds (unsaturated monomers (■)) and unsaturated dicarboxylic acids (unsaturated monomers (■)) ) are each used in the range of 0.2 to 1G weight %, but if both the unsaturated glycidyl compound and the unsaturated methylol compound are used in large amounts, they will gel during polymerization, and if both are used in small amounts, the desired physical properties will be affected. I can't get it. Moreover, if the former is large and the latter is small, the tensile elongation and tear strength of the workpiece will decrease, and vice versa, the tensile strength and tensile strength at heat will decrease. The unsaturated dicarboxylic acid contributes to interparticle crosslinking together with the unsaturated methylol compound, but if it is used in a large amount, gelation occurs during polymerization. In addition, if the amount is small, the interparticle crosslinking density will be low, and the physical properties of the processed product will be deteriorated.
本発明の更に好ましい不飽和単量体の使用割合は、
スチレン58〜85重量%
(1)の単量体39〜21重量%
(II)の単量体2〜61i量%
(III)の単量体1.5〜4重量%
(mV)の単量体0.5〜4重量%
が好ましい。また、本発明の水分散性樹脂組成物に対し
て部分メチル化メチロールメラミン樹脂を固形分比80
/20〜9515で併用することも好ましい。A more preferable proportion of unsaturated monomers used in the present invention is as follows: 58-85% by weight of styrene, 39-21% by weight of monomer (1), 2-61i% by weight of monomer (II), monomer of (III). 1.5 to 4% by weight (mV) of monomer and 0.5 to 4% by weight of monomer (mV) are preferred. Furthermore, the solid content ratio of the partially methylated methylolmelamine resin to the water-dispersible resin composition of the present invention is 80.
/20 to 9515 is also preferably used in combination.
本発明の水分散性樹脂組成物は、通常の乳化重合を用い
て製造することができる。この乳化重合で用いられる乳
化剤及び重合開始剤は特に限定しないが、不飽和単量体
系に応じて重合が円滑に行われるものを選ぶべきである
。乳化剤としては陰イオン性界面活性剤等及び非イオン
性界面活性剤等の使用もしくは併用が可能であるが、合
成樹脂エマルシヨンの機械的安定性等の向上のために反
応性乳化剤等及び、またはパラスチレンスルホン酸ソー
ダ、ビニルスルホン酸ソーダ、ソディアムメタアリルス
ルホン酸ソーダ、2アミノメチルプロパンスルホン酸等
、反応性モノマー等を併用することが好ましい。重合開
始剤としては、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、ベンゾイルパーオキサイド、
t−ブチルハイドロパーオキサイド、クメンハイドロパ
ーオキサイド等の過酸化物等が一般的に用いられるが、
特に水溶性開始剤が好適である。The water-dispersible resin composition of the present invention can be produced using conventional emulsion polymerization. The emulsifier and polymerization initiator used in this emulsion polymerization are not particularly limited, but they should be selected so that polymerization can be carried out smoothly depending on the unsaturated monomer system. As emulsifiers, anionic surfactants and nonionic surfactants can be used or used in combination, but reactive emulsifiers and/or parallax may be used to improve the mechanical stability of the synthetic resin emulsion. It is preferable to use reactive monomers such as sodium styrene sulfonate, sodium vinyl sulfonate, sodium metaallylsulfonate, and 2-aminomethylpropanesulfonic acid. As a polymerization initiator, persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, benzoyl peroxide,
Peroxides such as t-butyl hydroperoxide and cumene hydroperoxide are commonly used, but
Particularly suitable are water-soluble initiators.
尚、ポリマーのTgの設定について、ポリマーのTgを
10℃より低く設定すると結合剤の常態抗張力、熱時抗
張力が低下する。また、ポリマーのTgが40℃を超え
ると結合剤の引裂抗張力の低下及び柔軟性の゛喪失につ
ながる。そのためポリマーのTgは10℃〜40℃に設
定しておく必要がある。Regarding the setting of the Tg of the polymer, if the Tg of the polymer is set lower than 10° C., the normal tensile strength and tensile strength at heat of the binder decrease. Also, if the Tg of the polymer exceeds 40°C, this will lead to a decrease in the tear tensile strength of the binder and a loss of flexibility. Therefore, the Tg of the polymer needs to be set at 10°C to 40°C.
以下実施例により本発明を更に詳細に説明する。 The present invention will be explained in more detail with reference to Examples below.
尚例中の部及び%は特に記述のない限り重量基準である
。In addition, parts and percentages in the examples are based on weight unless otherwise specified.
実施例 1
水 44部
ポリオキシエチレン
アルキル硫酸塩(10%水溶液)7.5部2−アクリル
アミド、2−メチル
プロパンスルホン酸(10%水溶液)3部スチレン
30部
2−エチルへキシルアクリレート 18部2−ヒド
ロキシエチルメタクリレート 3部グリシジルメタク
リレート1.5部
N−メチロールアクリルアミド 1部イタコン
酸 0.5部を水溶性重合開始剤を使
用し、セミバッチ法により反応温度80〜85℃で乳化
重合してTgが19℃の水分散性樹脂組成物を得た。こ
のようにして得られた水分散性樹脂組成物に部分メチロ
ール化メラミン(ミルペンS M −800,昭和高分
子■製)を固形分比で15%添加して結合剤を得た。こ
の得られた結合剤をポリエステル不織布に樹脂付着量1
7%/web(固形分)を含浸加工して物性を測定した
。Example 1 Water 44 parts Polyoxyethylene alkyl sulfate (10% aqueous solution) 7.5 parts 2-acrylamide, 2-methylpropanesulfonic acid (10% aqueous solution) 3 parts Styrene
30 parts 2-ethylhexyl acrylate 18 parts 2-hydroxyethyl methacrylate 3 parts Glycidyl methacrylate 1.5 parts N-methylol acrylamide 1 part Itaconic acid 0.5 parts Using a water-soluble polymerization initiator, the reaction temperature was adjusted by semi-batch method. Emulsion polymerization was carried out at 80 to 85°C to obtain a water-dispersible resin composition having a Tg of 19°C. To the thus obtained water-dispersible resin composition, partially methylolated melamine (Milpen SM-800, manufactured by Showa Kobunshi ■) was added in an amount of 15% by solid content to obtain a binder. This obtained binder was applied to a polyester nonwoven fabric with a resin adhesion amount of 1
7%/web (solid content) was impregnated and the physical properties were measured.
実施例 2
実施例1におけるグリシジルメタクリレート1.5部を
0.5部、N−メチロールアクリルアミド1部を2.5
部に代えた以外、実施例1と同様に乳化重合し、得られ
た水分散性樹脂組成物を用いて実施例1と同じ方法で物
性を測定した。Example 2 1.5 parts of glycidyl methacrylate in Example 1 was added to 0.5 parts, and 1 part of N-methylolacrylamide was added to 2.5 parts.
Emulsion polymerization was carried out in the same manner as in Example 1, except that the amount was changed, and the physical properties were measured in the same manner as in Example 1 using the obtained water-dispersible resin composition.
実施例 3
実施例1におけるイタコン酸の代わりにマレイン酸を使
用した外は、実施例1と同じ方法で実施した。Example 3 The same method as in Example 1 was carried out except that maleic acid was used instead of itaconic acid in Example 1.
比較例 1〜8
実施例1における不飽和単量体の組成を表−1に記載の
如く変更した以外、実施例1と同じ方法で実施した。Comparative Examples 1 to 8 Comparative examples were carried out in the same manner as in Example 1 except that the composition of the unsaturated monomer in Example 1 was changed as shown in Table 1.
以上の結果を、まとめて表−1及び表−2に示す。The above results are summarized in Table-1 and Table-2.
l)樹脂加工不織布の調製
繊維目付量約110g/−のポリエステルスパンボンド
不織布に結合剤固形分が繊維目付量に対して17%/w
eb(dry)量付着するように含浸加工した後に15
0℃で3分間乾燥し、さらに180℃で3分間熱処理を
行った。l) Preparation of resin-treated nonwoven fabric A polyester spunbond nonwoven fabric with a fiber basis weight of approximately 110 g/- has a binder solid content of 17%/w based on the fiber basis weight.
15 after impregnating to adhere eb (dry) amount.
It was dried at 0°C for 3 minutes and then heat-treated at 180°C for 3 minutes.
2)抗張力測定
インストロン型引張試験機(島津製作所■製)を用いて
、20℃の雰囲気下で引張試験及び引裂試験、160℃
の雰囲気下で引張試験を行った。2) Tensile strength measurement Using an Instron type tensile testing machine (manufactured by Shimadzu Corporation), tensile test and tear test in an atmosphere of 20°C, 160°C
A tensile test was conducted in an atmosphere of
3)耐アルカリ性測定
50℃、pH13の水酸化カルシウム水溶液に樹脂加工
不織布を10日間浸漬した後水洗し十分乾燥した後、上
記インストロン型引張試験機(島津製作所■製)を用い
て、20℃の雰囲気下で引張試験を行うことで耐アルカ
リ抗張力保持性を求めた。3) Alkali resistance measurement The resin-treated nonwoven fabric was immersed in an aqueous calcium hydroxide solution with a pH of 13 at 50°C for 10 days, then washed with water and thoroughly dried. The alkali resistance tensile strength retention was determined by conducting a tensile test in an atmosphere of
表
2
不織布の評優結果
O:非常に良好
0:良 好
×:良くない
〔発明の効果〕
本発明の不織布及び紙用結合剤は10℃〜40℃といっ
た比較的低いTgを有している。比較的低いTgを有し
ている不織布及び紙用結合剤は熱に対する低い抵抗性及
び低い機械的強度を示しがちである。本発明の水分散性
樹脂組成物は比較的低いTgであるにもかかわらず、不
織布及び紙に対して優れた常態抗張力、引裂抗張力、熱
時抗張力、耐水・耐アルカリ性及び柔軟性を兼備してい
る。Table 2 Evaluation results of nonwoven fabrics O: Very good 0: Good . Nonwoven and paper binders with relatively low Tg tend to exhibit low resistance to heat and low mechanical strength. Although the water-dispersible resin composition of the present invention has a relatively low Tg, it has excellent normal tensile strength, tear tensile strength, hot tensile strength, water resistance, alkali resistance, and flexibility for nonwoven fabrics and paper. There is.
従って、屋根及び浴室等防水用の他に自動車、車両、フ
ィルター、土木シート、生活関連用不織布及び紙用結合
剤として極めて有効である。Therefore, it is extremely effective as a binder for waterproofing roofs, bathrooms, etc., as well as for automobiles, vehicles, filters, civil engineering sheets, nonwoven fabrics for daily life, and paper.
Claims (1)
、不飽和グリシジル化合物、不飽和メチロール化合物及
び不飽和ジカルボン酸それぞれの0.2〜10重量%の
存在下に乳化重合させて得られる、スチレン−(メタ)
アクリル酸アルキルエステル系共重合体の水分散性樹脂
組成物からなり、且つ前記共重合体のガラス転移点が1
0〜40℃であることを特徴とする不織布または紙含浸
用水分散性樹脂組成物。Styrene-(meth) is obtained by emulsion polymerization of styrene and (meth)acrylic acid alkyl ester in the presence of 0.2 to 10% by weight of each of an unsaturated glycidyl compound, an unsaturated methylol compound, and an unsaturated dicarboxylic acid. )
consisting of a water-dispersible resin composition of an acrylic acid alkyl ester copolymer, and the copolymer has a glass transition point of 1.
A water-dispersible resin composition for impregnating nonwoven fabric or paper, characterized in that the temperature is 0 to 40°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1209444A JPH0667988B2 (en) | 1989-08-11 | 1989-08-11 | Water-dispersible resin composition for impregnating non-woven fabric or paper |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1209444A JPH0667988B2 (en) | 1989-08-11 | 1989-08-11 | Water-dispersible resin composition for impregnating non-woven fabric or paper |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0374416A true JPH0374416A (en) | 1991-03-29 |
JPH0667988B2 JPH0667988B2 (en) | 1994-08-31 |
Family
ID=16572965
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1209444A Expired - Fee Related JPH0667988B2 (en) | 1989-08-11 | 1989-08-11 | Water-dispersible resin composition for impregnating non-woven fabric or paper |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0667988B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05188457A (en) * | 1992-01-09 | 1993-07-30 | Fuji Photo Film Co Ltd | Waterproof case |
-
1989
- 1989-08-11 JP JP1209444A patent/JPH0667988B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05188457A (en) * | 1992-01-09 | 1993-07-30 | Fuji Photo Film Co Ltd | Waterproof case |
Also Published As
Publication number | Publication date |
---|---|
JPH0667988B2 (en) | 1994-08-31 |
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