JP2020090596A - Coating composition and laminate - Google Patents
Coating composition and laminate Download PDFInfo
- Publication number
- JP2020090596A JP2020090596A JP2018227873A JP2018227873A JP2020090596A JP 2020090596 A JP2020090596 A JP 2020090596A JP 2018227873 A JP2018227873 A JP 2018227873A JP 2018227873 A JP2018227873 A JP 2018227873A JP 2020090596 A JP2020090596 A JP 2020090596A
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- coating composition
- resin emulsion
- mass
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- 239000008199 coating composition Substances 0.000 title claims abstract description 48
- 239000000839 emulsion Substances 0.000 claims abstract description 79
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- -1 acryl Chemical group 0.000 claims abstract description 41
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 26
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 24
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 23
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 18
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 13
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims abstract description 9
- 125000005396 acrylic acid ester group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 30
- 239000011521 glass Substances 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 239000002023 wood Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 241000208140 Acer Species 0.000 claims description 3
- 235000018185 Betula X alpestris Nutrition 0.000 claims description 3
- 235000018212 Betula X uliginosa Nutrition 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 241001070941 Castanea Species 0.000 claims description 3
- 235000014036 Castanea Nutrition 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 3
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- 241000123611 Dipterocarpaceae Species 0.000 claims description 3
- 241000219428 Fagaceae Species 0.000 claims description 3
- 241000218641 Pinaceae Species 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920000297 Rayon Polymers 0.000 claims description 3
- 235000004789 Rosa xanthina Nutrition 0.000 claims description 3
- 241000220222 Rosaceae Species 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 241000218220 Ulmaceae Species 0.000 claims description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000010425 asbestos Substances 0.000 claims description 3
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 claims description 3
- 239000005388 borosilicate glass Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 210000000085 cashmere Anatomy 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000005355 lead glass Substances 0.000 claims description 3
- 235000021374 legumes Nutrition 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229910052895 riebeckite Inorganic materials 0.000 claims description 3
- 239000005361 soda-lime glass Substances 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 210000002268 wool Anatomy 0.000 claims description 3
- 240000004731 Acer pseudoplatanus Species 0.000 claims description 2
- 235000002754 Acer pseudoplatanus Nutrition 0.000 claims description 2
- 244000144730 Amygdalus persica Species 0.000 claims description 2
- 235000006485 Platanus occidentalis Nutrition 0.000 claims description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 230000000422 nocturnal effect Effects 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000000126 substance Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002585 base Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 230000003068 static effect Effects 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000010559 graft polymerization reaction Methods 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 2
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000009120 camo Nutrition 0.000 description 2
- 235000005607 chanvre indien Nutrition 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
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- 239000003995 emulsifying agent Substances 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011487 hemp Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229940057950 sodium laureth sulfate Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- NSLNFHKUIKHPGY-UHFFFAOYSA-N 2,2,4,4,6,6,8-heptamethyl-8-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si]1(C)C1=CC=CC=C1 NSLNFHKUIKHPGY-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- URZHQOCYXDNFGN-UHFFFAOYSA-N 2,4,6-trimethyl-2,4,6-tris(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[Si](C)(CCC(F)(F)F)O[Si](C)(CCC(F)(F)F)O1 URZHQOCYXDNFGN-UHFFFAOYSA-N 0.000 description 1
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 1
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- 239000003377 acid catalyst Substances 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
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- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005446 heptyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 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
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
本発明は、コーティング用組成物に関するものであり、より詳しくは基材表面にコーティングすることで、透明性を維持し、摺動性を付与することができるエマルジョン型コーティング用組成物に関する。また、本発明は、このコーティング用組成物による皮膜が形成された積層体に関する。 The present invention relates to a coating composition, and more specifically to an emulsion-type coating composition capable of maintaining transparency and imparting slidability by coating the surface of a substrate. The present invention also relates to a laminate having a film formed by the coating composition.
近年、コーティング剤の分野においては、環境問題の点で有機溶剤系から水系へと分散媒の移行が進んでいる。ウレタン系、アクリル系、塩化ビニル系などのエマルジョンは優れた皮膜形成能があり、コーティング剤として広く用いられてきた。 In recent years, in the field of coating agents, the transfer of the dispersion medium from an organic solvent system to an aqueous system is progressing in view of environmental problems. Emulsions such as urethane-based, acrylic-based, and vinyl chloride-based emulsions have excellent film forming ability and have been widely used as coating agents.
また、シリコーン系樹脂は、基材に摺動性を付与することができる樹脂として知られている。しかしながら、シリコーン系の樹脂をコーティング剤として使用する場合には、塗膜が白化するなどの不具合があった。 Further, the silicone-based resin is known as a resin capable of imparting slidability to a base material. However, when a silicone-based resin is used as a coating agent, there are problems such as whitening of the coating film.
そこで、皮膜形成能を有するウレタン系、アクリル系、塩化ビニル系のエマルジョンとシリコーン系の樹脂を混合してコーティング剤として使用する方法が試みられている。しかし、混合することによって、シリコーン系樹脂の摺動性を発揮できなかったり、元のウレタン系、アクリル系や塩化ビニル系の性能を劣化させるなどして満足な性能を発揮していないのが現実である。 Therefore, a method has been attempted in which a urethane-based, acrylic-based, or vinyl chloride-based emulsion having a film-forming ability is mixed with a silicone-based resin and used as a coating agent. However, the fact that the silicone resin does not exhibit the slidability of the silicone resin, or deteriorates the performance of the original urethane-based, acrylic-based, and vinyl chloride-based materials by mixing them, is not a satisfactory performance. Is.
本発明者は、特開２０１３−６７７８７号（特許文献１）の公報の中で、ウレタン系、アクリル系、塩化ビニル系のエマルジョンとシリコーン系の樹脂を混合したコーティング剤が基材に撥水性を付与できることを開示している。しかし、摺動性と塗膜の透明性については改善の余地があった。 The inventors of the present invention have found that in JP-A-2013-67787 (Patent Document 1), a coating agent obtained by mixing a urethane-based, acrylic-based, vinyl chloride-based emulsion and a silicone-based resin has a water-repellent property on a substrate. It discloses that it can be granted. However, there was room for improvement in slidability and transparency of the coating film.
本発明は、上記事情に鑑みなされたもので、塩化ビニル系樹脂エマルジョン及び／又はアクリル系樹脂エマルジョンと混合した際に、透明性を維持しながら、シリコーンの摺動性を効果的に付与したエマルジョン型コーティング用組成物及びその皮膜が形成された積層体を提供することを目的とする。 The present invention has been made in view of the above circumstances, and when mixed with a vinyl chloride resin emulsion and/or an acrylic resin emulsion, an emulsion that effectively imparts silicone slidability while maintaining transparency. An object of the present invention is to provide a mold coating composition and a laminate having a film formed thereon.
本発明者は、上記目的を達成するために鋭意検討した結果、皮膜形成能を有する塩化ビニル系樹脂エマルジョン及び／又はアクリル系樹脂エマルジョンと特定のシリコーンアクリルグラフト共重合樹脂エマルジョンとを所定の割合で配合したコーティング用組成物を開発するに至った。 The present inventors have conducted extensive studies to achieve the above object, and as a result, a vinyl chloride resin emulsion and/or an acrylic resin emulsion having film-forming ability and a specific silicone acrylic graft copolymer resin emulsion at a predetermined ratio The inventors have developed a compounding composition for coating.
従って、本発明は、下記のコーティング用組成物及び積層体を提供する。
１．（Ａ）皮膜形成能を有する塩化ビニル系樹脂エマルジョン及び／又はアクリル系樹脂エマルジョン：固形分比で６０〜９９質量％、
（Ｂ）下記一般式（１）で示されるポリオルガノシロキサンとアクリル酸エステル単位又はメタクリル酸エステル単位とが質量比３０：７０〜９９：１の割合である、平均粒子径が１８０ｎｍ以下のシリコーンアクリルグラフト共重合樹脂エマルジョン：固形分比で１〜４０質量％
を含有することを特徴とするコーティング用組成物。
２．上記一般式（１）において、Ｒ1及びＸの各々の１価炭化水素基が、炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基又は炭素数６〜２０のアリール基である上記１記載のコーティング用組成物。
３．（Ｂ）シリコーンアクリルグラフト共重合樹脂エマルジョンの平均粒子径が５０〜１８０ｎｍである上記１又は２記載のコーティング用組成物。
４．（Ｂ）シリコーンアクリルグラフト共重合樹脂エマルジョンが、
（ｂ１）上記一般式（１）で示される平均粒子径が１８０ｎｍ以下のポリオルガノシロキサンと、
（ｂ２）アクリル酸エステル単量体又はメタクリル酸エステル単量体と、
（ｂ３）これと共重合可能な官能基含有単量体と
の乳化グラフト共重合物である上記１〜３のいずれかに記載のコーティング用組成物。
５．上記一般式（１）で表されるポリオルガノシロキサンの平均粒子径が５０〜１８０ｎｍである上記４記載のコーティング用組成物。
６．基材に塗布した際のヘーズ増加率が、塗布前の基材のヘーズ値に対して１５００％以下である上記１〜５のいずれかに記載のコーティング用組成物。
７．基材表面のコーティング用である上記１〜６のいずれかに記載のコーティング用組成物。
８．上記１〜７のいずれかに記載のコーティング用組成物による皮膜が基材の片面又は両面に形成されていることを特徴とする積層体。
９．基材が、ポリカーボネート、ポリスチレン、ポリエチレンテレフタレート、ポリ塩化ビニル、ポリエステル、セルロース、ジエチレングリコールビスアリルカーボネートポリマー、アクリロニトリル−ブタジエン−スチレンポリマー、ポリ（メタ）アクリル酸エステル、ポリウレタン及びエポキシ樹脂の群から選ばれるプラスチックである上記８記載の積層体。
１０．基材が、ソーダ石灰ガラス、石英ガラス、鉛ガラス、ホウ珪酸ガラス及び無アルカリガラスの群から選ばれるガラスである上記８記載の積層体。
１１．基材が、カエデ科、カバノキ科、クスノキ科、クリ科、ゴマノハグサ科、ナンヨウスギ科、ニレ科、ノウゼンカズラ科、バラ科、ヒノキ科、フタバガキ科、フトモモ科、ブナ科、マツ科、マメ科及びモクセイ科の群から選ばれる木材である上記８記載の積層体。
１２．基材が、木綿、麻、リンネル、羊毛、絹、カシミヤ、石綿、ポリアミド、ポリエステル、ビスコース、セルロース、ガラス及び炭素の群から選ばれる繊維である上記８記載の積層体。
１３．コーティング用組成物による皮膜の厚さが０．５〜５０μｍである上記８〜１２のいずれかに記載の積層体。
Therefore, the present invention provides the following coating composition and laminate.
1. (A) Vinyl chloride resin emulsion and/or acrylic resin emulsion having film forming ability: 60 to 99 mass% in terms of solid content,
(B) Silicone acrylic having an average particle diameter of 180 nm or less, in which the polyorganosiloxane represented by the following general formula (1) and the acrylic acid ester unit or the methacrylic acid ester unit have a mass ratio of 30:70 to 99:1. Graft copolymer resin emulsion: 1-40 mass% in terms of solid content
A coating composition comprising:
2. In the above general formula (1), each monovalent hydrocarbon group of R 1 and X is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The coating composition as described in 1 above.
3. (B) The coating composition according to 1 or 2 above, wherein the silicone-acrylic graft copolymer resin emulsion has an average particle size of 50 to 180 nm.
4. (B) Silicone acrylic graft copolymer resin emulsion
(B1) a polyorganosiloxane represented by the general formula (1) and having an average particle size of 180 nm or less,
(B2) an acrylic acid ester monomer or a methacrylic acid ester monomer,
(B3) The coating composition as described in any one of 1 to 3 above, which is an emulsion graft copolymer with a functional group-containing monomer copolymerizable therewith.
5. 5. The coating composition according to 4 above, wherein the polyorganosiloxane represented by the general formula (1) has an average particle size of 50 to 180 nm.
6. The coating composition according to any one of 1 to 5 above, wherein the rate of increase in haze when applied to a substrate is 1500% or less with respect to the haze value of the substrate before application.
7. 7. The coating composition according to any one of 1 to 6 above, which is used for coating the surface of a substrate.
8. A layered product, wherein a film made of the coating composition according to any one of 1 to 7 above is formed on one side or both sides of a substrate.
9. A plastic whose base material is selected from the group consisting of polycarbonate, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyester, cellulose, diethylene glycol bisallyl carbonate polymer, acrylonitrile-butadiene-styrene polymer, poly(meth)acrylic acid ester, polyurethane and epoxy resin. 9. The laminated body according to 8 above.
10. 9. The laminate according to the above 8, wherein the base material is a glass selected from the group consisting of soda-lime glass, quartz glass, lead glass, borosilicate glass and non-alkali glass.
11. The base material is a maple family, birch family, camphoraceae family, chestnut family, sycamore family, albacaraceae family, elm family, nocturnal vine family, rosaceae family, cypress family, dipterocarpaceae family, peach family, beech family, pine family, legume family and oxenaceae. The laminate according to the above 8, which is a wood selected from the group of the family.
12. 9. The laminate according to the above 8, wherein the base material is a fiber selected from the group consisting of cotton, hemp, linen, wool, silk, cashmere, asbestos, polyamide, polyester, viscose, cellulose, glass and carbon.
13. 13. The laminate according to any one of 8 to 12 above, wherein the coating composition has a thickness of 0.5 to 50 μm.
本発明のコーティング用組成物は、優れた透明性、摺動性を有し、該コーティング用組成物による皮膜が形成された積層体の外観を損なわずに高い耐摩耗性を維持することができる。また水系であるため、作業面・環境面で利点が大きい。 The coating composition of the present invention has excellent transparency and slidability, and can maintain high abrasion resistance without impairing the appearance of the laminate on which a film formed by the coating composition is formed. .. Also, since it is water-based, it has great advantages in terms of work and environment.
本発明は、（Ａ）成分として、皮膜形成能を有する塩化ビニル系樹脂エマルジョン及び／又はアクリル系樹脂エマルジョンと、（Ｂ）成分として、下記一般式（１）で示されるポリオルガノシロキサンとアクリル酸エステル単位又はメタクリル酸エステル単位とが質量比３０：７０〜９９：１の割合である、平均粒子径が５０〜１８０ｎｍのシリコーンアクリルグラフト共重合樹脂エマルジョンとを含有し、（Ａ）成分を固形分比で６０〜９９質量％、（Ｂ）成分を１〜４０質量％の範囲でそれぞれ配合するコーティング用組成物であり、基材に塗布した際のヘーズヘ増加率が、塗布前の基材のヘーズ値に対して１５００％以下であることを特徴とするコーティング用組成物である。 The present invention relates to a vinyl chloride resin emulsion and/or an acrylic resin emulsion having film forming ability as the component (A), and a polyorganosiloxane represented by the following general formula (1) and acrylic acid as the component (B). A silicone acrylic graft copolymer resin emulsion having an average particle size of 50 to 180 nm, in which the mass ratio of the ester unit or the methacrylic acid ester unit is 30:70 to 99:1, and the component (A) is a solid content. It is a coating composition in which the ratio of 60 to 99% by mass and the component (B) are respectively blended in the range of 1 to 40% by mass, and the increase rate of haze when applied to a base material is the haze of the base material before application. The coating composition is 1500% or less of the value.
（Ａ）皮膜形成能を有する塩化ビニル系樹脂エマルジョン及び／又はアクリル系樹脂エマルジョンは、公知の方法、例えばアニオン又はノニオン系乳化剤等を用いた乳化重合法で合成したものを用いてもよいし、市販品を使用してもよい。皮膜形成能とは、一定温度以上で、乾燥後の塗膜表面の粒子性がなくなり、かつ、乾燥時に細かいひび割れなどを起こさない性能である。皮膜形成のための乾燥温度範囲は特に限定されないが、好ましくは３０〜１５０℃、より好ましくは１００〜１５０℃である。 (A) The vinyl chloride resin emulsion and/or acrylic resin emulsion having film forming ability may be those synthesized by a known method, for example, an emulsion polymerization method using an anion or nonionic emulsifier, You may use a commercial item. The film-forming ability is a property that the particle property of the coating film surface after drying is eliminated at a certain temperature or higher and fine cracks and the like do not occur during drying. The drying temperature range for forming the film is not particularly limited, but is preferably 30 to 150°C, more preferably 100 to 150°C.
（Ａ）成分の塩化ビニル系樹脂エマルジョン及び／又はアクリル系樹脂エマルジョンが皮膜形成能を有するためには、粒子径が１０〜５００ｎｍであることが好ましい。粘度（２５℃）は１０〜５００ｍＰａ・ｓであるものを用いるとよい。また、ガラス転移温度（以下、Ｔｇと記載することがある）は、１２０℃以下であり、６０℃以下が好ましく、３０℃以下が更に好ましい。なお、ガラス転移温度の下限値は−５０℃が好ましい。ガラス転移温度は、ＪＩＳ Ｋ７１２１に基づき測定できる。 In order for the vinyl chloride resin emulsion and/or the acrylic resin emulsion as the component (A) to have a film-forming ability, the particle diameter is preferably 10 to 500 nm. The viscosity (25° C.) is preferably 10 to 500 mPa·s. Further, the glass transition temperature (hereinafter sometimes referred to as Tg) is 120° C. or lower, preferably 60° C. or lower, and more preferably 30° C. or lower. The lower limit of the glass transition temperature is preferably -50°C. The glass transition temperature can be measured based on JIS K7121.
（Ａ）成分の塩化ビニル系樹脂エマルジョンは、塩化ビニル単量体の単独重合体のみならず、塩化ビニル単量体と下記単量体の共重合体であっても良い。 The vinyl chloride resin emulsion as the component (A) may be not only a homopolymer of a vinyl chloride monomer but also a copolymer of a vinyl chloride monomer and the following monomer.
また、（Ａ）成分のアクリル系樹脂エマルジョンは下記の単量体から１種又は２種以上を混合した重合体である。
例えば、炭素数１〜１８のアルキル基を有するアルコールとの（メタ）アクリル酸エステル、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（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、グリシジル（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、ジエチレングリコールジ（メタ）アクリレート等を挙げることができる。なお、（メタ）アクリレートとは、アクリレートとメタクリレートの総称である。また、上記に加えて下記エチレン性不飽和単量体を併用しても良い。例えば、アクリロニトリル、酢酸ビニル、プロピオン酸ビニル、スチレン、アクリル酸、メタクリル酸、（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド等が挙げられる。
The acrylic resin emulsion as the component (A) is a polymer prepared by mixing one or more of the following monomers.
For example, (meth)acrylic acid ester with alcohol having an alkyl group having 1 to 18 carbon atoms, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl ( Examples thereof include (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, and diethylene glycol di(meth)acrylate. In addition, (meth)acrylate is a general term for acrylate and methacrylate. In addition to the above, the following ethylenically unsaturated monomer may be used in combination. Examples thereof include acrylonitrile, vinyl acetate, vinyl propionate, styrene, acrylic acid, methacrylic acid, (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide and the like.
市販の塩化ビニル系樹脂エマルジョンとしては、日信化学工業（株）製ビニブランが挙げられる。また、市販のアクリル系樹脂エマルジョンとしては、日信化学工業（株）製ビニブラン、ヘンケルジャパン社製ヨドゾール、東亞合成（株）製アロンなどが挙げられる。 Examples of commercially available vinyl chloride resin emulsions include VINYBLAN manufactured by Nisshin Chemical Industry Co., Ltd. Examples of commercially available acrylic resin emulsions include Vinibran manufactured by Nissin Chemical Industry Co., Ltd., Yodozol manufactured by Henkel Japan, and Aron manufactured by Toagosei Co., Ltd.
（Ａ）成分の皮膜形成能を有する塩化ビニル系樹脂エマルジョン及び／又はアクリル系樹脂エマルジョンの配合量は、コーティング組成物中、固形分で６０〜９９質量％であり、好ましくは６５〜９５質量％である。この樹脂エマルジョンが６０質量％未満であると、耐摩耗性など被膜特性が非常に悪くなるという不具合があり、９９質量％を超えると表面が滑らかでないために触感が悪いという不具合がある。 The amount of the vinyl chloride resin emulsion and/or acrylic resin emulsion having the film-forming ability of the component (A) is 60 to 99% by mass, preferably 65 to 95% by mass in terms of solid content in the coating composition. Is. If the content of this resin emulsion is less than 60% by mass, the coating properties such as abrasion resistance will be extremely deteriorated, and if it exceeds 99% by mass, the surface will not be smooth and the tactile sensation will be poor.
（Ｂ）成分のシリコーンアクリルグラフト共重合樹脂エマルジョンは、好ましくは、（ｂ１）下記一般式（１）で示されるポリオルガノシロキサンと（ｂ２）（メタ）アクリル酸エステル単量体と（ｂ３）これと共重合可能な官能基含有単量体との混合物とを、乳化グラフト重合させて得られるものである。 The silicone acrylic graft copolymer resin emulsion of the component (B) is preferably (b1) a polyorganosiloxane represented by the following general formula (1), (b2) a (meth)acrylic acid ester monomer and (b3) And a mixture with a functional group-containing monomer capable of copolymerization are obtained by emulsion graft polymerization.
（Ｂ）成分のシリコーンアクリルグラフト共重合樹脂エマルジョンは、（ｂ１）成分１００質量部に対して、（ｂ２）成分が１０〜１００質量部、（ｂ３）成分が０．０１〜２０質量部を用いて得ることが好ましく、更に（ｂ２）成分は４０〜１００質量部、（ｂ３）成分は０．０１〜５質量部がより好ましい。 The silicone acrylic graft copolymer resin emulsion of the component (B) uses 10 to 100 parts by mass of the component (b2) and 0.01 to 20 parts by mass of the component (b3) with respect to 100 parts by mass of the component (b1). The component (b2) is more preferably 40 to 100 parts by mass, and the component (b3) is more preferably 0.01 to 5 parts by mass.
ここで、（ｂ１）ポリオルガノシロキサンは、下記一般式（１）で示される。
ここで、Ｒ1は同一又は異種の置換もしくは非置換の炭素数１〜２０の１価炭化水素基であり、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基等のアルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基、ビニル基、アリル基等のアルケニル基、フェニル基、トリル基、ナフチル基等のアリール基、ビニルフェニル基等のアルケニルアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基、ビニルベンジル基、ビニルフェニルプロピル基等のアルケニルアラルキル基などや、これらの基の水素原子の一部又は全部がフッ素、臭素、塩素等のハロゲン原子、アクリロキシ基、メタクリロキシ基、カルボキシル基、アルコキシ基、アルケニルオキシ基、アミノ基、アルキル又はアルコキシもしくは（メタ）アクリロキシ置換アミノ基などで置換されたものが挙げられる。Ｒ1としては、好ましくはメチル基である。 Here, R 1 is the same or different, substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. Group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups, cyclopentyl group, cyclohexyl group, cycloheptyl group and other cycloalkyl groups, vinyl group, allyl group Such as alkenyl group, phenyl group, tolyl group, naphthyl group, etc. aryl group, vinylphenyl group, etc. alkenylaryl group, benzyl group, phenylethyl group, phenylpropyl group, etc. aralkyl group, vinylbenzyl group, vinylphenylpropyl group Alkenyl aralkyl groups such as, and some or all of the hydrogen atoms of these groups are halogen atoms such as fluorine, bromine, chlorine, acryloxy group, methacryloxy group, carboxyl group, alkoxy group, alkenyloxy group, amino group, alkyl Or the thing substituted by the alkoxy or the (meth)acryloxy substituted amino group etc. is mentioned. R 1 is preferably a methyl group.
Ｒ2はメルカプト基、アクリロキシ基もしくはメタクリロキシ基置換の炭素数１〜６のアルキル基、又はビニル基である。具体的には、メルカプトプロピル基、アクリロキシプロピル基、メタクリロキシプロピル基、ビニル基等が好ましい。 R 2 is a mercapto group, an acryloxy group or a methacryloxy group-substituted alkyl group having 1 to 6 carbon atoms, or a vinyl group. Specifically, a mercaptopropyl group, an acryloxypropyl group, a methacryloxypropyl group, a vinyl group and the like are preferable.
Ｘは同一又は異種の置換もしくは非置換の炭素数１〜２０の１価炭化水素基、炭素数１〜２０のアルコキシ基又はヒドロキシル基であり、非置換もしくは置換の炭素数１〜２０の１価炭化水素基としては、Ｒ1で例示したものと同様のものが例示でき、炭素数１〜２０のアルコキシ基として、具体的には、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、デシルオキシ基、テトラデシルオキシ基等が挙げられる。Ｘとして、好ましくはヒドロキシル基、メチル基、ブチル基、フェニル基である。 X is the same or different, substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms or hydroxyl group, and unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group are the same as those exemplified for R 1 , and specific examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a hexyloxy group. , Heptyloxy group, octyloxy group, decyloxy group, tetradecyloxy group and the like. X is preferably a hydroxyl group, a methyl group, a butyl group or a phenyl group.
ＹはＸ又は−［Ｏ−Ｓｉ（Ｘ）2］d−Ｘで示される同一又は異種の基である。 Y is the same or different group represented by X or -[O-Si(X) 2 ] d- X.
Ｚは炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基又はヒドロキシル基であり、好ましくはヒドロキシル基又はメチル基である。 Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, and preferably a hydroxyl group or a methyl group.
ａは１，０００より大きくなると得られる被膜の強度が不十分となるので、０〜１，０００の数、好ましくは０〜２００の数とされ、ｂは１００未満では被膜の柔軟性が乏しいものとなり、１０，０００より大きいとその引き裂き強度が低下するので、１００〜１０，０００の正数、好ましくは１，０００〜５，０００の正数とされる。ｃは１〜１０の正数であり、１０を超えると、コーティングした際に耐摩耗性が良化しないという不具合がある。
ｄは１〜１，０００、好ましくは１〜２００の正数とされる。また、架橋性の面から１分子中に少なくとも２個、好ましくは２〜４個のヒドロキシル基を有し、両末端に形成させたものを用いることがよい。
When a is larger than 1,000, the strength of the obtained coating becomes insufficient, so that it is a number of 0 to 1,000, preferably 0 to 200, and if b is less than 100, the flexibility of the coating is poor. Therefore, if it is more than 10,000, the tear strength is lowered, so that it is a positive number of 100 to 10,000, preferably 1,000 to 5,000. c is a positive number of 1 to 10, and if it exceeds 10, there is a problem that abrasion resistance does not improve when coated.
d is a positive number of 1 to 1,000, preferably 1 to 200. From the viewpoint of cross-linking property, it is preferable to use one having at least 2, preferably 2 to 4 hydroxyl groups in one molecule and formed at both ends.
このような（ｂ１）ポリオルガノシロキサンは、エマルジョンの形態で使用されることが好ましく、市販品を使用してもよいし、合成してもよい。合成する場合は、公知の乳化重合法で実施でき、例えばフッ素原子、（メタ）アクリロキシ基、カルボキシル基、ヒドロキシル基、アミノ基を有してもよい環状オルガノシロキサンあるいはα，ω−ジヒドロキシシロキサンオリゴマー、α，ω−ジアルコキシシロキサンオリゴマー、アルコキシシラン等と、下記一般式（２）で示されるシランカップリング剤を、アニオン系界面活性剤を用いて水中に乳化分散させた後、必要に応じて酸等の触媒を添加して重合反応を行うことにより容易に合成することができる。
Ｒ3 (4-e-f)Ｒ4 fＳｉ（ＯＲ5）e （２）
（式中、Ｒ3は重合性二重結合を有する１価有機基、特にアクリロキシ基又はメタクリロキシ基置換の炭素数１〜６のアルキル基を示す。Ｒ4は炭素数１〜４のアルキル基、Ｒ5は炭素数１〜４のアルキル基で、ｅは２〜３、ｆは０〜１の整数を示し、ｅ＋ｆ＝２〜３である。）
Such (b1) polyorganosiloxane is preferably used in the form of an emulsion, and a commercially available product may be used or it may be synthesized. When it is synthesized, it can be carried out by a known emulsion polymerization method, for example, a fluorine atom, a (meth)acryloxy group, a carboxyl group, a hydroxyl group, a cyclic organosiloxane which may have an amino group or an α,ω-dihydroxysiloxane oligomer, An α,ω-dialkoxysiloxane oligomer, an alkoxysilane, etc. and a silane coupling agent represented by the following general formula (2) are emulsified and dispersed in water using an anionic surfactant, and then an acid is added as necessary. It can be easily synthesized by adding a catalyst such as the above to carry out a polymerization reaction.
R 3 (4-ef) R 4 f Si(OR 5 ) e (2)
(In the formula, R 3 represents a monovalent organic group having a polymerizable double bond, particularly an alkyl group substituted with an acryloxy group or a methacryloxy group. R 4 represents an alkyl group having 1 to 4 carbon atoms, (R 5 is an alkyl group having 1 to 4 carbon atoms, e is 2 to 3, f is an integer of 0 to 1, and e+f=2 to 3).
上記環状オルガノシロキサンとしては、ヘキサメチルシクロトリシロキサン（Ｄ３）、オクタメチルシクロテトラシロキサン（Ｄ４）、デカメチルシクロペンタシロキサン（Ｄ５）、ドデカメチルシクロヘキサシロキサン（Ｄ６）、１，１−ジエチルヘキサメチルシクロテトラシロキサン、フェニルヘプタメチルシクロテトラシロキサン、１，１−ジフェニルヘキサメチルシクロテトラシロキサン、１，３，５，７−テトラビニルテトラメチルシクロテトラシロキサン、１，３，５，７−テトラメチルシクロテトラシロキサン、１，３，５，７−テトラシクロヘキシルテトラメチルシクロテトラシロキサン、トリス（３，３，３−トリフロロプロピル）トリメチルシクロトリシロキサン、１，３，５，７−テトラ（３−メタクリロキシプロピル）テトラメチルシクロテトラシロキサン、１，３，５，７−テトラ（３−アクリロキシプロピル）テトラメチルシクロテトラシロキサン、１，３，５，７−テトラ（３−カルボキシプロピル）テトラメチルシクロテトラシロキサン、１，３，５，７−テトラ（３−ビニロキシプロピル）テトラメチルシクロテトラシロキサン、１，３，５，７−テトラ（ｐ−ビニルフェニル）テトラメチルシクロテトラシロキサン、１，３，５，７−テトラ［３−（ｐ−ビニルフェニル）プロピル］テトラメチルシクロテトラシロキサン、１，３，５，７−テトラ（Ｎ−アクリロイル−Ｎ−メチル−３−アミノプロピル）テトラメチルシクロテトラシロキサン、１，３，５，７−テトラ（Ｎ，Ｎ−ビス（ラウロイル）−３−アミノプロピル）テトラメチルシクロテトラシロキサン等が例示される。好ましくは、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサンが用いられる。 Examples of the cyclic organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and 1,1-diethylhexamethyl. Cyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane Siloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane, 1,3,5,7-tetra(3-methacryloxypropyl) ) Tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3-acryloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3-carboxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3-vinyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(p-vinylphenyl)tetramethylcyclotetrasiloxane, 1,3,5,7 -Tetra[3-(p-vinylphenyl)propyl]tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(N-acryloyl-N-methyl-3-aminopropyl)tetramethylcyclotetrasiloxane, 1, Examples include 3,5,7-tetra(N,N-bis(lauroyl)-3-aminopropyl)tetramethylcyclotetrasiloxane. Preferably, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are used.
シランカップリング剤としては、具体的には、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルトリイソプロポキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシランなどのビニルシラン類；γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルトリプロポキシシラン、γ−（メタ）アクリロキシプロピルトリイソプロポキシシラン、γ−（メタ）アクリロキシプロピルトリブトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジプロポキシシラン、γ−（メタ）アクリロキシプロピルメチルジイソプロポキシシラン、γ−（メタ）アクリロキシプロピルメチルジブトキシシランなどのアクリルシラン類；γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルトリメトキシシランなどのメルカプトシラン類等が挙げられる。又はこれらを縮重合したオリゴマーはアルコールの発生が抑えられより好ましい場合がある。ここで、（メタ）アクリロキシは、アクリロキシ又はメタクリロキシを示す。これらシランカップリング剤は、環状オルガノシロキサン１００質量部に対し０．０１〜１０質量部使用することが好ましく、０．０１〜５質量部の使用が更に好ましい。０．０１質量部未満であると、コーティング剤とした際に透明性が低下し、１０質量部を超えると、摺動性が発揮できない可能性がある。 Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and other vinylsilanes; γ- (Meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropyltriisopropoxysilane, γ-( (Meth)acryloxypropyltributoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-( Acrylic silanes such as (meth)acryloxypropylmethyldiisopropoxysilane and γ-(meth)acryloxypropylmethyldibutoxysilane; mercaptosilanes such as γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropyltrimethoxysilane Is mentioned. Alternatively, oligomers obtained by polycondensation of these may be more preferable because the generation of alcohol is suppressed. Here, (meth)acryloxy means acryloxy or methacryloxy. These silane coupling agents are preferably used in an amount of 0.01 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the cyclic organosiloxane. If it is less than 0.01 parts by mass, the transparency of the coating agent may be deteriorated, and if it exceeds 10 parts by mass, the slidability may not be exhibited.
シランカップリング剤を共重合することにより、下記式中のｃを有するポリオルガノシロキサンとなり、（ｂ２）又は（ｂ３）成分の単量体をグラフトさせる効果が得られる。
重合に用いる重合触媒としては、公知の重合触媒を使用すればよい。中でも強酸が好ましく、塩酸、硫酸、ドデシルベンゼンスルホン酸、クエン酸、乳酸、アスコルビン酸が例示される。好ましくは乳化能を持つドデシルベンゼンスルホン酸である。
酸触媒の使用量としては、環状オルガノシロキサン１００質量部に対して０．０１〜１０質量部であることが好ましく、より好ましくは０．２〜２質量部である。
As the polymerization catalyst used for the polymerization, a known polymerization catalyst may be used. Of these, strong acids are preferable, and examples thereof include hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid. Dodecylbenzene sulfonic acid having emulsifying ability is preferable.
The amount of the acid catalyst used is preferably 0.01 to 10 parts by mass, and more preferably 0.2 to 2 parts by mass with respect to 100 parts by mass of the cyclic organosiloxane.
また、重合する際の界面活性剤としては、アニオン系界面活性剤として、ラウリル硫酸ナトリウム、ラウレス硫酸ナトリウム、Ｎ−アシルアミノ酸塩、Ｎ−アシルタウリン塩、脂肪族石けん、アルキルりん酸塩等が挙げられるが、中でも水に溶けやすく、ポリエチレンオキサイド鎖を持たないものが好ましい。更に好ましくは、Ｎ−アシルアミノ酸塩、Ｎ−アシルタウリン塩、脂肪族石けん及びアルキルりん酸塩であり、特に好ましくは、ラウロイルメチルタウリンナトリウム、ミリストイルメチルタウリンナトリウム、ラウリル硫酸ナトリウムである。
なお、アニオン系界面活性剤の使用量は、環状オルガノシロキサン１００質量部に対して０．１〜２０質量部であることが好ましく、より好ましくは０．５〜１０質量部である。
In addition, examples of the surfactant for polymerization include anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salt, N-acyl taurine salt, aliphatic soap and alkyl phosphate. However, among them, those which are easily soluble in water and have no polyethylene oxide chain are preferable. More preferred are N-acyl amino acid salts, N-acyl taurine salts, aliphatic soaps and alkyl phosphates, and particularly preferred are lauroyl methyl taurine sodium, myristoyl methyl taurine sodium, and sodium lauryl sulfate.
The amount of the anionic surfactant used is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the cyclic organosiloxane.
重合温度は５０〜７５℃が好ましく、重合時間は１０時間以上が好ましく、１５時間以上が更に好ましい。更に、重合後に５〜３０℃で１０時間以上熟成させることが特に好ましい。 The polymerization temperature is preferably 50 to 75° C., and the polymerization time is preferably 10 hours or longer, more preferably 15 hours or longer. Furthermore, it is particularly preferable to age at 5 to 30° C. for 10 hours or more after the polymerization.
このようにして得られた（ｂ１）オルガノポリシロキサンは平均粒子径が１８０ｎｍ以下、好ましくは５０〜１８０ｎｍ、更に好ましくは７０〜１７０ｎｍとなるように、スターバースト、高圧ホモジナイザー、連続式乳化機、コロイダルミル、ニーダーなど公知の微粒化方法で、粒子径を調整しておくことが好ましい。例えば、微粒子化条件としては、スターバーストなどで、５０〜３００ＭＰａの圧力で湿式微粒子化する方法、超音波分散機、好ましくは超音波ホモジナイザーを用いて分散処理することもできる。超音波ホモジナイザーの条件については、周波数２０〜２０００ｋＨｚ×出力２０〜１０００Ｗ×１〜１０時間の範囲とすることができる。 The thus-obtained (b1) organopolysiloxane has an average particle diameter of 180 nm or less, preferably 50 to 180 nm, more preferably 70 to 170 nm, in which a starburst, a high pressure homogenizer, a continuous emulsifier, a colloidal It is preferable to adjust the particle size by a known atomization method such as a mill or a kneader. For example, as the microparticulation conditions, a method of wet microparticulation under a pressure of 50 to 300 MPa, such as starburst, or an ultrasonic disperser, preferably an ultrasonic homogenizer, may be used for dispersion treatment. The conditions of the ultrasonic homogenizer can be set to a range of frequency 20 to 2000 kHz×output 20 to 1000 W×1 to 10 hours.
本発明に用いる（ｂ２）アクリル酸エステル又はメタクリル酸エステル（以下、「アクリル成分」ということがある。）は、ヒドロキシル基、アミド基、カルボキシル基等の官能基を持たないアクリル酸エステル単量体又はメタクリル酸エステル単量体を指し、炭素数１〜１０のアルキル基を有するアクリル酸エステル又はメタクリル酸エステルが好ましく、更にはアクリル成分のポリマーのガラス転移温度（以下、Ｔｇということがある）が４０℃以上、好ましくは６０℃以上になる単量体が好ましく、かかる単量体としては、メタクリル酸メチル、メタクリル酸イソプロピル、メタクリル酸エチル、メタクリル酸シクロヘキシル等が挙げられる。なお、Ｔｇの上限は、好ましくは２００℃以下、更に好ましくは１５０℃以下である。ガラス転移温度は、ＪＩＳ Ｋ７１２１に基づき測定できる。 The (b2) acrylic acid ester or methacrylic acid ester (hereinafter sometimes referred to as “acrylic component”) used in the present invention is an acrylic acid ester monomer having no functional group such as hydroxyl group, amide group or carboxyl group. Or a methacrylic acid ester monomer, preferably an acrylic acid ester or a methacrylic acid ester having an alkyl group having 1 to 10 carbon atoms, and further, a glass transition temperature (hereinafter sometimes referred to as Tg) of a polymer of an acrylic component. A monomer having a temperature of 40° C. or higher, preferably 60° C. or higher is preferable, and examples of such a monomer include methyl methacrylate, isopropyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate and the like. The upper limit of Tg is preferably 200°C or lower, more preferably 150°C or lower. The glass transition temperature can be measured based on JIS K7121.
（ｂ２）成分と共重合可能な官能基含有単量体（ｂ３）としては、カルボキシル基、アミド基、水酸基、ビニル基、アリル基等を含む不飽和結合を有する単量体であり、具体的には、メタクリル酸、アクリル酸、アクリルアマイド、メタクリル酸アリル、メタクリル酸ビニル、メタクリル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキシプロピルが挙げられ、これらを共重合することで相容性を向上させることが可能となる。 The functional group-containing monomer (b3) copolymerizable with the component (b2) is a monomer having an unsaturated bond containing a carboxyl group, an amide group, a hydroxyl group, a vinyl group, an allyl group, etc. Include methacrylic acid, acrylic acid, acrylic amide, allyl methacrylate, vinyl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. Improving compatibility by copolymerizing these. It becomes possible.
本発明の（Ｂ）シリコーンアクリルグラフト共重合樹脂エマルジョンは、上記のようにして得られた（ｂ１）ポリオルガノシロキサンに、（ｂ２）（メタ）アクリル酸エステル単量体と（ｂ３）これと共重合可能な官能基含有単量体との混合物を、乳化グラフト重合させる。 The (B) silicone-acrylic graft copolymer resin emulsion of the present invention is obtained by adding the (b2) (meth)acrylic acid ester monomer and (b3) together with the (b1) polyorganosiloxane obtained as described above. A mixture with a polymerizable functional group-containing monomer is subjected to emulsion graft polymerization.
グラフト重合させる際の式（１）のポリオルガノシロキサンと（メタ）アクリル酸エステル単量体との質量比（式（１）のポリオルガノシロキサンと（メタ）アクリル単位との質量比）は３０：７０〜９９：１であり、好ましくは６０：４０〜９９：１である。シリコーン成分が３０より少ないとコーティングした際に耐摩耗性が良化しないという不具合がある。 The mass ratio of the polyorganosiloxane of the formula (1) and the (meth)acrylic acid ester monomer (the mass ratio of the polyorganosiloxane of the formula (1) and the (meth)acrylic unit) during the graft polymerization is 30: It is 70 to 99:1, and preferably 60:40 to 99:1. If the silicone component is less than 30, there is a problem that the abrasion resistance does not improve when coated.
ここで使用されるラジカル開始剤としては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、過硫酸水素水、ｔ−ブチルハイドロパーオキサイド、過酸化水素が挙げられる。必要に応じ、酸性亜硫酸ナトリウム、ロンガリット、Ｌ−アスコルビン酸、酒石酸、糖類、アミン類等の還元剤を併用したレドックス系も使用することができる。 Examples of the radical initiator used here include persulfates such as potassium persulfate and ammonium persulfate, hydrogen persulfate water, t-butyl hydroperoxide, and hydrogen peroxide. If necessary, a redox system in which a reducing agent such as acidic sodium sulfite, rongalite, L-ascorbic acid, tartaric acid, saccharides, amines is used together can also be used.
既にポリオルガノシロキサンエマルジョン中に含まれている界面活性剤で十分にグラフト重合可能だが、安定性向上のためアニオン系界面活性剤として、ラウリル硫酸ナトリウム、ラウレス硫酸ナトリウム、Ｎ−アシルアミノ酸塩、Ｎ−アシルタウリン塩、脂肪族石けん、アルキルりん酸塩等を添加することができる。また、ポリオキシエチレンラウリルエーテル、ポリオキシエチレントリデシルエーテル等のノニオン系乳化剤を添加することもできる。 Graft polymerization can be sufficiently performed with a surfactant already contained in the polyorganosiloxane emulsion, but as an anionic surfactant for improving stability, sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salt, N- Acyl taurine salt, aliphatic soap, alkyl phosphate and the like can be added. Further, nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can be added.
（ｂ１）成分に対する（ｂ２）及び（ｂ３）成分のグラフト重合温度は２５〜５５℃が好ましく、２５〜４０℃が更に好ましい。また、重合時間は２〜８時間が好ましく、３〜６時間が更に好ましい。 The graft polymerization temperature of the components (b2) and (b3) with respect to the component (b1) is preferably 25 to 55°C, more preferably 25 to 40°C. The polymerization time is preferably 2 to 8 hours, more preferably 3 to 6 hours.
更に、グラフトポリマーの分子量、グラフト率を調整するために連鎖移動剤を添加することができる。 Furthermore, a chain transfer agent can be added to adjust the molecular weight and graft ratio of the graft polymer.
こうして得られたシリコーンアクリルグラフト共重合樹脂エマルジョン（Ｂ）は、（ｂ２）及び（ｂ３）成分がランダムにグラフトされているポリマーである。 The silicone acrylic graft copolymer resin emulsion (B) thus obtained is a polymer in which the components (b2) and (b3) are randomly grafted.
また、（Ｂ）成分であるシリコーンアクリルグラフト共重合樹脂エマルジョンの固形分は３５〜５０質量％が好ましい。また、粘度（２５℃）は、５００ｍＰａ・ｓ以下が好ましく、５０〜５００ｍＰａ・ｓが更に好ましい。粘度は回転粘度計にて測定できる。平均粒子径は、１８０ｎｍ以下、好ましくは５０〜１８０ｎｍ、さらに好ましくは８０〜１７０ｎｍである。平均粒子径が大きすぎる場合には、透明なコーティング剤が得られず、小さすぎる場合には、分散性が低下する問題がある。なお、平均粒子径は、レーザー回折／散乱式粒子径分布測定装置によって測定することができる。 The solid content of the silicone-acrylic graft copolymer resin emulsion as the component (B) is preferably 35 to 50% by mass. Further, the viscosity (25° C.) is preferably 500 mPa·s or less, and more preferably 50 to 500 mPa·s. Viscosity can be measured with a rotational viscometer. The average particle diameter is 180 nm or less, preferably 50 to 180 nm, more preferably 80 to 170 nm. If the average particle size is too large, a transparent coating agent cannot be obtained, and if the average particle size is too small, there is a problem that the dispersibility decreases. The average particle size can be measured by a laser diffraction/scattering particle size distribution measuring device.
（Ｂ）成分であるシリコーンアクリルグラフト共重合樹脂エマルジョンの配合量は、コーティング組成物中、固形分で１〜４０質量％であり、好ましくは５〜３０質量％である。シリコーンアクリルグラフト共重合樹脂エマルジョンが１質量％未満であると耐摩耗性において全く改善が見られないという不具合があり、４０質量％を超えると白化する上に耐摩耗性も低下していくという不具合がある。 The content of the silicone acrylic graft copolymer resin emulsion as the component (B) in the coating composition is 1 to 40% by mass, preferably 5 to 30% by mass in terms of solid content. If the silicone acrylic graft copolymer resin emulsion is less than 1% by mass, there is a problem that no improvement in abrasion resistance is observed, and if it exceeds 40% by mass, whitening and abrasion resistance decrease. There is.
本発明のコーティング用組成物は、（Ａ）皮膜形成能を有する塩化ビニル系樹脂エマルジョン及び／又はアクリル系樹脂エマルジョン、（Ｂ）シリコーンアクリルグラフト共重合樹脂エマルジョンを水系下でプロペラ式撹拌機やホモジナイザーなどの公知の混合調製方法によって混合することによって得られる。 The coating composition of the present invention comprises (A) a vinyl chloride resin emulsion and/or acrylic resin emulsion capable of forming a film and (B) a silicone-acryl graft copolymer resin emulsion in a water system under a propeller stirrer or a homogenizer. It can be obtained by mixing by a known mixing preparation method such as.
また、本発明のコーティング用組成物には、性能に影響を与えない範囲で、酸化防止剤、着色剤、紫外線吸収剤、光安定化剤、帯電防止剤、可塑剤、難燃剤、増粘剤、界面活性剤、造膜助剤などの有機溶剤、他の樹脂等を添加してもよい。 In addition, the coating composition of the present invention contains an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a plasticizer, a flame retardant, and a thickener as long as the performance is not affected. , Organic solvents such as surfactants and film-forming aids, and other resins may be added.
本発明のコーティング用組成物については、所望の高い透明性を確保する点から、基材に塗布した際のヘーズ増加率が、塗布前の基材のヘーズ値に対して１５００％以下であることが好適であり、基材の種類によるが、より好ましく１０００％以下とするものである。本発明で言う「ヘーズ」は、ＪＩＳ Ｋ７１３６（２０００年）の規格に従い、全光線透過率及び拡散透過率から下記式により算出されるＨＡＺＥ（曇価）である。
ＨＡＺＥ（曇価） ＝ （拡散透過率Ｔd／全光線透過率Ｔt）×１００ （％）
基材に塗布したヘーズの値は、例えば、日本電色工業社製のヘーズメーターによって測定することができる。また、コーティング用組成物の塗布前の基材のヘーズの値も上記と同様の規格にしたがって測定することができる。また、本発明でいう「ヘーズ増加率」は、基材のヘーズ値をＸ，コーティング組成物を塗布した後のヘーズ値をＹとすると、
［ヘーズ値の増加率（％）］ ＝ 〔（ Ｙ − Ｘ ） ／ Ｘ〕 × １００
で表すことができる。
Regarding the coating composition of the present invention, the rate of increase in haze when applied to a base material is 1500% or less relative to the haze value of the base material before application, in order to secure desired high transparency. Is preferable, and it is more preferably 1000% or less, though it depends on the kind of the base material. The “haze” referred to in the present invention is Haze (haze value) calculated from the total light transmittance and the diffuse transmittance according to the standard of JIS K7136 (2000) by the following formula.
Haze (haze value) = (diffuse transmittance Td /total light transmittance Tt ) x 100 (%)
The haze value applied to the base material can be measured, for example, by a haze meter manufactured by Nippon Denshoku Industries Co., Ltd. Further, the haze value of the base material before applying the coating composition can also be measured according to the same standard as above. Further, the "haze increase rate" in the present invention is defined as follows, where X is the haze value of the substrate and Y is the haze value after applying the coating composition.
[Increase rate of haze value (%)] = [(Y-X)/X] x 100
Can be expressed as
このようにして得られた本発明のコーティング用組成物を基材、例えば、プラスチック（ＰＥＴ、ＰＩ、合成皮革等）、硝子（汎用ガラス、ＳｉＯ2等）、金属（Ｓｉ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｏ、Ａｕ、Ａｇ、Ｔｉ、Ａｌ、Ｚｎ、Ｓｎ、Ｚｒ、それらの合金等）、木材、繊維（布、糸等）、紙、セラミック（酸化物、炭化物、窒化物等の焼成物など）などの基材の片面又は両面に塗布又は浸漬、乾燥（室温〜１５０℃）すると、樹脂の長所を維持しながら、シリコーン樹脂の撥水性、耐候性、耐熱性、耐寒性、ガス透過性、摺動性などの利点を、長期に亘って付与することができる。これは、皮膜形成能を有する樹脂と硬化性シリコーン樹脂が丈夫な海島構造を作っているためと考えられる。 The coating composition of the present invention thus obtained is used as a substrate, for example, plastic (PET, PI, synthetic leather, etc.), glass (general-purpose glass, SiO 2, etc.), metal (Si, Cu, Fe, Ni). , Co, Au, Ag, Ti, Al, Zn, Sn, Zr, alloys thereof, etc.), wood, fibers (cloth, threads, etc.), paper, ceramics (fired products such as oxides, carbides, nitrides etc.) When applied or dipped on one or both sides of a substrate such as, and dried (room temperature to 150°C), the water repellency, weather resistance, heat resistance, cold resistance, gas permeability, and sliding of the silicone resin are maintained while maintaining the advantages of the resin. Advantages such as mobility can be imparted over a long period of time. It is considered that this is because the resin capable of forming a film and the curable silicone resin form a durable sea-island structure.
ここで、プラスチック基材としては、ポリメチルメタクリレート等のポリ（メタ）アクリル酸エステル、ポリカーボネート、ポリスチレン、ポリエチレンテレフタレート、ポリ塩化ビニル、ポリエステル、セルロース、ジエチレングリコールビスアリルカーボネートポリマー、アクリロニトリル−ブタジエン−スチレンポリマー、ポリウレタン、及びエポキシ樹脂等が使用される。プラスチック加工品としては、自動車内装材や有機ガラス、電材や建材、建築物の外装材、液晶ディスプレイ等に使用する光学フィルム、光拡散フィルム、携帯電話、家電製品等がある。乾燥させる方法としては、室温下で１〜１０日間放置する方法が挙げられるが、硬化を迅速に進行させる観点から、２０〜１５０℃の温度で、１秒〜１０時間加熱する方法が好ましい。また、上記プラスチック基材が加熱によって変形や変色を引き起こしやすい材質からなるものである場合には、２０〜１００℃の比較的低温下で乾燥することが好ましい。 Here, as the plastic substrate, poly(meth)acrylic acid ester such as polymethylmethacrylate, polycarbonate, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyester, cellulose, diethylene glycol bisallyl carbonate polymer, acrylonitrile-butadiene-styrene polymer, Polyurethane, epoxy resin, etc. are used. Plastic processed products include automobile interior materials, organic glass, electric materials and building materials, building exterior materials, optical films used for liquid crystal displays, light diffusion films, mobile phones, home appliances, and the like. Examples of the method of drying include a method of leaving it at room temperature for 1 to 10 days, and from the viewpoint of rapid curing, a method of heating at a temperature of 20 to 150° C. for 1 second to 10 hours is preferable. Further, when the plastic base material is made of a material that is easily deformed or discolored by heating, it is preferably dried at a relatively low temperature of 20 to 100°C.
ガラス基材としては、ソーダ石灰ガラス、石英ガラス、鉛ガラス、ホウ珪酸ガラス、無アルカリガラス等が使用される。ガラス加工品としては、建築用板ガラス、自動車等車両用ガラス、レンズ用ガラス、鏡用ガラス、ディスプレイパネル用ガラス、太陽電池モジュール用ガラス等がある。乾燥させる方法としては、室温で１〜１０日程度放置したり、２０〜１５０℃、特に６０〜１５０℃の温度で、１秒〜１０時間加熱する方法が好ましい。 As the glass substrate, soda lime glass, quartz glass, lead glass, borosilicate glass, non-alkali glass or the like is used. Examples of glass processed products include glass for construction, glass for vehicles such as automobiles, glass for lenses, glass for mirrors, glass for display panels, and glass for solar cell modules. As a drying method, a method of leaving at room temperature for about 1 to 10 days or heating at a temperature of 20 to 150° C., particularly 60 to 150° C. for 1 second to 10 hours is preferable.
木材基材としては、カエデ科、カバノキ科、クスノキ科、クリ科、ゴマノハグサ科、ナンヨウスギ科、ニレ科、ノウゼンカズラ科、バラ科、ヒノキ科、フタバガキ科、フトモモ科、ブナ科、マツ科、マメ科、モクセイ科等の木材が使用される。木材加工品としては、木そのものを原料とする加工及び成形品、合板及び集成材及びそれらの加工及び成形品、及びそれらの組み合わせから選択されるものであってよく、例えば、建物の外装及び内装用資材を包含する住建築用資材、机などの家具類、木のおもちゃ、楽器等がある。２０〜１５０℃、特に５０〜１５０℃で０．５〜５時間熱風乾燥させる方法が好ましい。また、乾燥温度は１２０℃以下にすれば塗膜の変色を避けることができる。 As a wood base material, maple family, birch family, camphoraceae family, chestnut family, sedumaceae family, alpinaceae family, elm family, noctiperid family, rosaceae family, cypress family, dipterocarpaceae, phlox family, beech family, pine family, legume family. Wood from the family Asteraceae is used. The processed wood product may be selected from processed and molded products made from wood itself, plywood and laminated wood, processed and molded products thereof, and combinations thereof. For example, exterior and interior of buildings. There are materials for housing and construction, including furniture, desk furniture, wooden toys, musical instruments, etc. A method of drying with hot air at 20 to 150° C., particularly 50 to 150° C. for 0.5 to 5 hours is preferable. If the drying temperature is 120°C or lower, discoloration of the coating film can be avoided.
繊維基材としては、木綿、麻、リンネル、羊毛、絹、カシミヤ、石綿等の天然繊維及び、ポリアミド、ポリエステル、ビスコース、セルロース、ガラス、炭素等の化学繊維が例示される。繊維加工品としては、すべての種類の織物、編物、不織布、あるいはフィルム、紙等がある。乾燥させる方法としては、室温で１０分〜数十時間放置したり、２０〜１５０℃の温度で、０．５分〜５時間乾燥させる方法が好ましい。 Examples of the fiber base material include natural fibers such as cotton, hemp, linen, wool, silk, cashmere and asbestos, and chemical fibers such as polyamide, polyester, viscose, cellulose, glass and carbon. Textile products include woven fabrics, knitted fabrics, non-woven fabrics, films and papers of all kinds. As a method for drying, a method of leaving at room temperature for 10 minutes to several tens of hours or at 20 to 150° C. for 0.5 minutes to 5 hours is preferable.
本発明のコーティング用組成物を基材へコーティングする方法は、特に限定しないが、例えば、グラビアコーター、バーコーター、ブレードコーター、ロールコーター、エアーナイフコーター、スクリーンコーター、カーテンコーター、刷毛塗りなどの各種コーターによる塗布方法、スプレー塗布、浸漬等が挙げられる。 The method of coating the substrate with the coating composition of the present invention is not particularly limited, and examples thereof include gravure coater, bar coater, blade coater, roll coater, air knife coater, screen coater, curtain coater, and brush coating. Examples thereof include a coating method using a coater, spray coating, and dipping.
本発明のコーティング用組成物の基材への塗布量は、特に限定しないが、通常は、防汚性、施工作業性などの点から固形分換算で、好ましくは１〜３００ｇ／ｍ2、より好ましくは５〜１００ｇ／ｍ2の範囲または厚さ１〜５００μｍ、好ましくは５〜１００μｍで形成し、自然乾燥又は１００〜２００℃に加熱乾燥して成膜させるとよい。 The coating amount of the coating composition of the present invention to the substrate is not particularly limited, but usually, in terms of antifouling property, workability, etc., in terms of solid content, preferably 1 to 300 g/m 2 , more preferably The film is preferably formed in a range of 5 to 100 g/m 2 or a thickness of 1 to 500 μm, preferably 5 to 100 μm, and naturally dried or heated and dried at 100 to 200° C. to form a film.
以下、製造例、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において、部及び％はそれぞれ質量部、質量％を示す。 Hereinafter, the present invention will be specifically described with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, parts and% indicate parts by mass and% by mass, respectively.
［製造例１］
オクタメチルシクロテトラシロキサン６００ｇ、γ−メタクリロキシプロピルメチルジメトキシシラン０．６ｇ、ラウリル硫酸ナトリウム１２ｇをイオン交換水１０８ｇに溶解したもの、及びドデシルベンゼンスルホン酸６ｇを純水５４ｇに溶解したものを２Ｌのポリエチレン製ビーカーに仕込み、ホモミキサーで均一に乳化した後、イオン交換水４５０ｇを徐々に加えて希釈し、圧力３００ｋｇｆ／ｃｍ2で高圧ホモジナイザーに２回通し、均一な白色エマルジョンを得た。さらにスターバーストによる処理（スギノマシン）を１００ＭＰａで２回行った後、このエマルジョンを撹拌装置、温度計、還流冷却器の付いた２Ｌのガラスフラスコに移し、５０〜７０℃で２４時間重合反応を行った後、１０％炭酸ナトリウム水溶液１２ｇでｐＨ６〜８に中和した。このシリコーンエマルジョンは１０５℃で３時間乾燥後の不揮発分が４５．４％で、エマルジョン中のオルガノポリシロキサンは非流動性の軟ゲル状のものである。ここにメタクリル酸メチル（ＭＭＡ）２３８ｇを３〜５時間かけて滴下しながら３０℃で過酸化物と還元剤でレドックス反応を行うことでシリコーンへのアクリルグラフト共重合し、不揮発分４４．８％のシリコーンアクリルグラフト共重合樹脂エマルジョンを得た。
[Production Example 1]
Octamethylcyclotetrasiloxane 600 g, γ-methacryloxypropylmethyldimethoxysilane 0.6 g, sodium lauryl sulfate 12 g dissolved in ion-exchanged water 108 g, and dodecylbenzene sulfonic acid 6 g dissolved in pure water 54 g 2 L After being placed in a polyethylene beaker and uniformly emulsified with a homomixer, 450 g of ion-exchanged water was gradually added to dilute it and passed through a high-pressure homogenizer twice at a pressure of 300 kgf/cm 2 to obtain a uniform white emulsion. Further, after treatment with a starburst (Sugino Machine) twice at 100 MPa, this emulsion was transferred to a 2 L glass flask equipped with a stirrer, a thermometer, and a reflux condenser, and the polymerization reaction was carried out at 50 to 70° C. for 24 hours. After that, the solution was neutralized to pH 6-8 with 12 g of 10% sodium carbonate aqueous solution. This silicone emulsion has a nonvolatile content of 45.4% after being dried at 105° C. for 3 hours, and the organopolysiloxane in the emulsion is a non-flowing soft gel. 238 g of methyl methacrylate (MMA) was added dropwise thereto over 3 to 5 hours to carry out a redox reaction with a peroxide and a reducing agent at 30° C. to perform acrylic graft copolymerization on silicone, and a nonvolatile content of 44.8%. A silicone-acrylic graft copolymer resin emulsion of was obtained.
［製造例２〜５、比較製造例１〜３］
表１で示す配合比率の通り、製造例１と同様にシリコーンアクリルグラフト共重合樹脂エマルジョンを作成した。
[Production Examples 2 to 5, Comparative Production Examples 1 to 3]
According to the blending ratio shown in Table 1, a silicone-acryl graft copolymer resin emulsion was prepared in the same manner as in Production Example 1.
［比較製造例４］
表１で示す配合比率の通り、製造例１と同様にシリコーンエマルジョンを作成した。アクリルのグラフト反応は行なわなかった。
[Comparative Production Example 4]
According to the blending ratio shown in Table 1, a silicone emulsion was prepared in the same manner as in Production Example 1. No acrylic grafting reaction was performed.
上記の各製造例及び比較製造例で得られたエマルジョンの特性を表１に示す。なお、各測定は下記のように行った。 Table 1 shows the properties of the emulsions obtained in each of the above Production Examples and Comparative Production Examples. In addition, each measurement was performed as follows.
〔蒸発残分（固形分濃度）測定〕
試料約１ｇをアルミ箔製の皿に量り取り、１０５〜１１０℃に保った乾燥器に入れ、１時間加熱後、乾燥器から取り出してデシケーターの中にて放冷し、試料の乾燥後の重さを量り、次式により蒸発残分を算出した。
Ｗ ： 乾燥前の試料を入れたアルミ箔皿の質量（ｇ）
Ｌ ： アルミ箔皿の質量（ｇ）
Ｔ ： 乾燥後の試料を入れたアルミ箔皿の質量（ｇ）
アルミ箔皿の寸法：７０φ×１２ｈ（ｍｍ）
[Measurement of evaporation residue (solid content)]
Approximately 1 g of sample is weighed in an aluminum foil dish, put in a drier kept at 105 to 110°C, heated for 1 hour, taken out of the drier, and allowed to cool in a desiccator. The residue was weighed and the evaporation residue was calculated by the following formula.
W: Mass of aluminum foil tray containing sample before drying (g)
L: Mass of aluminum foil tray (g)
T: Mass of aluminum foil tray containing dried sample (g)
Aluminum foil tray dimensions: 70φ x 12h (mm)
〔平均粒子径測定〕
試料を０．０１ｇ計量し、レーザー回折式粒度分布測定装置（堀場製作所製、商品名：ＬＡ−９５０Ｖ２）を使用して、循環流量２、撹拌速度２の条件での平均粒子径（粒度累積分布の５０％に相当する粒子径の値）を測定した。
［測定条件］
測定温度：２５±１℃
溶媒：イオン交換水
[Measurement of average particle size]
0.01 g of the sample is weighed and a laser diffraction type particle size distribution measuring device (manufactured by Horiba, Ltd., trade name: LA-950V2) is used to measure the average particle size under the conditions of circulation flow rate 2 and stirring speed 2 (particle size cumulative distribution The value of the particle diameter corresponding to 50%) was measured.
[Measurement condition]
Measurement temperature: 25±1℃
Solvent: Ion exchange water
［塩化ビニル系樹脂エマルジョン（Ｉ）］
撹拌機、コンデンサー、温度計及び窒素ガス導入口を備えた重合容器に窒素置換後、イオン交換水６７質量部、ペレックスＳＳＬ（花王社製）４質量部、ノイゲンＬ−６１９０（第一工業製薬社製）５質量部、塩化ビニル５２質量部、アクリル酸２−エチルヘキシル４８質量部を仕込み、撹拌しながら６０℃に加温した。さらに過硫酸アンモニウム（開始剤）０．３質量部をイオン交換水１０質量部に溶解したものと亜硫酸水素ナトリウム０．１質量部をイオン交換水３質量部に溶解させたものを添加しレドックス系にて５〜１５時間重合反応させた。
重合内圧が０ＭＰaになった時点で残存モノマーを真空にて１０００ｐｐｍまで除去し、その後４０℃以下まで冷却して、重合体を得た。その後、防腐剤やイオン交換水を添加し、不揮発分４３％、Ｔｇが−３℃の塩化ビニル系樹脂エマルジョンを得た。
[Vinyl chloride resin emulsion (I)]
After nitrogen substitution in a polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet, 67 parts by mass of ion-exchanged water, 4 parts by mass of Perex SSL (manufactured by Kao Corporation), Neugen L-6190 (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by mass, 52 parts by mass of vinyl chloride and 48 parts by mass of 2-ethylhexyl acrylate were charged and heated to 60° C. with stirring. Further, 0.3 parts by mass of ammonium persulfate (initiator) dissolved in 10 parts by mass of ion-exchanged water and 0.1 parts by mass of sodium hydrogen sulfite dissolved in 3 parts by mass of ion-exchanged water were added to the redox system. For 5 to 15 hours.
When the internal pressure of the polymerization reached 0 MPa, the residual monomer was removed to 1000 ppm by vacuum and then cooled to 40° C. or lower to obtain a polymer. Then, a preservative and ion-exchanged water were added to obtain a vinyl chloride resin emulsion having a nonvolatile content of 43% and a Tg of -3°C.
［アクリル系樹脂エマルジョン（ＩＩ）］
撹拌装置、温度計、還流冷却器の付いた２Ｌのガラスフラスコにイオン交換水１０４質量部を投入し脱酸素を行った。アクリル酸エチル５７質量部、メタクリル酸メチル４２質量部、８０％メタクリル酸１質量部にアクアロンＨＳ−１０ ２質量部をイオン交換水２６質量部に溶解したものを投入してホモミキサーで乳化した。この乳化液を２Ｌガラスフラスコに５〜７時間かけて滴下しながら５０℃で過酸化物と還元剤でレドックス反応を行う事でラジカル重合し、不揮発分４０．４％、Ｔｇ２０℃のアクリル樹脂エマルジョンを得た。
[Acrylic resin emulsion (II)]
A 2 L glass flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 104 parts by mass of ion-exchanged water to perform deoxidation. 57 parts by mass of ethyl acrylate, 42 parts by mass of methyl methacrylate, 1 part by mass of 80% methacrylic acid and 2 parts by mass of Aqualon HS-10 dissolved in 26 parts by mass of ion-exchanged water were added and emulsified with a homomixer. This emulsion was added dropwise to a 2 L glass flask over 5 to 7 hours to carry out a redox reaction with a peroxide and a reducing agent at 50° C. to radically polymerize, and an acrylic resin emulsion having a nonvolatile content of 40.4% and Tg of 20° C. Got
［実施例１］
塩化ビニル系樹脂エマルジョンとして、上記塩化ビニル系樹脂エマルジョン（Ｉ）（粘度４００ｍＰａ・ｓ（２５℃）、平均粒径１５０ｎｍ、不揮発分約４３ｗｔ％）を用い、この樹脂エマルジョンを撹拌しているところに、製造例１で得られたシリコ−ンアクリルグラフト共重合樹脂エマルジョンを投入し、１０分以上撹拌の後、８０メッシュでろ過して、実施例１のコーティング用組成物を得た。
[Example 1]
As the vinyl chloride resin emulsion, the above vinyl chloride resin emulsion (I) (viscosity 400 mPa·s (25° C.), average particle diameter 150 nm, nonvolatile content about 43 wt%) was used, and the resin emulsion was stirred. The silicone-acryl graft copolymer resin emulsion obtained in Production Example 1 was added, and the mixture was stirred for 10 minutes or longer and filtered with 80 mesh to obtain a coating composition of Example 1.
［実施例２〜７、比較例１〜６］
表２（実施例２〜７）及び表３（比較例１〜６）で示した各成分の配合比率の通り、実施例１と同様の方法で各例のコーティング用組成物を作成した。なお、表２及び表３中で示す原料比率は固形分での質量比率である。
[Examples 2 to 7, Comparative Examples 1 to 6]
The coating composition of each example was prepared in the same manner as in Example 1 according to the blending ratio of each component shown in Table 2 (Examples 2 to 7) and Table 3 (Comparative Examples 1 to 6). The raw material ratios shown in Tables 2 and 3 are mass ratios in terms of solid content.
［実施例８］
実施例１の塩化ビニル系樹脂エマルジョンに代えて、上記アクリル系樹脂エマルジョン（ＩＩ）（粘度１０ｍＰａ・ｓ（２５℃）、平均粒径１００ｎｍ、不揮発分約４０．４ｗｔ％）を用いた以外は、実施例１と同様にコーティング用組成物を得た。
[Example 8]
Instead of the vinyl chloride resin emulsion of Example 1, the above acrylic resin emulsion (II) (viscosity 10 mPa·s (25° C.), average particle diameter 100 nm, nonvolatile content about 40.4 wt%) was used. A coating composition was obtained in the same manner as in Example 1.
［実施例９〜１４、比較例７〜１２］
表４（実施例９〜１４）及び表５（比較例７〜１２）で示した各成分の配合比率の通り、実施例１と同様の方法で各例のコーティング用組成物を作成した。なお、表２及び表３中で示す原料比率は不揮発分での質量比率である。
[Examples 9 to 14, Comparative Examples 7 to 12]
The coating composition of each example was prepared in the same manner as in Example 1 according to the blending ratio of each component shown in Table 4 (Examples 9 to 14) and Table 5 (Comparative Examples 7 to 12). The raw material ratios shown in Tables 2 and 3 are mass ratios of non-volatile components.
得られた各実施例及び各比較例のコーティング用組成物の「ヘーズ値・ヘーズ増加率」及び「静・動摩擦係数」を測定した。その数値を表２及び表３に示す。なお、各測定は下記のように行った。 The "haze value/haze increase rate" and "static/dynamic friction coefficient" of the obtained coating compositions of Examples and Comparative Examples were measured. The numerical values are shown in Tables 2 and 3. In addition, each measurement was performed as follows.
＜成膜方法＞
スライドガラス、ＰＥＴフィルム、アクリル板
各例のコーティング組成物をバーコーターにて塗布し、１０５℃×３分で乾燥を行い、ドライで約２３μｍになるように、スライドガラス、ＰＥＴフィルム及びアクリル板の各基材の上に塗膜を形成した。
<Film forming method>
Slide glass, PET film, acrylic plate The coating composition of each example was applied with a bar coater and dried at 105° C. for 3 minutes, and the slide glass, the PET film and the acrylic plate were dried so that the dry thickness was about 23 μm. A coating film was formed on each substrate.
＜ヘーズ値の測定＞
製品名「ヘーズメーター ＮＤＨ７０００」（日本電色工業社製）にて上記各例のコーティング組成物の塗膜を有する基材のヘーズ値を測定した。
<Measurement of haze value>
The haze value of the substrate having the coating film of the coating composition of each of the above examples was measured with the product name "Hazemeter NDH7000" (manufactured by Nippon Denshoku Industries Co., Ltd.).
（塩化ビニル系樹脂エマルジョン）
（１）スライドガラス（ヘーズ値０．７０％）でのヘーズ値の好ましい範囲は、０．７〜６．０％である。
（２）ＰＥＴフィルム（ヘーズ値１１％）でのヘーズ値の好ましい範囲は、１１．０〜２３．０％である。
（３）アクリル板（ヘーズ値０．２０％）でのヘーズ値の好ましい範囲は、０．２〜５．０％である。
(Vinyl chloride resin emulsion)
(1) The preferable range of the haze value on the slide glass (haze value 0.70%) is 0.7 to 6.0%.
(2) The preferable range of the haze value in the PET film (haze value 11%) is 11.0 to 23.0%.
(3) The preferable range of the haze value of the acrylic plate (haze value 0.20%) is 0.2 to 5.0%.
（アクリル樹脂エマルジョン）
（１）スライドガラス（ヘーズ値０．７０％）でのヘーズ値の好ましい範囲は、０．７〜１０．０％である
（２）アクリル板（ヘーズ値０．２０％）でのヘーズ値の好ましい範囲は、０．２〜５．０％である。
(Acrylic resin emulsion)
(1) The preferable range of the haze value on the slide glass (haze value 0.70%) is 0.7 to 10.0%. (2) The haze value on the acrylic plate (haze value 0.20%) A preferable range is 0.2 to 5.0%.
＜ヘーズの増加率＞
ヘーズの増加率は、下記式により求められる。
「ヘーズ値の増加率（％）」 ＝ 〔（ Ｙ − Ｘ ） ／ Ｘ〕 × １００
Ｘ：基材のヘーズ値
Ｙ：コーティング組成物を塗布した後のヘーズ値
上記ヘーズ値の増加率が１５００％以下であれば、透明性が高いと判断できる。一方、上記ヘーズ値の増加率が１５００％を超えると、積層体の透明性が悪くなり、白っぽく感じるようになる。
<Haze increase rate>
The rate of increase in haze is calculated by the following formula.
"Increase rate of haze value (%)" = [(Y-X)/X] x 100
X: haze value of the substrate Y: haze value after applying the coating composition If the increase rate of the haze value is 1500% or less, it can be determined that the transparency is high. On the other hand, when the increase rate of the haze value exceeds 1500%, the transparency of the laminate is deteriorated and the laminate feels whitish.
＜静・動摩擦係数測定＞
ＨＥＩＤＯＮ ＴＹＰＥ−３８（新東科学社製）にて１００ｇの金属圧子を上記各例の塗膜に垂直に接触させ、３ｃｍ／分で移動させた時の摩擦力を測定し、摩擦力から摩擦係数を算出した。
<Static/dynamic friction coefficient measurement>
A HEIDON TYPE-38 (manufactured by Shinto Kagaku Co., Ltd.) was used to make 100 g of a metal indenter vertically contact the coating film of each of the above examples, and the frictional force when moving at 3 cm/min was measured. Was calculated.
（塩化ビニル系樹脂エマルジョン）
（ｉ）スライドガラスでの静・動摩擦係数の好ましい範囲については、静摩擦係数が０．０１〜０．２０であり、動摩擦係数が０．０１〜０．１２である。
（ｉｉ）ＰＥＴフィルムでの静・動摩擦係数の好ましい範囲については、静摩擦係数が０．０１〜０．２０であり、動摩擦係数が０．０１〜０．１２である。
（ｉｉｉ）アクリル板での静・動摩擦係数の好ましい範囲については、静摩擦係数が０．０１〜０．２０であり、動摩擦係数が０．０１〜０．１２である。
(Vinyl chloride resin emulsion)
(I) Regarding the preferable range of the static/dynamic friction coefficient of the slide glass, the static friction coefficient is 0.01 to 0.20 and the dynamic friction coefficient is 0.01 to 0.12.
(Ii) Regarding the preferable range of the static/dynamic friction coefficient in the PET film, the static friction coefficient is 0.01 to 0.20 and the dynamic friction coefficient is 0.01 to 0.12.
(Iii) Regarding the preferable range of the static/dynamic friction coefficient of the acrylic plate, the static friction coefficient is 0.01 to 0.20 and the dynamic friction coefficient is 0.01 to 0.12.
（アクリル系樹脂エマルジョン）
（ｉ）スライドガラスでの静・動摩擦係数の好ましい範囲については、静摩擦係数が０．０１〜０．２５であり、動摩擦係数が０．０１〜０．１５である。
（ｉｉ）アクリル板での静・動摩擦係数の好ましい範囲については、静摩擦係数が０．０１〜０．３０であり、動摩擦係数が０．０１〜０．１５である。
(Acrylic resin emulsion)
(I) Regarding the preferable range of the static/dynamic friction coefficient on the slide glass, the static friction coefficient is 0.01 to 0.25 and the dynamic friction coefficient is 0.01 to 0.15.
(Ii) Regarding the preferable range of the static/dynamic friction coefficient of the acrylic plate, the static friction coefficient is 0.01 to 0.30 and the dynamic friction coefficient is 0.01 to 0.15.
Claims (13)
（Ｂ）下記一般式（１）で示されるポリオルガノシロキサンとアクリル酸エステル単位又はメタクリル酸エステル単位とが質量比３０：７０〜９９：１の割合である、平均粒子径が１８０ｎｍ以下のシリコーンアクリルグラフト共重合樹脂エマルジョン：固形分比で１〜４０質量％
を含有することを特徴とするコーティング用組成物。
(B) Silicone acrylic having an average particle diameter of 180 nm or less, in which the polyorganosiloxane represented by the following general formula (1) and the acrylic acid ester unit or the methacrylic acid ester unit have a mass ratio of 30:70 to 99:1. Graft copolymer resin emulsion: 1-40 mass% in terms of solid content
A coating composition comprising:
（ｂ１）上記一般式（１）で示される平均粒子径が１８０ｎｍ以下のポリオルガノシロキサンと、
（ｂ２）アクリル酸エステル単量体又はメタクリル酸エステル単量体と、
（ｂ３）これと共重合可能な官能基含有単量体と
の乳化グラフト共重合物である請求項１〜３のいずれか１項記載のコーティング用組成物。 (B) Silicone acrylic graft copolymer resin emulsion
(B1) a polyorganosiloxane represented by the general formula (1) and having an average particle size of 180 nm or less,
(B2) an acrylic acid ester monomer or a methacrylic acid ester monomer,
(B3) The coating composition according to any one of claims 1 to 3, which is an emulsion graft copolymer with a functional group-containing monomer copolymerizable therewith.
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| JP2022115399A (en) * | 2021-01-28 | 2022-08-09 | 日信化学工業株式会社 | Coating composition, coating composition for furniture and building interior, and laminate |
| JP2022115416A (en) * | 2021-01-28 | 2022-08-09 | 日信化学工業株式会社 | Coating composition for outer wall and building exterior, and laminate |
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| JP2001192424A (en) * | 1999-10-29 | 2001-07-17 | Dow Corning Toray Silicone Co Ltd | Emulsion composition of silicone-grafted vinylic copolymer |
| JP2001131461A (en) * | 1999-11-05 | 2001-05-15 | Nippon Synthetic Chem Ind Co Ltd:The | Silicon-containing aqueous coating agent composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022115399A (en) * | 2021-01-28 | 2022-08-09 | 日信化学工業株式会社 | Coating composition, coating composition for furniture and building interior, and laminate |
| JP2022115416A (en) * | 2021-01-28 | 2022-08-09 | 日信化学工業株式会社 | Coating composition for outer wall and building exterior, and laminate |
| JP7474205B2 (en) | 2021-01-28 | 2024-04-24 | 日信化学工業株式会社 | Coating composition for exterior walls and building exteriors, and laminate |
| JP7474204B2 (en) | 2021-01-28 | 2024-04-24 | 日信化学工業株式会社 | Coating composition, coating composition for furniture and building interiors, and laminate |
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