JP7485896B2 - Resin composition, resin particles, and lamination method - Google Patents
Resin composition, resin particles, and lamination method Download PDFInfo
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- JP7485896B2 JP7485896B2 JP2020005446A JP2020005446A JP7485896B2 JP 7485896 B2 JP7485896 B2 JP 7485896B2 JP 2020005446 A JP2020005446 A JP 2020005446A JP 2020005446 A JP2020005446 A JP 2020005446A JP 7485896 B2 JP7485896 B2 JP 7485896B2
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- resin
- resin particles
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- 239000011347 resin Substances 0.000 title claims description 215
- 229920005989 resin Polymers 0.000 title claims description 215
- 239000002245 particle Substances 0.000 title claims description 191
- 239000011342 resin composition Substances 0.000 title claims description 72
- 238000000034 method Methods 0.000 title claims description 20
- 238000003475 lamination Methods 0.000 title description 14
- 239000000178 monomer Substances 0.000 claims description 66
- 239000004094 surface-active agent Substances 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 239000000758 substrate Substances 0.000 claims description 42
- 239000011230 binding agent Substances 0.000 claims description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000007942 carboxylates Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 6
- 229920001225 polyester resin Polymers 0.000 claims description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 5
- 150000002430 hydrocarbons Chemical group 0.000 claims description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 3
- 125000006353 oxyethylene group Chemical group 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- -1 2-ethoxyethyl Chemical group 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 16
- 239000000725 suspension Substances 0.000 description 15
- 239000003505 polymerization initiator Substances 0.000 description 14
- 230000006835 compression Effects 0.000 description 9
- 238000007906 compression Methods 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 239000002612 dispersion medium Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 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 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000243 solution Substances 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000006177 alkyl benzyl group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- 229920002799 BoPET Polymers 0.000 description 1
- IWNLRYHTRXHMJE-UHFFFAOYSA-M Cl(=O)[O-].C(CCCCCCCCCCC)[N+](C)(C)CC1=CC=CC=C1 Chemical compound Cl(=O)[O-].C(CCCCCCCCCCC)[N+](C)(C)CC1=CC=CC=C1 IWNLRYHTRXHMJE-UHFFFAOYSA-M 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000000740 bleeding effect 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 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
- 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PVVUWCYTDNBWJC-UHFFFAOYSA-N n-benzyl-n-methyldodecan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCCCCCC[NH+](C)CC1=CC=CC=C1 PVVUWCYTDNBWJC-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 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
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical class OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000008569 process Effects 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
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- OGRPJZFGZFQRHZ-UHFFFAOYSA-M sodium;4-octoxy-4-oxo-3-sulfobutanoate Chemical compound [Na+].CCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O OGRPJZFGZFQRHZ-UHFFFAOYSA-M 0.000 description 1
- MWZFQMUXPSUDJQ-KVVVOXFISA-M sodium;[(z)-octadec-9-enyl] sulfate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCCOS([O-])(=O)=O MWZFQMUXPSUDJQ-KVVVOXFISA-M 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、樹脂組成物、樹脂粒子及び貼り合わせ方法に関する。 The present invention relates to a resin composition, resin particles, and a lamination method.
基材に粘着剤を塗布し、その上に別の基材を重ね、圧力を掛けて基材同士を貼り合わせる場合、貼付のための適正な圧力が掛かったかどうか（圧力履歴）を目視で確認することは難しい。 When applying an adhesive to a substrate, placing another substrate on top of it, and then applying pressure to bond the substrates together, it is difficult to visually check whether the appropriate pressure was applied (pressure history).
ところで、特許文献１には、密封容器に収容された飲料等の内容物の加熱殺菌のための高圧処理工程で使用される感圧インジケータ付容器が提案されている。この感圧インジケータは、基材シートと、基材シート上に設けられた顕色剤層と、顕色剤層上に設けられ、発色剤が含有されたカプセルを含む発色剤層とを有する。感圧インジケータ付容器を高圧処理した際、カプセルが破壊されて発色剤が顕色剤層側へ移行し、顕色剤層が高圧処理の圧力の程度に応じて不可逆に発色する。 Incidentally, Patent Document 1 proposes a container with a pressure-sensitive indicator for use in a high-pressure treatment process for thermal sterilization of contents such as beverages contained in a sealed container. This pressure-sensitive indicator has a base sheet, a color developer layer provided on the base sheet, and a color former layer provided on the color developer layer and including capsules containing a color former. When the container with the pressure-sensitive indicator is subjected to high-pressure treatment, the capsules are broken and the color former migrates to the color developer layer, and the color developer layer irreversibly develops color depending on the level of pressure in the high-pressure treatment.
貼り合わせる基材の少なくとも一方が透明な場合、貼り合わせる基材の間に上記感圧インジケータ及び粘着剤を配置して基材同士を貼り合わせると、感圧インジケータの発色により圧力履歴を確認できると考えられる。
しかし、この場合、貼り合わせ後に発色が透明な基材を通して観察されるため、用途によっては使用できない。また、上記感圧インジケータは、発色剤が含有されたカプセルの製造工程が煩雑なものであるため、生産性が低い問題もある。
When at least one of the substrates to be bonded is transparent, if the pressure-sensitive indicator and adhesive are placed between the substrates to be bonded and the substrates are bonded together, it is believed that the pressure history can be confirmed by the color change of the pressure-sensitive indicator.
However, in this case, since the color is observed through the transparent substrate after lamination, it cannot be used for some purposes. In addition, the pressure-sensitive indicator has a problem of low productivity because the manufacturing process of the capsules containing the color former is complicated.
本発明は、少なくとも一方が透明な基材同士の貼り合わせにおいて圧力履歴を示すことができる樹脂組成物、前記樹脂組成物に用いることが可能な樹脂粒子、及び少なくとも一方が透明な基材同士の貼り合わせにおいて圧力履歴を確認できる貼り合わせ方法を提供することを目的とする。 The present invention aims to provide a resin composition capable of indicating the pressure history when substrates, at least one of which is transparent, are bonded together, resin particles that can be used in the resin composition, and a bonding method that can confirm the pressure history when substrates, at least one of which is transparent, are bonded together.
本発明は、以下の態様を有する。
〔１〕樹脂バインダーと、前記樹脂バインダーに分散された、内部に複数の空孔を有する樹脂粒子とを含み、
加圧されたときに前記樹脂粒子が変形し、前記複数の空孔の体積が減少することを特徴とする樹脂組成物。
〔２〕前記樹脂粒子の２３℃下での１０％変形時の強度が、同一組成の中実樹脂粒子の前記強度の８０％以下である〔１〕の樹脂組成物。
〔３〕前記樹脂粒子の前記強度が１５ＭＰａ以下である〔２〕の樹脂組成物。
〔４〕前記樹脂粒子のガラス転移温度が８０℃以下である〔１〕～〔３〕のいずれかの樹脂組成物。
〔５〕前記樹脂粒子が、アクリル樹脂、スチレン樹脂、ビニル樹脂、ウレタン樹脂、ポリエステル樹脂、またはそれらの共重合体もしくは混合物からなる〔１〕～〔４〕のいずれかの樹脂組成物。
〔６〕前記樹脂バインダーが、アクリル樹脂、スチレン樹脂、ビニル樹脂、ウレタン樹脂、ポリエステル樹脂、エポキシ樹脂、またはそれらの共重合体もしくは混合物を含む〔１〕～〔５〕のいずれかの樹脂組成物。
〔７〕内部に複数の空孔を有し、
２３℃下での１０％変形時の強度が、同一組成の中実樹脂粒子の前記強度の８０％以下であることを特徴とする樹脂粒子。
〔８〕前記強度が１５ＭＰａ以下である〔７〕の樹脂粒子。
〔９〕ガラス転移温度が８０℃以下である〔７〕または〔８〕の樹脂粒子。
〔１０〕アクリル樹脂、スチレン樹脂、ビニル樹脂、ウレタン樹脂、ポリエステル樹脂、またはそれらの共重合体もしくは混合物からなる〔７〕～〔９〕のいずれかの樹脂粒子。
〔１１〕少なくとも一方が透明な第１の基材および第２の基材の間に〔１〕～〔６〕のいずれかの樹脂組成物を配置し、前記樹脂組成物のヘイズが低下するだけの圧力を掛けて前記第１の基材と前記第２の基材とを圧着することを特徴とする貼り合わせ方法。
The present invention has the following aspects.
[1] A toner cartridge comprising: a resin binder; and resin particles having a plurality of voids therein and dispersed in the resin binder;
A resin composition characterized in that, when pressurized, the resin particles are deformed and the volume of the plurality of pores is reduced.
[2] The resin composition according to [1], wherein the strength of the resin particles at 10% deformation at 23°C is 80% or less of the strength of solid resin particles of the same composition.
[3] The resin composition according to [2], wherein the strength of the resin particles is 15 MPa or less.
[4] The resin composition according to any one of [1] to [3], wherein the glass transition temperature of the resin particles is 80° C. or lower.
[5] The resin composition according to any one of [1] to [4], wherein the resin particles are made of an acrylic resin, a styrene resin, a vinyl resin, a urethane resin, a polyester resin, or a copolymer or mixture thereof.
[6] The resin composition according to any one of [1] to [5], wherein the resin binder comprises an acrylic resin, a styrene resin, a vinyl resin, a urethane resin, a polyester resin, an epoxy resin, or a copolymer or mixture thereof.
[7] Having a plurality of voids therein,
A resin particle having a strength at 23° C. under 10% deformation of 80% or less of the strength of a solid resin particle having the same composition.
[8] The resin particles according to [7], wherein the strength is 15 MPa or less.
[9] Resin particles according to [7] or [8], having a glass transition temperature of 80° C. or lower.
[10] Resin particles according to any one of [7] to [9], which are made of an acrylic resin, a styrene resin, a vinyl resin, a urethane resin, a polyester resin, or a copolymer or mixture thereof.
[11] A method for bonding a first substrate and a second substrate, at least one of which is transparent, comprising disposing a resin composition according to any one of [1] to [6] between the first substrate and the second substrate, and applying a pressure sufficient to reduce the haze of the resin composition to bond the first substrate and the second substrate together.
上記態様に係る樹脂組成物は、少なくとも一方が透明な基材同士の貼り合わせにおいて圧力履歴を示すことができる。
上記態様に係る樹脂粒子は、前記樹脂組成物に用いることが可能である。本発明の樹脂粒子を用いた樹脂組成物は、少なくとも一方が透明な基材同士の貼り合わせにおいて圧力履歴を示すことができる。
上記態様に係る貼り合わせ方法は、少なくとも一方が透明な基材同士の貼り合わせにおいて圧力履歴を確認できる。
The resin composition according to the above embodiment can show a pressure history when two substrates, at least one of which is transparent, are bonded to each other.
The resin particles according to the above embodiment can be used in the resin composition. The resin composition using the resin particles of the present invention can show a pressure history when two substrates, at least one of which is transparent, are bonded to each other.
The bonding method according to the above aspect makes it possible to check the pressure history when bonding base materials, at least one of which is transparent, together.
以下、好適な実施形態に基づいて本発明を説明する。
なお、本発明において、「１０％変形時の強度」とは、粒子径の１０％の圧縮変位に対する変形強度である。「変形強度」とは、粒子を平面圧子で圧縮するとき、粒子の変形に要する強度である。１０％変形時の強度は、ＪＩＳ Ｚ ８８４４：２０１９に規定される手順に則り、測定した結果を下記式（１）『平松らの式』に当てはめ算出した値となる。
Ｓｔ ＝ ２．８×Ｐ／πｄ２ 式（１）
ただし、Ｓｔは１０％変形時の強度（ＭＰａ）を示し、Ｐは試験力（Ｎ）を示し、ｄは樹脂粒子の粒子径（ｍｍ）を示す。１０％変形時の強度の測定条件は、直径５０μｍの平面圧子を用い、２３℃、５０％雰囲気下にて試験速度０．１４２２ｍＮ／ｓとする。
「粒子径」は、レーザー回折式粒度分布測定装置により測定される平均粒子径である。
「ガラス転移温度」（以下、「Ｔｇ」とも記す。）は、示差走査熱量計により測定される。
「ヘイズ」及び「全光線透過率」はそれぞれ、ヘイズメーターにより測定される。
The present invention will now be described based on preferred embodiments.
In the present invention, the "strength at 10% deformation" refers to the deformation strength with respect to a compressive displacement of 10% of the particle diameter. The "deformation strength" refers to the strength required to deform a particle when the particle is compressed with a flat indenter. The strength at 10% deformation is a value calculated by applying the measurement results to the following formula (1) "Hiramatsu et al.'s formula" in accordance with the procedure specified in JIS Z 8844:2019.
St = 2.8 × P / πd 2 Equation (1)
Here, St represents the strength (MPa) at 10% deformation, P represents the test force (N), and d represents the particle diameter (mm) of the resin particles. The conditions for measuring the strength at 10% deformation are a flat indenter with a diameter of 50 μm, 23° C., 50% humidity, and a test speed of 0.1422 mN/s.
The "particle size" is the average particle size measured by a laser diffraction particle size distribution measuring device.
The "glass transition temperature" (hereinafter also referred to as "Tg") is measured by a differential scanning calorimeter.
"Haze" and "total light transmittance" are each measured by a haze meter.
〔樹脂組成物〕
本発明の一実施形態に係る樹脂組成物は、樹脂バインダーと、前記樹脂バインダーに分散された、内部に複数の空孔を有する樹脂粒子（以下、「中空樹脂粒子」とも記す。）とを含む。
[Resin composition]
A resin composition according to one embodiment of the present invention contains a resin binder and resin particles having a plurality of voids therein (hereinafter also referred to as "hollow resin particles") dispersed in the resin binder.
樹脂バインダーは、バインダーとして一般的な樹脂であってよい。
樹脂バインダーは典型的には透明である。樹脂バインダーは、樹脂バインダーを用いて、少なくとも一方が透明な基材同士を貼り合わせた試験片を作成し、その試験片をヘイズメーターにて評価したときに、全光線透過率が８５％以上、且つヘイズが５％以下となる透明度を有することが好ましい。
試験片の具体的な作成手順は、樹脂組成物の代わりに樹脂バインダーのみを用いる以外は、後述する実施例に記載の（フィルムの貼り合わせ）における第二の積層体の作成手順と同様である。
樹脂バインダーは、透明度の観点から、アクリル樹脂、スチレン樹脂、ビニル樹脂、ウレタン樹脂、ポリエステル樹脂、エポキシ樹脂のいずれかの樹脂を含むことが好ましい。これらの樹脂の共重合体や混合物も使用できる。
The resin binder may be a resin commonly used as a binder.
The resin binder is typically transparent. When a test piece is prepared by bonding together substrates, at least one of which is transparent, using the resin binder and the test piece is evaluated with a haze meter, the resin binder preferably has a transparency such that the total light transmittance is 85% or more and the haze is 5% or less.
The specific procedure for preparing the test piece was the same as the procedure for preparing the second laminate in (Lamination of Films) described in the Examples below, except that only the resin binder was used instead of the resin composition.
From the viewpoint of transparency, the resin binder preferably contains any one of acrylic resin, styrene resin, vinyl resin, urethane resin, polyester resin, and epoxy resin. Copolymers and mixtures of these resins can also be used.
中空樹脂粒子は、内部に複数の空孔を有する。
また、中空樹脂粒子は、加圧されたときに変形可能である。
The hollow resin particles have a plurality of pores therein.
Additionally, the hollow resin particles are deformable when pressure is applied.
中空樹脂粒子は、その内部の複数の空孔によって光が散乱されるため、中空樹脂粒子を構成する樹脂が透明であっても、単独では白色を呈する。この中空樹脂粒子を含む樹脂組成物は、樹脂バインダーが透明であっても、空孔による光の散乱のために透明にはならず、曇り外観を呈する。
この樹脂組成物に適正な圧力を掛けると、圧力が掛かった部分で、中空樹脂粒子が圧力により変形し、粒子内部の複数の空孔の体積が減少する。場合によっては、中空樹脂粒子が圧力により破壊され、空孔内に樹脂バインダーが入り込む等によって空孔が消失する。その結果、圧力が掛かった部分のヘイズが低下する（透明度が高まる）。このヘイズの変化により圧力履歴を確認できる。
Since the hollow resin particles have a plurality of internal pores that scatter light, the hollow resin particles alone exhibit a white color even if the resin constituting the hollow resin particles is transparent, and a resin composition containing the hollow resin particles exhibits a cloudy appearance because the pores scatter light, even if the resin binder is transparent.
When an appropriate pressure is applied to this resin composition, the hollow resin particles are deformed in the areas where pressure is applied, and the volume of the multiple pores inside the particles decreases. In some cases, the hollow resin particles are destroyed by the pressure, and the pores disappear due to the resin binder entering the pores. As a result, the haze of the areas where pressure is applied decreases (transparency increases). The pressure history can be confirmed by this change in haze.
中空樹脂粒子を構成する樹脂は、一般的な樹脂であってよい。
中空樹脂粒子を構成する樹脂は典型的には透明である。また、圧着後のヘイズ変化を明確にするため、樹脂粒子を構成する樹脂の屈折率は樹脂バインダーを構成する樹脂の屈折率と近い値もしくは同等にすることが好ましい。
中空樹脂粒子は、透明度の観点から、アクリル樹脂、スチレン樹脂、ビニル樹脂、ウレタン樹脂、ポリエステル樹脂のいずれかの樹脂からなることが好ましい。これらの樹脂の共重合体や混合物も使用できる。これらの中でも、透明度や屈折率、強度の調整のしやすさの観点から、アクリル樹脂が好ましい。
The resin constituting the hollow resin particles may be a general resin.
The resin constituting the hollow resin particles is typically transparent. In order to clarify the haze change after compression bonding, it is preferable that the refractive index of the resin constituting the resin particles is close to or equal to the refractive index of the resin constituting the resin binder.
From the viewpoint of transparency, the hollow resin particles are preferably made of any one of acrylic resin, styrene resin, vinyl resin, urethane resin, and polyester resin. Copolymers and mixtures of these resins can also be used. Among these, acrylic resin is preferred from the viewpoint of ease of adjusting transparency, refractive index, and strength.
中空樹脂粒子のＴｇ、つまり中空樹脂粒子を構成する樹脂のＴｇは、８０℃以下であることが好ましい。中空樹脂粒子のＴｇが８０℃以下であれば、樹脂組成物に圧力を掛けたときに中空樹脂粒子が変形しやすく、ヘイズが変化しやすいので、圧力履歴を確認しやすい。中空樹脂粒子のＴｇは、７０℃以下であることがより好ましい。
中空樹脂粒子のＴｇは、製造時及び保存時の安定性の観点から、４０℃以上であることが好ましい。
The Tg of the hollow resin particles, i.e., the Tg of the resin constituting the hollow resin particles, is preferably 80° C. or less. If the Tg of the hollow resin particles is 80° C. or less, the hollow resin particles are easily deformed when pressure is applied to the resin composition, and the haze is easily changed, making it easy to check the pressure history. The Tg of the hollow resin particles is more preferably 70° C. or less.
From the viewpoint of stability during production and storage, the hollow resin particles preferably have a Tg of 40° C. or higher.
中空樹脂粒子の２３℃下での１０％変形時の強度（以下、「強度ａ」とも記す。）は、同一組成の中実樹脂粒子の２３℃下での１０％変形時の強度（以下、「強度ｂ」とも記す。）の８０％以下であることが好ましい。
中実樹脂粒子の「中実」とは、粒子内部に空隙を有さないことを示す。「同一組成」とは、中実樹脂粒子を構成する樹脂が、中空樹脂粒子を構成する樹脂と同一であること、つまり樹脂を構成する単量体の種類と比率が同一であること、を示す。中実樹脂粒子の粒子径は、中空樹脂粒子の粒子径と同一とする。
強度ｂに対する強度ａの比率は、中空樹脂粒子の空隙量（空隙率）の指標である。強度ａが強度ｂの８０％以下であれば、後述する初期ヘイズが高くなり、樹脂組成物に圧力を掛けたときのヘイズ変化を大きくしやすい。ヘイズ変化が大きいほど、圧力履歴を確認しやすい。強度ａは、強度ｂの６０％以下であることがより好ましい。
It is preferable that the strength of a hollow resin particle at 23°C when deformed by 10% (hereinafter also referred to as "strength a") is 80% or less of the strength of a solid resin particle of the same composition at 23°C when deformed by 10% (hereinafter also referred to as "strength b")
The "solid" in solid resin particles means that there is no void inside the particle. The "same composition" means that the resin constituting the solid resin particles is the same as the resin constituting the hollow resin particles, that is, the types and ratios of the monomers constituting the resin are the same. The particle diameter of the solid resin particles is the same as that of the hollow resin particles.
The ratio of the strength a to the strength b is an index of the void volume (porosity) of the hollow resin particles. If the strength a is 80% or less of the strength b, the initial haze described below is high, and it is easy to increase the haze change when pressure is applied to the resin composition. The larger the haze change, the easier it is to check the pressure history. It is more preferable that the strength a is 60% or less of the strength b.
強度ａは、１５ＭＰａ以下であることが好ましい。強度ａが１５ＭＰａ以下であれば、圧力に対する感度が適切となり、樹脂組成物に適正な圧力が掛かったことを判別しやすい。強度ａは、１３ＭＰａ以下であることがより好ましい。
また、強度ａは、３ＭＰａ以上であることが好ましい。強度ａが３ＭＰａ以上であれば、中空樹脂粒子を樹脂バインダーに分散させる際に空孔を維持しやすい。
強度ａは、中空樹脂粒子のＴｇにより調整できる。中空樹脂粒子のＴｇが低いほど、強度ａが低くなる傾向がある。
The strength a is preferably 15 MPa or less. If the strength a is 15 MPa or less, the sensitivity to pressure becomes appropriate, and it is easy to determine that an appropriate pressure has been applied to the resin composition. The strength a is more preferably 13 MPa or less.
The strength a is preferably 3 MPa or more. If the strength a is 3 MPa or more, the pores are easily maintained when the hollow resin particles are dispersed in a resin binder.
The strength a can be adjusted by the Tg of the hollow resin particles. The lower the Tg of the hollow resin particles, the lower the strength a tends to be.
中空樹脂粒子としては、強度ａが強度ｂの８０％以下かつ１５ＭＰａ以下であり、Ｔｇが８０℃以下であるものが好ましい。強度ａ、Ｔｇそれぞれのより好ましい値は前記のとおりである。 Preferably, the hollow resin particles have a strength a of 80% or less of the strength b and 15 MPa or less, and a Tg of 80°C or less. The more preferable values of the strength a and Tg are as described above.
中空樹脂粒子の粒子径は、特に限定されないが、例えば、０．５～５００μｍであってよく、０．５～１００μｍであってよく、１～５０μｍであってよい。 The particle diameter of the hollow resin particles is not particularly limited, but may be, for example, 0.5 to 500 μm, 0.5 to 100 μm, or 1 to 50 μm.
中空樹脂粒子の一例として、重合性不飽和炭化水素基を有する重合性単量体を、水を主体とした分散媒に分散させ、懸濁化し、重合させる樹脂粒子の重合において、少なくとも、後述する界面活性剤Ａを分散剤として用いることで得られる中空樹脂粒子が挙げられる。この中空樹脂粒子の製造方法については後で詳しく説明する。 One example of hollow resin particles is hollow resin particles obtained by dispersing, suspending, and polymerizing a polymerizable monomer having a polymerizable unsaturated hydrocarbon group in a water-based dispersion medium, using at least surfactant A, which will be described later, as a dispersant. The method for producing hollow resin particles will be described in detail later.
本実施形態に係る樹脂組成物は、必要に応じて、樹脂バインダー及び中空樹脂粒子以外の他の成分をさらに含んでいてもよい。他の成分としては、例えば、タッキファイヤー、表面調整剤、脱泡剤等の各種の添加剤が挙げられる。
本実施形態に係る樹脂組成物は、必要に応じて、例えば樹脂組成物の塗工性を高める観点から、水、有機溶剤等の液状媒体をさらに含んでいてもよい。
The resin composition according to the present embodiment may further contain other components in addition to the resin binder and the hollow resin particles, as necessary. Examples of the other components include various additives such as a tackifier, a surface conditioner, and a defoamer.
The resin composition according to the present embodiment may further contain a liquid medium such as water or an organic solvent, as necessary, for example from the viewpoint of improving the coatability of the resin composition.
樹脂組成物中、中空樹脂粒子の含有量は、樹脂バインダー１００質量部に対し、５～３０質量部が好ましく、５～２０質量部がより好ましく、１０～２０質量部がさらに好ましい。中空樹脂粒子の含有量が前記範囲の下限値以上であれば、樹脂組成物に圧力を掛ける前後でのヘイズの変化が大きくなり、圧力履歴をより確認しやすい。中空樹脂粒子の含有量が前記範囲の上限値以下であれば、樹脂バインダーの特性を大きく損なうことはない。 The content of hollow resin particles in the resin composition is preferably 5 to 30 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 10 to 20 parts by mass, per 100 parts by mass of the resin binder. If the content of hollow resin particles is equal to or greater than the lower limit of the above range, the change in haze before and after pressure is applied to the resin composition becomes large, making it easier to check the pressure history. If the content of hollow resin particles is equal to or less than the upper limit of the above range, the properties of the resin binder are not significantly impaired.
樹脂組成物中、樹脂バインダーと中空樹脂粒子との合計の含有量は、例えば、樹脂組成物の全固形分１００質量％に対し、２０質量％以上であってよく、５０質量％以上であってよく、１００質量％であってもよい。
樹脂組成物が液状媒体を含む場合、液状媒体の含有量は、例えば、樹脂組成物の総質量に対し、２０～８０質量％であってよく、３０～７０質量％であってよく、４０～６０質量％であってよい。
In the resin composition, the total content of the resin binder and the hollow resin particles may be, for example, 20 mass% or more, 50 mass% or more, or may be 100 mass%, relative to 100 mass% of the total solid content of the resin composition.
When the resin composition contains a liquid medium, the content of the liquid medium may be, for example, 20 to 80 mass% relative to the total mass of the resin composition. It may be 30 to 70 mass% or 40 to 60 mass%.
本実施形態に係る樹脂組成物は、後述する実施例に示す方法により測定される初期ヘイズと熱圧着後ヘイズとの差（初期ヘイズ（％）－熱圧着後ヘイズ（％））が３０％以上であることが好ましく、６０％以上であることがより好ましい。この差が前記下限値以上であれば、圧力履歴を確認しやすい。
初期ヘイズは、初期ヘイズと熱圧着後ヘイズとの差を大きくする観点から、６０％以上であることが好ましく、８０％以上であることがより好ましい。
熱圧着後ヘイズは、貼り合わせ後の外観の観点から、３０％以下であることが好ましく、２０％以下であることがより好ましい。
In the resin composition according to the present embodiment, the difference between the initial haze and the haze after thermocompression bonding (initial haze (%)--haze after thermocompression bonding (%)) measured by the method shown in the examples described later is preferably 30% or more, and more preferably 60% or more. If this difference is equal to or more than the lower limit, it is easy to confirm the pressure history.
From the viewpoint of increasing the difference between the initial haze and the haze after thermocompression bonding, the initial haze is preferably 60% or more, and more preferably 80% or more.
From the viewpoint of appearance after lamination, the haze after thermocompression bonding is preferably 30% or less, and more preferably 20% or less.
本実施形態に係る樹脂組成物は、樹脂バインダー、中空樹脂粒子、必要に応じて他の成分、液状媒体を混合することにより製造できる。 The resin composition according to this embodiment can be produced by mixing a resin binder, hollow resin particles, and, if necessary, other components and a liquid medium.
中空樹脂粒子の製造方法としては、特に限定するものではないが、中空樹脂粒子の製造方法の一実施形態として、重合性不飽和炭化水素基を有する重合性単量体を、水を主体とした分散媒に分散させ、懸濁化し、重合させる樹脂粒子の重合において、少なくとも、後述する界面活性剤Ａを分散剤として用いる方法が挙げられる。この方法では、界面活性剤Ａの作用により、重合前の重合性単量体の液滴内に複数の水滴が取り込まれ、その状態のまま重合性単量体を重合させるので、粒子内部に複数の空孔を有する樹脂粒子が得られる。 The method for producing hollow resin particles is not particularly limited, but one embodiment of the method for producing hollow resin particles is a method in which a polymerizable monomer having a polymerizable unsaturated hydrocarbon group is dispersed in a water-based dispersion medium, suspended, and polymerized to produce resin particles, and at least a surfactant A described below is used as a dispersant. In this method, multiple water droplets are incorporated into the droplets of the polymerizable monomer before polymerization due to the action of the surfactant A, and the polymerizable monomer is polymerized in this state, resulting in resin particles with multiple voids inside the particle.
以下、好適な実施形態に基づいて本実施形態に係る中空樹脂粒子の製造方法を説明する。なお、本発明において、「（メタ）アクリル酸（（メタ）アクリレート）」は、アクリル酸（アクリレート）およびメタクリル酸（メタクリレート）の総称である。 The method for producing hollow resin particles according to this embodiment will be described below based on a preferred embodiment. In the present invention, "(meth)acrylic acid ((meth)acrylate)" is a general term for acrylic acid (acrylate) and methacrylic acid (methacrylate).
本実施形態に係る中空樹脂粒子の製造方法に用いる構成成分について詳細に説明する。 The components used in the method for producing hollow resin particles according to this embodiment are described in detail below.
［構成成分］
（界面活性剤Ａ）
界面活性剤Ａは、下記式（２）で表される。
Ｔ１Ｏ－（ＲＯ）ｎ（ＥＯ）ｍ－Ｔ２ …（２）
式（２）中、Ｔ１は水素原子、炭素数１～１８のアルキル基、または炭素数２～１８のアルケニル基であり、Ｔ２は水素原子、スルホン酸基、スルホン酸塩基、カルボン酸基、カルボン酸塩基、リン酸基、リン酸塩基、アミノ基、またはアンモニウム基であり、ＲＯは炭素数３～１８のオキシアルキレン基であり、ｎは１～５０の整数であり、ＥＯはオキシエチレン基を示し、ｍは０～２００の整数である。
樹脂粒子中に界面活性剤Ａが残存した場合に、ブリードを抑制できるという点で、Ｔ１はアルケニル基であることが好ましい。
[Structural component]
(Surfactant A)
The surfactant A is represented by the following formula (2).
T 1 O-(RO)n(EO)m-T 2 ... (2)
In formula (2), T1 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms; T2 is a hydrogen atom, a sulfonic acid group, a sulfonate group, a carboxylate group, a carboxylate group, a phosphoric acid group, a phosphate group, an amino group, or an ammonium group; RO is an oxyalkylene group having 3 to 18 carbon atoms; n is an integer of 1 to 50; EO is an oxyethylene group; and m is an integer of 0 to 200.
In the case where surfactant A remains in the resin particles, T1 is preferably an alkenyl group, since bleeding can be suppressed.
なお、界面活性剤Ａは、市販品を用いることができる。界面活性剤Ａである市販品のアニオン性の界面活性剤としては、例えば、第一工業製薬のアクアロンＫＨシリーズ、ハイテノーＸＪ－６３０Ｓもしくは花王製のラテムルＰＤ－１０４、ラテムルＰＤ－１０５等が挙げられる。界面活性剤Ａである市販品のノニオン性の界面活性剤としては、例えば、第一工業製薬のノイゲンＸＬシリーズ、花王のラテムル－４２０、４３０、４５０、エマルゲンＬＳシリーズ、エマルゲンＭＳシリーズ、エマルゲンＰＰシリーズおよび青木油脂工業社製ファインサーフＮＤＢシリーズ、ＩＤＥＰシリーズ、ワンダーサーフＮＤＲシリーズ、ＩＤシリーズ、Ｓシリーズ等が挙げられる。 Surfactant A may be a commercially available product. Examples of commercially available anionic surfactants that are surfactant A include Aqualon KH series and Hiteno XJ-630S from Daiichi Kogyo Seiyaku Co., Ltd., and Latemul PD-104 and Latemul PD-105 from Kao Co., Ltd. Examples of commercially available nonionic surfactants that are surfactant A include Noigen XL series from Daiichi Kogyo Seiyaku Co., Ltd., Latemul-420, 430, 450, Emulgen LS series, Emulgen MS series, Emulgen PP series from Kao Co., Ltd., and Finesurf NDB series, IDEP series, Wondersurf NDR series, ID series, S series, etc. from Aoki Oil Industries Co., Ltd.
本実施形態および以下に示す実施形態における界面活性剤Ａの使用量は、例えば、後述する重合性単量体１００質量部（質量％）に対して０．０５～５．０質量部（質量％）であることが好ましい。上記範囲（０．０５～５．０質量部）で界面活性剤Ａを用いた場合、安定的に中空樹脂粒子が形成されやすい。界面活性剤Ａの使用量が、０．０５質量部未満であると中空構造が不完全となり、５．０質量部より大きいと粒子を構成する樹脂の特性を損なう恐れがある。 In this embodiment and the embodiments described below, the amount of surfactant A used is preferably, for example, 0.05 to 5.0 parts by mass (% by mass) per 100 parts by mass (% by mass) of the polymerizable monomer described below. When surfactant A is used in the above range (0.05 to 5.0 parts by mass), hollow resin particles are likely to be formed stably. If the amount of surfactant A used is less than 0.05 parts by mass, the hollow structure will be incomplete, and if it is more than 5.0 parts by mass, the properties of the resin that constitutes the particles may be impaired.
なお、本明細書において、界面活性剤Ａを「一般式（１）で表された界面活性剤（第１の界面活性剤）」と示すこともあり、「第２の界面活性剤」と示すこともある。
界面活性剤Ａを「第１の界面活性剤」、「第２の界面活性剤」と示すことがあるのは、以下に詳述する製造工程において、複数回界面活性剤Ａを別途用いて中空樹脂粒子を調製する場合があるためである。
すなわち、中空樹脂粒子の調製において、例えば、２回の工程に分けて、界面活性剤Ａを添加する際に、２回の工程で界面活性剤Ａを区別して示す場合に、理解を容易にするために、「第１の界面活性剤」、「第２の界面活性剤」のように呼ぶことがある。
なお、「第２の界面活性剤」としては、本発明の効果を阻害しない範囲で、上述の界面活性剤Ａとは異なる界面活性剤を用いてもよい。
なお、「第２の界面活性剤」に代えて、本発明の効果を阻害しない範囲で、後述する「任意の分散剤」を用いてもよい。
「第２の界面活性剤」および「任意の分散剤」は任意の１種類のものを単独で用いてもよく、任意の複数のものを組み合わせて用いてもよい。
In this specification, surfactant A is sometimes referred to as "the surfactant represented by general formula (1) (first surfactant)" and sometimes referred to as "the second surfactant."
Surfactant A is sometimes referred to as the "first surfactant" or the "second surfactant" because, in the manufacturing process described in detail below, surfactant A may be used separately multiple times to prepare hollow resin particles.
That is, in the preparation of hollow resin particles, for example, when surfactant A is added in two separate steps, when it is necessary to distinguish between the two steps, the surfactants may be referred to as a "first surfactant" and a "second surfactant" for ease of understanding.
As the "second surfactant", a surfactant different from the above-mentioned surfactant A may be used as long as it does not impair the effects of the present invention.
In addition, instead of the "second surfactant", an "optional dispersant" described later may be used within a range that does not impair the effects of the present invention.
The "second surfactant" and the "optional dispersant" may be any one of the above-mentioned types used alone or any combination of a plurality of the above-mentioned types used together.
（重合性単量体）
重合性単量体は、重合性不飽和炭化水素基を有する重合性単量体であり、例えば、（メタ）アクリル単量体、および芳香族ビニル単量体が挙げられる。
なお、本明細書において、「重合性不飽和炭化水素基を有する重合性単量体」を、単に「重合性単量体」と呼ぶことがある。
(Polymerizable monomer)
The polymerizable monomer is a polymerizable monomer having a polymerizable unsaturated hydrocarbon group, and examples thereof include a (meth)acrylic monomer and an aromatic vinyl monomer.
In this specification, the "polymerizable monomer having a polymerizable unsaturated hydrocarbon group" may be simply referred to as the "polymerizable monomer".
（メタ）アクリル単量体は、例えば、単官能（メタ）アクリレート、および二官能以上の重合性官能基を有する多官能（メタ）アクリレートが挙げられる。 Examples of (meth)acrylic monomers include monofunctional (meth)acrylates and polyfunctional (meth)acrylates having difunctional or higher polymerizable functional groups.
単官能（メタ）アクリレートとしては、具体的には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸へプチル、（メタ）アクリル酸オクチル等の（メタ）アクリル酸アルキルエステル；（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸２－（ｎ－プロポキシ）エチル、（メタ）アクリル酸２－（ｎ－ブトキシ）エチル、（メタ）アクリル酸３－メトキシプロピル、（メタ）アクリル酸３－エトキシプロピル、（メタ）アクリル酸２－（ｎ－プロポキシ）プロピル、（メタ）アクリル酸２－（ｎ－ブトキシ）プロピル等の（メタ）アクリル酸アルコキシアルキルエステル；（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸イソボルニル等の脂環構造を有する（メタ）アクリル酸エステル等が挙げられる。これらは、１種単独で用いてもよく、２種以上を併用してもよい。 Specific examples of monofunctional (meth)acrylates include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, and octyl (meth)acrylate; (meth)acrylic acid alkoxyalkyl esters such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(n-propoxy)ethyl (meth)acrylate, 2-(n-butoxy)ethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 2-(n-propoxy)propyl (meth)acrylate, and 2-(n-butoxy)propyl (meth)acrylate; and (meth)acrylic acid esters having an alicyclic structure such as cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate. These may be used alone or in combination of two or more.
多官能（メタ）アクリレートとしては、エチレンオキシド（ＥＯ）が１～９の（ポリ）エチレングリコールジ（メタ）アクリレート、炭素数４～９のアルキレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等の（メタ）アクリル基を少なくとも２つ以上有する（メタ）アクリル酸エステル等が挙げられる。これらは、１種単独で用いてもよく、２種以上を併用してもよい。 Examples of polyfunctional (meth)acrylates include (poly)ethylene glycol di(meth)acrylates having 1 to 9 ethylene oxide (EO), alkylene glycol di(meth)acrylates having 4 to 9 carbon atoms, and (meth)acrylic acid esters having at least two or more (meth)acrylic groups, such as trimethylolpropane tri(meth)acrylate. These may be used alone or in combination of two or more.
芳香族ビニル単量体としては、例えば、スチレン系単量体、ジビニルベンゼンが挙げられ、スチレン系単量体が好ましい。
スチレン系単量体としては、例えば、スチレン、α－メチルスチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ｏ－クロロスチレン、ｍ－クロロスチレン、ｐ－クロロスチレン等が挙げられる。これらは、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of the aromatic vinyl monomer include styrene-based monomers and divinylbenzene, with styrene-based monomers being preferred.
Examples of styrene monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, etc. These may be used alone or in combination of two or more.
本実施形態に係る重合性単量体においては、上記（メタ）アクリル単量体において、上記単官能（メタ）アクリレートと、上記多官能（メタ）アクリレートと、を組み合わせて用いてもよく、（メタ）アクリル単量体と、芳香族ビニル単量体と、を組み合わせて用いてもよい。さらに他の単量体を組み合わせてもよい。
本実施形態に係る中空樹脂粒子を製造する際の重合性単量体における、上記単官能（メタ）アクリレート、上記多官能（メタ）アクリレート、および芳香族ビニル単量体の比率は特に限定されないが、例えば、単官能（メタ）アクリレートが２０～９５質量部であってもよく、多官能（メタ）アクリレートが１～１５質量部であってもよく、芳香族ビニル単量体が１０～５０質量部であってもよい。
他の単量体としては、本発明の効果を阻害せずに、（メタ）アクリル単量体と共重合可能であれば特に制限されないが、例えば、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、アクリロニトリル等を用いてよい。
In the polymerizable monomer according to the present embodiment, the (meth)acrylic monomer may be used in combination with the monofunctional (meth)acrylate and the polyfunctional (meth)acrylate, or may be used in combination with an aromatic vinyl monomer. Further, other monomers may be used in combination.
The ratio of the monofunctional (meth)acrylate, the polyfunctional (meth)acrylate, and the aromatic vinyl monomer in the polymerizable monomers when producing the hollow resin particles according to this embodiment is not particularly limited, but may be, for example, 20 to 95 parts by mass of the monofunctional (meth)acrylate, 1 to 15 parts by mass of the polyfunctional (meth)acrylate, and 10 to 50 parts by mass of the aromatic vinyl monomer.
The other monomer is not particularly limited as long as it is copolymerizable with the (meth)acrylic monomer without impairing the effects of the present invention. For example, vinyl acetate, vinyl propionate, vinyl chloride, acrylonitrile, etc. may be used.
必要に応じて連鎖移動剤等の添加剤を用いてもよい。 Additives such as chain transfer agents may be used if necessary.
（油溶性重合開始剤）
油溶性重合開始剤としては、例えば、過酸化ベンゾイル、過酸化ラウロイル等の過酸化物系開始剤、及び、２，２’－アゾビス（２－メチルブチロニトリル）、２，２’－アゾビス（イソブチロニトリル）等の油溶性アゾ系重合開始剤等が挙げられる。
(Oil-soluble polymerization initiator)
Examples of the oil-soluble polymerization initiator include peroxide-based initiators such as benzoyl peroxide and lauroyl peroxide, and oil-soluble azo-based polymerization initiators such as 2,2'-azobis(2-methylbutyronitrile) and 2,2'-azobis(isobutyronitrile).
油溶性重合開始剤の使用量は、例えば、重合性単量体１００質量部に対して、０．０５～３．０質量部であってもよく、０．１～２．０質量部が好ましく、０．２～１．５質量部がより好ましい。油溶性重合開始剤の使用量が０．０５質量部以上であれば、未反応のまま残存する重合性単量体の割合を減らすことができる。一方、油溶性重合開始剤の使用量が３．０質量部以下であれば、油溶性重合開始剤が分解した分解物が不純物として残るのを抑制できる。 The amount of oil-soluble polymerization initiator used may be, for example, 0.05 to 3.0 parts by mass, preferably 0.1 to 2.0 parts by mass, and more preferably 0.2 to 1.5 parts by mass, per 100 parts by mass of polymerizable monomer. If the amount of oil-soluble polymerization initiator used is 0.05 parts by mass or more, the proportion of polymerizable monomer remaining unreacted can be reduced. On the other hand, if the amount of oil-soluble polymerization initiator used is 3.0 parts by mass or less, decomposition products of the oil-soluble polymerization initiator can be suppressed from remaining as impurities.
（任意の界面活性剤）
本発明の効果を阻害しない範囲で、上記の界面活性剤Ａ以外の界面活性剤として、以下に示す任意の界面活性剤（上記の界面活性剤Ａとは異なる界面活性剤）を用いてもよい。
換言すれば、本発明の効果を阻害しない範囲で、上記界面活性剤Ａに加えて、適宜界面活性剤を加えてもよい。
(Optional Surfactant)
As a surfactant other than the above-mentioned surfactant A, any of the surfactants shown below (surfactants different from the above-mentioned surfactant A) may be used as long as the effects of the present invention are not impaired.
In other words, in addition to the surfactant A, an appropriate surfactant may be added as long as the effects of the present invention are not impaired.
任意の界面活性剤としては、例えば、アニオン系界面活性剤またはカチオン系界面活性剤が挙げられる。 The optional surfactant may be, for example, an anionic surfactant or a cationic surfactant.
アニオン系界面活性剤としては、具体的には、オレイン酸ナトリウム、ステアリン酸ナトリウム等の高級脂肪酸塩類；ドデシルベンゼンスルホン酸ナトリウム、ドデシルジフェニルエーテルスルホン酸ジナトリウム等のアルキル（もしくはアリール）スルホン酸塩類；ラウリル硫酸ナトリウム、オレイル硫酸ナトリウム等のアルキル（もしくはアルケニル）硫酸エステル類；ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンオレイルエーテル硫酸アンモニウム、ポリオキシエチレンスチレン化フェニルエーテル硫酸アンモニウム等のポリオキシエチレンアルキル（もしくはアルケニル）エーテル硫酸塩類；ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルアリールエーテル硫酸エステル塩類；モノオクチルスルホコハク酸ナトリウム、ジ－２－エチルへキシルスルホコハク酸ナトリウム、ジオクチルスルホコハク酸ナトリウム、ポリオキシエチレンラウリルスルホコハク酸ナトリウム等のアルキルスルホコハク酸エステル塩、またはこれらの誘導体類等が挙げられる。これらアニオン系界面活性剤は、１種単独で用いてもよく、２種以上を併用してもよい。 Specific examples of anionic surfactants include higher fatty acid salts such as sodium oleate and sodium stearate; alkyl (or aryl) sulfonates such as sodium dodecylbenzenesulfonate and disodium dodecyldiphenylethersulfonate; alkyl (or alkenyl) sulfates such as sodium lauryl sulfate and sodium oleyl sulfate; polyoxyethylene alkyl (or alkenyl) ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene oleyl ether sulfate, and ammonium polyoxyethylene styrenated phenyl ether sulfate; polyoxyethylene alkylaryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate; alkyl sulfosuccinates such as sodium monooctyl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, sodium dioctyl sulfosuccinate, and sodium polyoxyethylene lauryl sulfosuccinate, or derivatives thereof. These anionic surfactants may be used alone or in combination of two or more.
カチオン系界面活性剤としては、具体的には、ドデシルベンジルメチルアンモニウムクロライド等のアルキルベンジルメチルアンモニウム塩；ドデシルトリメチルアンモニウムクロライド、ステアリルトリメチルアンモニウムクロライド、セチルトリメチルアンモニウムクロライド等のアルキルトリメチルアンモニウム塩；ジデシルジメチルアンモニウムクロライド、ジステアリルジメチルンモニウムクロライド等のジアルキルジメチルアンモニウム塩；ドデシルベンジルジメチルアンモニウムクロライト等のアルキルベンジルジメチルアンモニウム塩；等の四級アンモニウム塩が挙げられる。これらカチオン系界面活性剤は、１種単独で用いてもよく、２種以上を併用してもよい。 Specific examples of cationic surfactants include alkyl benzyl methyl ammonium salts such as dodecyl benzyl methyl ammonium chloride; alkyl trimethyl ammonium salts such as dodecyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, and cetyl trimethyl ammonium chloride; dialkyl dimethyl ammonium salts such as didecyl dimethyl ammonium chloride and distearyl dimethyl ammonium chloride; and alkyl benzyl dimethyl ammonium salts such as dodecyl benzyl dimethyl ammonium chlorite; and quaternary ammonium salts. These cationic surfactants may be used alone or in combination of two or more.
（任意の分散剤）
重合の安定性を向上させるため、本発明の効果を阻害しない範囲で、任意の分散剤を用いてもよい。任意の分散剤としては、例えば以下のものが挙げられる。
有機系分散剤としては、ポリビニルアルコール、セルロース、ポリビニルピロリドン等が挙げられる。
無機系分散剤としては、第三リン酸カルシウム、炭酸カルシウム等が挙げられる。
これらの分散剤は、１種単独で用いてもよく、２種以上を併用してもよい。
(Optional Dispersant)
In order to improve the stability of the polymerization, any dispersant may be used within a range that does not impair the effects of the present invention. Examples of the optional dispersant include the following.
Examples of the organic dispersant include polyvinyl alcohol, cellulose, and polyvinylpyrrolidone.
Examples of inorganic dispersants include calcium tertiary phosphate and calcium carbonate.
These dispersants may be used alone or in combination of two or more kinds.
（分散媒）
分散媒はイオン交換水等の公知の水を単独で用いてもよく、適宜、アルコール等の水と混和する公知の溶媒を併用してもよい。
「水を主体とした分散媒」とは、本発明の目的および効果を阻害しない範囲においては特に限定されないが、分散媒１００質量％中の水が５０質量％以上であってよく、７０質量％以上であってよく、９０質量％以上であってもよく、分散媒が水のみであってもよい。
(Dispersion medium)
As the dispersion medium, known water such as ion-exchanged water may be used alone, or a known solvent miscible with water such as alcohol may be used in combination as appropriate.
The term "dispersion medium mainly composed of water" is not particularly limited as long as it does not impair the object and effect of the present invention, but the water content of 100% by mass of the dispersion medium may be 50% by mass or more, 70% by mass or more, or 90% by mass or more, or the dispersion medium may be only water.
なお、本明細書においては、界面活性剤と同様に、分散媒、溶媒として用いる水を「第１の水」、「第２の水」と呼ぶことがある。
例えば、２回の工程に分けて、水を添加する際に、２回の工程で水を区別して示す場合に、理解を容易にするために、「第１の水」、「第２の水」のように呼ぶことがある。
In this specification, like the surfactant, the water used as a dispersion medium or a solvent may be referred to as "first water" or "second water".
For example, when water is added in two separate steps, the water may be referred to as "first water" and "second water" to distinguish between the two steps for ease of understanding.
［中空樹脂粒子の製造方法（第一実施形態）］
第一実施形態に係る中空樹脂粒子の製造方法では、連続相を水、分散相を重合性単量体とした懸濁液を、ホモミキサー等の撹拌機を用いた撹拌によって製造し、その後重合する。詳細には、以下の通りである。
（工程１）
水中に界面活性剤Ａを混合した界面活性剤Ａ－水混合液（第１混合液）を、例えば、ホモミキサー等の撹拌機を備え付けた容器に入れる。界面活性剤Ａ－水混合液を、撹拌機を用いて攪拌し、攪拌された界面活性剤Ａ－水混合液に、油溶性重合開始剤と重合性単量体との混合液（第２混合液）を添加する。
これにより、界面活性剤Ａ－水混合液中に、油溶性重合開始剤と重合性単量体との混合液を分散させてＯ／Ｗ（ｏｉｌ ｉｎ ｗａｔｅｒ）型の懸濁液（連続相が水となり、分散相が重合性単量体となるように調製された懸濁液、水中に重合性単量体が分散した分散液）を製造する。
換言すれば、本実施形態においては、前記懸濁液を調製する際に、前記界面活性剤Ａおよび前記水を含む第１混合液と、前記重合性単量体および前記油溶性重合開始剤を含む第２混合液を準備し、前記第１混合液に、前記第２混合液を加えて、水中に重合性単量体を分散させることにより、前記懸濁液を調製することができる。
（工程２）
その後、前記懸濁液を重合する。
これにより中空樹脂粒子を得ることができる。
[Method for producing hollow resin particles (first embodiment)]
In the method for producing hollow resin particles according to the first embodiment, a suspension containing water as a continuous phase and a polymerizable monomer as a dispersed phase is produced by stirring using a stirrer such as a homomixer, and then polymerized. The details are as follows.
(Step 1)
A surfactant A-water mixed liquid (first mixed liquid) obtained by mixing surfactant A in water is placed in a container equipped with a stirrer such as a homomixer. The surfactant A-water mixed liquid is stirred using the stirrer, and a mixed liquid (second mixed liquid) of an oil-soluble polymerization initiator and a polymerizable monomer is added to the stirred surfactant A-water mixed liquid.
In this way, a mixture of an oil-soluble polymerization initiator and a polymerizable monomer is dispersed in a surfactant A-water mixture to produce an O/W (oil in water) type suspension (a suspension prepared so that the continuous phase is water and the dispersed phase is the polymerizable monomer, a dispersion in which the polymerizable monomer is dispersed in water).
In other words, in the present embodiment, when preparing the suspension, a first mixed liquid containing the surfactant A and the water, and a second mixed liquid containing the polymerizable monomer and the oil-soluble polymerization initiator are prepared, and the second mixed liquid is added to the first mixed liquid to disperse the polymerizable monomer in water, thereby preparing the suspension.
(Step 2)
The suspension is then polymerized.
In this way, hollow resin particles can be obtained.
第一実施形態によって得られる中空樹脂粒子は、内部に複数の空孔を有し、表面に凹凸構造を有する。中空樹脂粒子の断面を、走査型電子顕微鏡（ＳＥＭ）により観察すると、粒子内部が多孔質構造となっていることが確認できる。 The hollow resin particles obtained by the first embodiment have multiple voids inside and an uneven surface structure. When the cross section of the hollow resin particles is observed with a scanning electron microscope (SEM), it can be confirmed that the inside of the particles has a porous structure.
［中空樹脂粒子の製造方法（第二実施形態）］
第二実施形態に係る中空樹脂粒子の製造方法は、詳細には、以下の通りである。
（工程１）
油溶性重合開始剤と重合性単量体と界面活性剤Ａの混合液（油溶性重合開始剤－重合性単量体－界面活性剤Ａ混合液、第３混合液）を調製し、油溶性重合開始剤－重合性単量体－界面活性剤Ａ混合液をホモミキサー等の撹拌機を用いて攪拌する。攪拌された油溶性重合開始剤－重合性単量体－界面活性剤Ａ混合液中に水（第１の水）を分散させて、連続相を重合性単量体、分散相を水とした分散液（Ｗ／Ｏ型（ｗａｔｅｒ ｉｎ ｏｉｌ型）の分散液）を調製する。
すなわち、油溶性重合開始剤－重合性単量体－界面活性剤Ａ混合液中に水が分散した分散液を得る。
（工程２）
工程１の後、第２の界面活性剤または任意の分散剤と水（第２の水）との混合液（第４混合液）を、撹拌機で撹拌中の上記分散液に加えることにより、連続相が水、分散相が重合性単量体となるよう相転換（分散相転換）をした懸濁液（Ｗ／Ｏ／Ｗ型（ｗａｔｅｒ ｉｎ ｏｉｌ ｉｎ ｗａｔｅｒ型）の懸濁液）を製造する。
すなわち、連続相が水となり、分散層が重合性単量体となるように調製された（水に重合性単量体が分散した）懸濁液を得る。
換言すれば、本実施形態においては、前記懸濁液を調製する際に、（工程１）として、前記界面活性剤と前記重合性単量体と前記油溶性重合開始剤とを含む第３混合液と、前記水と、を準備し、前記第３混合液に水を加え、（工程２）としてさらに第２の界面活性剤または任意の分散剤と水とを含む第４混合液を前記第３混合液に添加することにより前記懸濁液を調製することができる。
（工程３）
さらに、（工程２）の後、前記懸濁液を重合する。
これにより中空樹脂粒子を得ることができる。
[Method for producing hollow resin particles (second embodiment)]
The method for producing hollow resin particles according to the second embodiment is as follows in detail.
(Step 1)
A mixed liquid of an oil-soluble polymerization initiator, a polymerizable monomer, and a surfactant A (oil-soluble polymerization initiator-polymerizable monomer-surfactant A mixed liquid, third mixed liquid) is prepared, and the oil-soluble polymerization initiator-polymerizable monomer-surfactant A mixed liquid is stirred using a stirrer such as a homomixer. Water (first water) is dispersed in the stirred oil-soluble polymerization initiator-polymerizable monomer-surfactant A mixed liquid to prepare a dispersion in which the continuous phase is the polymerizable monomer and the dispersed phase is water (W/O type (water in oil) type dispersion).
That is, a dispersion in which water is dispersed in a mixture of an oil-soluble polymerization initiator, a polymerizable monomer and surfactant A is obtained.
(Step 2)
After step 1, a mixture (fourth mixture) of a second surfactant or an arbitrary dispersant and water (second water) is added to the above dispersion being stirred with a stirrer, thereby producing a suspension in which phase inversion (dispersed phase inversion) has been performed so that the continuous phase is water and the dispersed phase is a polymerizable monomer (a W/O/W (water in oil in water) type suspension).
That is, a suspension is obtained in which the continuous phase is water and the dispersed phase is the polymerizable monomer (the polymerizable monomer is dispersed in water).
In other words, in the present embodiment, when preparing the suspension, in (step 1), a third mixed liquid containing the surfactant, the polymerizable monomer, and the oil-soluble polymerization initiator, and water are prepared, water is added to the third mixed liquid, and in (step 2), a fourth mixed liquid containing a second surfactant or an optional dispersant, and water is further added to the third mixed liquid, thereby preparing the suspension.
(Step 3)
Furthermore, after (step 2), the suspension is polymerized.
In this way, hollow resin particles can be obtained.
第二実施形態によって得られる中空樹脂粒子は、内部に複数の空孔を有し、表面が平滑である（凹凸構造を有さない）。中空樹脂粒子の断面を、走査型電子顕微鏡（ＳＥＭ）により観察すると、粒子内部が多孔質構造となっていることが確認できる。 The hollow resin particles obtained by the second embodiment have multiple voids inside and a smooth surface (no uneven structure). When the cross section of the hollow resin particles is observed with a scanning electron microscope (SEM), it can be confirmed that the inside of the particle has a porous structure.
なお、中実樹脂粒子は、例えば、界面活性剤Ａの代わりに、界面活性剤Ａ以外の界面活性剤を用いる他は、中空樹脂粒子と同様の製造方法により製造できる。 The solid resin particles can be produced by the same method as the hollow resin particles, except that, for example, a surfactant other than surfactant A is used instead of surfactant A.
〔貼り合わせ方法〕
本発明の一実施形態に係る貼り合わせ方法は、少なくとも一方が透明な第１の基材および第２の基材の間に前記した樹脂組成物を配置し、樹脂組成物のヘイズが低下するだけの圧力を掛けて第１の基材と第２の基材とを圧着する。圧着は、室温下での圧着でもよく熱圧着でもよい。
[Lamination method]
In a lamination method according to an embodiment of the present invention, the resin composition is placed between a first substrate and a second substrate, at least one of which is transparent, and the first substrate and the second substrate are pressure-bonded to each other by applying a pressure sufficient to reduce the haze of the resin composition. The pressure bonding may be performed at room temperature or by thermal compression bonding.
第１の基材および第２の基材は、いずれか一方が透明で他方が不透明でもよく、両方が透明でもよい。第１の基材および第２の基材の少なくとも一方が透明であることで、透明な基材を通して、樹脂組成物のヘイズの低下を視認できる。
透明な基材の透明度は、樹脂組成物のヘイズの変化を視認可能であればよいが、例えば、全光線透過率が８０％以上であることが好ましい。
Either the first substrate or the second substrate may be transparent and the other may be opaque, or both may be transparent. When at least one of the first substrate and the second substrate is transparent, the reduction in haze of the resin composition can be visually confirmed through the transparent substrate.
The transparency of the transparent substrate may be such that a change in haze of the resin composition can be visually confirmed, and it is preferable that the total light transmittance is, for example, 80% or more.
第１の基材、第２の基材それぞれの材質としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリカーボネート等の樹脂、ガラス、セラミックス等が挙げられる。
第１の基材、第２の基材それぞれの形状としては、例えば、フィルム状、板状、その他の各種の不定形状が挙げられる。
第１の基材および第２の基材それぞれの材質、形状等は同一でも異なってもよい。
Examples of the material for each of the first and second substrates include resins such as polyethylene terephthalate (PET) and polycarbonate, glass, and ceramics.
The shape of each of the first substrate and the second substrate may be, for example, a film, a plate, or any other various indefinite shape.
The first and second substrates may be the same or different in terms of material, shape, etc.
第１の基材および第２の基材の間に樹脂組成物を配置する方法としては、例えば、第１の基材の表面に樹脂組成物を塗工し、必要に応じて乾燥して皮膜を形成し、皮膜の上に第２の基材を貼り合わせる方法が挙げられる。このときの貼り合わせは、中空樹脂粒子内部の複数の空孔が消失しない条件で行う。
皮膜の膜厚は、特に限定されないが、例えば、１０～３０μｍである。
Examples of the method for disposing the resin composition between the first substrate and the second substrate include a method in which the resin composition is applied to the surface of the first substrate, dried as necessary to form a film, and the second substrate is laminated onto the film. The lamination is performed under conditions in which the multiple pores inside the hollow resin particles are not lost.
The thickness of the coating is not particularly limited, but is, for example, 10 to 30 μm.
圧着圧力は、例えば、０．１～１．０ＭＰａである。
圧着時間は、圧着圧力によっても異なるが、例えば、５～２０分間である。
熱圧着の場合の熱圧着温度は、例えば、８０～１５０℃である。
圧力を掛ける前後の皮膜のヘイズの差（圧力を掛ける前のヘイズ－圧力を掛けた後のヘイズ）は、３０％以上であることが好ましく、６０％以上であることがより好ましい。この差が前記下限値以上であれば、圧力履歴を確認しやすい。
The pressure for compression is, for example, 0.1 to 1.0 MPa.
The bonding time varies depending on the bonding pressure, but is, for example, 5 to 20 minutes.
In the case of thermocompression bonding, the thermocompression temperature is, for example, 80 to 150°C.
The difference in haze of the coating before and after application of pressure (haze before application of pressure - haze after application of pressure) is preferably 30% or more, and more preferably 60% or more. If this difference is equal to or more than the lower limit, it is easy to check the pressure history.
以下、本発明を実施例によって具体的に説明するが、本発明はこれらに限定されない。 The present invention will be specifically described below with reference to examples, but the present invention is not limited to these.
＜実施例１＞
（中空樹脂粒子の調製）
以下に示す手順にて、表１に示す組成にて、中空樹脂粒子を調製した。
重合性単量体であるメチルメタクリレートの６０質量部、ｎ－ブチルアクリレートの３０部、エチレングリコールジメタクリレートの１０質量部、界面活性剤Ａである第一工業製薬製ノイゲンＸＬ－４００Ｄの０．２質量部、油溶性開始剤である２，２’－アゾビス（２－メチルブチロニトリル）の１．０質量部を混合し、混合液（第３混合液）を調製した。
第３混合液をホモミキサーに入れて攪拌し、攪拌された第３混合液に水（第１の水）の３０質量部を添加した。これにより、連続相を重合性単量体、分散層を水とした分散液（Ｗ／Ｏ型（ｗａｔｅｒ ｉｎ ｏｉｌ型）の分散液）を得た。
別途、水（第２の水）の２７０質量部、ポリビニルアルコールの１．０質量部を混合し、混合液（第４混合液）を調製した。
次に、第４混合液を、先に調製した上記分散液に加えて攪拌し、連続相が水、分散層が重合性単量体となるよう相転換をした懸濁液（Ｗ／Ｏ／Ｗ型（ｗａｔｅｒ ｉｎ ｏｉｌ ｉｎ ｗａｔｅｒ型）の懸濁液）を調製した。
得られた懸濁液を、攪拌機、コンデンサ、温度計、窒素導入管を付した４口フラスコに投入し、窒素封入下で７５℃まで昇温度し、７５℃で４時間反応させた。その度、得られた中空樹脂粒子水分散液をろ過し、５００質量部の水で洗浄後、６０℃で１２時間乾燥して中空樹脂粒子を得た。
Example 1
(Preparation of hollow resin particles)
Hollow resin particles were prepared according to the following procedure and the composition shown in Table 1.
A mixed liquid (third mixed liquid) was prepared by mixing 60 parts by mass of methyl methacrylate as a polymerizable monomer, 30 parts by mass of n-butyl acrylate, 10 parts by mass of ethylene glycol dimethacrylate, 0.2 parts by mass of Noigen XL-400D manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as surfactant A, and 1.0 part by mass of 2,2'-azobis(2-methylbutyronitrile) as an oil-soluble initiator.
The third mixed solution was put into a homomixer and stirred, and 30 parts by mass of water (first water) was added to the stirred third mixed solution, thereby obtaining a dispersion solution (a W/O (water in oil) type dispersion solution) in which the continuous phase was the polymerizable monomer and the dispersed phase was water.
Separately, 270 parts by mass of water (second water) and 1.0 part by mass of polyvinyl alcohol were mixed to prepare a mixed liquid (fourth mixed liquid).
Next, the fourth mixed liquid was added to the above dispersion liquid previously prepared and stirred, to prepare a suspension in which the phase was inverted so that the continuous phase was water and the dispersed phase was the polymerizable monomer (a W/O/W (water in oil in water) type suspension).
The obtained suspension was placed in a four-neck flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube, and the temperature was raised to 75° C. under nitrogen sealing, and the reaction was carried out for 4 hours at 75° C. After each reaction, the obtained aqueous dispersion of hollow resin particles was filtered, washed with 500 parts by mass of water, and then dried at 60° C. for 12 hours to obtain hollow resin particles.
中空樹脂粒子について、走査型電子顕微鏡（ＳＥＭ、日本電子社製）を用いて、粒子表面と粒子断面とを観察したところ、粒子表面は平滑であり、粒子断面に多孔質構造が観察された。図１に、この中空樹脂粒子の粒子断面のＳＥＭ像を示す。
示差走査熱量計（ＤＳＣ、島津製作所製）を用いて、中空樹脂粒子のＴｇを測定したところ、Ｔｇは５０℃であった。
レーザー回折式粒度分布測定装置（島津製作所社製）を用いて、中空樹脂粒子の平均粒子径を測定したところ、平均粒子径は８μｍであった。
前記した「１０％変形時の強度」の測定方法に従って、微小圧縮試験機（島津製作所製）にて中空樹脂粒子の２３℃下での１０％変形時の強度（強度ａ）を測定したところ、強度ａは６ＭＰａであった。
When the surface and cross section of the hollow resin particles were observed using a scanning electron microscope (SEM, manufactured by JEOL Ltd.), the particle surface was found to be smooth, and a porous structure was observed on the cross section of the hollow resin particles. Figure 1 shows an SEM image of the cross section of the hollow resin particles.
The Tg of the hollow resin particles was measured using a differential scanning calorimeter (DSC, manufactured by Shimadzu Corporation) and was found to be 50°C.
The average particle size of the hollow resin particles was measured using a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation) and was found to be 8 μm.
According to the above-mentioned method for measuring "strength at 10% deformation", the strength (strength a) of the hollow resin particles at 10% deformation at 23°C was measured using a microcompression tester (manufactured by Shimadzu Corporation), and the strength a was 6 MPa.
（樹脂組成物の調製）
樹脂バインダー溶液（樹脂バインダー：２－エチルへキシルアクリレート（２ＥＨＡ）とアクリル酸（ＡＡ）と２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）との共重合体、２ＥＨＡ／ＡＡ／ＨＥＭＡ＝９４／１／５（質量比）、溶媒：酢酸エチル、固形分濃度：４０質量％）に、先に調製した上記中空樹脂粒子を添加し、樹脂組成物を調製した。樹脂組成物中の中空樹脂粒子の含有量は、樹脂バインダー１００質量％に対して１０質量％とした。
(Preparation of Resin Composition)
The hollow resin particles prepared above were added to a resin binder solution (resin binder: a copolymer of 2-ethylhexyl acrylate (2EHA), acrylic acid (AA) and 2-hydroxyethyl methacrylate (HEMA), 2EHA/AA/HEMA = 94/1/5 (mass ratio), solvent: ethyl acetate, solid content concentration: 40 mass%) to prepare a resin composition. The content of the hollow resin particles in the resin composition was 10 mass% with respect to 100 mass% of the resin binder.
（フィルムの貼り合わせ）
ポリエチレンテレフタレート（ＰＥＴ）フィルムに、先に調製した上記樹脂組成物を塗工し、１００℃で１０分間乾燥して膜厚２０μｍの皮膜を形成した。次に、皮膜の上に別のＰＥＴフィルムを配置し、上から貼り合わせて第一の積層体を得た。次に、第一の積層体全体に、１３０℃、０．５ＭＰａ、５分間の条件で熱圧着処理を施して第二の積層体を得た。
(Laminating the film)
The resin composition prepared above was applied to a polyethylene terephthalate (PET) film and dried at 100° C. for 10 minutes to form a film having a thickness of 20 μm. Next, another PET film was placed on the film and laminated from above to obtain a first laminate. Next, the entire first laminate was subjected to a thermocompression treatment under conditions of 130° C., 0.5 MPa, and 5 minutes to obtain a second laminate.
（初期ヘイズおよび熱圧着後ヘイズの評価）
上記フィルムの貼り合わせにおいて、ヘイズメーター（村上色彩技術研究所製）により、第一の積層体、第二の積層体それぞれのヘイズを測定し、第一の積層体のヘイズを初期ヘイズ、第二の積層体のヘイズを熱圧着後ヘイズとした。結果を表１に示す。
(Evaluation of initial haze and haze after heat and pressure bonding)
In laminating the above films, the haze of each of the first laminate and the second laminate was measured using a haze meter (manufactured by Murakami Color Research Laboratory), and the haze of the first laminate was taken as the initial haze, and the haze of the second laminate was taken as the haze after thermocompression bonding. The results are shown in Table 1.
なお、樹脂組成物の代わりに樹脂バインダー溶液のみを用いて第二の積層体を作成し、ヘイズメーター（村上色彩技術研究所製）により全光線透過率及びヘイズを測定したところ、全光線透過率は８９％、ヘイズは４％であった。 A second laminate was made using only the resin binder solution instead of the resin composition, and the total light transmittance and haze were measured using a haze meter (manufactured by Murakami Color Research Laboratory). The total light transmittance was 89% and the haze was 4%.
＜実施例２＞
（中空樹脂粒子の調製）
重合性単量体を、メチルメタクリレートを６５質量部、エチルアクリレートを２５部、エチレングリコールジメタクリレートを１０質量部とした他は実施例１と同様に、中空樹脂粒子を調製した。
中空樹脂粒子について、実施例１と同様に、ＳＥＭを用いて粒子表面と粒子断面とを観察したところ、粒子表面は平滑であり、粒子断面に多孔質構造が観察された。中空樹脂粒子の特性を表１に示す。
Example 2
(Preparation of hollow resin particles)
Hollow resin particles were prepared in the same manner as in Example 1, except that the polymerizable monomers were 65 parts by mass of methyl methacrylate, 25 parts by mass of ethyl acrylate, and 10 parts by mass of ethylene glycol dimethacrylate.
The particle surfaces and cross sections of the hollow resin particles were observed using an SEM in the same manner as in Example 1. The particle surfaces were found to be smooth, and a porous structure was observed on the cross sections of the hollow resin particles. The properties of the hollow resin particles are shown in Table 1.
（樹脂組成物の調製、フィルムの貼り合わせ、初期ヘイズおよび熱圧着後ヘイズの評価）
中空樹脂粒子を上記中空樹脂粒子に変更した他は実施例１と同様に、樹脂組成物を調製し、フィルムを貼り合わせ、初期ヘイズおよび熱圧着後ヘイズを評価した。結果を表１に示す。
(Preparation of Resin Composition, Lamination of Film, Evaluation of Initial Haze and Haze after Heat and Compression Bonding)
Except for changing the hollow resin particles to the above hollow resin particles, a resin composition was prepared, a film was laminated, and the initial haze and the haze after heat and pressure bonding were evaluated in the same manner as in Example 1. The results are shown in Table 1.
＜実施例３＞
（中空樹脂粒子の調製）
重合性単量体を、メチルメタクリレートを３０質量部、ｎ－ブチルアクリレートを３０部、エチレングリコールジメタクリレートを１０質量部、スチレンを３０部とした他は実施例１と同様に、中空樹脂粒子を調製した。
中空樹脂粒子について、実施例１と同様に、ＳＥＭを用いて粒子表面と粒子断面とを観察したところ、粒子表面は平滑であり、粒子断面に多孔質構造が観察された。中空樹脂粒子の特性を表１に示す。
Example 3
(Preparation of hollow resin particles)
Hollow resin particles were prepared in the same manner as in Example 1, except that the polymerizable monomers were 30 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl acrylate, 10 parts by mass of ethylene glycol dimethacrylate, and 30 parts by mass of styrene.
The particle surfaces and cross sections of the hollow resin particles were observed using an SEM in the same manner as in Example 1. The particle surfaces were found to be smooth, and a porous structure was observed on the cross sections of the hollow resin particles. The properties of the hollow resin particles are shown in Table 1.
（樹脂組成物の調製、フィルムの貼り合わせ、初期ヘイズおよび熱圧着後ヘイズの評価）
中空樹脂粒子を上記中空樹脂粒子に変更した他は実施例１と同様に、樹脂組成物を調製し、フィルムを貼り合わせを行った。初期ヘイズおよび熱圧着後ヘイズを表１に示す。
(Preparation of Resin Composition, Lamination of Film, Evaluation of Initial Haze and Haze after Heat and Compression Bonding)
Except for changing the hollow resin particles to the above hollow resin particles, a resin composition was prepared and a film was laminated in the same manner as in Example 1. The initial haze and the haze after thermocompression bonding are shown in Table 1.
＜実施例４＞
（中空樹脂粒子の調製）
重合性単量体を、メチルメタクリレートを１０質量部、エチレングリコールジメタクリレートを１０質量部、ｎ－ブチルメタクリレートを８０部とし、界面活性剤ＡをノイゲンＸＬ－４００Ｄから花王製のエマルゲン３５０に変更した他は実施例１と同様に、中空樹脂粒子を調製した。
中空樹脂粒子について、実施例１と同様に、ＳＥＭを用いて粒子表面と粒子断面とを観察したところ、粒子表面は平滑であり、粒子断面に多孔質構造が観察された。中空樹脂粒子の特性を表１に示す。
Example 4
(Preparation of hollow resin particles)
Hollow resin particles were prepared in the same manner as in Example 1, except that the polymerizable monomers were 10 parts by mass of methyl methacrylate, 10 parts by mass of ethylene glycol dimethacrylate, and 80 parts by mass of n-butyl methacrylate, and the surfactant A was changed from Noigen XL-400D to Emulgen 350 manufactured by Kao Corporation.
The particle surfaces and cross sections of the hollow resin particles were observed using an SEM in the same manner as in Example 1. The particle surfaces were found to be smooth, and a porous structure was observed on the cross sections of the hollow resin particles. The properties of the hollow resin particles are shown in Table 1.
（樹脂組成物の調製、フィルムの貼り合わせ、初期ヘイズおよび熱圧着後ヘイズの評価）
中空樹脂粒子を上記中空樹脂粒子に変更した他は実施例１と同様に、樹脂組成物を調製し、フィルムを貼り合わせ、初期ヘイズおよび熱圧着後ヘイズを評価した。結果を表１に示す。
(Preparation of Resin Composition, Lamination of Film, Evaluation of Initial Haze and Haze after Heat and Compression Bonding)
Except for changing the hollow resin particles to the above hollow resin particles, a resin composition was prepared, a film was laminated, and the initial haze and the haze after heat and pressure bonding were evaluated in the same manner as in Example 1. The results are shown in Table 1.
＜実施例５＞
（中空樹脂粒子の調製）
重合性単量体を、メチルメタクリレートを８０質量部、エチレングリコールジメタクリレートを１０質量部、ｎ－ブチルメタクリレートを１０部とした他は実施例１と同様に、中空樹脂粒子を調製した。
中空樹脂粒子について、実施例１と同様に、ＳＥＭを用いて粒子表面と粒子断面とを観察したところ、粒子表面は平滑であり、粒子断面に多孔質構造が観察された。中空樹脂粒子の特性を表１に示す。
Example 5
(Preparation of hollow resin particles)
Hollow resin particles were prepared in the same manner as in Example 1, except that the polymerizable monomers were 80 parts by mass of methyl methacrylate, 10 parts by mass of ethylene glycol dimethacrylate, and 10 parts by mass of n-butyl methacrylate.
The particle surfaces and cross sections of the hollow resin particles were observed using an SEM in the same manner as in Example 1. The particle surfaces were found to be smooth, and a porous structure was observed on the cross sections of the hollow resin particles. The properties of the hollow resin particles are shown in Table 1.
（樹脂組成物の調製、フィルムの貼り合わせ、初期ヘイズおよび熱圧着後ヘイズの評価）
中空樹脂粒子を上記中空樹脂粒子に変更した他は実施例１と同様に、樹脂組成物を調製し、フィルムを貼り合わせ、初期ヘイズおよび熱圧着後ヘイズを評価した。結果を表１に示す。
(Preparation of Resin Composition, Lamination of Film, Evaluation of Initial Haze and Haze after Heat and Compression Bonding)
Except for changing the hollow resin particles to the above hollow resin particles, a resin composition was prepared, a film was laminated, and the initial haze and the haze after heat and pressure bonding were evaluated in the same manner as in Example 1. The results are shown in Table 1.
＜実施例６＞
（中空樹脂粒子の調製）
ノイゲンＸＬ－４００Ｄの配合量を０．２質量部から０．０２質量部に変更した他は実施例１と同様に、中空樹脂粒子を調製した。
中空樹脂粒子について、実施例１と同様に、ＳＥＭを用いて粒子表面と粒子断面とを観察したところ、粒子表面は平滑であり、粒子断面に多孔質構造が観察されたが、実施例１に比べ、粒子断面に占める空孔の面積の割合が少なかった。中空樹脂粒子の特性を表１に示す。
Example 6
(Preparation of hollow resin particles)
Hollow resin particles were prepared in the same manner as in Example 1, except that the blending amount of Noigen XL-400D was changed from 0.2 parts by mass to 0.02 parts by mass.
The particle surfaces and cross sections of the hollow resin particles were observed using an SEM in the same manner as in Example 1. The particle surfaces were smooth and a porous structure was observed on the cross sections of the particles, but the proportion of the area of the pores in the cross sections of the particles was smaller than in Example 1. The properties of the hollow resin particles are shown in Table 1.
（樹脂組成物の調製、フィルムの貼り合わせ、初期ヘイズおよび熱圧着後ヘイズの評価）
中空樹脂粒子を上記中空樹脂粒子に変更した他は実施例１と同様に、樹脂組成物を調製し、フィルムを貼り合わせ、初期ヘイズおよび熱圧着後ヘイズを評価した。結果を表１に示す。
(Preparation of Resin Composition, Lamination of Film, Evaluation of Initial Haze and Haze after Heat and Compression Bonding)
Except for changing the hollow resin particles to the above hollow resin particles, a resin composition was prepared, a film was laminated, and the initial haze and the haze after heat and pressure bonding were evaluated in the same manner as in Example 1. The results are shown in Table 1.
＜比較例１＞
（樹脂粒子の調製）
ノイゲンＸＬ－４００Ｄの０．２質量部を界面活性剤Ａ以外の界面活性剤であるＡＤＥＫＡ製のアデカリアソープＳＲ－１０の１質量部に変更した他は実施例１と同様に、樹脂粒子を調製した。
樹脂粒子について、実施例１と同様に、ＳＥＭを用いて粒子表面と粒子断面とを観察したところ、樹脂粒子は中実の単純粒子であった。すなわち、樹脂粒子は、粒子表面は平滑であり、粒子断面に多孔質構造は観察されなかった。樹脂粒子の特性を表１に示す。
<Comparative Example 1>
(Preparation of Resin Particles)
Resin particles were prepared in the same manner as in Example 1, except that 0.2 parts by mass of Noigen XL-400D was changed to 1 part by mass of Adeka Reasoap SR-10 manufactured by ADEKA, which is a surfactant other than surfactant A.
The resin particles were observed on the surface and cross section using an SEM in the same manner as in Example 1, and were found to be solid simple particles. That is, the resin particles had smooth surfaces and no porous structure was observed on the cross section. The properties of the resin particles are shown in Table 1.
（樹脂組成物の調製、フィルムの貼り合わせ、初期ヘイズおよび熱圧着後ヘイズの評価）
中空樹脂粒子を上記樹脂粒子に変更した他は実施例１と同様に、樹脂組成物を調製し、フィルムを貼り合わせ、初期ヘイズおよび熱圧着後ヘイズを評価した。結果を表１に示す。
(Preparation of Resin Composition, Lamination of Film, Evaluation of Initial Haze and Haze after Heat and Compression Bonding)
Except for changing the hollow resin particles to the above resin particles, a resin composition was prepared, a film was laminated, and the initial haze and the haze after heat and pressure bonding were evaluated in the same manner as in Example 1. The results are shown in Table 1.
表１中の略号は下記化合物を示す。
ＭＭＡ:メチルメタアクリレート。
ＢＡ：ｎ－ブチルアクリレート。
ＥＡ：エチルアクリレート。
ＥＧ：エチレングリコールジメタクリレート。
Ｓｔ：スチレン。
ＢＭＡ：ｎ－ブチルメタアクリレート。
開始剤：油溶性重合開始剤。
表１中、各成分の配合量の単位は質量部である。空欄の部分は、その成分を使用していないことを意味する。
表１中、「強度」は、２３℃下での１０％変形時の強度を意味する。
「強度ａ／強度ｂ」は、中空樹脂粒子の強度（強度ａ）の、同一組成の中実樹脂粒子の強度（強度ｂ）に対する割合（％）を意味する。実施例１、６においては、比較例１の樹脂粒子の強度を強度ｂ（１００％）として強度ａ／強度ｂの値を算出した。実施例２～５においては、実施例２～５それぞれの（中空樹脂粒子の調製）においてノイゲンＸＬ－４００Ｄの０．０２質量部をアデカリアソープＳＲ－１０の１質量部に変更して作成した中実樹脂粒子の強度を強度ｂ（１００％）として強度ａ／強度ｂの値を算出した。
The abbreviations in Table 1 represent the following compounds.
MMA: methyl methacrylate.
BA: n-butyl acrylate.
EA: ethyl acrylate.
EG: ethylene glycol dimethacrylate.
St: styrene.
BMA: n-butyl methacrylate.
Initiator: oil-soluble polymerization initiator.
In Table 1, the amount of each component is expressed in parts by mass. A blank space indicates that the component was not used.
In Table 1, "strength" means the strength at 10% deformation at 23°C.
"Strength a/strength b" means the ratio (%) of the strength of a hollow resin particle (strength a) to the strength of a solid resin particle of the same composition (strength b). In Examples 1 and 6, the strength a/strength b value was calculated by taking the strength of the resin particles of Comparative Example 1 as strength b (100%). In Examples 2 to 5, the strength a/strength b value was calculated by taking the strength b (100%) of the strength of solid resin particles prepared by changing 0.02 part by mass of Noigen XL-400D to 1 part by mass of ADEKA REASOAP SR-10 in each of Examples 2 to 5 (preparation of hollow resin particles).
以上に示すように、中空樹脂粒子を含む実施例１～６の樹脂組成物は、圧力が掛かった部分のヘイズが低下しており、ヘイズの変化によって圧力履歴を示すことが確認できた。
これらのうち、強度ａ／強度ｂが８０％以下、強度ａが１５ＭＰａ以下の実施例１～４の樹脂組成物は、初期ヘイズが高く、熱圧着後のヘイズが低く、圧力履歴の視認性に優れていた。
実施例５の樹脂組成物は、強度ａ／強度ｂが８０％以下であるが、強度ａが１５ＭＰａを超えているので、上記の熱圧着処理条件では熱圧着後のヘイズが比較的高かった。しかし、熱圧着処理条件を変更する（例えば圧力を高くする）ことで、熱圧着後のヘイズをより低くできると考えられる。
As described above, in the resin compositions of Examples 1 to 6 containing hollow resin particles, the haze was reduced in the areas where pressure was applied, and it was confirmed that the pressure history was indicated by the change in haze.
Among these, the resin compositions of Examples 1 to 4 in which the strength a/strength b was 80% or less and the strength a was 15 MPa or less had high initial haze, low haze after thermocompression bonding, and excellent visibility of the pressure history.
The resin composition of Example 5 had a strength a/strength b ratio of 80% or less, but the strength a exceeded 15 MPa, so the haze after thermocompression bonding was relatively high under the above thermocompression bonding conditions. However, it is believed that the haze after thermocompression bonding can be reduced by changing the thermocompression bonding conditions (for example, by increasing the pressure).
以上に、本発明の実施形態を説明したが、実施形態における各構成及びそれらの組み合わせ等は一例であり、本発明の趣旨から逸脱しない範囲内で、構成の付加、省略、置換、及びその他の変更が可能である。また、本発明は実施形態によって限定されない。 Although the embodiments of the present invention have been described above, each configuration and their combinations in the embodiments are merely examples, and additions, omissions, substitutions, and other modifications of the configurations are possible without departing from the spirit of the present invention. Furthermore, the present invention is not limited to the embodiments.
本発明の樹脂組成物は、圧力が掛かった部分のヘイズが低下するので、少なくとも一方が透明な基材同士の貼り合わせにおいて圧力履歴を示すことができる。したがって、本発明の樹脂組成物によれば、例えばヒートシール等の熱圧着を要する接着面において、処理ムラを可視化できる。
また、本発明の樹脂組成物は、複雑な形状の基材を接着面に貼り合わせる際に、圧着により中空樹脂粒子の変形を伴うことで、接着面と樹脂との間に生じた微細な隙間を埋め、接着力を高めるといった効果が期待できる。
本発明の樹脂組成物は、粘着剤（感圧接着剤）、ヒートシール剤等として使用できる。
The resin composition of the present invention reduces haze in the area where pressure is applied, and can therefore show the pressure history when two substrates, at least one of which is transparent, are bonded together. Therefore, the resin composition of the present invention can visualize processing unevenness on an adhesive surface that requires thermocompression bonding, such as heat sealing.
In addition, when the resin composition of the present invention is used to bond a substrate having a complex shape to an adhesive surface, the hollow resin particles are deformed by pressure bonding, which is expected to have the effect of filling minute gaps that occur between the adhesive surface and the resin, thereby increasing the adhesive strength.
The resin composition of the present invention can be used as an adhesive (pressure-sensitive adhesive), a heat sealing agent, or the like.
Claims (11)
加圧されたときに前記樹脂粒子が変形し、前記複数の空孔の体積が減少して圧力がかかった部分のヘイズが低下することを特徴とする樹脂組成物。
Ｔ１Ｏ－（ＲＯ）ｎ（ＥＯ）ｍ－Ｔ２ …（２）
式（２）中、Ｔ１は水素原子、炭素数１～１８のアルキル基、または炭素数２～１８のアルケニル基であり、Ｔ２は水素原子、スルホン酸基、スルホン酸塩基、カルボン酸基、カルボン酸塩基、リン酸基、リン酸塩基、アミノ基、またはアンモニウム基であり、ＲＯは炭素数３～１８のオキシアルキレン基であり、ｎは１～５０の整数であり、ＥＯはオキシエチレン基を示し、ｍは０～２００の整数である。 The present invention relates to a method for producing a polymerizable composition comprising: a resin binder; and resin particles dispersed in the resin binder, the resin particles being hollow resin particles having a plurality of pores therein, the hollow resin particles being obtained by polymerizing droplets of a polymerizable monomer having a polymerizable unsaturated hydrocarbon group, the droplets having a plurality of water droplets entrapped therein , using a surfactant A represented by the following formula (2) as a dispersant, the polymerizable monomer including at least the (meth)acrylic monomer out of a (meth)acrylic monomer and an aromatic vinyl monomer,
A resin composition characterized in that, when pressurized, the resin particles are deformed, the volume of the plurality of pores is reduced, and the haze of the portion to which pressure is applied is reduced.
T 1 O-(RO)n(EO)m-T 2 ... (2)
In formula (2), T1 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms; T2 is a hydrogen atom, a sulfonic acid group, a sulfonate group, a carboxylate group, a carboxylate group, a phosphoric acid group, a phosphate group, an amino group, or an ammonium group; RO is an oxyalkylene group having 3 to 18 carbon atoms; n is an integer of 1 to 50; EO is an oxyethylene group; and m is an integer of 0 to 200.
２３℃下での１０％変形時の強度が、同一組成の中実樹脂粒子の前記強度の８０％以下であることを特徴とする樹脂粒子。
Ｔ１Ｏ－（ＲＯ）ｎ（ＥＯ）ｍ－Ｔ２ …（２）
式（２）中、Ｔ１は水素原子、炭素数１～１８のアルキル基、または炭素数２～１８のアルケニル基であり、Ｔ２は水素原子、スルホン酸基、スルホン酸塩基、カルボン酸基、カルボン酸塩基、リン酸基、リン酸塩基、アミノ基、またはアンモニウム基であり、ＲＯは炭素数３～１８のオキシアルキレン基であり、ｎは１～５０の整数であり、ＥＯはオキシエチレン基を示し、ｍは０～２００の整数である。 The present invention relates to hollow resin particles having a plurality of voids therein, which are obtained by polymerizing droplets of a polymerizable monomer having a polymerizable unsaturated hydrocarbon group, the droplets having a plurality of water droplets entrapped therein, using a surfactant A represented by the following formula (2) as a dispersant, the polymerizable monomer including at least the (meth)acrylic monomer out of a (meth)acrylic monomer and an aromatic vinyl monomer:
A resin particle having a strength at 23° C. under 10% deformation of 80% or less of the strength of a solid resin particle having the same composition.
T 1 O-(RO)n(EO)m-T 2 ... (2)
In formula (2), T1 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms; T2 is a hydrogen atom, a sulfonic acid group, a sulfonate group, a carboxylate group, a carboxylate group, a phosphoric acid group, a phosphate group, an amino group, or an ammonium group; RO is an oxyalkylene group having 3 to 18 carbon atoms; n is an integer of 1 to 50; EO is an oxyethylene group; and m is an integer of 0 to 200.
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