JP5677922B2 - Curing agent and / or curing accelerator encapsulating capsule, and thermosetting resin composition - Google Patents
Curing agent and / or curing accelerator encapsulating capsule, and thermosetting resin composition Download PDFInfo
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- JP5677922B2 JP5677922B2 JP2011211404A JP2011211404A JP5677922B2 JP 5677922 B2 JP5677922 B2 JP 5677922B2 JP 2011211404 A JP2011211404 A JP 2011211404A JP 2011211404 A JP2011211404 A JP 2011211404A JP 5677922 B2 JP5677922 B2 JP 5677922B2
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- curing agent
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- curing accelerator
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- 239000003795 chemical substances by application Substances 0.000 title claims description 114
- 239000002775 capsule Substances 0.000 title claims description 81
- 239000011342 resin composition Substances 0.000 title claims description 27
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 38
- 239000011737 fluorine Substances 0.000 claims description 38
- -1 siloxane compound Chemical class 0.000 claims description 32
- 239000011148 porous material Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 37
- 239000002904 solvent Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 25
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 23
- 239000011259 mixed solution Substances 0.000 description 21
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 18
- 239000012736 aqueous medium Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 239000003822 epoxy resin Substances 0.000 description 15
- 229920000647 polyepoxide Polymers 0.000 description 15
- 239000000839 emulsion Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 125000001165 hydrophobic group Chemical group 0.000 description 8
- 229920001169 thermoplastic Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 7
- 238000005338 heat storage Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920006254 polymer film Polymers 0.000 description 7
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000011354 acetal resin Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229920006324 polyoxymethylene Polymers 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 208000034189 Sclerosis Diseases 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229920000592 inorganic polymer Polymers 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000006359 acetalization reaction Methods 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- PBODPHKDNYVCEJ-UHFFFAOYSA-M 1-benzyl-3-dodecyl-2-methylimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCN1C=C[N+](CC=2C=CC=CC=2)=C1C PBODPHKDNYVCEJ-UHFFFAOYSA-M 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- PAPPEKHULAQSEJ-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)propanenitrile Chemical compound N#CC(C)C1=NC=CN1 PAPPEKHULAQSEJ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- AVMSWPWPYJVYKY-UHFFFAOYSA-N 2-Methylpropyl formate Chemical compound CC(C)COC=O AVMSWPWPYJVYKY-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- HJICXYKHCXZZOD-UHFFFAOYSA-N C(#N)C(C)C=1N=C(NC1)C.C(C1=CC=CC=C1)N1C(=NC=C1)C1=CC=CC=C1 Chemical compound C(#N)C(C)C=1N=C(NC1)C.C(C1=CC=CC=C1)N1C(=NC=C1)C1=CC=CC=C1 HJICXYKHCXZZOD-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000007877 V-601 Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JWFDXYFGKKNJNN-UHFFFAOYSA-N diethoxy(2,2,2-trifluoroethoxy)silane Chemical compound FC(CO[SiH](OCC)OCC)(F)F JWFDXYFGKKNJNN-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- JKGQTAALIDWBJK-UHFFFAOYSA-N fluoro(trimethoxy)silane Chemical compound CO[Si](F)(OC)OC JKGQTAALIDWBJK-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003203 poly(dimethylsilylene-co-phenylmethyl- silylene) polymer Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001709 polysilazane 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XVYIJOWQJOQFBG-UHFFFAOYSA-N triethoxy(fluoro)silane Chemical compound CCO[Si](F)(OCC)OCC XVYIJOWQJOQFBG-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Description
本発明は、硬化性樹脂組成物に配合された場合に優れた熱保存安定性及び速硬化性を発揮することができる硬化剤及び／又は硬化促進剤内包カプセルに関する。また、本発明は、該硬化剤及び／又は硬化促進剤内包カプセルを含有する熱硬化性樹脂組成物に関する。 The present invention relates to a curing agent and / or curing accelerator-encapsulating capsule capable of exhibiting excellent thermal storage stability and rapid curability when blended in a curable resin composition. Moreover, this invention relates to the thermosetting resin composition containing this hardening | curing agent and / or hardening accelerator inclusion capsule.
エポキシ樹脂は、接着剤、シール剤、コーティング剤等の様々な用途に用いられている。一般に、エポキシ樹脂には、硬化反応を進行させるための成分として硬化剤が、また、硬化性を向上させるための成分として硬化促進剤が添加される。特に、硬化剤又は硬化促進剤とエポキシ樹脂とを安定な一液にするために、潜在性をもたせた硬化剤又は硬化促進剤が多用されている。このような潜在性硬化剤又は硬化促進剤には、配合されたエポキシ樹脂組成物の安定性を低下させることなく、硬化時には速やかに硬化を進行させることが求められている。 Epoxy resins are used in various applications such as adhesives, sealants, and coating agents. Generally, a curing agent is added to the epoxy resin as a component for causing the curing reaction to proceed, and a curing accelerator is added as a component for improving the curability. In particular, in order to make a curing agent or a curing accelerator and an epoxy resin into a stable liquid, a latent curing agent or a curing accelerator is frequently used. Such latent curing agents or curing accelerators are required to rapidly cure during curing without reducing the stability of the blended epoxy resin composition.
潜在性硬化剤又は硬化促進剤としては、硬化剤又は硬化促進剤をシェルで被覆したマイクロカプセル型硬化剤が知られている。
例えば、特許文献１及び２には、アミンアダクト等のエポキシ樹脂用硬化剤をエポキシ樹脂により被覆した硬化剤が記載されている。しかしながら、シェルが熱硬化性樹脂であることから、これらの硬化剤は、コア剤が膨張しても熱硬化性樹脂からなるシェルが破壊されにくく、硬化反応が遅いという問題があった。また、熱硬化性樹脂の代わりに熱可塑性樹脂からなるシェルを用いた硬化剤も検討されているが、依然としてエポキシ樹脂組成物の安定性及び速硬化性を充分に両立するには至っていない。
As a latent curing agent or curing accelerator, a microcapsule type curing agent in which a curing agent or a curing accelerator is coated with a shell is known.
For example, Patent Documents 1 and 2 describe a curing agent obtained by coating a curing agent for an epoxy resin such as an amine adduct with an epoxy resin. However, since the shell is a thermosetting resin, these curing agents have a problem that even if the core agent expands, the shell made of the thermosetting resin is not easily broken and the curing reaction is slow. Moreover, although the hardening | curing agent using the shell which consists of thermoplastic resins instead of a thermosetting resin is also examined, it has not yet reached the balance of stability and quick-curing property of an epoxy resin composition enough.
一方、特許文献３には、アミン化合物を多孔質微粒子内に内包し、さらにその表面を高分子化合物で被覆することによりアミン化合物を保持し、特定の外部要因によりアミン化合物を放出する多孔質微粒子状潜在性硬化剤も記載されている。しかしながら、このような硬化剤であっても、エポキシ樹脂組成物の安定性及び速硬化性を充分に両立することは難しかった。 On the other hand, Patent Document 3 discloses a porous fine particle in which an amine compound is encapsulated in a porous fine particle, and the amine compound is retained by coating the surface with a polymer compound, and the amine compound is released due to a specific external factor. A latent latent curing agent is also described. However, even with such a curing agent, it has been difficult to sufficiently achieve both stability and rapid curability of the epoxy resin composition.
本発明は、硬化性樹脂組成物に配合された場合に優れた熱保存安定性及び速硬化性を発揮することができる硬化剤及び／又は硬化促進剤内包カプセルを提供することを目的とする。また、本発明は、該硬化剤及び／又は硬化促進剤内包カプセルを含有する熱硬化性樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a capsule containing a curing agent and / or a curing accelerator capable of exhibiting excellent thermal storage stability and rapid curability when blended in a curable resin composition. Moreover, an object of this invention is to provide the thermosetting resin composition containing this hardening | curing agent and / or hardening accelerator inclusion capsule.
本発明は、コア剤として硬化剤及び／又は硬化促進剤を内包する硬化剤及び／又は硬化促進剤内包カプセルであって、前記コア剤を被覆するシェルは、微細孔を有し、かつ、表面に、フッ素元素を含有するシロキサン化合物を有する硬化剤及び／又は硬化促進剤内包カプセルである。
以下、本発明を詳述する。
The present invention is a curing agent and / or a curing accelerator-encapsulating capsule containing a curing agent and / or a curing accelerator as a core agent, wherein the shell covering the core agent has micropores and has a surface And a curing agent and / or a curing accelerator-containing capsule having a siloxane compound containing an elemental fluorine.
The present invention is described in detail below.
本発明者は、硬化剤及び／又は硬化促進剤を内包する硬化剤及び／又は硬化促進剤内包カプセルにおいて、シェルに微細孔を有するものとすることにより、硬化剤及び／又は硬化促進剤の放出性を高め、硬化性樹脂組成物に配合された場合の速硬化性を改善できると考えた。しかしながら、このような硬化剤及び／又は硬化促進剤内包カプセルは、シェルに微細孔を有するために硬化剤及び／又は硬化促進剤の保持性の観点からは不充分であり、硬化性樹脂組成物に配合された場合に熱保存安定性が低下していた。また、微細孔を有するシェルを厚くした場合にも、熱保存安定性及び速硬化性を充分に両立することは難しかった。 The inventor releases the curing agent and / or the curing accelerator by making the shell have micropores in the curing agent and / or the curing accelerator-encapsulating capsule encapsulating the curing agent and / or the curing accelerator. It was considered that the quick curability can be improved when blended in the curable resin composition. However, such a curing agent and / or curing accelerator-encapsulating capsule is insufficient from the viewpoint of retention of the curing agent and / or the curing accelerator because it has micropores in the shell, and the curable resin composition When it was blended, the heat storage stability was lowered. In addition, even when the shell having fine pores is made thick, it is difficult to sufficiently achieve both heat storage stability and fast curability.
硬化剤及び／又は硬化促進剤の保持性が低下する原因を検討した結果、本発明者は、シェルと、液体状の硬化剤及び／又は硬化促進剤との濡れ性が高い（接触角が小さい）ことにより、毛管現象によって液体状の硬化剤及び／又は硬化促進剤が漏出してしまうことを見出した。硬化剤及び／又は硬化促進剤がイミダゾール化合物である場合には特に、シェルとの濡れ性が高くなり、漏出が生じやすい。
このような問題に対し、本発明者は、シェルを、微細孔を有し、かつ、表面に、フッ素元素を含有するシロキサン化合物を有するものとすることにより、硬化性樹脂組成物に配合された場合の熱保存安定性及び速硬化性を共に改善できることを見出し、本発明を完成させるに至った。これは、シェルが表面に、フッ素元素を含有するシロキサン化合物を有することにより、シェルと、液体状の硬化剤及び／又は硬化促進剤との濡れ性が低下し、保管時には毛管現象による液体状の硬化剤及び／又は硬化促進剤の漏出を抑制できる一方で、硬化時には硬化剤及び／又は硬化促進剤が気体状となり、シェルの微細孔を容易に通過するためと考えられる。
As a result of examining the cause of the decrease in retention of the curing agent and / or curing accelerator, the present inventor has high wettability between the shell and the liquid curing agent and / or curing accelerator (small contact angle). Thus, it was found that the liquid curing agent and / or curing accelerator leaked out by capillary action. In particular, when the curing agent and / or the curing accelerator is an imidazole compound, the wettability with the shell increases and leakage tends to occur.
In order to solve such a problem, the present inventor has formulated a shell into the curable resin composition by having a fine pore and having a siloxane compound containing a fluorine element on the surface. The present inventors have found that both heat storage stability and fast curability can be improved, and the present invention has been completed. This is because the shell has a siloxane compound containing elemental fluorine on the surface, so that the wettability between the shell and the liquid curing agent and / or curing accelerator decreases, and the liquid state due to capillary action during storage is reduced. While leakage of the curing agent and / or curing accelerator can be suppressed, it is considered that the curing agent and / or curing accelerator is in a gaseous state at the time of curing and easily passes through the micropores of the shell.
本発明の硬化剤及び／又は硬化促進剤内包カプセルは、コア剤として硬化剤及び／又は硬化促進剤を内包し、該コア剤をシェルで被覆する。
上記シェルは、微細孔を有し、かつ、表面に、フッ素元素を含有するシロキサン化合物を有する。シェルを、微細孔を有し、かつ、表面に、フッ素元素を含有するシロキサン化合物を有するものとすることにより、硬化性樹脂組成物に配合された場合の熱保存安定性及び速硬化性を高めることができる。
The curing agent and / or curing accelerator-encapsulating capsule of the present invention encapsulates a curing agent and / or a curing accelerator as a core agent, and coats the core agent with a shell.
The shell has fine pores and has a siloxane compound containing a fluorine element on the surface. By making the shell have fine pores and having a siloxane compound containing a fluorine element on the surface, the heat storage stability and quick curability when blended in the curable resin composition are improved. be able to.
上記微細孔の平均径は、好ましい下限が１ｎｍ、好ましい上限が１００ｎｍである。平均径が１ｎｍ未満であると、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要することがある。平均径が１００ｎｍを超えると、硬化性樹脂組成物に配合された場合の硬化剤及び／又は硬化促進剤内包カプセルの熱保存安定性が低下することがある。平均径のより好ましい下限は５ｎｍ、より好ましい上限は３０ｎｍである。
なお、微細孔の平均径は、走査型電子顕微鏡により倍率５００００倍でカプセルを観察、撮影し、撮影した写真からノギスで無作為に抽出した５０個のカプセルの微細孔径を直接測定することで求めることができる。
As for the average diameter of the micropores, a preferred lower limit is 1 nm and a preferred upper limit is 100 nm. When the average diameter is less than 1 nm, the release property of the curing agent and / or curing accelerator is lowered, and the curing reaction may take a long time. When the average diameter exceeds 100 nm, the thermal storage stability of the capsule containing the curing agent and / or curing accelerator when blended in the curable resin composition may be lowered. A more preferable lower limit of the average diameter is 5 nm, and a more preferable upper limit is 30 nm.
The average diameter of the micropores is obtained by observing and photographing the capsules with a scanning electron microscope at a magnification of 50000 times, and directly measuring the micropore diameters of 50 capsules randomly extracted with a caliper from the photographed photographs. be able to.
シェルの表面には、微細孔部分の表面も、微細孔以外の部分の表面も含まれる。特に、フッ素元素を含有するシロキサン化合物を微細孔部分の表面に存在させることにより、毛管現象による液体状の硬化剤及び／又は硬化促進剤の漏出を抑制でき、硬化性樹脂組成物に配合された場合の硬化剤及び／又は硬化促進剤内包カプセルの熱保存安定性を向上させることができる。 The surface of the shell includes the surface of the fine pore portion and the surface of the portion other than the fine pore portion. In particular, by allowing a siloxane compound containing elemental fluorine to be present on the surface of the fine pore portion, leakage of a liquid curing agent and / or curing accelerator due to capillary action can be suppressed, and the curable resin composition was blended. In this case, the heat storage stability of the capsule containing the curing agent and / or the curing accelerator can be improved.
微細孔を有し、かつ、表面に、フッ素元素を含有するシロキサン化合物を有するシェルを形成する方法として、硬化剤及び／又は硬化促進剤と、シェルを構成するポリマーとを油性溶媒に溶解した混合溶液（１）を、水性媒体に分散させて乳化液（１）とし、次いで、加熱等により油性溶媒を除去してシェルを構成するポリマーを析出させ、微細孔を有するシェルを形成した後、フッ素含有シランカップリング剤により表面処理を行う方法が好ましい。また、シェルを構成するポリマーを油性溶媒に溶解した混合溶液（２）を、水性媒体に分散させて乳化液（２）とし、次いで、混合溶液（２）の液滴に硬化剤及び／又は硬化促進剤を含浸させ、更に、加熱等により油性溶媒を除去してシェルを構成するポリマーを析出させ、微細孔を有するシェルを形成した後、フッ素含有シランカップリング剤により表面処理を行う方法も好ましい。
なお、微細孔が形成される理由としては、加熱等により油性溶媒を除去する際に、油性溶媒の抜け道としてシェルに微細孔が形成されるものと考えられる。
As a method of forming a shell having a fine pore and having a siloxane compound containing a fluorine element on the surface, mixing a curing agent and / or a curing accelerator and a polymer constituting the shell dissolved in an oily solvent The solution (1) is dispersed in an aqueous medium to obtain an emulsion (1), and then the oily solvent is removed by heating or the like to precipitate a polymer constituting the shell to form a shell having fine pores. A method of performing a surface treatment with a contained silane coupling agent is preferred. Further, the mixed solution (2) in which the polymer constituting the shell is dissolved in an oily solvent is dispersed in an aqueous medium to obtain an emulsion (2), and then a hardener and / or a curing agent is added to the droplets of the mixed solution (2). Also preferred is a method of impregnating with an accelerator and further removing the oily solvent by heating or the like to precipitate a polymer constituting the shell to form a shell having micropores, followed by surface treatment with a fluorine-containing silane coupling agent. .
The reason why the micropores are formed is considered to be that micropores are formed in the shell as an escape route of the oily solvent when the oily solvent is removed by heating or the like.
上記フッ素含有シランカップリング剤として、例えば、トリメトキシフルオロシラン、トリエトキシフルオロシラン、トリイソプロポキシフルオロシラン、トリフルオロプロピルトリメトキシシラン、トリフルオロトリエトキシシラン等が挙げられる。なかでも、トリフルオロプロピルトリメトキシシランが好ましい。 Examples of the fluorine-containing silane coupling agent include trimethoxyfluorosilane, triethoxyfluorosilane, triisopropoxyfluorosilane, trifluoropropyltrimethoxysilane, and trifluorotriethoxysilane. Of these, trifluoropropyltrimethoxysilane is preferable.
上記フッ素含有シランカップリング剤の市販品として、例えば、ＫＢＭ−７１０３（信越化学工業社製、トリフルオロプロピルトリメトキシシラン）等が挙げられる。 Examples of commercially available fluorine-containing silane coupling agents include KBM-7103 (manufactured by Shin-Etsu Chemical Co., Ltd., trifluoropropyltrimethoxysilane).
上記フッ素含有シランカップリング剤の添加量は、シェルを構成するポリマー５重量部に対する好ましい下限が０．０５重量部、好ましい上限が１重量部である。添加量が０．０５重量部未満であると、フッ素含有シランカップリング剤による表面処理が不充分となり、毛管現象による液体状の硬化剤及び／又は硬化促進剤の漏出を充分に抑制できず、硬化性樹脂組成物に配合された場合の硬化剤及び／又は硬化促進剤内包カプセルの熱保存安定性が低下することがある。添加量が１重量部を超えると、シェルの微細孔が埋められてしまい、硬化性樹脂組成物に配合された場合の硬化剤及び／又は硬化促進剤内包カプセルの速硬化性が低下することがある。添加量のより好ましい下限は０．１重量部、より好ましい上限は０．５重量部である。 As for the addition amount of the fluorine-containing silane coupling agent, a preferable lower limit with respect to 5 parts by weight of the polymer constituting the shell is 0.05 part by weight, and a preferable upper limit is 1 part by weight. When the addition amount is less than 0.05 parts by weight, the surface treatment with the fluorine-containing silane coupling agent becomes insufficient, and leakage of the liquid curing agent and / or curing accelerator due to capillary phenomenon cannot be sufficiently suppressed, The thermal storage stability of the capsule containing the curing agent and / or curing accelerator when mixed with the curable resin composition may be lowered. When the addition amount exceeds 1 part by weight, the micropores of the shell are filled, and the rapid curability of the capsule containing the curing agent and / or curing accelerator when blended in the curable resin composition may be reduced. is there. The more preferable lower limit of the addition amount is 0.1 parts by weight, and the more preferable upper limit is 0.5 parts by weight.
また、微細孔を有し、かつ、表面に、フッ素元素を含有するシロキサン化合物を有するシェルを形成する方法として、硬化剤及び／又は硬化促進剤と、シェルを構成するポリマーと、フッ素含有シロキサンポリマーとを油性溶媒に溶解した混合溶液（３）を、水性媒体に分散させて乳化液（３）とし、次いで、加熱等により油性溶媒を除去してシェルを構成するポリマー及びフッ素含有シロキサンポリマーを析出させる方法も好ましい。また、シェルを構成するポリマーと、フッ素含有シロキサンポリマーとを油性溶媒に溶解した混合溶液（４）を、水性媒体に分散させて乳化液（４）とし、次いで、混合溶液（４）の液滴に硬化剤及び／又は硬化促進剤を含浸させ、更に、加熱等により油性溶媒を除去してシェルを構成するポリマー及びフッ素含有シロキサンポリマーを析出させる方法も好ましい。
これらの場合にも、微細孔が形成される理由としては、加熱等により油性溶媒を除去する際に、油性溶媒の抜け道としてシェルに微細孔が形成されるものと考えられる。
Moreover, as a method of forming a shell having a fine pore and having a siloxane compound containing a fluorine element on the surface, a curing agent and / or a curing accelerator, a polymer constituting the shell, and a fluorine-containing siloxane polymer A mixed solution (3) obtained by dissolving in an oily solvent is dispersed in an aqueous medium to obtain an emulsion (3). Then, the oily solvent is removed by heating or the like to precipitate a polymer constituting the shell and a fluorine-containing siloxane polymer. The method of making it also preferable. Further, a mixed solution (4) in which a polymer constituting the shell and a fluorine-containing siloxane polymer are dissolved in an oily solvent is dispersed in an aqueous medium to obtain an emulsion (4), and then a droplet of the mixed solution (4) Also preferred is a method of impregnating with a curing agent and / or a curing accelerator and further removing the oily solvent by heating or the like to precipitate the polymer constituting the shell and the fluorine-containing siloxane polymer.
In these cases as well, the reason why the fine pores are formed is considered to be that fine pores are formed in the shell as an escape route of the oily solvent when the oily solvent is removed by heating or the like.
上記フッ素含有シロキサンポリマーとして、例えば、フッ素シリコーン、フッ素樹脂−シロキサングラフト型ポリマー等が挙げられる。なかでも、フッ素とシロキサンとの相乗効果が発現しやすいことから、フッ素樹脂−シロキサングラフト型ポリマーが好ましい。 Examples of the fluorine-containing siloxane polymer include fluorine silicone, a fluororesin-siloxane graft polymer, and the like. Of these, a fluororesin-siloxane graft type polymer is preferable because a synergistic effect of fluorine and siloxane is easily exhibited.
上記フッ素含有シロキサンポリマーの市販品として、例えば、ＫＰ−９１１（信越化学工業社製、フッ素シリコーン）、ＺＸ−００７−Ｃ、ＺＸ−００１、ＺＸ−０１７、ＺＸ−０２２、ＺＸ−０２２−Ｈ、ＺＸ−０４７−Ｄ、ＺＸ−０５８−Ａ、ＺＸ−２１２、ＺＸ−２０１、ＺＸ−２０２（以上、Ｔ＆Ｋ ＴＯＫＡ社製、フッ素樹脂−シロキサングラフト型ポリマー）等が挙げられる。 Examples of commercially available fluorine-containing siloxane polymers include KP-911 (manufactured by Shin-Etsu Chemical Co., Ltd., fluorine silicone), ZX-007-C, ZX-001, ZX-017, ZX-022, ZX-022-H, ZX-047-D, ZX-058-A, ZX-212, ZX-201, ZX-202 (above, manufactured by T & K TOKA, a fluororesin-siloxane graft type polymer) and the like.
上記フッ素含有シロキサンポリマーの添加量は、シェルを構成するポリマー５重量部に対する好ましい下限が０．０５重量部、好ましい上限が１重量部である。添加量が０．０５重量部未満であると、シェルの表面に存在するフッ素元素を含有するシロキサン化合物の量が低下し、毛管現象による液体状の硬化剤及び／又は硬化促進剤の漏出を充分に抑制できず、硬化性樹脂組成物に配合された場合の硬化剤及び／又は硬化促進剤内包カプセルの熱保存安定性が低下することがある。添加量が１重量部を超えると、シェルの微細孔が埋められてしまい、硬化性樹脂組成物に配合された場合の硬化剤及び／又は硬化促進剤内包カプセルの速硬化性が低下することがある。添加量のより好ましい下限は０．１重量部、より好ましい上限は０．５重量部である。 As for the addition amount of the fluorine-containing siloxane polymer, a preferable lower limit with respect to 5 parts by weight of the polymer constituting the shell is 0.05 part by weight, and a preferable upper limit is 1 part by weight. When the amount added is less than 0.05 parts by weight, the amount of the siloxane compound containing fluorine element present on the surface of the shell is reduced, and the leakage of the liquid curing agent and / or curing accelerator due to capillary action is sufficient. In some cases, the heat storage stability of the capsule containing the curing agent and / or curing accelerator when blended in the curable resin composition may be reduced. When the addition amount exceeds 1 part by weight, the micropores of the shell are filled, and the rapid curability of the capsule containing the curing agent and / or curing accelerator when blended in the curable resin composition may be reduced. is there. The more preferable lower limit of the addition amount is 0.1 parts by weight, and the more preferable upper limit is 0.5 parts by weight.
シェル表面へのフッ素元素を含有するシロキサン化合物の存在は、シェルと同様の組成を有するシェルポリマーフィルムを別途作製し、このシェルポリマーフィルムと硬化剤及び／又は硬化促進剤との接触角を測定することで確認することができる。接触角を測定する方法として、例えば、接触角計を用いる方法、液滴の水平方向から写真を撮影して直接計測する方法等が挙げられる。
シェルポリマーフィルムと硬化剤及び／又は硬化促進剤との接触角の好ましい下限は６０°である。接触角が６０°未満であると、シェルの表面に存在するフッ素元素を含有するシロキサン化合物の量が低下し、液体状の硬化剤及び／又は硬化促進剤との濡れ性が高くなることで、温度にかかわらず、毛管現象によって液体状の硬化剤及び／又は硬化促進剤がカプセル外に漏出しやすくなることがある。接触角のより好ましい下限は６５°、更に好ましい下限は７０°である。
The presence of a siloxane compound containing elemental fluorine on the shell surface is prepared by separately preparing a shell polymer film having the same composition as the shell, and measuring the contact angle between the shell polymer film and the curing agent and / or curing accelerator. This can be confirmed. As a method for measuring the contact angle, for example, a method using a contact angle meter, a method of directly taking a photograph from the horizontal direction of a droplet, and the like can be cited.
A preferred lower limit of the contact angle between the shell polymer film and the curing agent and / or curing accelerator is 60 °. When the contact angle is less than 60 °, the amount of the siloxane compound containing fluorine element present on the surface of the shell is reduced, and the wettability with the liquid curing agent and / or curing accelerator is increased. Regardless of the temperature, the liquid curing agent and / or curing accelerator may easily leak out of the capsule due to capillary action. A more preferred lower limit of the contact angle is 65 °, and a more preferred lower limit is 70 °.
上記シェルを構成するポリマーは、硬化剤及び／又は硬化促進剤の放出性を高めるためには、熱可塑性ポリマーを含有することが好ましい。上記熱可塑性ポリマーは、親水性基と疎水性基とを有する熱可塑性ポリマー、水酸基を有するポリビニルアセタール樹脂、又は、アクリロニトリルに由来するセグメントを有する共重合体を含有することが好ましい。
上記親水性基と疎水性基とを有する熱可塑性ポリマーにおける親水性基として、例えば、グリシジル基、水酸基、カルボキシル基、スルホン基等が挙げられる。なかでも、グリシジル基が好ましい。上記親水性基と疎水性基とを有する熱可塑性ポリマーにおける疎水性基として、例えば、フェニル基、メチル基、エチル基、プロピル基、メタクリル基等が挙げられる。なかでも、フェニル基が好ましい。
The polymer constituting the shell preferably contains a thermoplastic polymer in order to enhance the release of the curing agent and / or curing accelerator. The thermoplastic polymer preferably contains a thermoplastic polymer having a hydrophilic group and a hydrophobic group, a polyvinyl acetal resin having a hydroxyl group, or a copolymer having a segment derived from acrylonitrile.
Examples of the hydrophilic group in the thermoplastic polymer having the hydrophilic group and the hydrophobic group include a glycidyl group, a hydroxyl group, a carboxyl group, and a sulfone group. Of these, a glycidyl group is preferable. Examples of the hydrophobic group in the thermoplastic polymer having the hydrophilic group and the hydrophobic group include a phenyl group, a methyl group, an ethyl group, a propyl group, and a methacryl group. Of these, a phenyl group is preferred.
上記親水性基と疎水性基とを有する熱可塑性ポリマーとして、具体的には例えば、ポリスチレン誘導体、ポリメタクリル酸誘導体等が挙げられる。なかでも、ポリスチレン誘導体が好ましい。
上記ポリスチレン誘導体は、上記親水性基と上記疎水性基とを有していればよく、例えば、上記親水性基としてグリシジル基を有し、上記疎水性基としてポリスチレン骨格に由来するフェニル基を有するポリスチレン誘導体が好ましい。
Specific examples of the thermoplastic polymer having the hydrophilic group and the hydrophobic group include polystyrene derivatives and polymethacrylic acid derivatives. Of these, polystyrene derivatives are preferred.
The polystyrene derivative only needs to have the hydrophilic group and the hydrophobic group. For example, the polystyrene derivative has a glycidyl group as the hydrophilic group and a phenyl group derived from a polystyrene skeleton as the hydrophobic group. Polystyrene derivatives are preferred.
上記親水性基と疎水性基とを有する熱可塑性ポリマーの重量平均分子量は、好ましい下限が５０００、好ましい上限が１０万である。重量平均分子量が５０００未満であると、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性又は耐溶剤性が低下し、硬化性樹脂組成物に配合された場合の貯蔵安定性が低下することがある。重量平均分子量が１０万を超えると、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要することがある。 As for the weight average molecular weight of the thermoplastic polymer which has the said hydrophilic group and hydrophobic group, a preferable minimum is 5000 and a preferable upper limit is 100,000. When the weight average molecular weight is less than 5,000, the strength, heat resistance or solvent resistance of the capsule containing the curing agent and / or curing accelerator is lowered, and the storage stability when blended in the curable resin composition is lowered. Sometimes. When the weight average molecular weight exceeds 100,000, the release property of the curing agent and / or the curing accelerator is lowered, and the curing reaction may take a long time.
上記水酸基を有するポリビニルアセタール樹脂は、通常、ポリ酢酸ビニルのけん化反応により得られたポリビニルアルコールを、アルデヒドでアセタール化することにより得られる。上記アセタール化に使用するアルデヒドとして、例えば、ホルムアルデヒド、アセトアルデヒド、パラアセトアルデヒド、ブチルアルデヒド等が挙げられる。なかでも、ブチルアルデヒドが好ましい。
上記水酸基を有するポリビニルアセタール樹脂の水酸基の含有量、アセタール化度、原料であるポリ酢酸ビニルのアセチル基に由来するアセチル基の含有量、重量平均分子量等を調整することにより、目的に合わせてシェルの物性を調整することができる。
The polyvinyl acetal resin having a hydroxyl group is usually obtained by acetalizing polyvinyl alcohol obtained by a saponification reaction of polyvinyl acetate with an aldehyde. Examples of the aldehyde used for the acetalization include formaldehyde, acetaldehyde, paraacetaldehyde, butyraldehyde and the like. Of these, butyraldehyde is preferred.
By adjusting the hydroxyl content, the degree of acetalization, the content of acetyl groups derived from the acetyl group of polyvinyl acetate as a raw material, the weight average molecular weight, etc. of the polyvinyl acetal resin having a hydroxyl group, the shell can be tailored to the purpose. The physical properties of can be adjusted.
上記水酸基を有するポリビニルアセタール樹脂の重量平均分子量は、好ましい下限が５０００、好ましい上限が５０万である。重量平均分子量が５０００未満であると、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性又は耐溶剤性が低下し、硬化性樹脂組成物に配合された場合の貯蔵安定性が低下することがある。重量平均分子量が５０万を超えると、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要することがある。重量平均分子量のより好ましい下限は３万、より好ましい上限は３０万である。 As for the weight average molecular weight of the said polyvinyl acetal resin which has a hydroxyl group, a preferable minimum is 5000 and a preferable upper limit is 500,000. When the weight average molecular weight is less than 5,000, the strength, heat resistance, or solvent resistance of the capsule containing the curing agent and / or curing accelerator decreases, and the storage stability when blended in the curable resin composition decreases. Sometimes. When the weight average molecular weight exceeds 500,000, the release property of the curing agent and / or the curing accelerator is lowered, and the curing reaction may take a long time. The more preferable lower limit of the weight average molecular weight is 30,000, and the more preferable upper limit is 300,000.
上記水酸基を有するポリビニルアセタール樹脂の市販品として、例えば、ＢＬ−１０（積水化学工業社製）、ＢＬ−２Ｈ（積水化学工業社製）、ＢＭ−Ｓ（積水化学工業社製）、ＢＨ−３（積水化学工業社製）、♯−３０００Ｋ（電気化学工業社製）、ＭＯＷＩＴＡＬ Ｂ６０Ｔ（クラレ社製）等が挙げられる。 As a commercial item of the polyvinyl acetal resin which has the said hydroxyl group, for example, BL-10 (made by Sekisui Chemical Co., Ltd.), BL-2H (made by Sekisui Chemical Co., Ltd.), BM-S (made by Sekisui Chemical Co., Ltd.), BH-3 (Manufactured by Sekisui Chemical Co., Ltd.), # -3000K (manufactured by Denki Kagaku Kogyo Co., Ltd.), MOWITAL B60T (manufactured by Kuraray Co., Ltd.) and the like.
熱可塑性ポリマーにアクリロニトリルに由来するセグメントを有する共重合体を用いることにより、シェルのガスバリア性及び耐溶剤性を向上させることができる。
上記アクリロニトリルに由来するセグメントを有する共重合体において、上記アクリロニトリルに由来するセグメント以外の他のモノマーに由来するセグメントは特に限定されない。上記他のモノマーとして、例えば、ビニル基を有する化合物等のラジカル重合性モノマーが挙げられる。上記ビニル基を有する化合物は特に限定されず、例えば、グリシジルメタクリレート（ＧＭＡ）、メチルメタクリレート（ＭＭＡ）等のメタクリル酸エステル、アクリル酸エステル、スチレン、ジビニルベンゼン、塩化ビニリデン、ビニルアルコール、ビニルピロリドン、エチレングリコールジメタクリレート、ブタジエン等が挙げられる。なかでも、スチレン、グリシジルメタクリレート（ＧＭＡ）、メチルメタクリレート（ＭＭＡ）が好ましい。
By using a copolymer having a segment derived from acrylonitrile as the thermoplastic polymer, the gas barrier property and solvent resistance of the shell can be improved.
In the copolymer having a segment derived from acrylonitrile, a segment derived from another monomer other than the segment derived from acrylonitrile is not particularly limited. As said other monomer, radical polymerizable monomers, such as a compound which has a vinyl group, are mentioned, for example. The compound having a vinyl group is not particularly limited, and examples thereof include methacrylic acid esters such as glycidyl methacrylate (GMA) and methyl methacrylate (MMA), acrylic acid esters, styrene, divinylbenzene, vinylidene chloride, vinyl alcohol, vinyl pyrrolidone, and ethylene. Examples include glycol dimethacrylate and butadiene. Of these, styrene, glycidyl methacrylate (GMA), and methyl methacrylate (MMA) are preferable.
上記アクリロニトリルに由来するセグメントを有する共重合体の重量平均分子量は、好ましい下限が５０００、好ましい上限が１０万である。重量平均分子量が５０００未満であると、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性又は耐溶剤性が低下し、硬化性樹脂組成物に配合された場合の貯蔵安定性が低下することがある。重量平均分子量が１０万を超えると、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要することがある。重量平均分子量のより好ましい下限は８０００、より好ましい上限は５万であり、更に好ましい下限は１万、更に好ましい上限は３万である。 As for the weight average molecular weight of the copolymer having a segment derived from acrylonitrile, a preferable lower limit is 5000 and a preferable upper limit is 100,000. When the weight average molecular weight is less than 5,000, the strength, heat resistance or solvent resistance of the capsule containing the curing agent and / or curing accelerator is lowered, and the storage stability when blended in the curable resin composition is lowered. Sometimes. When the weight average molecular weight exceeds 100,000, the release property of the curing agent and / or the curing accelerator is lowered, and the curing reaction may take a long time. The more preferred lower limit of the weight average molecular weight is 8000, the more preferred upper limit is 50,000, the still more preferred lower limit is 10,000, and the more preferred upper limit is 30,000.
上記シェルを構成するポリマーは、更に、無機ポリマーを含有してもよい。シェルを構成するポリマーに無機ポリマーを用いることにより、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性及び耐溶剤性が向上し、例えば溶剤と混合する場合であっても好適に用いられる。 The polymer constituting the shell may further contain an inorganic polymer. By using an inorganic polymer for the polymer constituting the shell, the strength, heat resistance and solvent resistance of the capsule containing the curing agent and / or curing accelerator are improved. For example, it can be suitably used even when mixed with a solvent. .
上記無機ポリマーとして、分子中に２個以上の炭素数１〜６のアルコキシ基を有し、かつ、Ｓｉ、Ａｌ、Ｚｒ及びＴｉからなる群より選択される少なくとも１種の金属元素を含有する有機金属化合物の重合体が好ましい。このような有機金属化合物の重合体として、例えば、シリコーン樹脂、ポリボロシロキサン樹脂、ポリカルボシラン樹脂、ポリシラスチレン樹脂、ポリシラザン樹脂、ポリチタノカルボシラン樹脂等が挙げられる。なかでも、シリコーン樹脂が好ましく、グリシジル基を有するシリコーン樹脂がより好ましい。 Organic having at least one metal element selected from the group consisting of Si, Al, Zr, and Ti as the inorganic polymer, having 2 or more C1-C6 alkoxy groups in the molecule Polymers of metal compounds are preferred. Examples of such a polymer of an organometallic compound include silicone resins, polyborosiloxane resins, polycarbosilane resins, polysilastyrene resins, polysilazane resins, and polytitanocarbosilane resins. Among these, a silicone resin is preferable, and a silicone resin having a glycidyl group is more preferable.
上記硬化剤及び／又は硬化促進剤は、硬化時に気体状となってシェルの微細孔を容易に通過するためには、融点が１００℃未満であることが好ましく、例えば、三級アミン化合物、イミダゾール化合物等のアミン化合物、又は、リン系触媒等が挙げられる。なかでも、硬化性に優れることから、イミダゾール化合物が好ましい。
上記イミダゾール化合物は特に限定されず、例えば、２−ウンデシルイミダゾール、１，２−ジメチルイミダゾール、２−エチル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、１−ドデシル−２−メチル−３−ベンジルイミダゾリウムクロライド、及び、これらの付加体等が挙げられる。
The curing agent and / or curing accelerator is preferably in a gaseous state upon curing and has a melting point of less than 100 ° C. in order to easily pass through the micropores of the shell. For example, a tertiary amine compound, imidazole Examples thereof include amine compounds such as compounds, and phosphorus-based catalysts. Especially, since it is excellent in sclerosis | hardenability, an imidazole compound is preferable.
The imidazole compound is not particularly limited. For example, 2-undecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, and These adducts can be mentioned.
また、上記イミダゾール化合物として、疎水性イミダゾール化合物を用いることが好ましい。なお、疎水性イミダゾール化合物とは、水に最大限溶解させたときの濃度が５重量％未満であるイミダゾール化合物を意味する。
上記疎水性イミダゾール化合物は、炭素数１１以上の炭化水素基を有するイミダゾール化合物が好ましい。上記炭素数１１以上の炭化水素基を有するイミダゾール化合物として、例えば、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、１−シアノエチルイミダゾール等が挙げられる。なかでも、２−ウンデシルイミダゾールが好ましい。
Moreover, it is preferable to use a hydrophobic imidazole compound as the imidazole compound. The hydrophobic imidazole compound means an imidazole compound having a concentration of less than 5% by weight when dissolved in water to the maximum.
The hydrophobic imidazole compound is preferably an imidazole compound having a hydrocarbon group having 11 or more carbon atoms. Examples of the imidazole compound having a hydrocarbon group having 11 or more carbon atoms include 2-undecylimidazole, 2-heptadecylimidazole, 1-cyanoethylimidazole, and the like. Of these, 2-undecylimidazole is preferable.
本発明の硬化剤及び／又は硬化促進剤内包カプセルのシェル厚みは、好ましい下限が０．０５μｍ、好ましい上限が０．８μｍである。シェル厚みが０．０５μｍ未満であると、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性又は耐溶剤性が低下し、硬化性樹脂組成物に配合された場合の貯蔵安定性が低下することがある。シェル厚みが０．８μｍを超えると、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要することがある。シェル厚みのより好ましい下限は０．０８μｍ、より好ましい上限は０．５μｍである。
なお、硬化剤及び／又は硬化促進剤内包カプセルのシェル厚みとは、下記式（１）により算出される、カプセルの体積と内包体積比率から算出したシェルの体積を、カプセルの表面積で割ることで求められる値を意味する。
シェル厚み＝｛カプセルの体積−（カプセルの体積×内包体積比率）｝／カプセルの表面積 （１）
The preferable lower limit of the shell thickness of the capsule containing the curing agent and / or curing accelerator of the present invention is 0.05 μm, and the preferable upper limit is 0.8 μm. When the shell thickness is less than 0.05 μm, the strength, heat resistance or solvent resistance of the capsule containing the curing agent and / or curing accelerator is lowered, and the storage stability when blended in the curable resin composition is lowered. There are things to do. When the shell thickness exceeds 0.8 μm, the release property of the curing agent and / or curing accelerator is lowered, and the curing reaction may take a long time. A more preferable lower limit of the shell thickness is 0.08 μm, and a more preferable upper limit is 0.5 μm.
In addition, the shell thickness of the encapsulating capsule containing the curing agent and / or curing accelerator is obtained by dividing the volume of the shell calculated from the capsule volume and the encapsulating volume ratio calculated by the following formula (1) by the surface area of the capsule. Means the desired value.
Shell thickness = {Capsule volume− (Capsule volume × Internal volume ratio)} / Capsule surface area (1)
本発明の硬化剤及び／又は硬化促進剤内包カプセルの内包体積比率は、好ましい下限が３０体積％、好ましい上限が７０体積％である。内包体積比率が３０体積％未満であると、硬化剤及び／又は硬化促進剤の放出性が低下し、硬化反応に長時間を要したり硬化剤及び／又は硬化促進剤内包カプセルを多量に配合する必要が生じたりすることがある。内包体積比率が７０体積％を超えると、硬化剤及び／又は硬化促進剤内包カプセルのシェルが薄くなりすぎて強度、耐熱性又は耐溶剤性が低下し、貯蔵安定性が低下することがある。内包体積比率のより好ましい下限は４０体積％、より好ましい上限は６０体積％である。
なお、硬化剤及び／又は硬化促進剤内包カプセルの内包体積比率は、平均粒子径を用いて算出したカプセルの体積とガスクロマトグラフィーを用いて測定したコア剤の含有量から、下記式（２）により算出される値を意味する。
内包体積比率（％）＝（コア剤の含有量（重量％）×コア剤の比重（ｇ／ｃｍ３））／カプセルの体積（ｃｍ３） （２）
The preferable lower limit of the encapsulating volume ratio of the curing agent and / or curing accelerator-encapsulating capsule of the present invention is 30% by volume, and the preferable upper limit is 70% by volume. When the encapsulated volume ratio is less than 30% by volume, the release property of the curing agent and / or curing accelerator is lowered, and it takes a long time for the curing reaction or a large amount of the encapsulating capsule containing the curing agent and / or curing accelerator is incorporated. May need to be done. If the encapsulated volume ratio exceeds 70% by volume, the shell of the encapsulating capsule containing the curing agent and / or curing accelerator may become too thin, resulting in a decrease in strength, heat resistance or solvent resistance, and storage stability may be decreased. A more preferable lower limit of the inclusion volume ratio is 40% by volume, and a more preferable upper limit is 60% by volume.
The encapsulated volume ratio of the capsulating agent and / or the accelerating agent-encapsulating capsule is expressed by the following formula (2) from the capsule volume calculated using the average particle diameter and the content of the core agent measured using gas chromatography. Means the value calculated by.
Encapsulated volume ratio (%) = (content of core agent (% by weight) × specific gravity of core agent (g / cm 3 )) / volume of capsule (cm 3 ) (2)
本発明の硬化剤及び／又は硬化促進剤内包カプセルの平均粒子径は、好ましい下限が０．５μｍ、好ましい上限が１０μｍである。平均粒子径が０．５μｍ未満であると、所望の範囲の内包率を維持しようとすると、硬化剤及び／又は硬化促進剤内包カプセルの強度、耐熱性又は耐溶剤性が低下し、硬化性樹脂組成物に配合された場合の貯蔵安定性が低下することがある。平均粒子径が１０μｍを超えると、硬化剤及び／又は硬化促進剤内包カプセルを硬化性樹脂組成物に配合した場合に、加熱により硬化剤及び／又は硬化促進剤が放出された後、大きなボイドが生じて硬化物の信頼性が低下することがある。平均粒子径のより好ましい上限は３．０μｍである。
なお、硬化剤及び／又は硬化促進剤内包カプセルの平均粒子径とは、走査型電子顕微鏡を用いて１視野に約１００個のカプセルが観察できる倍率で観察し、任意に選択した５０個のカプセルの最長径をノギスで測定した平均値を意味する。
The preferable lower limit of the average particle size of the curing agent and / or curing accelerator-encapsulating capsule of the present invention is 0.5 μm, and the preferable upper limit is 10 μm. If the average particle size is less than 0.5 μm, the strength, heat resistance or solvent resistance of the capsules containing the curing agent and / or curing accelerator will be reduced when maintaining the encapsulation rate within the desired range. Storage stability when blended into the composition may be reduced. When the average particle size exceeds 10 μm, when the curing agent and / or curing accelerator-encapsulating capsule is blended with the curable resin composition, a large void is generated after the curing agent and / or the curing accelerator is released by heating. It may occur and the reliability of the cured product may be reduced. A more preferable upper limit of the average particle diameter is 3.0 μm.
The average particle size of the capsules containing the curing agent and / or curing accelerator is 50 capsules arbitrarily selected by observing at a magnification at which about 100 capsules can be observed in one visual field using a scanning electron microscope. Means the average value of the longest diameter measured with calipers.
本発明の硬化剤及び／又は硬化促進剤内包カプセルを製造する方法は、上述したように、硬化剤及び／又は硬化促進剤と、シェルを構成するポリマーとを油性溶媒に溶解した混合溶液（１）を、水性媒体に分散させて乳化液（１）とし、次いで、加熱等により油性溶媒を除去してシェルを構成するポリマーを析出させ、微細孔を有するシェルを形成した後、フッ素含有シランカップリング剤により表面処理を行う方法が好ましい。また、シェルを構成するポリマーを油性溶媒に溶解した混合溶液（２）を、水性媒体に分散させて乳化液（２）とし、次いで、混合溶液（２）の液滴に硬化剤及び／又は硬化促進剤を含浸させ、更に、加熱等により油性溶媒を除去してシェルを構成するポリマーを析出させ、微細孔を有するシェルを形成した後、フッ素含有シランカップリング剤により表面処理を行う方法も好ましい。 As described above, the method for producing the capsule containing the curing agent and / or curing accelerator of the present invention is a mixed solution (1) in which the curing agent and / or the curing accelerator and the polymer constituting the shell are dissolved in an oily solvent. ) Is dispersed in an aqueous medium to obtain an emulsion (1), and then the oily solvent is removed by heating or the like to precipitate a polymer constituting the shell, thereby forming a shell having micropores, and then a fluorine-containing silane cup. A method of performing surface treatment with a ring agent is preferred. Further, the mixed solution (2) in which the polymer constituting the shell is dissolved in an oily solvent is dispersed in an aqueous medium to obtain an emulsion (2), and then a hardener and / or a curing agent is added to the droplets of the mixed solution (2). Also preferred is a method of impregnating with an accelerator and further removing the oily solvent by heating or the like to precipitate a polymer constituting the shell to form a shell having micropores, followed by surface treatment with a fluorine-containing silane coupling agent. .
また、硬化剤及び／又は硬化促進剤と、シェルを構成するポリマーと、フッ素含有シロキサンポリマーとを油性溶媒に溶解した混合溶液（３）を、水性媒体に分散させて乳化液（３）とし、次いで、加熱等により油性溶媒を除去してシェルを構成するポリマー及びフッ素含有シロキサンポリマーを析出させる方法も好ましい。また、シェルを構成するポリマーと、フッ素含有シロキサンポリマーとを油性溶媒に溶解した混合溶液（４）を、水性媒体に分散させて乳化液（４）とし、次いで、混合溶液（４）の液滴に硬化剤及び／又は硬化促進剤を含浸させ、更に、加熱等により油性溶媒を除去してシェルを構成するポリマー及びフッ素含有シロキサンポリマーを析出させる方法も好ましい。 Further, a mixed solution (3) obtained by dissolving a curing agent and / or a curing accelerator, a polymer constituting the shell, and a fluorine-containing siloxane polymer in an oily solvent is dispersed in an aqueous medium to obtain an emulsion (3). Next, a method of removing the oily solvent by heating or the like and precipitating the polymer constituting the shell and the fluorine-containing siloxane polymer is also preferable. Further, a mixed solution (4) in which a polymer constituting the shell and a fluorine-containing siloxane polymer are dissolved in an oily solvent is dispersed in an aqueous medium to obtain an emulsion (4), and then a droplet of the mixed solution (4) Also preferred is a method of impregnating with a curing agent and / or a curing accelerator and further removing the oily solvent by heating or the like to precipitate the polymer constituting the shell and the fluorine-containing siloxane polymer.
上記油性溶媒は特に限定されず、例えば、ベンゼン、イソプレン、ヘキサン、ヘプタン、シクロヘキサン、ギ酸イソブチル、酢酸メチル、酢酸エチル、ジプロピルエーテル、ジブチルエーテル、エタノール、アリルアルコール、１−プロパノール、２−プロパノール、ｔ−ブチルアルコール、アセトン、エチルメチルケトン、Ｎ，Ｎ−ジメチルホルムアミド、アセトニトリル等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 The oily solvent is not particularly limited. For example, benzene, isoprene, hexane, heptane, cyclohexane, isobutyl formate, methyl acetate, ethyl acetate, dipropyl ether, dibutyl ether, ethanol, allyl alcohol, 1-propanol, 2-propanol, Examples thereof include t-butyl alcohol, acetone, ethyl methyl ketone, N, N-dimethylformamide, acetonitrile and the like. These may be used alone or in combination of two or more.
上記水性媒体は特に限定されず、例えば、水に、乳化剤、分散安定剤等を添加した水性媒体が用いられる。上記乳化剤は特に限定されず、例えば、アルキル硫酸スルホン酸塩、アルキルベンゼンスルホン酸塩、アルキル硫酸トリエタノールアミン、ポリオキシエチレンアルキルエーテル等が挙げられる。上記分散安定剤は特に限定されず、例えば、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレングリコール等が挙げられる。 The aqueous medium is not particularly limited, and for example, an aqueous medium in which an emulsifier, a dispersion stabilizer and the like are added to water is used. The emulsifier is not particularly limited, and examples thereof include alkyl sulfate sulfonate, alkyl benzene sulfonate, alkyl sulfate triethanolamine, and polyoxyethylene alkyl ether. The dispersion stabilizer is not particularly limited, and examples thereof include polyvinyl alcohol, polyvinyl pyrrolidone, and polyethylene glycol.
上記乳化液（１）〜（４）を調製する際には、混合溶液（１）〜（４）に水性媒体を添加してもよく、水性媒体に混合溶液（１）〜（４）を添加してもよい。乳化方法として、例えば、ホモジナイザーを用いて攪拌する方法、超音波照射により乳化する方法、マイクロチャネル又はＳＰＧ膜を通過させて乳化する方法、スプレーで噴霧する方法、転相乳化法等が挙げられる。 When preparing the emulsions (1) to (4), an aqueous medium may be added to the mixed solutions (1) to (4), and the mixed solutions (1) to (4) are added to the aqueous medium. May be. Examples of the emulsification method include a method of stirring using a homogenizer, a method of emulsifying by ultrasonic irradiation, a method of emulsifying by passing through a microchannel or an SPG film, a method of spraying with a spray, and a phase inversion emulsification method.
上記混合溶液（２）又は（４）の液滴に硬化剤及び／又は硬化促進剤を含浸させる方法として、例えば、乳化液（２）又は（４）に液体状の硬化剤及び／又は硬化促進剤を添加し、乳化液（２）又は（４）を攪拌する方法が好ましい。
また、例えば、乳化液（２）又は（４）に固体状の硬化剤及び／又は硬化促進剤を添加し、固体状の硬化剤及び／又は硬化促進剤の融点以上に乳化液（２）又は（４）を加熱して、固体状の硬化剤及び／又は硬化促進剤を液体状とする方法も挙げられる。なかでも、固体状の硬化剤及び／又は硬化促進剤の融点以上かつ１００℃未満に乳化液（２）又は（４）を加熱して、水性媒体を蒸発させることなく硬化剤及び／又は硬化促進剤を含浸させる方法が好ましい。
As a method for impregnating the liquid droplets of the mixed solution (2) or (4) with a curing agent and / or a curing accelerator, for example, the emulsion (2) or (4) is a liquid curing agent and / or curing acceleration. A method of adding an agent and stirring the emulsion (2) or (4) is preferred.
Further, for example, a solid curing agent and / or a curing accelerator is added to the emulsion (2) or (4), and the emulsion (2) or the melting point of the solid curing agent and / or the curing accelerator is higher than the melting point. The method of heating (4) and making a solid hardening | curing agent and / or hardening accelerator into a liquid form is also mentioned. Among these, the emulsified liquid (2) or (4) is heated to the melting point of the solid curing agent and / or curing accelerator and to less than 100 ° C. to cure the curing agent and / or curing without evaporating the aqueous medium. A method of impregnating the agent is preferred.
油性溶媒を除去してシェルを構成するポリマー、フッ素含有シロキサンポリマー等を析出させる方法として、３０〜７０℃に加熱する方法が好ましく、加熱に加えて、０．０９５〜０．０８０ＭＰａの圧力となるよう設定して減圧を行う方法がより好ましい。 As a method of precipitating the polymer constituting the shell by removing the oily solvent, the fluorine-containing siloxane polymer, etc., a method of heating to 30 to 70 ° C. is preferable, and in addition to heating, a pressure of 0.095 to 0.080 MPa is obtained. A method in which the pressure is reduced under such settings is more preferable.
得られた硬化剤及び／又は硬化促進剤内包カプセルは、純水を用いて繰り返して洗浄された後、真空乾燥等により乾燥されてもよい。 The obtained curing agent and / or curing accelerator-encapsulating capsule may be repeatedly washed with pure water and then dried by vacuum drying or the like.
本発明の硬化剤及び／又は硬化促進剤内包カプセルは、硬化性樹脂組成物に配合された場合に優れた熱保存安定性及び速硬化性を発揮することができることから、エポキシ樹脂等の熱硬化性樹脂用の潜在性硬化剤又は硬化促進剤として好適に用いられる。
本発明の硬化剤及び／又は硬化促進剤内包カプセルと、熱硬化性化合物とを含有する熱硬化性樹脂組成物もまた、本発明の１つである。
The curing agent and / or curing accelerator-encapsulating capsule of the present invention can exhibit excellent thermal storage stability and fast curability when blended in a curable resin composition, and thus thermosetting epoxy resins and the like. It is suitably used as a latent curing agent or curing accelerator for a conductive resin.
A thermosetting resin composition containing the capsule containing the curing agent and / or curing accelerator of the present invention and a thermosetting compound is also one aspect of the present invention.
本発明によれば、硬化性樹脂組成物に配合された場合に優れた熱保存安定性及び速硬化性を発揮することができる硬化剤及び／又は硬化促進剤内包カプセルを提供することができる。また、本発明によれば、該硬化剤及び／又は硬化促進剤内包カプセルを含有する熱硬化性樹脂組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, when it mix | blends with a curable resin composition, the hardening | curing agent and / or hardening accelerator inclusion capsule which can exhibit the outstanding heat | fever storage stability and rapid sclerosis | hardenability can be provided. Moreover, according to this invention, the thermosetting resin composition containing this hardening | curing agent and / or hardening accelerator inclusion capsule can be provided.
以下に実施例を掲げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Examples of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
（実施例１）
酢酸エチル１２０重量部と、イソプロピルアルコール（ＩＰＡ）５０重量部と、メタノール２５重量部との混合溶媒に、シェルを構成するポリマーとしてスチレン系誘導体ポリマー（マープルーフＧ−０１３０ＳＰ、日油社製）２．１重量部と、グリシジル基を有するシロキサン（Ｘ−４１−１０５３、信越化学工業社製）２．１重量部と、２−ウンデシルイミダゾール３重量部とを溶解させることで混合溶液を得た。
この混合溶液に、乳化剤としてポリオキシエチレンラウリルエーテル２重量部を溶解した水性媒体６８０重量部を添加して、そこへ酢酸２重量部を添加したのち、２時間撹拌を行った。その後、得られた溶液を減圧装置付反応機中に入れて７０℃で４時間溶媒を除去することで、微細孔を有する粒子を得た。得られた粒子を、イオン交換水２７０重量部と、メタノール３０重量部と、２５重量％アンモニア水溶液１．９重量部との混合物中に分散させたのち、フッ素含有シランカップリング剤としてトリフルオロプロピルトリメトキシシラン（ＫＢＭ−７１０３、信越化学工業社製）０．４重量部を添加して、１２時間以上室温で撹拌を行った。その後、得られた粒子を、純水を用いて繰り返し洗浄したのち、真空乾燥を行うことで、硬化促進剤内包カプセルを得た。
なお、得られた硬化促進剤内包カプセルのシェルが微細孔を有することは、走査型電子顕微鏡により確認した。走査型電子顕微鏡により倍率５００００倍でカプセルを観察、撮影し、撮影した写真からノギスで無作為に抽出した５０個のカプセルの微細孔径を測定したところ、微細孔の平均径は３０ｎｍであった。
Example 1
In a mixed solvent of 120 parts by weight of ethyl acetate, 50 parts by weight of isopropyl alcohol (IPA), and 25 parts by weight of methanol, a styrene derivative polymer (Marproof G-0130SP, manufactured by NOF Corporation) 2 as a polymer constituting the shell 2 0.1 parts by weight, 2.1 parts by weight of siloxane having a glycidyl group (X-41-1053, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3 parts by weight of 2-undecylimidazole were obtained to obtain a mixed solution. .
To this mixed solution was added 680 parts by weight of an aqueous medium in which 2 parts by weight of polyoxyethylene lauryl ether was dissolved as an emulsifier, and 2 parts by weight of acetic acid was added thereto, followed by stirring for 2 hours. Thereafter, the obtained solution was put into a reactor equipped with a decompression device, and the solvent was removed at 70 ° C. for 4 hours to obtain particles having fine pores. The obtained particles were dispersed in a mixture of 270 parts by weight of ion-exchanged water, 30 parts by weight of methanol, and 1.9 parts by weight of a 25% by weight aqueous ammonia solution, and then trifluoropropyl as a fluorine-containing silane coupling agent. 0.4 parts by weight of trimethoxysilane (KBM-7103, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature for 12 hours or more. Thereafter, the obtained particles were repeatedly washed with pure water and then vacuum-dried to obtain a curing accelerator-encapsulating capsule.
In addition, it confirmed with the scanning electron microscope that the shell of the obtained hardening accelerator inclusion | encapsulation capsule had a micropore. Capsules were observed and photographed with a scanning electron microscope at a magnification of 50000 times, and the fine pore diameters of 50 capsules randomly extracted with a caliper were measured from the photographed photographs. The average pore diameter was 30 nm.
（実施例２）
酢酸エチル１２０重量部と、イソプロピルアルコール（ＩＰＡ）５０重量部と、メタノール２５重量部との混合溶液に、シェルを構成するポリマーとしてスチレン系誘導体ポリマー（マープルーフＧ−０１３０ＳＰ、日油社製）２．１重量部と、グリシジル基を有するシロキサン（Ｘ−４１−１０５３、信越化学工業社製）２．１重量部と、フッ素含有シロキサンポリマーとしてフッ素シリコーン（ＫＰ−９１１、信越化学工業社製）０．５重量部と、２−ウンデシルイミダゾール３重量部とを溶解させることで混合溶液を得た。
この混合溶液に、乳化剤としてポリオキシエチレンラウリルエーテル２重量部を溶解した水性媒体６８０重量部を添加して、そこへ酢酸２重量部を添加したのち、２時間撹拌を行った。その後、得られた溶液を減圧装置付反応機中に入れて７０℃で４時間溶媒を除去することで、微細孔を有する粒子を得た。得られた粒子を、純水を用いて繰り返し洗浄したのち、真空乾燥を行うことで、硬化促進剤内包カプセルを得た。
なお、得られた硬化促進剤内包カプセルのシェルが微細孔を有することは、走査型電子顕微鏡により確認した。走査型電子顕微鏡により倍率５００００倍でカプセルを観察、撮影し、撮影した写真からノギスで無作為に抽出した５０個のカプセルの微細孔径を測定したところ、微細孔の平均径は２５ｎｍであった。
(Example 2)
In a mixed solution of 120 parts by weight of ethyl acetate, 50 parts by weight of isopropyl alcohol (IPA), and 25 parts by weight of methanol, a styrene derivative polymer (Marproof G-0130SP, manufactured by NOF Corporation) 2 as a polymer constituting the shell 2 0.1 part by weight, 2.1 parts by weight of siloxane having a glycidyl group (X-41-1053, manufactured by Shin-Etsu Chemical Co., Ltd.), and fluorine-containing siloxane polymer as fluorosilicone (KP-911, manufactured by Shin-Etsu Chemical Co., Ltd.) 0 A mixed solution was obtained by dissolving 0.5 part by weight and 3 parts by weight of 2-undecylimidazole.
To this mixed solution was added 680 parts by weight of an aqueous medium in which 2 parts by weight of polyoxyethylene lauryl ether was dissolved as an emulsifier, and 2 parts by weight of acetic acid was added thereto, followed by stirring for 2 hours. Thereafter, the obtained solution was put into a reactor equipped with a decompression device, and the solvent was removed at 70 ° C. for 4 hours to obtain particles having fine pores. The obtained particles were repeatedly washed with pure water and then vacuum-dried to obtain a curing accelerator-encapsulating capsule.
In addition, it confirmed with the scanning electron microscope that the shell of the obtained hardening accelerator inclusion | encapsulation capsule had a micropore. Capsules were observed and photographed with a scanning electron microscope at a magnification of 50000 times, and the fine pore diameters of 50 capsules randomly extracted with a caliper were measured from the photographed photographs. The average pore diameter was 25 nm.
（実施例３）
フッ素シリコーン（ＫＰ−９１１、信越化学工業社製）０．５重量部の代わりに、フッ素樹脂−シロキサングラフト型ポリマー（ＺＸ−０２２−Ｈ、Ｔ＆Ｋ ＴＯＫＡ社製）０．５重量部を用いたこと以外は実施例２と同様にして、硬化促進剤内包カプセルを得た。
なお、得られた硬化促進剤内包カプセルのシェルが微細孔を有することは、走査型電子顕微鏡により確認した。走査型電子顕微鏡により倍率５００００倍でカプセルを観察、撮影し、撮影した写真からノギスで無作為に抽出した５０個のカプセルの微細孔径を測定したところ、微細孔の平均径は１５ｎｍであった。
Example 3
Instead of 0.5 parts by weight of fluorosilicone (KP-911, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.5 parts by weight of fluororesin-siloxane graft polymer (ZX-022-H, manufactured by T & K TOKA) was used. Except for the above, a curing accelerator-encapsulating capsule was obtained in the same manner as in Example 2.
In addition, it confirmed with the scanning electron microscope that the shell of the obtained hardening accelerator inclusion | encapsulation capsule had a micropore. Capsules were observed and photographed with a scanning electron microscope at a magnification of 50000 times, and when the fine pore diameters of 50 capsules randomly extracted with a caliper were measured from the photographed photographs, the average pore diameter was 15 nm.
（実施例４）
フッ素シリコーン（ＫＰ−９１１、信越化学工業社製）０．５重量部の代わりに、フッ素樹脂−シロキサングラフト型ポリマー（ＺＸ−０４７−Ｄ、Ｔ＆Ｋ ＴＯＫＡ社製）０．５重量部を用いたこと以外は実施例２と同様にして、硬化促進剤内包カプセルを得た。
なお、得られた硬化促進剤内包カプセルのシェルが微細孔を有することは、走査型電子顕微鏡により確認した。走査型電子顕微鏡により倍率５００００倍でカプセルを観察、撮影し、撮影した写真からノギスで無作為に抽出した５０個のカプセルの微細孔径を測定したところ、微細孔の平均径は１５ｎｍであった。
Example 4
Instead of 0.5 part by weight of fluorosilicone (KP-911, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.5 part by weight of fluororesin-siloxane graft polymer (ZX-047-D, manufactured by T & K TOKA) was used. Except for the above, a curing accelerator-encapsulating capsule was obtained in the same manner as in Example 2.
In addition, it confirmed with the scanning electron microscope that the shell of the obtained hardening accelerator inclusion | encapsulation capsule had a micropore. Capsules were observed and photographed with a scanning electron microscope at a magnification of 50000 times, and when the fine pore diameters of 50 capsules randomly extracted with a caliper were measured from the photographed photographs, the average pore diameter was 15 nm.
（比較例１）
スチレンモノマー５．１重量部と、メタクリル酸メチル１．５重量部と、グリシジル基を有するシロキサン（Ｘ−４１−１０５３、信越化学工業社製）６．６重量部とに、２−ウンデシルイミダゾール２．７重量部を溶解させた。そこへ２，２’−アゾビスイソ酪酸ジメチル（Ｖ−６０１）１．３重量部を溶解させることで混合溶液を得た。
この混合溶液に、分散剤として５重量％のポリビニルアルコール（ＧＭ−１４、日本合成化学社製）を添加した水性媒体７６重量部を添加し、数分間マグネットスターラーで撹拌したのち、イオン交換水３０２重量部を添加してホモジナイザーを用いて１２０００ｒｐｍ、１０分乳化を行った。この乳化液を反応容器に移し、酢酸１．１重量部を加えて８５℃、９時間重合をすることで粒子を得た。その後、得られた粒子を、純水を用いて繰り返し洗浄したのち、真空乾燥を行うことで、硬化促進剤内包カプセルを得た。
なお、走査型電子顕微鏡により倍率５００００倍でカプセルを観察、撮影し、撮影した写真から、得られた硬化促進剤内包カプセルのシェルが微細孔を有さないことを確認した。
(Comparative Example 1)
2-Undecylimidazole is added to 5.1 parts by weight of styrene monomer, 1.5 parts by weight of methyl methacrylate, and 6.6 parts by weight of siloxane having a glycidyl group (X-41-1053, manufactured by Shin-Etsu Chemical Co., Ltd.). 2.7 parts by weight were dissolved. A mixed solution was obtained by dissolving 1.3 parts by weight of dimethyl 2,2′-azobisisobutyrate (V-601).
To this mixed solution, 76 parts by weight of an aqueous medium to which 5% by weight of polyvinyl alcohol (GM-14, manufactured by Nippon Synthetic Chemical Co., Ltd.) was added as a dispersant was added, stirred for several minutes with a magnetic stirrer, and then ion-exchanged water 302. A part by weight was added, and emulsification was performed using a homogenizer at 12000 rpm for 10 minutes. The emulsion was transferred to a reaction vessel, 1.1 parts by weight of acetic acid was added, and polymerization was performed at 85 ° C. for 9 hours to obtain particles. Thereafter, the obtained particles were repeatedly washed with pure water and then vacuum-dried to obtain a curing accelerator-encapsulating capsule.
The capsules were observed and photographed with a scanning electron microscope at a magnification of 50000 times, and it was confirmed from the photographed photographs that the shell of the obtained curing accelerator-encapsulating capsules did not have micropores.
（比較例２）
トリフルオロプロピルトリメトキシシラン（ＫＢＭ−７１０３、信越化学工業社製）による処理を行わなかったこと以外は実施例１と同様にして、硬化促進剤内包カプセルを得た。
なお、得られた硬化促進剤内包カプセルのシェルが微細孔を有することは、走査型電子顕微鏡により確認した。走査型電子顕微鏡により倍率５００００倍でカプセルを観察、撮影し、撮影した写真からノギスで無作為に抽出した５０個のカプセルの微細孔径を測定したところ、微細孔の平均径は３０ｎｍであった。
(Comparative Example 2)
A curing accelerator-encapsulating capsule was obtained in the same manner as in Example 1 except that the treatment with trifluoropropyltrimethoxysilane (KBM-7103, manufactured by Shin-Etsu Chemical Co., Ltd.) was not performed.
In addition, it confirmed with the scanning electron microscope that the shell of the obtained hardening accelerator inclusion | encapsulation capsule had a micropore. Capsules were observed and photographed with a scanning electron microscope at a magnification of 50000 times, and the fine pore diameters of 50 capsules randomly extracted with a caliper were measured from the photographed photographs. The average pore diameter was 30 nm.
＜評価＞
実施例及び比較例で用いた各材料、又は、実施例及び比較例で得られた硬化促進剤内包カプセルについて以下の評価を行った。結果を表１に示した。
<Evaluation>
The following evaluation was performed about each material used by the Example and the comparative example, or the hardening accelerator inclusion capsule obtained by the Example and the comparative example. The results are shown in Table 1.
（１）シェルと硬化促進剤との濡れ性（接触角）
シェルを構成するポリマーと、必要に応じてフッ素含有シロキサンポリマーとを有機溶剤中へ溶解させ、そのポリマー溶液を塗工したのち、有機溶剤を除去し、必要に応じてフッ素含有シランカップリング剤により表面処理することにより、実施例及び比較例で得られた硬化促進剤内包カプセルのシェルと同様の組成を有するシェルポリマーフィルムを得た。得られたシェルポリマーフィルムを１００℃のホットプレート上にのせ、予め１００℃で予熱しておいた硬化促進剤０．０３ｍＬをシェルポリマーフィルム上に滴下した。シェルポリマーフィルムと硬化促進剤との接触付近の写真を、液滴の水平方向からデジタルカメラで撮影した。撮影した写真から直接、分度器を用いてシェルと硬化促進剤との接触角を測定した。
(1) Wettability (contact angle) between shell and curing accelerator
The polymer constituting the shell and, if necessary, the fluorine-containing siloxane polymer are dissolved in an organic solvent. After coating the polymer solution, the organic solvent is removed, and if necessary, a fluorine-containing silane coupling agent is used. By performing the surface treatment, a shell polymer film having a composition similar to that of the shell of the curing accelerator-encapsulating capsule obtained in Examples and Comparative Examples was obtained. The obtained shell polymer film was placed on a hot plate at 100 ° C., and 0.03 mL of a curing accelerator preheated at 100 ° C. was dropped onto the shell polymer film. A photograph near the contact between the shell polymer film and the curing accelerator was taken with a digital camera from the horizontal direction of the droplet. The contact angle between the shell and the curing accelerator was measured directly from the photographed photo using a protractor.
（２）硬化促進剤の保持性
融点測定機（ＡＴＭ−０２、アズワン社製）を用いて、１００℃の条件下で硬化促進剤内包カプセルを加熱し、硬化促進剤が放出されるまでの時間（硬化促進剤の保持時間）を測定した。
(2) Curing accelerator retention melting point (ATM-02, manufactured by ASONE Co., Ltd.) Time until the curing accelerator is released under the condition of 100 ° C. and the curing accelerator is released. (Holding time of curing accelerator) was measured.
（３）熱保存安定性
エポキシ樹脂（ＥＸＡ−８３０−ＣＲＰ、ＤＩＣ社製）３重量部及び酸無水物硬化剤（ＹＨ３０７、三菱化学社製）２重量部中に、硬化促進剤内包カプセルを０．５７重量部添加して、公転自転撹拌機で撹拌した後、得られたエポキシ樹脂組成物を１２０℃のオーブンに入れて、３０分毎にエポキシ樹脂組成物の粘度を測定することで初期粘度に対する粘度上昇倍率（経時粘度／初期粘度）を求めた。
なお、粘度の測定は、Ｅ型粘度計（ＴＶＥ−２５Ｈ、東機産業社製、φ２４ｍｍローターを使用）を用いて、２５℃、０．５ｒｐｍの条件で行った。
(3) Heat storage stability epoxy resin (EXA-830-CRP, manufactured by DIC) 3 parts by weight and acid anhydride curing agent (YH307, manufactured by Mitsubishi Chemical) 2 parts by weight of curing accelerator-containing capsules After adding 57 parts by weight and stirring with a revolutionary rotating agitator, the obtained epoxy resin composition was put in an oven at 120 ° C., and the viscosity of the epoxy resin composition was measured every 30 minutes to obtain an initial viscosity. Viscosity increase ratio (viscosity with time / initial viscosity) was determined.
The viscosity was measured using an E-type viscometer (TVE-25H, manufactured by Toki Sangyo Co., Ltd., using a φ24 mm rotor) under the conditions of 25 ° C. and 0.5 rpm.
（４）速硬化性（硬化速度の測定）
エポキシ樹脂（ＥＸＡ−８３０−ＣＲＰ、ＤＩＣ社製）３重量部及び酸無水物硬化剤（ＹＨ３０７、三菱化学社製）２重量部中に、硬化促進剤内包カプセルを０．５７重量部添加して、公転自転撹拌機で撹拌した後、得られたエポキシ樹脂組成物を２１０℃に熱したホットプレート上に置いたスライドガラスの上に滴下して、エポキシ樹脂組成物が硬化するまでの時間（硬化時間）を測定した。
(4) Fast curability (Measurement of cure speed)
0.57 parts by weight of a curing accelerator-containing capsule was added to 3 parts by weight of an epoxy resin (EXA-830-CRP, manufactured by DIC) and 2 parts by weight of an acid anhydride curing agent (YH307, manufactured by Mitsubishi Chemical Corporation). After stirring with a revolutionary rotating agitator, the obtained epoxy resin composition was dropped on a glass slide placed on a hot plate heated to 210 ° C., and the time until the epoxy resin composition was cured (curing Time).
本発明によれば、硬化性樹脂組成物に配合された場合に優れた熱保存安定性及び速硬化性を発揮することができる硬化剤及び／又は硬化促進剤内包カプセルを提供することができる。また、本発明によれば、該硬化剤及び／又は硬化促進剤内包カプセルを含有する熱硬化性樹脂組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, when it mix | blends with a curable resin composition, the hardening | curing agent and / or hardening accelerator inclusion capsule which can exhibit the outstanding heat | fever storage stability and rapid sclerosis | hardenability can be provided. Moreover, according to this invention, the thermosetting resin composition containing this hardening | curing agent and / or hardening accelerator inclusion capsule can be provided.
Claims (2)
前記コア剤を被覆するシェルは、微細孔を有し、かつ、表面に、フッ素元素を含有するシロキサン化合物を有する
ことを特徴とする硬化剤及び／又は硬化促進剤内包カプセル。 A curing agent and / or a curing accelerator-encapsulating capsule containing a curing agent and / or a curing accelerator as a core agent,
The shell covering the core agent has fine pores, and has a siloxane compound containing elemental fluorine on the surface, and a capsule containing a curing agent and / or a curing accelerator.
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