JPWO2020121939A1 - Silicone Pressure Sensitive Adhesive Compositions and Their Applications - Google Patents
Silicone Pressure Sensitive Adhesive Compositions and Their Applications Download PDFInfo
- Publication number
- JPWO2020121939A1 JPWO2020121939A1 JP2020560005A JP2020560005A JPWO2020121939A1 JP WO2020121939 A1 JPWO2020121939 A1 JP WO2020121939A1 JP 2020560005 A JP2020560005 A JP 2020560005A JP 2020560005 A JP2020560005 A JP 2020560005A JP WO2020121939 A1 JPWO2020121939 A1 JP WO2020121939A1
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- group
- pressure
- component
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 173
- 239000000203 mixture Substances 0.000 title claims abstract description 156
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 136
- 239000010410 layer Substances 0.000 claims abstract description 132
- 230000001070 adhesive effect Effects 0.000 claims abstract description 43
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 27
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- -1 siloxane units Chemical group 0.000 claims description 85
- 239000000853 adhesive Substances 0.000 claims description 42
- 239000000758 substrate Substances 0.000 claims description 27
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 21
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 125000000962 organic group Chemical group 0.000 claims description 12
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 238000010998 test method Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 9
- 239000010703 silicon Substances 0.000 abstract description 8
- 238000001723 curing Methods 0.000 description 58
- 239000000463 material Substances 0.000 description 52
- 239000000047 product Substances 0.000 description 28
- 150000002430 hydrocarbons Chemical group 0.000 description 27
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 23
- 239000012790 adhesive layer Substances 0.000 description 19
- 125000003342 alkenyl group Chemical group 0.000 description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 11
- 229930195734 saturated hydrocarbon Natural products 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 125000004430 oxygen atom Chemical group O* 0.000 description 8
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 6
- 125000006038 hexenyl group Chemical group 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000005452 alkenyloxyalkyl group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 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 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- ZFJFYUXFKXTXGT-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-[dimethyl(trimethylsilyloxy)silyl]oxy-dimethylsilane Chemical compound C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C ZFJFYUXFKXTXGT-UHFFFAOYSA-N 0.000 description 2
- NRTJGTSOTDBPDE-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C NRTJGTSOTDBPDE-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 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 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- HMVBQEAJQVQOTI-UHFFFAOYSA-N 3,5-dimethylhex-3-en-1-yne Chemical compound CC(C)C=C(C)C#C HMVBQEAJQVQOTI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- BPMGYFSWCJZSBA-UHFFFAOYSA-N C[SiH](C)O[SiH3] Chemical compound C[SiH](C)O[SiH3] BPMGYFSWCJZSBA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YTEISYFNYGDBRV-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)oxy-dimethylsilyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)O[Si](C)C YTEISYFNYGDBRV-UHFFFAOYSA-N 0.000 description 1
- BGISVIDNIBCUTN-UHFFFAOYSA-N [bis[(dimethyl-$l^{3}-silanyl)oxy]-methylsilyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(O[Si](C)C)O[Si](C)C BGISVIDNIBCUTN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002521 alkyl halide group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- 150000004862 dioxolanes Chemical group 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 244000144985 peep Species 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
実質的に溶剤をほとんど含有しなくても塗工可能な粘度を有し、硬化性に優れ、良好な接着特性を有する感圧接着層を形成する、シリコーン感圧接着剤組成物およびその用途を提供する。本発明は、(A)脂肪族不飽和炭素−炭素結合含有基を有し、シロキサン重合度が5〜250の範囲である、鎖状オルガノポリシロキサン、(B)分子鎖両末端のみにケイ素結合水素原子を有する直鎖状オルガノハイドロジェンポリシロキサン、(C)オルガノポリシロキサン樹脂、(D)分子内に少なくとも3個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサンを含有し、(B)成分中のSiHに対するSiH/Vi比が、0.90〜1.30の範囲にあり、(B)成分と(D)成分を合わせたSiHに対するSiH/Vi比が、0.95〜1.35の範囲であり、粘度が1,000〜300,000mPa・sの範囲であり、かつ、有機溶媒の含有量が組成物全体の20質量%未満である、シリコーン感圧接着剤組成物、を提供する。Silicone pressure-sensitive adhesive compositions and their uses that form a pressure-sensitive adhesive layer that has a viscosity that allows coating with substantially no solvent, has excellent curability, and has good adhesive properties. offer. The present invention comprises (A) a chain organopolysiloxane having an aliphatic unsaturated carbon-carbon bond-containing group and having a siloxane polymerization degree in the range of 5 to 250, and (B) a silicon bond only at both ends of the molecular chain. It contains a linear organohydrogenpolysiloxane having a hydrogen atom, (C) an organopolysiloxane resin, and (D) an organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule, and the component (B). The SiH / Vi ratio to SiH inside is in the range of 0.90 to 1.30, and the SiH / Vi ratio to SiH including the components (B) and (D) is 0.95-1.35. Provided is a silicone pressure-sensitive adhesive composition, which is in the range, has a viscosity in the range of 1,000 to 300,000 mPa · s, and has an organic solvent content of less than 20% by mass based on the whole composition. ..
Description
本発明は、シリコーン感圧接着剤組成物に関する。また、本発明は、当該組成物を硬化させてなる接着剤層または弾性粘着部材、当該組成物を硬化させてなる接着剤層を含む積層体等の用途に関する。 The present invention relates to a silicone pressure sensitive adhesive composition. The present invention also relates to applications such as an adhesive layer or elastic adhesive member obtained by curing the composition, and a laminate containing an adhesive layer obtained by curing the composition.
ポリシロキサン系感圧接着剤組成物は、アクリル系やゴム系の感圧接着剤組成物と比較して、電気絶縁性、耐熱性、耐寒性、各種被着体に対する粘着性に優れるので、耐熱性粘着テープ、電気絶縁性粘着テープ、ヒートシールテープ、メッキマスキングテープ等に使用されている。これらのポリシロキサン系感圧接着剤組成物は、その硬化機構により、付加反応硬化型、縮合反応硬化型、パーオキサイド硬化型などに分類される。室温放置もしくは加熱によって速やかに硬化し、副生物を発生しないので、付加反応硬化型の感圧接着剤組成物が汎用されている。 The polysiloxane-based pressure-sensitive adhesive composition is superior in electrical insulation, heat resistance, cold resistance, and adhesiveness to various adherends as compared with acrylic and rubber-based pressure-sensitive adhesive compositions. It is used in adhesive tapes, electrically insulating adhesive tapes, heat seal tapes, plated masking tapes, etc. These polysiloxane-based pressure-sensitive adhesive compositions are classified into an addition reaction curing type, a condensation reaction curing type, a peroxide curing type, and the like according to the curing mechanism. Addition reaction curing type pressure-sensitive adhesive compositions are widely used because they are rapidly cured by being left at room temperature or heated and do not generate by-products.
ポリシロキサン系感圧接着剤の上記特性および必要に応じて高い透明性を実現できる性質を生かし、近年、スマートデバイス等の先端エレクトロニクス材料および表示素子分野への応用が検討されている。このようなデバイスは、電極層、表示層を含む複数層からなるフィルムを透明基材の間に挟みこんだ構造をとっており、電極層、表示層の保護および層間の接着性改良を目的に、耐熱・耐寒性に優れるポリシロキサン系感圧接着剤が有効に作用することが期待される。 Taking advantage of the above-mentioned characteristics of the polysiloxane-based pressure-sensitive adhesive and the property of realizing high transparency as needed, application to advanced electronic materials such as smart devices and display element fields has been studied in recent years. Such a device has a structure in which a film composed of a plurality of layers including an electrode layer and a display layer is sandwiched between transparent substrates, for the purpose of protecting the electrode layer and the display layer and improving the adhesiveness between the layers. It is expected that a polysiloxane-based pressure-sensitive adhesive having excellent heat resistance and cold resistance will work effectively.
しかしながら、ポリシロキサン系感圧接着剤は、一般的に有機溶剤に溶解して商品化されていることから、その用途が限定されていた。特に近年、世界各国の環境規制強化の方向性から、無溶剤型のポリシロキサン系感圧接着剤の開発が強く望まれている。例えば特許文献1〜4には、無溶剤型のポリシロキサン系感圧接着剤が開示されているが、溶剤型のポリシロキサン系感圧接着剤と比較すると、各種特性において改善が望まれていた。 However, since polysiloxane-based pressure-sensitive adhesives are generally dissolved in organic solvents and commercialized, their uses have been limited. Particularly in recent years, the development of solvent-free polysiloxane-based pressure-sensitive adhesives has been strongly desired from the direction of tightening environmental regulations in various countries around the world. For example, Patent Documents 1 to 4 disclose solvent-free polysiloxane-based pressure-sensitive adhesives, but improvements in various properties have been desired as compared with solvent-based polysiloxane-based pressure-sensitive adhesives. ..
本発明は上記課題を解決すべくなされたものであり、低溶剤型または無溶剤型の組成物として、実質的に溶剤をほとんど含有しなくても塗工可能な粘度を有し、硬化性に優れ、硬化反応により形成したポリオルガノシロキサン系感圧接着剤が、良好な接着強度、タック、高温保持力をバランス良く有する感圧接着層を形成する、シリコーン感圧接着剤組成物を提供することを目的とする。ここで感圧接着剤の高温保持力とは、感圧接着剤を用いて2つの基材を接着させたときに、高温においても基材間で接着位置のずれや、2つの基材の分離が起こらずに接着力を維持できる性質をいう。さらに、本発明は、当該シリコーン感圧接着剤組成物の硬化物の感圧接着層としての使用、広汎な用途における弾性粘着部材としての使用およびそれらを備えた機器または装置を提供することを目的とする。 The present invention has been made to solve the above problems, and as a low-solvent type or solvent-free type composition, has a viscosity that allows coating with substantially no solvent, and has curability. To provide a silicone pressure-sensitive adhesive composition in which a polyorganosiloxane-based pressure-sensitive adhesive formed by an excellent curing reaction forms a pressure-sensitive adhesive layer having a good balance of adhesive strength, tack, and high-temperature holding power. With the goal. Here, the high-temperature holding power of the pressure-sensitive adhesive means that when two base materials are bonded using a pressure-sensitive adhesive, the bonding position is displaced between the base materials and the two base materials are separated even at a high temperature. It refers to the property that the adhesive strength can be maintained without causing the occurrence. A further object of the present invention is to provide a cured product of the silicone pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer, use as an elastic pressure-sensitive adhesive member in a wide range of applications, and an apparatus or apparatus provided with them. And.
本発明者らは上記課題について鋭意検討した結果、本発明に到達した。すなわち、本発明の目的の一つは、
[1](A)一分子中に少なくとも2個の、脂肪族不飽和炭素−炭素結合含有基を有し、そのシロキサン重合度が5〜250の範囲である、直鎖状又は分岐鎖状オルガノポリシロキサン、
(B)分子鎖両末端のみにケイ素結合水素原子を有する直鎖状オルガノハイドロジェンポリシロキサン、
(C)分子内にR3SiO1/2(式中、Rは互いに独立して一価有機基を表す)で表されるシロキサン単位(M単位)、及び、SiO4/2で表されるシロキサン単位(Q単位)を含むオルガノポリシロキサン樹脂、
(D)分子内に少なくとも3個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、および
(E)ヒドロシリル化反応触媒
を含有し、
(B)成分中のケイ素結合水素原子のモル数の(A)成分中の脂肪族不飽和炭素−炭素結合含有基のモル数に対する比が、0.90〜1.30の範囲にあり、
(B)成分と(D)成分を合わせたケイ素結合水素原子のモル数の(A)成分中の脂肪族不飽和炭素−炭素結合含有基のモル数に対する比が、0.95〜1.35の範囲であり、
25℃における組成物全体の粘度が1,000〜300,000mPa・sの範囲であり、かつ、
有機溶媒の含有量が組成物全体の20質量%未満である、
シリコーン感圧接着剤組成物
により達成される。The present inventors have arrived at the present invention as a result of diligent studies on the above problems. That is, one of the objects of the present invention is
[1] (A) A linear or branched organogen having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule and having a siloxane degree of polymerization in the range of 5 to 250. Polysiloxane,
(B) A linear organohydrogenpolysiloxane having a silicon-bonded hydrogen atom only at both ends of the molecular chain,
(C) Intramolecularly represented by R 3 SiO 1/2 (in the formula, R represents a monovalent organic group independently of each other) in siloxane units (M units) and SiO 4/2. Organopolysiloxane resin containing siloxane units (Q units),
It contains (D) an organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule, and (E) a hydrosilylation reaction catalyst.
The ratio of the number of moles of the silicon-bonded hydrogen atom in the component (B) to the number of moles of the aliphatic unsaturated carbon-carbon bond-containing group in the component (A) is in the range of 0.99 to 1.30.
The ratio of the number of moles of silicon-bonded hydrogen atoms including the components (B) and (D) to the number of moles of aliphatic unsaturated carbon-carbon bond-containing groups in the component (A) is 0.95-1.35. Is in the range of
The viscosity of the entire composition at 25 ° C. is in the range of 1,000 to 300,000 mPa · s, and
The content of the organic solvent is less than 20% by weight of the total composition.
Achieved by silicone pressure sensitive adhesive compositions.
また、本発明の課題は、以下のシリコーン感圧接着剤組成物により好適に解決されうる。
[2] (A)成分〜(D)成分の合計量を100質量部としたとき、
(A)成分および(B)成分の合計量が、10〜80質量部の範囲であり、
(C)成分の量が10〜80質量部の範囲であり、
(D)成分の量が、0.01〜10質量部の範囲であることを特徴とする、
[1]のシリコーン感圧接着剤組成物。
[3] (D)成分が、
(D1)分子内に少なくとも3個のケイ素結合水素原子を有する環状オルガノハイドロジェンポリシロキサン、および
(D2)分子鎖末端にケイ素結合水素原子を有さず、分子内に少なくとも3個のケイ素結合水素原子を有する直鎖状または分岐鎖状のオルガノハイドロジェンポリシロキサン
からなる群から選ばれる少なくとも1種類以上である、
[1]または[2]のシリコーン感圧接着剤組成物。
[4] 当該組成物の硬化により得られる厚み40μmの感圧接着層の、SUS基板に対する、JIS Z 0237に従う180°引き剥がし試験方法を用いて引張速度300mm/minにより測定された粘着力が100〜2500gf/inchの範囲であることを特徴とする、[1]乃至[3]のいずれか1項に記載のシリコーン感圧接着剤組成物。
[5] 有機溶媒の含有量が組成物全体の0〜5質量%の範囲にあり、無溶媒型ないし低溶媒型の組成物である、[1]乃至[4]のいずれか1項に記載のシリコーン感圧接着剤組成物。Further, the problem of the present invention can be suitably solved by the following silicone pressure-sensitive adhesive composition.
[2] When the total amount of the components (A) to (D) is 100 parts by mass,
The total amount of the component (A) and the component (B) is in the range of 10 to 80 parts by mass.
The amount of the component (C) is in the range of 10 to 80 parts by mass.
The amount of the component (D) is in the range of 0.01 to 10 parts by mass.
The silicone pressure-sensitive adhesive composition of [1].
[3] The component (D) is
(D1) Cyclic organohydrogenpolysiloxane having at least 3 silicon-bonded hydrogen atoms in the molecule, and (D2) Silicon-bonded hydrogen having no silicon-bonded hydrogen atom at the end of the molecular chain and having at least 3 silicon-bonded hydrogen atoms in the molecule. At least one selected from the group consisting of linear or branched organohydrogenpolysiloxane having atoms.
The silicone pressure-sensitive adhesive composition of [1] or [2].
[4] The adhesive force of the pressure-sensitive adhesive layer having a thickness of 40 μm obtained by curing the composition, measured at a tensile speed of 300 mm / min using a 180 ° peeling test method according to JIS Z 0237, is 100. The silicone pressure-sensitive adhesive composition according to any one of [1] to [3], which is in the range of ~ 2500 gf / inch.
[5] The item according to any one of [1] to [4], wherein the content of the organic solvent is in the range of 0 to 5% by mass of the whole composition, and the composition is a solvent-free type or a low solvent type. Silicone pressure sensitive adhesive composition.
同様に、本発明の課題は、以下の感圧接着剤層、積層体、弾性粘着部材およびそれを以下の用途に用いることにより好適に解決されうる。
[6] [1]乃至[5]のいずれか1項に記載のシリコーン感圧接着剤組成物を硬化してなる感圧接着剤層。
[7] フィルム状基材上に、[1]乃至[5]のいずれか1項に記載のシリコーン感圧接着剤組成物を硬化してなる感圧接着剤層を備えた積層体。
[8] 1または2以上のフィルム状基材を含み、前記フィルム状基材上に当該感圧接着剤層に対する剥離層が設けられている、[7]に記載の積層体。
[9] フィルム状基材、
該フィルム状基材上に形成された第1剥離層、
該剥離層上に[1]乃至[5]のいずれか1項に記載のシリコーン感圧接着剤組成物を塗工し硬化させて形成された感圧接着層、及び
該感圧接着層上に積層された第2剥離層
を含む、[7]または[8]の積層体。
[10] [1]乃至[5]のいずれか1項記載のシリコーン感圧接着剤組成物を硬化してなる、弾性粘着部材。
[11] [10]に記載の弾性粘着部材を含む電子機器または電気的装置。Similarly, the problems of the present invention can be suitably solved by using the following pressure-sensitive adhesive layers, laminates, elastic adhesive members and the following applications.
[6] A pressure-sensitive adhesive layer obtained by curing the silicone pressure-sensitive adhesive composition according to any one of [1] to [5].
[7] A laminate provided with a pressure-sensitive adhesive layer obtained by curing the silicone pressure-sensitive adhesive composition according to any one of [1] to [5] on a film-like substrate.
[8] The laminate according to [7], which comprises one or more film-like substrates and is provided with a release layer for the pressure-sensitive adhesive layer on the film-like substrate.
[9] Film-like substrate,
The first release layer formed on the film-like substrate,
On the pressure-sensitive adhesive layer formed by applying and curing the silicone pressure-sensitive adhesive composition according to any one of [1] to [5] on the release layer, and on the pressure-sensitive adhesive layer. The laminated body of [7] or [8] including the laminated second release layer.
[10] An elastic pressure-sensitive adhesive member obtained by curing the silicone pressure-sensitive adhesive composition according to any one of [1] to [5].
[11] An electronic device or an electrical device including the elastic adhesive member according to [10].
本発明のシリコーン感圧接着剤組成物は、低溶剤型または無溶剤型の組成物として、実質的に溶剤をほとんど含有しなくても塗工可能な粘度を有し、ヒドロシリル化反応による硬化性に優れ、かつ、硬化して、実用上十分な粘着力、タック、高温保持力を備え、かつ、硬化後の接着層の機械的強度、伸びに優れ、実用上十分な接着性を有する感圧接着層を形成することができる。さらに、当該シリコーン感圧接着剤組成物の硬化物は、感圧接着層、電子材料または表示装置用部材として好適に使用することができ、それらを備えた電気・電子部品または表示装置は、幅広い温度領域において接着層の粘弾性が十分であるので、低温から室温を含む温度領域において、電子部品等の基材に対する密着不良の問題を生じにくい感圧接着層を形成することができるため、電子部品等の工業化が容易であり、かつ、得られる電子部品等の性能改善が期待されるという利点を有する。 The silicone pressure-sensitive adhesive composition of the present invention has a viscosity that allows coating as a low-solvent type or solvent-free type composition with substantially no solvent, and is curable by a hydrosilylation reaction. Excellent and hardened, has sufficient adhesive strength, tack, and high temperature holding power for practical use, and has excellent mechanical strength and elongation of the adhesive layer after curing, and has sufficient adhesiveness for practical use. An adhesive layer can be formed. Further, the cured product of the silicone pressure-sensitive adhesive composition can be suitably used as a pressure-sensitive adhesive layer, an electronic material or a member for a display device, and the electric / electronic parts or display devices provided with them are wide-ranging. Since the viscoelasticity of the adhesive layer is sufficient in the temperature region, it is possible to form a pressure-sensitive adhesive layer that is less likely to cause a problem of poor adhesion to a substrate such as an electronic component in a temperature region including low temperature to room temperature. It has the advantages that the industrialization of parts and the like is easy and the performance of the obtained electronic parts and the like is expected to be improved.
[シリコーン感圧接着剤組成物]
まず、本発明にかかるシリコーン感圧接着剤組成物について説明する。当該組成物は、低溶剤型または無溶剤型の組成物として、実質的に有機溶媒を含有しない組成であっても実用上十分な塗工性を有し、ヒドロシリル化反応を含む硬化反応により速やかに硬化し、実用上十分な粘着力を有し、感圧接着剤層が機械的強度、伸びに優れる感圧接着層を形成するものである。以下、その各構成成分、技術的特徴であるオルガノポリシロキサン範囲、その鎖状オルガノポリシロキサンに対するオルガノポリシロキサンレジンの質量比、および感圧接着層の特性について説明する。[Silicone pressure sensitive adhesive composition]
First, the silicone pressure-sensitive adhesive composition according to the present invention will be described. As a low-solvent type or solvent-free type composition, the composition has practically sufficient coatability even if the composition does not substantially contain an organic solvent, and is rapidly subjected to a curing reaction including a hydrosilylation reaction. The pressure-sensitive adhesive layer forms a pressure-sensitive adhesive layer having excellent mechanical strength and elongation. Hereinafter, each component, the range of organopolysiloxane which is a technical feature, the mass ratio of the organopolysiloxane resin to the chain organopolysiloxane, and the characteristics of the pressure-sensitive adhesive layer will be described.
本発明のシリコーン感圧接着剤組成物は、
(A)一分子中に少なくとも2個の、脂肪族不飽和炭素−炭素結合含有基を有し、そのシロキサン重合度が5〜250の範囲である、直鎖状又は分岐鎖状オルガノポリシロキサン、
(B)分子鎖両末端のみにケイ素結合水素原子を有する直鎖状オルガノハイドロジェンポリシロキサン、
(C)分子内にR3SiO1/2(式中、Rは互いに独立して一価有機基を表す)で表されるシロキサン単位(M単位)、及び、SiO4/2で表されるシロキサン単位(Q単位)を含むオルガノポリシロキサン樹脂、
(D)分子内に少なくとも3個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、および
(E)ヒドロシリル化反応触媒
を含有してなり、有機溶媒の含有量が組成物全体の20質量%未満であり、取扱作業性の見地から、さらに、所望する場合は(F)硬化遅延剤を含有してもよく、本発明の目的に反しない範囲で、その他の添加剤を含むものであってよい。以下、各成分について説明する。The silicone pressure-sensitive adhesive composition of the present invention
(A) A linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule and having a siloxane degree of polymerization in the range of 5 to 250.
(B) A linear organohydrogenpolysiloxane having a silicon-bonded hydrogen atom only at both ends of the molecular chain,
(C) Intramolecularly represented by R 3 SiO 1/2 (in the formula, R represents a monovalent organic group independently of each other) in siloxane units (M units) and SiO 4/2. Organopolysiloxane resin containing siloxane units (Q units),
It contains (D) an organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule, and (E) a hydrosilylation reaction catalyst, and the content of the organic solvent is less than 20% by mass of the entire composition. Therefore, from the viewpoint of workability in handling, (F) a curing retarder may be contained if desired, and other additives may be contained within a range not contrary to the object of the present invention. .. Hereinafter, each component will be described.
[(A)成分]
(A)成分は、一分子中に少なくとも2個の、脂肪族不飽和炭素−炭素結合含有基を有し、そのシロキサン重合度が5〜250の範囲である、直鎖状又は分岐鎖状オルガノポリシロキサンであり、本組成物の主剤(ベースポリマー)である。シロキサン重合度が5〜250の範囲である(A)成分を使用することで、組成物の全体粘度を低減することができ、低溶媒型または無溶媒型の組成物を設計し、実質的に有機溶媒を含有しなくても、組成物全体として実用上十分な塗工性を実現することができる。(A)成分は、単一のオルガノポリシロキサンであってもよく、2種以上のオルガノポリシロキサンの混合物でもよい。[(A) component]
The component (A) is a linear or branched organogen having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule and having a siloxane degree of polymerization in the range of 5 to 250. It is a polysiloxane and is the main component (base polymer) of the present composition. By using the component (A) having a siloxane degree of polymerization in the range of 5 to 250, the overall viscosity of the composition can be reduced, and a low-solvent type or non-solvent type composition can be designed and substantially. Even if it does not contain an organic solvent, it is possible to realize practically sufficient coatability as a whole composition. The component (A) may be a single organopolysiloxane or a mixture of two or more organopolysiloxanes.
このような(A)成分であるオルガノポリシロキサンのシロキサン重合度は5〜250の範囲であり、5〜200が好ましく、5〜180の範囲が更により好ましい。また、(A)成分は、(A1)シロキサン重合度が5〜50の範囲であるオルガノポリシロキサンであってよく、(A1)成分と(A2)シロキサン重合度が51〜250の範囲、好適には51〜200の範囲であるオルガノポリシロキサンの混合物であってもよい。(A)成分のシロキサン重合度が前記上限を超えると、組成物全体の粘度が上昇する傾向があり、有機溶媒を多量に用いないと塗工が困難となる場合がある。一方、(A)成分のシロキサン重合度が前記下限未満では組成物の硬化性および粘着性能が低下する場合がある。本発明の技術的効果の見地から、(A)成分の50質量%以上が、(A1)シロキサン重合度が5〜50の範囲であるオルガノポリシロキサンであることが好ましく、これにより組成物の全体粘度を低減することができる利点がある。 The degree of siloxane polymerization of the organopolysiloxane as the component (A) is in the range of 5 to 250, preferably 5 to 200, and even more preferably 5 to 180. The component (A) may be an organopolysiloxane having a degree of polymerization of (A1) siloxane in the range of 5 to 50, and the component (A1) and the degree of polymerization of (A2) siloxane are preferably in the range of 51 to 250. May be a mixture of organopolysiloxanes in the range 51-200. If the degree of siloxane polymerization of the component (A) exceeds the above upper limit, the viscosity of the entire composition tends to increase, and coating may be difficult unless a large amount of organic solvent is used. On the other hand, if the degree of siloxane polymerization of the component (A) is less than the above lower limit, the curability and adhesive performance of the composition may deteriorate. From the viewpoint of the technical effect of the present invention, it is preferable that 50% by mass or more of the component (A) is (A1) an organopolysiloxane having a degree of polymerization of siloxane in the range of 5 to 50, whereby the entire composition is formed. There is an advantage that the viscosity can be reduced.
(A)成分は、分子内に少なくとも2個の脂肪族不飽和炭素−炭素結合含有基を有する。このような脂肪族不飽和炭素−炭素結合含有基としては、アルケニル基、アルケニルオキシアルキル基、アクリロキシアルキル基又はメタクリロキシアルキル基が例示され、特にアルケニル基が好ましい。具体的には、アルケニル基は、ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基等であり、ビニル基またはヘキセニル基が特に好ましい。また、これらの脂肪族不飽和炭素−炭素結合含有基はケイ素原子に結合していることが好ましい。 The component (A) has at least two aliphatic unsaturated carbon-carbon bond-containing groups in the molecule. Examples of such an aliphatic unsaturated carbon-carbon bond-containing group include an alkenyl group, an alkenyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, and an alkenyl group is particularly preferable. Specifically, the alkenyl group is a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group or the like, and a vinyl group or a hexenyl group is particularly preferable. Further, these aliphatic unsaturated carbon-carbon bond-containing groups are preferably bonded to a silicon atom.
脂肪族不飽和炭素−炭素結合含有基はシロキサン分子鎖末端及び分子鎖側鎖のいずれに存在してもよく、或いは、これらの両方に存在してもよい。 The aliphatic unsaturated carbon-carbon bond-containing group may be present at either the end of the siloxane molecular chain or the side chain of the siloxane, or may be present at both of them.
脂肪族不飽和炭素−炭素結合含有基の含有量は、(A)成分の質量に対して0.001〜10質量%が好ましく、0.005〜8.50質量%が好ましく、0.01〜7.5質量%がより好ましい。特に、脂肪族不飽和炭素−炭素結合含有基中のビニル(CH2=CH−)部分の含有量(以下、「ビニル含有量」という)が、0.005〜10.0質量%の範囲が好ましく、0.005〜8.50質量%の範囲が特に好ましい。The content of the aliphatic unsaturated carbon-carbon bond-containing group is preferably 0.001 to 10% by mass, preferably 0.005 to 8.50% by mass, and 0.01 to 0.01 to the mass of the component (A). 7.5% by mass is more preferable. In particular, the content of the vinyl (CH 2 = CH-) portion in the aliphatic unsaturated carbon-carbon bond-containing group (hereinafter referred to as “vinyl content”) is in the range of 0.005 to 10.0% by mass. The range of 0.005 to 8.50% by mass is preferable, and the range of 0.005 to 8.50% by mass is particularly preferable.
(A)成分は、脂肪族不飽和炭素−炭素結合含有基以外の有機基として、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基等のアルキル基;フェニル基、トリル基、キシリル基、ナフチル基等のアリール基;ベンジル基、フェネチル基等のアラルキル基;クロロメチル基、3−クロロプロピル基、3,3,3−トリフロロプロピル基等のハロゲン化アルキル基などを含んでもよい。工業的見地から、特に、メチル基、フェニル基を含むことが好ましい。 The component (A) is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a heptyl group; a phenyl group, as an organic group other than the aliphatic unsaturated carbon-carbon bond-containing group. Aryl groups such as trill group, xsilyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; alkyl halide groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group. May include. From an industrial point of view, it is particularly preferable to contain a methyl group and a phenyl group.
このような(A)成分としては、一般式:
R1 3SiO(R1 2SiO)m1SiR1 3
で表される直鎖状のオルガノポリシロキサンであることが好ましい。ただし、(A)成分は、その一部に、R1SiO3/2で表される分岐シロキサン単位及びSiO4/2で表される分岐シロキサン単位からなる群から選択される単位を一分子当たり平均0〜5個の範囲で含んでいてもよく、したがって分岐鎖状のオルガノポリシロキサンであってもよい。Such a component (A) includes a general formula:
R 1 3 SiO (R 1 2 SiO) m1 SiR 1 3
It is preferably a linear organopolysiloxane represented by. However, the component (A) includes a unit selected from the group consisting of a branched siloxane unit represented by R 1 SiO 3/2 and a branched siloxane unit represented by SiO 4/2 per molecule. It may be contained in the range of 0 to 5 on average, and therefore may be a branched-chain organopolysiloxane.
式中、各R1は独立に、置換又は非置換の、一価炭化水素基であり、一価炭化水素基としては既述した脂肪族不飽和炭素−炭素結合含有基及びその他の有機基が例示される。但し、一分子中、少なくとも2個のR1は脂肪族不飽和炭素−炭素結合含有基であり、好ましくはアルケニル基、より好ましくはビニル基またはヘキセニル基である。また、式中、“m1+2”であるシロキサン重合度は5〜230の範囲内の数であることが好ましく、5〜200の範囲の数であることがより好ましく、5〜190の範囲の数であることが、特に好ましい。なお、“+2”は直鎖状分子の両末端のシロキサン単位を加算したものであり、さらに、0〜5個の範囲で、R1SiO3/2で表される分岐シロキサン単位及びSiO4/2で表される分岐シロキサン単位から選択される単位を含んでもよい。なお、R1SiO3/2で表される分岐シロキサン単位に対しては1個の、SiO4/2で表される分岐シロキサン単位に対しては2個のR1 3SiO1/2単位が分子内に追加されて、当該分岐シロキサン単位に対応する分子鎖末端を形成する。In the formula, each R 1 is an independently substituted or unsubstituted monovalent hydrocarbon group, and the monovalent hydrocarbon group includes the above-mentioned aliphatic unsaturated carbon-carbon bond-containing group and other organic groups. Illustrated. However, in one molecule, at least two R 1 are aliphatic unsaturated carbon - is carbon bond-containing group, preferably an alkenyl group, more preferably vinyl or hexenyl group. Further, in the formula, the degree of siloxane polymerization of "m1 + 2" is preferably a number in the range of 5 to 230, more preferably a number in the range of 5 to 200, and a number in the range of 5 to 190. It is particularly preferable to have. In addition, "+2" is the sum of the siloxane units at both ends of the linear molecule, and further, in the range of 0 to 5, the branched siloxane unit represented by R 1 SiO 3/2 and the SiO 4 / A unit selected from the branched siloxane units represented by 2 may be included. One R 1 3 SiO 1/2 unit is used for the branched siloxane unit represented by R 1 SiO 3/2 , and two R 1 3 SiO 1/2 units are used for the branched siloxane unit represented by SiO 4/2. It is added intramolecularly to form the end of the molecular chain corresponding to the branched siloxane unit.
上の一般式において、両末端のR1 3SiO1/2単位における、R1は脂肪族不飽和炭素−炭素結合含有基以外の有機基であることが好ましく、これらの両末端におけるR1はアルキル基であることが好ましく、工業的見地から、特に、メチル基が好ましい。In the above general formula, in R 1 3 SiO 1/2 units at both ends, R 1 is an aliphatic unsaturated carbon - is preferably an organic group other than carbon bond-containing group, the R 1 in these both ends It is preferably an alkyl group, and from an industrial point of view, a methyl group is particularly preferable.
(A)成分の室温における性状はオイル状であり、(A)成分の粘度は25℃において1mPa・s以上であることが好ましい。特に、本発明にかかるシリコーン感圧接着剤組成物を低溶媒型または無溶媒型の組成物として設計する場合、塗工性の見地から、(A)成分の粘度が25℃において1mPa・s以上、100000mPa・s以下であることが好ましい。 The property of the component (A) at room temperature is oily, and the viscosity of the component (A) is preferably 1 mPa · s or more at 25 ° C. In particular, when the silicone pressure-sensitive adhesive composition according to the present invention is designed as a low-solvent type or non-solvent type composition, the viscosity of the component (A) is 1 mPa · s or more at 25 ° C. from the viewpoint of coatability. , 100,000 mPa · s or less is preferable.
なお、これらのアルケニル基含有オルガノポリシロキサンは、接点障害防止等の見地から、揮発性または低分子量のシロキサンオリゴマー(オクタメチルテトラシロキサン(D4)、デカメチルペンタシロキサン(D5)等)が低減ないし除去されていることが好ましい。その程度は所望により設計可能であるが、成分(A)全体の1質量%未満、各シロキサンオリゴマーごとに0.1質量%未満としてもよく、必要に応じ、ガスクロマトグラフにて検出限界付近まで低減してもよい。 From the viewpoint of preventing contact failure, these alkenyl group-containing organopolysiloxanes reduce or remove volatile or low molecular weight siloxane oligomers (octamethyltetrasiloxane (D4), decamethylpentasiloxane (D5), etc.). It is preferable that it is. The degree can be designed as desired, but may be less than 1% by mass of the entire component (A) and less than 0.1% by mass for each siloxane oligomer, and if necessary, reduced to near the detection limit by gas chromatography. You may.
(B)成分は、分子鎖両末端のみにケイ素結合水素原子を有する直鎖状オルガノハイドロジェンポリシロキサンであり、ヒドロシリル化反応において、主に(A)成分の鎖長延長剤として機能し、硬化反応物(粘着剤層)の伸びおよび柔軟性を改善する成分である。このような(B)成分を、(A)成分中の脂肪族不飽和炭素−炭素結合含有基に対して特定量使用することで、本組成物を硬化して得られる硬化反応物中に分子鎖長が延伸された構造が一定以上含まれ、弾性粘着部材としての接着性および保持力が著しく改善される。 The component (B) is a linear organohydrogenpolysiloxane having a silicon-bonded hydrogen atom only at both ends of the molecular chain, and in the hydrosilylation reaction, mainly functions as a chain length extender for the component (A) and is cured. It is a component that improves the elongation and flexibility of the reaction product (adhesive layer). By using such a component (B) in a specific amount with respect to the aliphatic unsaturated carbon-carbon bond-containing group in the component (A), the molecule is contained in the curing reaction product obtained by curing the present composition. A structure in which the chain length is extended is included to a certain extent or more, and the adhesiveness and holding power as an elastic adhesive member are remarkably improved.
このような(B)成分は、下式で示される分子鎖両末端にSiH基を含有するポリオルガノシロキサンであってよい。 Such component (B) may be a polyorganosiloxane containing SiH groups at both ends of the molecular chain represented by the following formula.
(B)成分の具体例として、例えば、1,1,3,3−テトラメチルジシロキサン、1,1,3,3,5,5−ヘキサメチルトリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン共重合体及びこれらのオルガノポリシロキサンの2種以上の混合物が例示される。 Specific examples of the component (B) include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, and dimethylhydrogensiloxy groups at both ends of the molecular chain. Blocked dimethylpolysiloxane, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer at both ends of the molecular chain, dimethylhydrogensiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer at both ends of the molecular chain, and their organopolysiloxane Two or more mixtures are exemplified.
更に、このような(B)成分として、更に次のようなオルガノポリシロキサンも例示される。なお、式中、Me、Phは、それぞれ、メチル基、フェニル基を示し、m2は1〜100の整数であり、n2は1〜50の整数である。
HMe2SiO(Me2SiO)m2SiMe2H
HMe2SiO(Ph2SiO)m2SiMe2H
HMePhSiO(Ph2SiO)m2SiMePhH
HMePhSiO(Ph2SiO)m2(MePhSiO)n2SiMePhH
HMePhSiO(Ph2SiO)m2(Me2SiO)n2SiMePhHFurther, as such a component (B), the following organopolysiloxane is also exemplified. In the formula, Me and Ph represent a methyl group and a phenyl group, respectively, m2 is an integer of 1 to 100, and n2 is an integer of 1 to 50.
HMe 2 SiO (Me 2 SiO) m2 SiMe 2 H
HMe 2 SiO (Ph 2 SiO) m2 SiMe 2 H
HMePhSiO (Ph 2 SiO) m2 SiMePhH
HMePhSiO (Ph 2 SiO) m2 ( MePhSiO) n2 SiMePhH
HMePhSiO (Ph 2 SiO) m2 ( Me 2 SiO) n2 SiMePhH
なお、これらの(B)成分は、接点障害防止等の見地から、揮発性または低分子量のシロキサンオリゴマー(オクタメチルテトラシロキサン(D4)、デカメチルペンタシロキサン(D5)等)が低減ないし除去されていることが好ましい。その程度は所望により設計可能であるが、(B)成分全体の1質量%未満、各シロキサンオリゴマーごとに0.1質量%未満としてもよく、必要に応じ、検出限界付近まで低減してもよい。 From the viewpoint of preventing contact failure, these components (B) have reduced or removed volatile or low molecular weight siloxane oligomers (octamethyltetrasiloxane (D4), decamethylpentasiloxane (D5), etc.). It is preferable to have. The degree can be designed as desired, but it may be less than 1% by mass of the whole component (B), less than 0.1% by mass for each siloxane oligomer, and may be reduced to near the detection limit if necessary. ..
前記の(B)成分中のケイ素結合水素原子の含有量は特に限定されるものではないが、本発明の技術的効果の見地から、SiH基中のH含有量が、0.01〜3.0質量%の範囲が好ましく、0.05〜2.00質量%の範囲が特に好ましい。 The content of the silicon-bonded hydrogen atom in the component (B) is not particularly limited, but from the viewpoint of the technical effect of the present invention, the H content in the SiH group is 0.01 to 3. The range of 0% by mass is preferable, and the range of 0.05 to 2.00% by mass is particularly preferable.
[(A)成分と(B)成分のSiH/Vi比]
上記のとおり、(B)成分は、分子鎖両末端のみにヒドロシリル化反応可能なケイ素結合水素原子を有する直鎖状シロキサンであって、硬化物における鎖長延長剤として機能し、硬化物の伸びおよび柔軟性を改善する。当該技術的効果は、(B)成分中のケイ素結合水素原子のモル数と(A)成分中のアルケニル基等の脂肪族不飽和炭素−炭素結合含有基のモル数との比(物質量比)が、0.90〜1.30の範囲にあることが必要であり、0.90〜1.10の範囲、0.90〜1.00の範囲にあることが特に好ましい。当該下限未満では、糊残り等の原因となる場合があり、当該上限を超えると粘着力が不十分となる場合がある。[SiH / Vi ratio of component (A) and component (B)]
As described above, the component (B) is a linear siloxane having a silicon-bonded hydrogen atom capable of hydrosilylation reaction only at both ends of the molecular chain, which functions as a chain length extender in the cured product and extends the cured product. And improve flexibility. The technical effect is the ratio (material amount ratio) of the number of moles of silicon-bonded hydrogen atoms in the component (B) to the number of moles of aliphatic unsaturated carbon-carbon bond-containing groups such as alkenyl groups in the component (A). ) Needs to be in the range of 0.99 to 1.30, and is particularly preferably in the range of 0.99 to 1.10 and 0.99 to 1.00. If it is less than the lower limit, it may cause adhesive residue, etc., and if it exceeds the upper limit, the adhesive strength may be insufficient.
[(C)成分]
(C)成分はオルガノポリシロキサン樹脂であり、基材への粘着力を付与する粘着付与成分であり、当該成分の使用量により、本組成物の硬化物の粘着力および感圧接着性能を微粘着〜強粘着性まで調整することが可能である。[(C) component]
The component (C) is an organopolysiloxane resin, which is a pressure-sensitive adhesive component that imparts adhesive force to a substrate. Depending on the amount of the component used, the adhesive force and pressure-sensitive adhesive performance of the cured product of the present composition are slightly reduced. It is possible to adjust from adhesive to strong adhesive.
(C)成分は、分子内に(a)R3SiO1/2(式中、Rは、互いに独立して一価有機基を表す)で表されるシロキサン単位(M単位)、及び、(b)SiO4/2で表されるシロキサン単位(Q単位)を含むオルガノポリシロキサン樹脂である。M単位対Q単位のモル比は、0.5〜2.0(M単位/Q単位)であることが好ましい。このモル比が0.5未満である場合には基材への粘着力が低下することがあり、2.0より大きい場合には粘着層を構成する物質の凝集力が低下するからである。The component (C) is a siloxane unit (M unit) represented by (a) R 3 SiO 1/2 (in the formula, R represents a monovalent organic group independently of each other) in the molecule, and ( b) An organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO 4/2. The molar ratio of M units to Q units is preferably 0.5 to 2.0 (M units / Q units). This is because if the molar ratio is less than 0.5, the adhesive force to the substrate may decrease, and if it is larger than 2.0, the cohesive force of the substances constituting the adhesive layer decreases.
特に、(a)M単位と(b)Q単位のモル比はM単位:Q単位=0.50:1.00〜1.50:1.00の範囲にあることが好ましく、0.55:1.00〜1.20:1.00の範囲がより好ましく、0.60:1.00〜1.10:1.00が更により好ましい。上記モル比は、29Si核磁気共鳴によって容易に測定することができる。In particular, the molar ratio of (a) M unit and (b) Q unit is preferably in the range of M unit: Q unit = 0.50: 1.00 to 1.50: 1.00, and 0.55: The range of 1.00 to 1.20: 1.00 is more preferable, and 0.60: 1.00 to 1.10: 1.00 is even more preferable. The molar ratio can be easily measured by 29 Si nuclear magnetic resonance.
(C)成分は一般単位式:(R3SiO1/2)a(SiO4/2)b(式中、Rは互いに独立して一価有機基であり、a及びbはそれぞれ正数であり、a+b=1、a/b=0.5〜1.5である)で表されるオルガノポリシロキサン樹脂であることが好ましい。The component (C) is a general unit formula: (R 3 SiO 1/2 ) a (SiO 4/2 ) b (In the formula, R is a monovalent organic group independently of each other, and a and b are positive numbers, respectively. It is preferable that the organopolysiloxane resin is represented by (a + b = 1, a / b = 0.5 to 1.5).
(C)成分は(a)M単位と(b)Q単位のみから構成されてもよいが、R2SiO2/2単位(D単位)、及び/又は、RSiO3/2単位(T単位)を含んでもよい。なお、式中、Rは、互いに独立して一価有機基を表す。(C)成分中の(a)M単位と(b)Q単位の合計含有量は好ましくは50重量%以上であり、更に好ましくは80重量%以上であり、特に好ましくは100重量%である。The component (C) may be composed of only (a) M units and (b) Q units, but R 2 SiO 2/2 units (D units) and / or RSiO 3/2 units (T units). May include. In the formula, R represents a monovalent organic group independently of each other. The total content of (a) M unit and (b) Q unit in the component (C) is preferably 50% by weight or more, more preferably 80% by weight or more, and particularly preferably 100% by weight.
一価有機基は、特に限定されるものではないが、例えば、脂肪族不飽和炭素−炭素結合含有基、及び、脂肪族不飽和炭素−炭素結合不含基に分けることができ、(C)成分の一価有機基はそれぞれが独立にいずれかであることができる。 The monovalent organic group is not particularly limited, but can be divided into, for example, an aliphatic unsaturated carbon-carbon bond-containing group and an aliphatic unsaturated carbon-carbon bond-free group (C). Each monovalent organic group of the component can be either independently.
脂肪族不飽和炭素−炭素結合含有基、及び、脂肪族不飽和炭素−炭素結合不含基には、それぞれ、一価不飽和炭化水素基及び酸素原子含有一価不飽和炭化水素基、並びに、一価飽和炭化水素基及び酸素原子含有一価飽和炭化水素基が含まれる。 The aliphatic unsaturated carbon-carbon bond-containing group and the aliphatic unsaturated carbon-carbon bond-free group include a monounsaturated hydrocarbon group, an oxygen atom-containing monounsaturated hydrocarbon group, and an oxygen atom-containing monounsaturated hydrocarbon group, respectively. Includes monovalent saturated hydrocarbon groups and oxygen atom-containing monovalent saturated hydrocarbon groups.
一価不飽和又は飽和炭化水素基としては、例えば、炭素原子数2〜12の、好ましくは炭素原子数2〜8の、より好ましくは炭素原子数2〜6の、置換若しくは非置換の、一価不飽和炭化水素基、並びに、炭素原子数1〜12の、置換若しくは非置換の、一価飽和炭化水素基が挙げられる。 The monounsaturated or saturated hydrocarbon group may be, for example, a substituted or unsubstituted one having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. Examples include valent unsaturated hydrocarbon groups and substituted or unsubstituted monovalent saturated hydrocarbon groups having 1 to 12 carbon atoms.
炭素原子数2〜12の、好ましくは炭素原子数2〜8の、より好ましくは炭素原子数2〜6の、非置換一価不飽和炭化水素基としては、例えば、ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基が挙げられる。炭素原子数2〜12の、好ましくは炭素原子数2〜8の、より好ましくは炭素原子数2〜6の、置換一価不飽和炭化水素基としては、例えば、これらの一価不飽和炭化水素基の水素原子の一部がハロゲン原子(フッ素、塩素、臭素又はヨウ素)等によって置換されたものが挙げられる。 The unsubstituted monounsaturated hydrocarbon group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms includes, for example, a vinyl group, an allyl group, and propenyl. Examples thereof include an alkenyl group such as a group, a butenyl group, a pentenyl group and a hexenyl group. Substituted monounsaturated hydrocarbon groups having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms include, for example, these monovalent unsaturated hydrocarbons. Examples thereof include those in which a part of the hydrogen atom of the group is replaced by a halogen atom (fluorine, chlorine, bromine or iodine) or the like.
炭素原子数1〜12の非置換一価飽和炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ペンチル基、ヘキシル基、オクチル基等のアルキル基;シクロヘキシル基、シクロヘプチル基等のシクロアルキル基;フェニル基、トリル基、キシリル基等のアリール基;ベンジル基、α−メチルスチリル基及び2−フェニルエチル基等のアラルキル基が挙げられる。炭素原子数1〜12の置換一価飽和炭化水素基としては、例えば、これらの一価不飽和炭化水素基の水素原子の一部がハロゲン原子(フッ素、塩素、臭素又はヨウ素)等によって置換されたものが挙げられる。具体的には、フッ化一価飽和炭化水素基、例えば3,3,3−トリフルオロプロピル基、4,4,5,5,5−ペンタフルオロブチル基、3,3,4,4,5,5,6,6,6−ノナフルオロヘキシル基等のパーフロロアルキル基;塩素化一価飽和炭化水素基、例えば3−クロロプロピル基等のクロロアルキル基、ジクロロフェニル基等のクロロフェニル基が挙げられる。 Examples of the unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group and an octyl group; a cyclohexyl group and a cycloheptyl group. Cycloalkyl group; aryl group such as phenyl group, tolyl group, xsilyl group; aralkyl group such as benzyl group, α-methylstyryl group and 2-phenylethyl group can be mentioned. As the substituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, for example, a part of the hydrogen atom of these monounsaturated hydrocarbon groups is substituted with a halogen atom (fluorine, chlorine, bromine or iodine) or the like. Can be mentioned. Specifically, monovalent fluorinated hydrocarbon groups such as 3,3,3-trifluoropropyl group, 4,4,5,5,5-pentafluorobutyl group, 3,3,4,5,5 , 5, 6, 6, 6-Perfluoroalkyl groups such as nonafluorohexyl groups; chlorinated monovalent saturated hydrocarbon groups such as chloroalkyl groups such as 3-chloropropyl groups and chlorophenyl groups such as dichlorophenyl groups. ..
一価飽和炭化水素基としては、炭素原子数1〜12の置換若しくは非置換のアルキル基が好ましい。炭素原子数1〜12の置換若しくは非置換のアルキル基としてはメチル基が好ましい。一価不飽和炭化水素基としては、炭素原子数2〜12の置換若しくは非置換のアルケニル基が好ましい。炭素原子数2〜12の置換若しくは非置換のアルケニル基としてはビニル基が好ましい。 As the monovalent saturated hydrocarbon group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms is preferable. A methyl group is preferable as the substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. As the monounsaturated hydrocarbon group, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms is preferable. A vinyl group is preferable as the substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms.
酸素原子含有一価不飽和又は飽和炭化水素基としては、例えば、炭素原子数2〜12の、置換若しくは非置換の、酸素原子含有一価不飽和炭化水素基、並びに、炭素原子数1〜12の、置換若しくは非置換の、酸素原子含有一価飽和炭化水素基が挙げられる。 Examples of the oxygen atom-containing monounsaturated or saturated hydrocarbon group include a substituted or unsubstituted, oxygen atom-containing monounsaturated hydrocarbon group having 2 to 12 carbon atoms and 1 to 12 carbon atoms. , Substituted or unsubstituted, oxygen atom-containing monovalent saturated hydrocarbon groups.
炭素原子数2〜12の、置換若しくは非置換の酸素原子含有一価不飽和炭化水素基としては、例えば、アルケニルオキシアルキル基、アクリロキシアルキル基、メタクリロキシアルキル基等が挙げられる。 Examples of the substituted or unsubstituted oxygen atom-containing monounsaturated hydrocarbon group having 2 to 12 carbon atoms include an alkenyloxyalkyl group, an acryloxyalkyl group, and a methacryloxyalkyl group.
アルケニルオキシアルキル基としては、例えば、アリルオキシメチル基、3−アリルオキシプロピル基等が挙げられる。アクリロキシアルキル基としては、例えば、アクリロキシメチル基、3−アクリロキシプロピル基等が挙げられる。メタクリロキシアルキル基としては、例えば、メタクリロキシメチル基、3−メタクリロキシプロピル基等が挙げられる。 Examples of the alkenyloxyalkyl group include an allyloxymethyl group and a 3-allyloxypropyl group. Examples of the acryloxyalkyl group include an acryloximethyl group and a 3-acryloxypropyl group. Examples of the methacryloxyalkyl group include a methacryloxymethyl group and a 3-methacryloxypropyl group.
炭素原子数1〜12の、置換若しくは非置換の、酸素原子含有一価飽和炭化水素基としては、例えば、炭素原子数1〜12のアルコキシ基等が挙げられる。 Examples of the substituted or unsubstituted oxygen atom-containing monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include an alkoxy group having 1 to 12 carbon atoms.
炭素原子数1〜12のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、イソプロポキシ基等が挙げられる。 Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group and the like.
[水酸基または加水分解性基の低減]
(C)成分中の水酸基またはアルコキシ基等の加水分解性基は、レジン構造中のシロキサン単位のうち、T単位またはQ単位などのケイ素原子に直接結合しており、原料となるシラン由来またはシランが加水分解した結果、生じた基であるので、合成したオルガノポリシロキサンレジンをトリメチルシラン等のシリル化剤で加水分解処理することで水酸基または加水分解性基の含有量を低減することができる。これにより、硬化物中において分子量の大きいオルガノポリシロキサンレジン構造が形成されることを抑制し、当該組成物の低温における硬化性および得られる感圧接着層の貯蔵弾性率をさらに改善できる場合がある。[Reduction of hydroxyl groups or hydrolyzable groups]
The hydrolyzable group such as a hydroxyl group or an alkoxy group in the component (C) is directly bonded to a silicon atom such as a T unit or a Q unit among the siloxane units in the resin structure, and is derived from silane as a raw material or silane. Is a group produced as a result of hydrolysis, so the content of hydroxyl group or hydrolyzable group can be reduced by hydrolyzing the synthesized organopolysiloxane resin with a silylating agent such as trimethylsilane. As a result, it may be possible to suppress the formation of an organopolysiloxane resin structure having a large molecular weight in the cured product, and further improve the curability of the composition at low temperature and the storage elastic modulus of the obtained pressure-sensitive adhesive layer. ..
[(C1)硬化反応性オルガノポリシロキサン樹脂]
本発明の一態様では、(C)成分の少なくとも一部が、(C1)分子内に(Alk)R’2SiO1/2(式中、Alkは互いに独立して脂肪族不飽和炭素−炭素結合含有基を表し、R’は互いに独立して脂肪族不飽和炭素−炭素結合不含基を表す)で表されるシロキサン単位(M単位)、及び、SiO4/2で表されるシロキサン単位(Q単位)を少なくとも含む硬化反応性オルガノポリシロキサン樹脂であってよい。[(C1) Curing-reactive organopolysiloxane resin]
In one aspect of the present invention, (C) at least a portion of the component, (C1) (Alk) R '2 SiO 1/2 ( wherein in the molecule, aliphatic unsaturated carbon Alk independently of one another are - carbon Represents a bond-containing group, R'represents an aliphatic unsaturated carbon-carbon bond-free group independently of each other), a siloxane unit (M unit), and a siloxane unit represented by SiO 4/2. It may be a cure-reactive organopolysiloxane resin containing at least (Q unit).
上記の態様では、Alkである脂肪族不飽和炭素−炭素結合含有基は、既述した、アルケニル基、アルケニルオキシアルキル基、アクリロキシアルキル基及びメタクリロキシアルキル基からなる群から独立に選択される基であることが好ましい。また、R’である脂肪族不飽和炭素−炭素結合不含基は、既述した、アルキル基、アリール基及びアラルキル基からなる群から独立に選択される基であることが好ましい。また、これらの基の一部はハロゲン原子等によって置換されていてもよい。工業的見地からは、Alkである脂肪族不飽和炭素−炭素結合含有基は、ビニル基、アリル基又はヘキセニル基であってよく、R’である脂肪族不飽和炭素−炭素結合不含基は独立にメチル基、フェニル基等であることが好ましい。 In the above embodiment, the aliphatic unsaturated carbon-carbon bond-containing group which is an Alk is independently selected from the above-mentioned group consisting of an alkenyl group, an alkenyloxyalkyl group, an acryloxyalkyl group and a methacryloxyalkyl group. It is preferably a group. Further, the aliphatic unsaturated carbon-carbon bond-free group, which is R', is preferably a group independently selected from the above-mentioned group consisting of an alkyl group, an aryl group and an aralkyl group. In addition, some of these groups may be substituted with halogen atoms or the like. From an industrial point of view, the aliphatic unsaturated carbon-carbon bond-containing group that is Alk may be a vinyl group, an allyl group or a hexenyl group, and the aliphatic unsaturated carbon-carbon bond-free group that is R'is It is preferably a methyl group, a phenyl group or the like independently.
上記の態様において、(C1)硬化反応性オルガノポリシロキサン樹脂以外の(C)成分が存在する場合は当該(C)成分は非硬化反応性であることが好ましい。この場合、非硬化反応性(C)成分のRは既述した脂肪族不飽和炭素−炭素結合不含基であることが好ましく、独立に、アルキル基、アリール基又はアラルキル基であることがより好ましい。また、これらの基の一部はハロゲン原子等によって置換されていてもよい。工業的見地からは、Rである脂肪族不飽和炭素−炭素結合不含基は独立に、メチル基、フェニル基等であることが好ましい。 In the above embodiment, when the component (C) other than the (C1) curing-reactive organopolysiloxane resin is present, the component (C) is preferably non-curing-reactive. In this case, the R of the non-curable reactive (C) component is preferably an aliphatic unsaturated carbon-carbon bond-free group as described above, and is more likely to be an alkyl group, an aryl group or an aralkyl group independently. preferable. In addition, some of these groups may be substituted with halogen atoms or the like. From an industrial point of view, it is preferable that the aliphatic unsaturated carbon-carbon bond-free group, which is R, is independently a methyl group, a phenyl group, or the like.
(C)成分に占める(C1)硬化反応性オルガノポリシロキサン樹脂の割合は特に限定されるものではないが、本発明の組成物又はその硬化物に感圧接着剤として適度な硬さを実現するためには、(C)成分全体を100質量%とした場合、(C)成分の50重量%以下が好ましく、30重量%以下がより好ましく、20重量%以下が更により好ましい。好適には、(C)成分中に占める(C1)成分の含有量は、0〜20質量%の範囲であり、0〜15質量%の範囲が特に好ましく、本発明の組成物又はその硬化物からなる感圧接着剤が、表示装置や太陽電池モジュール等の接着層として適度な硬さと柔軟性を備えることができる。 The ratio of the (C1) curing-reactive organopolysiloxane resin to the (C) component is not particularly limited, but the composition of the present invention or the cured product thereof is provided with an appropriate hardness as a pressure-sensitive adhesive. Therefore, when the total amount of the component (C) is 100% by weight, 50% by weight or less of the component (C) is preferable, 30% by weight or less is more preferable, and 20% by weight or less is even more preferable. Preferably, the content of the component (C1) in the component (C) is in the range of 0 to 20% by mass, particularly preferably in the range of 0 to 15% by mass, and the composition of the present invention or a cured product thereof. The pressure-sensitive adhesive made of the above material can have appropriate hardness and flexibility as an adhesive layer for a display device, a solar cell module, or the like.
本発明において、(C)成分は一般単位式:(R3SiO1/2)a(SiO4/2)b(式中、Rは互いに独立して一価有機基であり、a及びbはそれぞれ正数であり、a+b=1、a/b=0.5〜1.5である)で表されるオルガノポリシロキサン樹脂であって、Rの90モル%以上が独立に炭素数1〜6のアルキル基またはフェニル基であることが好ましく、Rの95〜100モル%が独立にメチル基またはフェニル基であることが特に好ましく、(C)成分中の水酸基または加水分解性基の含有量が全ケイ素に対して0〜7モル%(水酸基として0.0〜1.50質量%)の範囲であるレジン(MQレジンとも呼ばれる)を使用することが最も好ましい。In the present invention, the component (C) is a general unit formula: (R 3 SiO 1/2 ) a (SiO 4/2 ) b (In the formula, R is a monovalent organic group independently of each other, and a and b are Organopolysiloxane resin represented by (a + b = 1, a / b = 0.5 to 1.5), each of which is a positive number, and 90 mol% or more of R independently has 1 to 6 carbon atoms. Is preferably an alkyl group or a phenyl group, and 95 to 100 mol% of R is particularly preferably a methyl group or a phenyl group, and the content of the hydroxyl group or the hydrolyzable group in the component (C) is high. Most preferably, a resin (also called MQ resin) in the range of 0 to 7 mol% (0.0 to 1.50% by mass as a hydroxyl group) with respect to total silicon is used.
このような(C)成分として、例えば、
(Me3SiO1/2)0.45(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(SiO4/2)0.60(HO1/2)0.10
(Me3SiO1/2)0.52(SiO4/2)0.48(HO1/2)0.01
(Me3SiO1/2)0.40(Me2ViSiO1/2)0.05 (SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.45(SiO4/2)0.55(MeO1/2)0.10
(Me3SiO1/2)0.25(Me2PhSiO1/2)0.20(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(Me2SiO2/2)0.05(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(MeSiO3/2)0.05(SiO4/2)0.55(HO1/2)0.05
(Me3SiO1/2)0.40(Me2SiO2/2)0.05(MeSiO3/2)0.05(SiO4/2)0.50(HO1/2)0.05
(Me:メチル基、Ph:フェニル基、Vi:ビニル基、MeO:メトキシ基、HO:ケイ素原子結合水酸基。なお、ケイ素原子に対する水酸基の相対量を表すために、ケイ素原子含有単位の添字の合計量を1としており、(HO)1/2単位の添字が当該相対量を示す)
を挙げることができる。なお、接点障害防止等の見地から、(C)成分中の低分子量のシロキサンオリゴマーが低減ないし除去されていても良い。As such a component (C), for example,
(Me 3 SiO 1/2) 0.45 ( SiO 4/2) 0.55 (HO 1/2) 0.05
(Me 3 SiO 1/2) 0.40 ( SiO 4/2) 0.60 (HO 1/2) 0.10
(Me 3 SiO 1/2) 0.52 ( SiO 4/2) 0.48 (HO 1/2) 0.01
(Me 3 SiO 1/2) 0.40 ( Me 2 ViSiO 1/2) 0.05 (SiO 4/2) 0.55 (HO 1/2) 0.05
(Me 3 SiO 1/2) 0.45 ( SiO 4/2) 0.55 (MeO 1/2) 0.10
(Me 3 SiO 1/2) 0.25 ( Me 2 PhSiO 1/2) 0.20 (SiO 4/2) 0.55 (HO 1/2) 0.05
(Me 3 SiO 1/2) 0.40 ( Me 2 SiO 2/2) 0.05 (SiO 4/2) 0.55 (HO 1/2) 0.05
(Me 3 SiO 1/2) 0.40 ( MeSiO 3/2) 0.05 (SiO 4/2) 0.55 (HO 1/2) 0.05
(Me 3 SiO 1/2) 0.40 ( Me 2 SiO 2/2) 0.05 (MeSiO 3/2) 0.05 (SiO 4/2) 0.50 (HO 1/2) 0.05
(Me: methyl group, Ph: phenyl group, Vi: vinyl group, MeO: methoxy group, HO: silicon atom-bonded hydroxyl group. In order to express the relative amount of hydroxyl group with respect to the silicon atom, the sum of the subscripts of the silicon atom-containing units The quantity is 1, and the subscript of (HO) 1/2 unit indicates the relative quantity.)
Can be mentioned. From the viewpoint of preventing contact failure, the low molecular weight siloxane oligomer in the component (C) may be reduced or removed.
(C)成分は、本発明のシリコーン感圧接着剤組成物に粘着力を付与する成分であるから、その配合量は組成物の(A)〜(D)成分の質量の総和を100質量部とした場合、10〜80質量部の範囲が好ましい。(C)成分の配合量が前記下限未満では、本発明のシリコーン感圧接着剤組成物に十分な粘着力を付与できない場合がある。一方、(C)成分の配合量が前記上限を超えると、本発明のシリコーン感圧接着剤組成物が硬くなりすぎるため、特に感圧接着剤としての使用に適さない場合がある。ただし、微粘着性の組成設計が求められる場合、(C)成分の含有量を10質量部以下に抑制してもよい。 Since the component (C) is a component that imparts adhesive strength to the silicone pressure-sensitive adhesive composition of the present invention, the blending amount thereof is 100 parts by mass of the total mass of the components (A) to (D) of the composition. In the case of, the range of 10 to 80 parts by mass is preferable. If the blending amount of the component (C) is less than the above lower limit, it may not be possible to impart sufficient adhesive strength to the silicone pressure-sensitive adhesive composition of the present invention. On the other hand, if the blending amount of the component (C) exceeds the upper limit, the silicone pressure-sensitive adhesive composition of the present invention becomes too hard, so that it may not be particularly suitable for use as a pressure-sensitive adhesive. However, when a slightly adhesive composition design is required, the content of the component (C) may be suppressed to 10 parts by mass or less.
[(D)成分]
(D)成分は、(B)成分と異なり、一分子内に少なくとも3個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサンであり、(A)成分/(D)成分とのヒドロシリル化反応において、架橋剤として機能し、その添加量に応じて硬化物の硬さを調整する成分である。一般に3個のケイ素結合水素原子はそれぞれが異なるケイ素原子と結合している。このような(D)成分を(A)成分に対して一定の量的範囲で使用することにより、組成物全体の硬化反応性を改善して良好な硬化特性と適度な硬さ(架橋密度)を実現し、かつ、硬化物の粘着力および硬化後の表面タックを実用上良好な範囲に設計することができる。[(D) component]
Unlike the component (B), the component (D) is an organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms in one molecule, and in the hydrosilylation reaction with the component (A) / component (D). , A component that functions as a cross-linking agent and adjusts the hardness of the cured product according to the amount added. Generally, each of the three silicon-bonded hydrogen atoms is bonded to a different silicon atom. By using such a component (D) in a certain quantitative range with respect to the component (A), the curing reactivity of the entire composition is improved, and good curing characteristics and appropriate hardness (crosslink density) are obtained. It is possible to design the adhesive strength of the cured product and the surface tack after curing within a practically good range.
このような(D)成分は、(D1)分子内に少なくとも3個のケイ素結合水素原子を有する環状オルガノハイドロジェンポリシロキサンおよび(D2)分子鎖末端にケイ素結合水素原子を有さず、分子内に少なくとも3個のケイ素結合水素原子を有する直鎖状または分岐鎖状のオルガノハイドロジェンポリシロキサンからなる群から選ばれる少なくとも1種類以上であってよい。また、(D)成分は上記の(D1)または(D2)成分のいずれかのカテゴリーのみに属する2種類以上のオルガノハイドロジェンポリシロキサンからなる混合物であってもよい。 Such a component (D) does not have a cyclic organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule (D1) and a silicon-bonded hydrogen atom at the end of the (D2) molecular chain, and is intramolecular. It may be at least one selected from the group consisting of linear or branched organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms. Further, the component (D) may be a mixture consisting of two or more kinds of organohydrogenpolysiloxanes belonging only to any category of the above components (D1) or (D2).
(D1)成分である環状オルガノハイドロジェンポリシロキサンは、たとえば、下記式:
[(R3HSiO)m3(R3 2SiO)m4]
で表される。ここで、m3+m4は3〜20の範囲の数であり、m3は3以上の数であり、m4は0以上の数である。R3は、アルケニル基を除く炭素数1〜10の一価炭化水素基であり、R2と同様の基が例示でき、好適には、メチル基及びフェニル基から独立に選択される基である。The cyclic organohydrogenpolysiloxane as the component (D1) is described by, for example, the following formula:
[(R 3 HSiO) m3 (R 3 2 SiO) m4 ]
It is represented by. Here, m3 + m4 is a number in the range of 3 to 20, m3 is a number of 3 or more, and m4 is a number of 0 or more. R 3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms excluding the alkenyl group, and a group similar to R 2 can be exemplified, preferably a group independently selected from a methyl group and a phenyl group. ..
(D2)成分である分子鎖末端にケイ素結合水素原子を有さず、分子内に少なくとも3個のケイ素結合水素原子を有する直鎖状または分岐鎖状のオルガノハイドロジェンポリシロキサンは、側鎖部分に少なくとも3個のケイ素結合水素原子を有し、分子鎖末端がトリアルキルシロキシ基、アリールジアルキルシロキシ基等で封鎖されたポリオルガノハイドジェンシロキサンまたはオルガノハイドジェンシロキサン・ジオルガノシロキサンコポリマー等のオルガノハイドロジェンポリシロキサンである。そのシロキサン重合度は5〜500の範囲であり、5〜200の範囲であることが好ましい。 The linear or branched organohydrogenpolysiloxane having no silicon-bonded hydrogen atom at the end of the molecular chain as a component (D2) and having at least three silicon-bonded hydrogen atoms in the molecule is a side chain portion. Organohydro having at least 3 silicon-bonded hydrogen atoms and having a molecular chain end sealed with a trialkylsiloxy group, an aryldialkylsiloxy group, etc. Genpolysiloxane. The degree of siloxane polymerization is in the range of 5 to 500, preferably in the range of 5 to 200.
具体的には、(D)成分として、1,3,5,7−テトラメチルシクロテトラシロキサン、トリス(ジメチルハイドロジェンシロキシ)メチルシラン、トリス(ジメチルハイドロジェンシロキシ)フェニルシラン、1−(3−グリシドキシプロピル)−1,3,5,7−テトラメチルシクロテトラシロキサン、1,5−ジ(3−グリシドキシプロピル)−1,3,5,7−テトラメチルシクロテトラシロキサン、1−(3−グリシドキシプロピル)−5−トリメトキシシリルエチル−1,3,5,7−テトラメチルシクロテトラシロキサン、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン・ジメチルシロキサン共重合体、メチルトリス(ジメチルシロキシ)シラン、テトラキス(ジメチルシロキシシラン)、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジメチルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・メチルフェニルシロキサン共重合体等が例示される。 Specifically, as the component (D), 1,3,5,7-tetramethylcyclotetrasiloxane, tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1- (3-glyce) Sidoxypropyl) -1,3,5,7-Tetramethylcyclotetrasiloxane, 1,5-di (3-glycidoxypropyl) -1,3,5,7-Tetramethylcyclotetrasiloxane, 1-( 3-glycidoxypropyl) -5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends of the molecular chain, trimethylsiloxy group at both ends of the molecular chain Blocked dimethylsiloxane / methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer at both ends of the molecular chain, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane at both ends of the molecular chain Polymer, methyltris (dimethylsiloxy) silane, tetrakis (dimethylsiloxysilane), trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends of the molecular chain, trimethylsiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane copolymer at both ends of the molecular chain, Examples thereof include methylhydrogensiloxane and methylphenylsiloxane copolymers that block trimethylsiloxy groups at both ends of the molecular chain.
[(A)成分に対する(B)成分および(D)成分中のSiH/Vi比]
本発明の組成物は、(B)成分と(A)成分のSiH/Vi比に加えて、組成物全体における(B)成分および(D)成分中のケイ素結合水素原子のモル数と(A)成分中のアルケニル基等の脂肪族不飽和炭素−炭素結合含有基のモル数との比(物質量比)が、0.95〜1.35の範囲にあることが必要である。当該範囲内において、全体の架橋密度が適度に調整され、(B)成分との関係で伸びおよび粘弾性に優れ、かつ、(D)成分との関係で適度な硬さを備え、硬化後の表面タックが好適な範囲にある粘着層が実現可能である。SiH/Vi比(ケイ素結合水素原子のモル数/脂肪族不飽和炭素−炭素結合含有基のモル数)が当該下限未満では、糊残り等の原因となる場合があり、当該上限を超えると粘着力が不十分となる場合がある。[SiH / Vi ratio in component (B) and component (D) to component (A)]
In the composition of the present invention, in addition to the SiH / Vi ratio of the component (B) and the component (A), the number of moles of silicon-bonded hydrogen atoms in the components (B) and (D) in the entire composition and (A). ) The ratio (material amount ratio) of the aliphatic unsaturated carbon-carbon bond-containing group such as the alkenyl group to the number of moles in the component needs to be in the range of 0.95 to 1.35. Within this range, the overall crosslink density is appropriately adjusted, excellent in elongation and viscoelasticity in relation to the component (B), and having an appropriate hardness in relation to the component (D), after curing. An adhesive layer having a suitable surface tack range can be realized. If the SiH / Vi ratio (the number of moles of silicon-bonded hydrogen atoms / the number of moles of aliphatic unsaturated carbon-carbon bond-containing groups) is less than the lower limit, it may cause adhesive residue, etc., and if it exceeds the upper limit, it becomes sticky. The force may be insufficient.
[(E)成分]
(E)成分として本発明にかかる無溶剤又は低溶剤型シリコーン感圧接着剤組成物は、ヒドロシリル化反応触媒を含む。ヒドロシリル化反応触媒としては、白金系触媒、ロジウム系触媒、パラジウム系触媒が例示され、本組成物の硬化を著しく促進できることから白金系触媒が好ましい。この白金系触媒としては、白金微粉末、塩化白金酸、塩化白金酸のアルコール溶液、白金−アルケニルシロキサン錯体、白金−オレフィン錯体、白金−カルボニル錯体が例示され、特に、白金−アルケニルシロキサン錯体が好ましい。このアルケニルシロキサンとしては、1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン、1,3,5,7−テトラメチル−1,3,5,7−テトラビニルシクロテトラシロキサン、これらのアルケニルシロキサンのメチル基の一部をニトリル類、アミド類、ジオキソラン類、及びスルホラン類からなる群から選択される基、エチル基、フェニル基等で置換したアルケニルシロキサン、これらのアルケニルシロキサンのビニル基をアリル基、ヘキセニル基等で置換したアルケニルシロキサンが例示される。特に、この白金−アルケニルシロキサン錯体の安定性が良好であることから、1,3−ジビニル−1,1,3,3−テトラメチルジシロキサンであることが好ましく、アルケニルシロキサン溶液の形態で添加することが好ましい。加えて、取扱作業性および組成物のポットライフの改善の見地から、これらのヒドロシリル化反応触媒は、シリコーン樹脂、ポリカーボネート樹脂、アクリル樹脂等の熱可塑性樹脂中に分散あるいはカプセル化した触媒である、ヒドロシリル化反応触媒含有熱可塑性樹脂微粒子、特に、白金含有ヒドロシリル化反応触媒を含む熱可塑性樹脂微粒子であってもよい。なお、ヒドロシリル化反応を促進する触媒としては、鉄、ルテニウム、鉄/コバルトなどの非白金系金属触媒を用いてもよい。[(E) component]
The solvent-free or low-solvent type silicone pressure-sensitive adhesive composition according to the present invention as the component (E) contains a hydrosilylation reaction catalyst. Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferable because they can significantly accelerate the curing of the present composition. Examples of the platinum-based catalyst include platinum fine powder, platinum chloride, an alcohol solution of platinum chloride, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex, and a platinum-alkenylsiloxane complex is particularly preferable. .. Examples of this alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane. Alkenylsiloxanes in which some of the methyl groups of these alkenylsiloxanes are replaced with groups selected from the group consisting of nitriles, amides, dioxolanes, and sulfolanes, ethyl groups, phenyl groups, etc., and vinyls of these alkenylsiloxanes. An alkenylsiloxane in which the group is substituted with an allyl group, a hexenyl group, or the like is exemplified. In particular, since the platinum-alkenylsiloxane complex has good stability, it is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and is added in the form of an alkenylsiloxane solution. Is preferable. In addition, from the viewpoint of improving handling workability and pot life of the composition, these hydrosilylation reaction catalysts are catalysts dispersed or encapsulated in thermoplastic resins such as silicone resin, polycarbonate resin and acrylic resin. Hydrosilylation reaction catalyst-containing thermoplastic resin fine particles, particularly, thermoplastic resin fine particles containing a platinum-containing hydrosilylation reaction catalyst may be used. As the catalyst for promoting the hydrosilylation reaction, a non-platinum metal catalyst such as iron, ruthenium, or iron / cobalt may be used.
本発明において、ヒドロシリル化反応触媒の含有量は特に制限されるものではないが、組成物中の固形分の合計量に対し、上述した金属、特に白金系金属量が0.1〜200pmの範囲となる範囲であり、0.1〜150ppm、0.1〜100ppmの範囲であってよく、0.1〜50ppmの範囲であってもよい。ここで、白金系金属は、白金、ロジウム、パラジウム、ルテニウム、イリジウムからなるVIII族の金属元素であるが、実用上、ヒドロシリル化反応触媒の配位子を除いた白金系金属の含有量が上記範囲であることが好ましい。なお、固形分とは、本発明にかかるシリコーン感圧接着剤組成物を硬化反応させた場合に、硬化層を形成する成分(主として主剤、接着付与成分、架橋剤、触媒およびその他の不揮発性成分)であり、加熱硬化時及び場合によっては加熱硬化後に揮発する溶媒等の揮発性成分を含まない。 In the present invention, the content of the hydrosilylation reaction catalyst is not particularly limited, but the amount of the above-mentioned metal, particularly the platinum-based metal, is in the range of 0.1 to 200 pm with respect to the total amount of solids in the composition. It may be in the range of 0.1 to 150 ppm, 0.1 to 100 ppm, or 0.1 to 50 ppm. Here, the platinum-based metal is a group VIII metal element composed of platinum, rhodium, palladium, ruthenium, and iridium, but practically, the content of the platinum-based metal excluding the ligand of the hydrosilylation reaction catalyst is as described above. It is preferably in the range. The solid content is a component (mainly a main agent, an adhesion-imparting component, a cross-linking agent, a catalyst, and other non-volatile components) that forms a cured layer when the silicone pressure-sensitive adhesive composition according to the present invention is cured. ), And does not contain volatile components such as solvents that volatilize during heat curing and in some cases after heat curing.
本発明にかかるシリコーン感圧接着剤組成物中の白金系金属の含有量が50ppm以下(45ppm以下,35ppm以下,30ppm以下,25ppm以下または20ppm以下)である場合、硬化後、あるいは加熱や紫外線等の高エネルギー線に暴露した場合、特に、透明な感圧接着層の変色や着色を抑制できる場合がある。一方、オルガノポリシロキサン組成物の硬化性の見地から、白金系金属の含有量は、0.1ppm以上であり、当該下限を下回ると硬化不良の原因となる場合がある。 When the content of the platinum-based metal in the silicone pressure-sensitive adhesive composition according to the present invention is 50 ppm or less (45 ppm or less, 35 ppm or less, 30 ppm or less, 25 ppm or less or 20 ppm or less), after curing, heating, ultraviolet rays, etc. When exposed to high-energy rays, it may be possible to suppress discoloration and coloring of the transparent pressure-sensitive adhesive layer. On the other hand, from the viewpoint of curability of the organopolysiloxane composition, the content of the platinum-based metal is 0.1 ppm or more, and if it is less than the lower limit, it may cause curing failure.
[(F)成分]
(F)成分は硬化遅延剤であり、組成物中の脂肪族不飽和炭素−炭素結合含有基とケイ素結合水素原子との架橋反応を抑制して、常温での可使時間を延長し、保存安定性を向上するために配合するものである。硬化遅延剤は、本発明の硬化性のシリコーン感圧接着剤組成物の可使時間を長くしたい場合に用いることが好ましい。特に、実用上は、本発明の無溶剤又は低溶剤型シリコーン感圧接着剤組成物には、一般に、硬化遅延剤を用いることが好ましい。[(F) component]
The component (F) is a curing retarder, which suppresses the cross-linking reaction between the aliphatic unsaturated carbon-carbon bond-containing group and the silicon-bonded hydrogen atom in the composition, prolongs the pot life at room temperature, and stores the product. It is compounded to improve stability. The curing retarder is preferably used when it is desired to prolong the pot life of the curable silicone pressure-sensitive adhesive composition of the present invention. In particular, in practical use, it is generally preferable to use a curing retarder in the solvent-free or low-solvent type silicone pressure-sensitive adhesive composition of the present invention.
具体的には、(F)成分はアセチレン系化合物、エンイン化合物、有機窒素化合物、有機燐化合物、オキシム化合物、リン系化合物が例示される。具体的には、3−メチル−1−ブチン−3−オール、3,5−ジメチル−1−ヘキシン−3−オール、3−メチル−1−ペンチン−3−オール、1−エチニル−1−シクロヘキサノール、フェニルブチノール等のアルキンアルコール;3−メチル−3−ペンテン−1−イン、3,5−ジメチル−1−ヘキシン−3−イン等のエンイン化合物;2−エチニル−4−メチル−2−ペンテン、1,3,5,7−テトラメチル−1,3,5,7−テトラビニルシクロテトラシロキサン、1,3,5,7−テトラメチル−1,3,5,7−テトラヘキセニルシクロテトラシロキサン等のメチルアルケニルシクロシロキサン;ベンゾトリアゾールが例示される。 Specifically, the component (F) is exemplified by an acetylene compound, an enin compound, an organic nitrogen compound, an organic phosphorus compound, an oxime compound, and a phosphorus compound. Specifically, 3-methyl-1-butin-3-ol, 3,5-dimethyl-1-hexin-3-ol, 3-methyl-1-pentyne-3-ol, 1-ethynyl-1-cyclo Alkyne alcohols such as hexanol and phenylbutinol; enein compounds such as 3-methyl-3-penten-1-in, 3,5-dimethyl-1-hexin-3-in; 2-ethynyl-4-methyl-2- Penten 1,3,5,7-Tetramethyl-1,3,5,7-Tetravinylcyclotetrasiloxane 1,3,5,7-Tetramethyl-1,3,5,7-Tetrahexenylcyclotetra Methylalkenylcyclosiloxane such as siloxane; benzotriazole is exemplified.
組成物の硬化挙動の見地から、本発明のシリコーン感圧接着剤組成物は、組成物の調製後室温で8時間後に粘度の増大が1.5倍以内であり、80〜200℃で硬化可能であることが好ましい。増粘が抑制されていることは、取扱作業性、ポットライフ、硬化後の特性の見地から重要であり、一定以上の高温(80〜200℃)で硬化させることで硬化性を確保することができるためである。なお、このような組成物は上記の各成分およびヒドロシリル化触媒と(F)成分の好適な組み合わせおよび配合量を選択することで、実現可能である。 From the viewpoint of the curing behavior of the composition, the silicone pressure-sensitive adhesive composition of the present invention has a viscosity increase of 1.5 times or less after 8 hours at room temperature after preparation of the composition, and can be cured at 80 to 200 ° C. Is preferable. Suppression of thickening is important from the viewpoint of handling workability, pot life, and characteristics after curing, and it is possible to secure curability by curing at a high temperature (80 to 200 ° C) above a certain level. Because it can be done. Such a composition can be realized by selecting a suitable combination and blending amount of each of the above components, the hydrosilylation catalyst and the component (F).
[低溶剤型/無溶剤型組成物]
本発明にかかるシリコーン感圧接着剤組成物は、その構成成分が比較的低粘度であるので、低溶剤型乃至無溶剤型の組成物が設計可能であり、有機溶剤の含有量が少量乃至実質的に有機溶剤を含有しない組成であっても、実用上十分な塗工性を実現することができる。具体的には、有機溶媒の含有量が組成物全体の20質量%未満であり、15質量%未満であり、実質的に0〜5質量%の範囲内であることが特に好ましい。一方、本組成物の基材への濡れ性改良を目的とする場合、あるいは(B)成分に付随する溶媒として不可避的に(B)成分に含まれる場合、有機溶剤を特に前述した範囲で少量含むことは可能である。有機溶剤は、塗工作業性などを考慮してその種類及び配合量を調整するが、無溶剤型又は低溶剤型シリコーン感圧接着剤の組成設計の見地から、有機溶剤の使用量は極力少量とすることが好ましい。有機溶剤としては、例えばトルエン、キシレン、ベンゼンなどの芳香族炭化水素系溶剤、ヘプタン、ヘキサン、オクタン、イソパラフィンなどの脂肪族炭化水素系溶剤、酢酸エチル、酢酸イソブチルなどのエステル系溶剤、ジイソプロプルエーテル、1,4−ジオキサンなどのエーテル系溶剤、トリクロロエチレン、パークロロエチレン、塩化メチレンなどの塩素化脂肪族炭化水素系溶剤、溶剤揮発油などが挙げられ、これらから選択される1種以上を用いることができ、シート状基材への濡れ性などに応じて2種以上を組み合わせてもよい。[Low solvent type / solventless type composition]
Since the constituent components of the silicone pressure-sensitive adhesive composition according to the present invention have a relatively low viscosity, a low-solvent type to a solvent-free type composition can be designed, and the content of the organic solvent is small to substantial. Even if the composition does not contain an organic solvent, practically sufficient coatability can be realized. Specifically, it is particularly preferable that the content of the organic solvent is less than 20% by mass, less than 15% by mass, and substantially in the range of 0 to 5% by mass of the entire composition. On the other hand, when the purpose is to improve the wettability of the composition to the substrate, or when it is unavoidably contained in the component (B) as a solvent accompanying the component (B), a small amount of the organic solvent is used, especially in the above-mentioned range. It is possible to include. The type and blending amount of the organic solvent are adjusted in consideration of coating workability, etc., but the amount of the organic solvent used is as small as possible from the viewpoint of composition design of the solvent-free type or low solvent type silicone pressure-sensitive adhesive. Is preferable. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene, xylene and benzene, aliphatic hydrocarbon solvents such as heptane, hexane, octane and isoparaffin, ester solvents such as ethyl acetate and isobutyl acetate, and diisopropl. Examples include ether, ether solvents such as 1,4-dioxane, chlorinated aliphatic hydrocarbon solvents such as trichloroethylene, perchloroethylene and methylene chloride, solvent volatile oils, etc., and one or more selected from these is used. Two or more kinds may be combined depending on the wettability to the sheet-like substrate and the like.
本発明にかかるシリコーン感圧接着剤組成物は、本発明の技術的効果を損なわない範囲で、任意で、上記成分以外の成分を含むことができる。例えば、接着促進剤;ポリジメチルシロキサンまたはポリジメチルジフェニルシロキサンなどの非反応性のオルガノポリシロキサン;フェノール系、キノン系、アミン系、リン系、ホスファイト系、イオウ系、またはチオエーテル系などの酸化防止剤;トリアゾール系またはベンゾフェノン系などの光安定剤;リン酸エステル系、ハロゲン系、リン系、またはアンチモン系などの難燃剤;カチオン系界面活性剤、アニオン系界面活性剤、または非イオン系界面活性剤などからなる1種類以上の帯電防止剤などを含むことができる。なお、これらの成分のほか、顔料、染料、無機微粒子(補強性フィラー、誘電性フィラー、導電性フィラー、熱伝導性フィラー)などを任意で配合することもできる。 The silicone pressure-sensitive adhesive composition according to the present invention may optionally contain components other than the above components as long as the technical effects of the present invention are not impaired. For example, adhesion promoters; non-reactive organopolysiloxanes such as polydimethylsiloxane or polydimethyldiphenylsiloxane; antioxidants such as phenolic, quinone, amine, phosphorus, surfactant, sulfur, or thioethers. Agents; light stabilizers such as triazole or benzophenone; flame retardants such as phosphate, halogen, phosphorus, or antimony; cationic surfactants, anionic surfactants, or nonionic surfactants It can contain one or more kinds of antistatic agents and the like composed of agents and the like. In addition to these components, pigments, dyes, inorganic fine particles (reinforcing filler, dielectric filler, conductive filler, thermally conductive filler) and the like can be optionally blended.
[(A´)分子内に炭素−炭素二重結合含有反応性基を含まない鎖状オルガノポリシロキサン]
本発明にかかるシリコーン感圧接着剤組成物には、アルケニル基、アクリル基、メタクリル基等の炭素−炭素二重結合含有反応性基もケイ素結合水素原子も含まないポリジメチルシロキサンまたはポリジメチルジフェニルシロキサンなどの非反応性のオルガノポリシロキサンを配合することができ、これにより、後述する感圧接着層の損失係数(tanδ)、貯蔵弾性率(G’)および損失弾性率(G’’)を改善することができる場合がある。例えば、水酸基末端を有するポリジメチルシロキサンまたはポリジメチルジフェニルシロキサンの使用により、感圧接着層の損失係数を増加させることができ、そのような組成物は、本発明の範囲に包含される。[(A') Chain organopolysiloxane containing no carbon-carbon double bond-containing reactive group in the molecule]
The silicone pressure-sensitive adhesive composition according to the present invention contains polydimethylsiloxane or polydimethyldiphenylsiloxane that does not contain a carbon-carbon double bond-containing reactive group such as an alkenyl group, an acrylic group, or a methacryl group, or a silicon-bonded hydrogen atom. Non-reactive organopolysiloxanes such as, etc. can be blended, thereby improving the loss coefficient (tan δ), storage elasticity (G') and loss elasticity (G ″) of the pressure-sensitive adhesive layer described later. May be possible. For example, the use of polydimethylsiloxane or polydimethyldiphenylsiloxane with hydroxyl end ends can increase the loss factor of the pressure sensitive adhesive layer, such compositions are within the scope of the invention.
[組成物全体の粘度]
本発明のシリコーン感圧接着剤組成物は、25℃における組成物全体の粘度が1,000〜300,000mPa・sの範囲であり、組成物全体の粘度が1,000〜250,000mPa・sの範囲であることが好ましい。特に、有機溶媒の含有量を組成物全体の20質量%未満とした場合に、組成物全体の粘度が1,000〜100,000mPa・sの範囲であることが好ましい。[Viscosity of the entire composition]
In the silicone pressure-sensitive adhesive composition of the present invention, the viscosity of the entire composition at 25 ° C. is in the range of 1,000 to 300,000 mPa · s, and the viscosity of the entire composition is 1,000 to 250,000 mPa · s. It is preferably in the range of. In particular, when the content of the organic solvent is less than 20% by mass of the entire composition, the viscosity of the entire composition is preferably in the range of 1,000 to 100,000 mPa · s.
本発明にかかるシリコーン感圧接着剤組成物の調製方法は特に限定されず、それぞれの成分を均質に混合することによって行われる。必要に応じて上述した量の範囲内で少量の有機溶剤を加えてもよく、公知の攪拌機または混練機を用いて、0〜200℃の温度で混合して調製してもよい。 The method for preparing the silicone pressure-sensitive adhesive composition according to the present invention is not particularly limited, and it is carried out by uniformly mixing the respective components. If necessary, a small amount of organic solvent may be added within the above-mentioned amount range, or the mixture may be prepared by mixing at a temperature of 0 to 200 ° C. using a known stirrer or kneader.
本発明のオルガノポリシロキサン組成物は、基材上に塗工することによって塗膜を形成し、80〜200℃の温度条件下、好適には、90〜190℃の温度条件下で加熱することによって硬化物とする。塗工方法としては、グラビアコート、オフセットコート、オフセットグラビア、ロールコート、リバースロールコート、エアナイフコート、カーテンコート、及びコンマコートが例示される。 The organopolysiloxane composition of the present invention forms a coating film by coating on a substrate and is heated under a temperature condition of 80 to 200 ° C., preferably 90 to 190 ° C. To make a cured product. Examples of the coating method include gravure coat, offset coat, offset gravure, roll coat, reverse roll coat, air knife coat, curtain coat, and comma coat.
[感圧接着性および粘着力の範囲]
本発明のシリコーン感圧接着剤組成物は、ヒドロシリル化反応により当該組成物を硬化させてなる硬化層が感圧接着性であることを特徴とする。本発明の感圧接着層は、上記の構成を有し、実用上十分な粘着力を発現することから、公知のシリコーン感圧接着剤を所望により置き換えて利用可能である。[Range of pressure-sensitive adhesiveness and adhesive strength]
The silicone pressure-sensitive adhesive composition of the present invention is characterized in that the cured layer obtained by curing the composition by a hydrosilylation reaction is pressure-sensitive adhesive. Since the pressure-sensitive adhesive layer of the present invention has the above-mentioned structure and exhibits practically sufficient adhesive force, it can be used by replacing a known silicone pressure-sensitive adhesive as desired.
具体的には、本発明のシリコーン感圧接着剤組成物を硬化させてなる厚み40μmの感圧接着層の、SUS基剤に対する、JIS Z 0237に従う180°引き剥がし試験方法を用いて引張速度300mm/minにより測定された粘着力が100〜2500gf/inchの範囲にある感圧接着層を設計可能であり、500〜2250gf/inchの範囲にある感圧接着層が好適である。なお、上記の厚み(40μm)は、本発明にかかる硬化層の粘着力を客観的に定義するための基準となる硬化層自体の厚みであり、本発明のオルガノポリシロキサン組成物は厚み40μmに限らず、任意の厚みの硬化層または感圧接着層として利用することができることは言うまでもない。 Specifically, a pressure-sensitive adhesive layer having a thickness of 40 μm obtained by curing the silicone pressure-sensitive adhesive composition of the present invention has a tensile speed of 300 mm using a 180 ° peeling test method according to JIS Z 0237 for a SUS base. It is possible to design a pressure-sensitive adhesive layer having an adhesive strength in the range of 100 to 2500 gf / inch measured by / min, and a pressure-sensitive adhesive layer in the range of 500 to 2250 gf / inch is preferable. The above thickness (40 μm) is the thickness of the cured layer itself, which is a reference for objectively defining the adhesive force of the cured layer according to the present invention, and the organopolysiloxane composition of the present invention has a thickness of 40 μm. Needless to say, it can be used as a cured layer or a pressure-sensitive adhesive layer having an arbitrary thickness.
[感圧接着剤層としての使用]
本発明の硬化物は、特に、感圧接着剤層として使用することができる。また、被着体との密着性を向上させるために、感圧接着剤層または基材の表面に対してプライマー処理、コロナ処理、エッチング処理、プラズマ処理等の表面処理を行ってもよい。ただし、本発明の感圧接着剤層は、上記のとおり、表示デバイス等の基材への密着性に優れることから、必要に応じ、これらの工程を加えてさらに被着体との密着性を向上させてもよく、これらの工程を省くことにより、より高い生産効率を実現してもよい。[Use as a pressure-sensitive adhesive layer]
The cured product of the present invention can be used, in particular, as a pressure-sensitive adhesive layer. Further, in order to improve the adhesion to the adherend, the surface of the pressure-sensitive adhesive layer or the base material may be subjected to surface treatment such as primer treatment, corona treatment, etching treatment, and plasma treatment. However, as described above, the pressure-sensitive adhesive layer of the present invention has excellent adhesion to a base material such as a display device, and therefore, if necessary, these steps are added to further improve the adhesion to the adherend. It may be improved, or higher production efficiency may be realized by omitting these steps.
本発明に係るシリコーン感圧接着剤組成物は、剥離ライナーに塗工した後、上記の温度条件下で加熱することにより硬化させ、剥離ライナーを剥がしてフィルム状基材、テープ状基材、またはシート状基材(以下、「フィルム状基材」という)と貼り合せたり、フィルム状基材に塗工した後、上記の温度条件下で加熱することにより硬化させ、前記基材の表面に感圧接着剤層を形成することができる。これらのフィルム状基材上に本発明に係るオルガノポリシロキサン組成物を硬化してなる硬化層、特にフィルム状の感圧接着剤層を備えた積層体は、粘着テープ、絆創膏、低温支持体、転写フィルム、ラベル、エンブレム及び装飾又は説明用の標示に使用してもよい。更に、本発明に係るオルガノポリシロキサン組成物を硬化してなる硬化層は、自動車部品、玩具、電子回路、又はキーボードの組み立てに使用してもよい。あるいは、本発明に係るオルガノポリシロキサン組成物を硬化してなる硬化層、特にフィルム状の感圧接着剤層は、積層タッチスクリーン又はフラットパネルディスプレイの構築に使用してもよい。 The silicone pressure-sensitive adhesive composition according to the present invention is applied to a release liner and then cured by heating under the above temperature conditions, and the release liner is peeled off to form a film-like base material, a tape-like base material, or a tape-like base material. After being bonded to a sheet-like base material (hereinafter referred to as "film-like base material") or coated on a film-like base material, it is cured by heating under the above temperature conditions, and the surface of the base material is felt. A pressure adhesive layer can be formed. A cured layer obtained by curing the organopolysiloxane composition according to the present invention on these film-like substrates, particularly a laminate having a film-like pressure-sensitive adhesive layer, is an adhesive tape, an adhesive plaster, a low-temperature support, and the like. It may be used for transfer films, labels, emblems and decorative or explanatory markings. Further, the cured layer obtained by curing the organopolysiloxane composition according to the present invention may be used for assembling automobile parts, toys, electronic circuits, or keyboards. Alternatively, a cured layer obtained by curing the organopolysiloxane composition according to the present invention, particularly a film-like pressure-sensitive adhesive layer, may be used for constructing a laminated touch screen or a flat panel display.
基材の種類として、板紙,ダンボール紙,クレーコート紙,ポリオレフィンラミネート紙,特にはポリエチレンラミネート紙,合成樹脂フィルム・シート,天然繊維布,合成繊維布,人工皮革布,金属箔が例示される。特に、合成樹脂フィルム・シートが好ましく、合成樹脂として、ポリイミド、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリカーボネート、ポリエチレンテレフタレート、シクロポリオレフィン、ナイロン(登録商標)が例示される。特に耐熱性が要求される場合には、ポリイミド、ポリエーテルエーテルケトン、ポリエチレンナフタレート(PEN)、液晶ポリアリレート、ポリアミドイミド、ポリエーテルスルフォン等の耐熱性合成樹脂のフィルムが好適である。一方、表示デバイス等視認性が求められる用途においては、透明基材、具体的にはポリプロピレン、ポリスチレン、ポリ塩化ビニリデン、ポリカーボネート、ポリエチレンテレフタレート、PEN等の透明材料が好適である。 Examples of the type of the base material include paperboard, cardboard, clay coat paper, polyolefin laminated paper, particularly polyethylene laminated paper, synthetic resin film / sheet, natural fiber cloth, synthetic fiber cloth, artificial leather cloth, and metal foil. In particular, synthetic resin films and sheets are preferable, and examples of the synthetic resin include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, cyclopolyolefin, and nylon (registered trademark). When heat resistance is particularly required, a film of a heat-resistant synthetic resin such as polyimide, polyetheretherketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamideimide, or polyethersulfone is suitable. On the other hand, in applications where visibility is required such as display devices, transparent substrates, specifically transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and PEN are suitable.
上記基材はフィルム状またはシート状であることが好ましい。その厚さは特に制限されず、用途に応じて所望の厚さで設計することができる。さらに、支持フィルムと感圧接着層の密着性を向上させるために、プライマー処理、コロナ処理、エッチング処理、プラズマ処理された支持フィルムを用いてもよい。また、フィルム状基材の感圧接着層面と反対面には、傷つき防止、汚れ防止、指紋付着防止、防眩、反射防止、帯電防止などの処理などの表面処理されたものであってもよい。 The base material is preferably in the form of a film or a sheet. The thickness is not particularly limited, and a desired thickness can be designed according to the application. Further, in order to improve the adhesion between the support film and the pressure-sensitive adhesive layer, a support film that has been subjected to primer treatment, corona treatment, etching treatment, or plasma treatment may be used. Further, the surface of the film-like base material opposite to the pressure-sensitive adhesive layer surface may be surface-treated such as scratch prevention, stain prevention, fingerprint adhesion prevention, antiglare, antireflection, antistatic and the like. ..
シリコーン感圧接着剤組成物の基材への塗工方法としては、グラビアコート、オフセットコート、オフセットグラビア、オフセット転写ロールコーター等を用いたロールコート、リバースロールコート、エアナイフコート、カーテンフローコーター等を用いたカーテンコート、コンマコート、マイヤーバー、その他公知の硬化層を形成する目的で使用される方法が制限なく使用できる。 As a method of applying the silicone pressure-sensitive adhesive composition to the base material, a gravure coat, an offset coat, an offset gravure, a roll coat using an offset transfer roll coater, a reverse roll coat, an air knife coat, a curtain flow coater, etc. The used curtain coat, comma coat, Meyer bar, and other methods used for the purpose of forming a known cured layer can be used without limitation.
基材へのシリコーン感圧接着剤組成物の塗工量は表示装置等の用途に応じて所望の厚さで設計することができ、一例として、硬化したあとの感圧接着層の厚みとして1〜1,000μmであり、5〜900μmであってよく、10〜800μmであってよいが、これらに限定されるものではない。 The amount of the silicone pressure-sensitive adhesive composition applied to the base material can be designed to a desired thickness according to the application such as a display device. As an example, the thickness of the pressure-sensitive adhesive layer after curing is 1 It may be ~ 1,000 μm, may be 5 to 900 μm, and may be 10 to 800 μm, but is not limited thereto.
本発明に係る感圧接着層は、その要求特性に応じて単層であっても2層以上の感圧接着層を積層してなる複層であってもよい。複層の感圧接着層は、一層ずつ作成した感圧接着剤フィルムを貼り合わせてもよく、剥離層を備えたフィルム基材上等で、感圧接着層形成性オルガノポリシロキサン組成物を塗工して硬化させる工程を複数回行ってもよい。 The pressure-sensitive adhesive layer according to the present invention may be a single layer or a plurality of layers formed by laminating two or more pressure-sensitive adhesive layers, depending on the required characteristics. The pressure-sensitive adhesive film prepared one by one may be bonded to the multi-layered pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer-forming organopolysiloxane composition is applied on a film substrate provided with a release layer or the like. The step of working and curing may be performed a plurality of times.
本発明に係る感圧接着層は、部材間の接着ないし粘着機能のほか、誘電層、導電層、放熱層、絶縁層、補強層等から選ばれる他の機能層としての役割を付与されていてもよい。 The pressure-sensitive adhesive layer according to the present invention is given a role as another functional layer selected from a dielectric layer, a conductive layer, a heat radiating layer, an insulating layer, a reinforcing layer, etc., in addition to an adhesive or adhesive function between members. May be good.
本発明の無溶剤型又は低溶剤型シリコーン感圧接着剤組成物を硬化してなる硬化層が感圧接着層、特に、感圧接着剤フィルムである場合、当該硬化層は、剥離コーティング能を有する剥離層を備えたフィルム基材上に、剥離可能な状態で粘着した積層体フィルムとして取り扱うことが好ましい。剥離層は剥離ライナー、セパレーター、離型層あるいは剥離コーティング層と呼ばれることもあり、好適には、シリコーン系剥離剤、フッ素系剥離剤、アルキド系剥離剤、またはフルオロシリコーン系剥離剤等の剥離コーティング能を有する剥離層である。あるいは、剥離層なしに、基材表面に物理的に微細な凹凸を形成させた基材または本発明の感圧接着層と付着しにくい材料からなる基材自体の上に感圧接着剤層を形成してもよい。特に本発明にかかる積層体においては、剥離層として、硬化性のフルオロシリコーン系剥離剤を硬化させてなる剥離層の使用が好ましい。 When the cured layer obtained by curing the solvent-free or low-solvent silicone pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive layer, particularly a pressure-sensitive adhesive film, the cured layer has a peeling coating ability. It is preferable to handle it as a laminated film which is adhered in a peelable state on a film base material provided with a peeling layer. The release layer is sometimes called a release liner, a separator, a release layer or a release coating layer, and is preferably a release coating such as a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, or a fluorosilicone-based release agent. It is a release layer having a function. Alternatively, without a release layer, a pressure-sensitive adhesive layer is formed on a base material having physically fine irregularities formed on the surface of the base material or a base material itself made of a material that does not easily adhere to the pressure-sensitive adhesive layer of the present invention. It may be formed. In particular, in the laminate according to the present invention, it is preferable to use a release layer obtained by curing a curable fluorosilicone-based release agent as the release layer.
本発明の無溶剤型又は低溶剤型シリコーン感圧接着剤組成物を硬化してなる硬化物は、上記のような粘弾性と接着力を併せ持つため、弾性粘着部材として、各種の電子機器または電気的装置の部材として有用である。特に、電子材料、表示装置用部材またはトランスデューサー用部材(センサ、スピーカー、アクチュエーター、およびジェネレーター用を含む)として有用であり、当該硬化物の好適な用途は、電子部品または表示装置の部材である。本発明にかかる硬化物は透明でも不透明であってもよいが、フィルム形状の硬化物、特に実質的に透明な感圧接着剤フィルムは、表示パネルまたはディスプレイ用の部材として好適であり、特に、画面を指先等で接触することにより機器、特に電子機器を操作可能な所謂タッチパネル用途に特に有用である。また、不透明な弾性粘着層は、透明性が要求されず、粘着層自体に一定の伸縮性または柔軟性が求められるセンサ、スピーカー、アクチュエーター等に用いられるフィルム状またはシート状部材の用途に特に有用である。 Since the cured product obtained by curing the solvent-free or low-solvent silicone pressure-sensitive adhesive composition of the present invention has both viscoelasticity and adhesive strength as described above, various electronic devices or electric devices can be used as elastic adhesive members. It is useful as a member of a target device. In particular, it is useful as an electronic material, display device member or transducer member (including for sensors, speakers, actuators, and generators), and a suitable use for the cured product is an electronic component or display device member. .. The cured product according to the present invention may be transparent or opaque, but a film-shaped cured product, particularly a substantially transparent pressure-sensitive adhesive film, is suitable as a member for a display panel or a display, and in particular, It is particularly useful for so-called touch panel applications in which devices, especially electronic devices, can be operated by touching the screen with a fingertip or the like. Further, the opaque elastic adhesive layer is particularly useful for applications of film-like or sheet-like members used in sensors, speakers, actuators, etc., where transparency is not required and the adhesive layer itself is required to have a certain degree of elasticity or flexibility. Is.
[粘着テープとしての使用]
本発明のシリコーン感圧接着剤組成物からなる感圧接着剤を含む物品は、粘着テープであってよく、上記の合成樹脂フィルム・シート、金属箔、織布、不織布、紙等の繊維製品からなるシート状部材と上記の粘着層を備えることを特徴とする。このような粘着テープの種類は、特に制限されるものではなく、絶縁テープ、耐熱テープ、ハンダマスキングテープ、マイカテープバインダー、仮止めテープ(シリコーンゴム部品等の仮止めテープを特に含む)、スプライシングテープ(シリコーン剥離紙用スプライシングテープを特に含む)があげられる。[Use as adhesive tape]
The article containing the pressure-sensitive adhesive composed of the silicone pressure-sensitive adhesive composition of the present invention may be an adhesive tape, and is derived from the above-mentioned synthetic resin film / sheet, metal foil, woven fabric, non-woven fabric, paper and other textile products. It is characterized by including a sheet-like member and the above-mentioned adhesive layer. The types of such adhesive tapes are not particularly limited, and are insulating tapes, heat-resistant tapes, solder masking tapes, mica tape binders, temporary fixing tapes (including temporary fixing tapes such as silicone rubber parts), and splicing tapes. (In particular, splicing tape for silicone release paper) can be mentioned.
特に、本発明のシリコーン感圧接着剤組成物を硬化してなる感圧接着層は、従来のシリコーン感圧接着層と同等の感圧接着特性を実現可能であり、かつ、硬化不良や硬化性の低下の問題を生じることなく、表示デバイス等の基材への密着性を改善できる。 In particular, the pressure-sensitive adhesive layer obtained by curing the silicone pressure-sensitive adhesive composition of the present invention can realize pressure-sensitive adhesive characteristics equivalent to those of the conventional silicone pressure-sensitive adhesive layer, and has poor curing and curability. Adhesion to a base material such as a display device can be improved without causing the problem of deterioration.
[積層体および感圧接着シート]
次に、本発明に係る積層体および上記の感圧接着層の一種である感圧接着シートについて説明する。[Laminate and pressure-sensitive adhesive sheet]
Next, the laminate according to the present invention and the pressure-sensitive adhesive sheet which is a kind of the above-mentioned pressure-sensitive adhesive layer will be described.
本発明の積層体は、上記のフィルム状基材上に、上記のシリコーン感圧接着剤組成物を硬化してなる感圧接着剤層を備えた積層体であり、好適には、これらのフィルム状基材に当該感圧接着剤層に対する剥離層が設けられている。 The laminate of the present invention is a laminate having a pressure-sensitive adhesive layer obtained by curing the above-mentioned silicone pressure-sensitive adhesive composition on the above-mentioned film-like base material, and preferably these films. A release layer for the pressure-sensitive adhesive layer is provided on the shaped substrate.
本発明の積層体では、シート状基材が少なくとも1つの剥離層を備えており、当該剥離層が感圧接着層と接触していることが好ましい。これにより、感圧接着層をシート状基材から容易に剥離することができる。剥離層に含まれる剥離剤は特には限定されるものではなく、上記同様、シリコーン系剥離剤、フッ素系剥離剤、アルキド系剥離剤、及びフルオロシリコーン系剥離剤等を挙げることができる。 In the laminate of the present invention, it is preferable that the sheet-like base material has at least one release layer, and the release layer is in contact with the pressure-sensitive adhesive layer. As a result, the pressure-sensitive adhesive layer can be easily peeled off from the sheet-like base material. The release agent contained in the release layer is not particularly limited, and examples thereof include a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, and a fluorosilicone-based release agent.
特に、本発明の積層体は、フィルム状基材から分離した感圧接着剤層を単独で取り扱うことができてもよく、フィルム状基材は二つであってもよい。
具体的には、
フィルム状基材、
該フィルム状基材上に形成された第1剥離層、
該剥離層上に上記のシリコーン感圧接着剤組成物を塗工し硬化させて形成された感圧接着層、及び
該感圧接着層上に積層された第2剥離層
を備えるものであってよい。In particular, the laminate of the present invention may be able to handle the pressure-sensitive adhesive layer separated from the film-like base material alone, or may have two film-like base materials.
In particular,
Film-like substrate,
The first release layer formed on the film-like substrate,
It is provided with a pressure-sensitive adhesive layer formed by applying and curing the above-mentioned silicone pressure-sensitive adhesive composition on the release layer, and a second release layer laminated on the pressure-sensitive adhesive layer. good.
同様に、上記の形態の積層体は、例えば、上記のシリコーン感圧接着剤組成物をフィルム状基材上に形成された一方の剥離層上に塗工し硬化させることにより、感圧接着層を形成させ、当該感圧接着層上に、他の剥離層を積層して形成させてもよい。 Similarly, the laminate of the above-mentioned form is obtained by, for example, applying the above-mentioned silicone pressure-sensitive adhesive composition onto one of the release layers formed on the film-like substrate and curing the pressure-sensitive adhesive layer. May be formed, and another release layer may be laminated on the pressure-sensitive adhesive layer.
また、上記の形態の積層体は、例えば、上記のシリコーン感圧接着剤組成物を第1のフィルム状基材及び第2のフィルム状基材に挟み、加熱しつつ、プレス又はロールで一定の厚みに成形した後、前記組成物を硬化させることによって製造してもよい。 Further, in the laminate of the above-mentioned form, for example, the above-mentioned silicone pressure-sensitive adhesive composition is sandwiched between the first film-like base material and the second film-like base material, and while being heated, it is constant by pressing or rolling. It may be produced by curing the composition after molding to a thickness.
第1のシート基材は第1の剥離層を備えていてもよく、或いは、第1のシート基材自体が剥離性を備えるものであってもよい。同様に、第2のシート基材は第2の剥離層を備えていてもよく、或いは、第2のシート基材自体が剥離性を備えるものであってもよい。第1のシート基材及び/又は第2のシート基材が第1の剥離層及び/又は第2の剥離層を備える場合は、感圧接着層は第1の剥離層及び/又は第2の剥離層に接触することが好ましい。 The first sheet base material may include a first release layer, or the first sheet base material itself may have peelability. Similarly, the second sheet base material may include a second release layer, or the second sheet base material itself may have peelability. If the first sheet substrate and / or the second sheet substrate comprises a first release layer and / or a second release layer, the pressure sensitive adhesive layer is the first release layer and / or the second release layer. It is preferable to contact the release layer.
剥離性を有するシート基材としては、例えば、フッ素樹脂製フィルム等の剥離性を有する材質からなるシート基材、或いは、ポリオレフィンフィルム等の剥離性がないか若しくは低い材質にシリコーン、フッ素樹脂等の剥離剤を添加したものからなるシート基材が挙げられる。一方、剥離層を備えるシート基材としては、例えば、シリコーン、フッ素樹脂等の剥離剤をコーティングしたポリオレフィンフィルム等が挙げられる。 Examples of the sheet base material having peelability include a sheet base material made of a material having peelability such as a fluororesin film, or a material having no or low peelability such as a polyolefin film such as silicone or fluororesin. Examples thereof include a sheet base material made of a material to which a release agent is added. On the other hand, examples of the sheet base material provided with the release layer include a polyolefin film coated with a release agent such as silicone and fluororesin.
本発明の積層体は、例えば、感圧接着層を被着体に適用後に、被着体に接着したフィルム状基材から感圧接着層を剥離することにより使用することができる。 The laminate of the present invention can be used, for example, by applying the pressure-sensitive adhesive layer to the adherend and then peeling the pressure-sensitive adhesive layer from the film-like base material adhered to the adherend.
感圧接着層の厚みは、5〜10000μmであるのが好ましく、中でも10μm以上或いは8000μm以下、その中でも20μm以上或いは5000μmであるのが特に好ましい。 The thickness of the pressure-sensitive adhesive layer is preferably 5 to 10000 μm, particularly preferably 10 μm or more or 8000 μm or less, and particularly preferably 20 μm or more or 5000 μm.
[表示パネルまたはディスプレイ用の部材]
本発明の組成物を硬化してなる硬化物は、積層タッチスクリーン又はフラットパネルディスプレイの構築に使用することができ、その具体的な使用方法は、感圧接着剤層(特に、シリコーンPSA(感圧接着剤))の公知の使用方法を特に制限なく用いることができる。[Display panel or display member]
The cured product obtained by curing the composition of the present invention can be used for constructing a laminated touch screen or a flat panel display, and a specific method of use thereof is a pressure-sensitive adhesive layer (particularly, silicone PSA (feeling)). A known method of using the pressure adhesive)) can be used without particular limitation.
例えば、本発明の組成物を硬化してなる硬化物は、前記の特表2014−522436号または特表2013−512326等で開示された光学的に透明なシリコーン系感圧接着剤フィルムあるいは粘着剤層として、タッチパネル等の表示デバイスの製造に用いることができる。具体的には、本発明の組成物を硬化してなる硬化物は、特表2013−512326に記載の粘着層または粘着フィルムとして、特に制限なく用いることができる。 For example, the cured product obtained by curing the composition of the present invention is an optically transparent silicone-based pressure-sensitive adhesive film or pressure-sensitive adhesive disclosed in Japanese Patent Application Laid-Open No. 2014-522436 or Japanese Patent Application Laid-Open No. 2013-512326. As a layer, it can be used in the manufacture of display devices such as touch panels. Specifically, the cured product obtained by curing the composition of the present invention can be used without particular limitation as the pressure-sensitive adhesive layer or pressure-sensitive adhesive film shown in Special Table 2013-512326.
一例として、本発明にかかるタッチパネルは、一面に導電層が形成されている伝導性プラスチックフィルム等の基材、及び当該導電層が形成された側またはその反対側の面に付着されている本発明の組成物を硬化してなる硬化層を含むタッチパネルであってよい。当該基材は、シート状またはフィルム状基材であることが好ましく、樹脂フィルムまたはガラス板が例示される。また、前記伝導層が形成されている基材は、一面にITO層が形成されている樹脂フィルムまたはガラス板、特に、ポリエチレンテレフタレートフィルムであってよい。これらは、前記の特表2013−512326等に開示されている。 As an example, the touch panel according to the present invention is the present invention attached to a base material such as a conductive plastic film having a conductive layer formed on one surface thereof, and a surface on the side where the conductive layer is formed or the opposite side. The touch panel may include a cured layer obtained by curing the composition of. The base material is preferably a sheet-like or film-like base material, and a resin film or a glass plate is exemplified. Further, the base material on which the conductive layer is formed may be a resin film or a glass plate having an ITO layer formed on one surface, particularly a polyethylene terephthalate film. These are disclosed in the above-mentioned special table 2013-512326 and the like.
その他、本発明のシリコーン感圧接着剤組成物を硬化してなる硬化物は、タッチパネル等の表示デバイスの製造に用いる偏光板用接着フィルムとして用いてもよく、特開2013−065009号公報に記載のタッチパネルとディスプレイモジュール間の貼合に用いる感圧接着層として用いてもよい。 In addition, the cured product obtained by curing the silicone pressure-sensitive adhesive composition of the present invention may be used as an adhesive film for a polarizing plate used in the manufacture of a display device such as a touch panel, and is described in Japanese Patent Application Laid-Open No. 2013-60509. It may be used as a pressure-sensitive adhesive layer used for bonding between the touch panel and the display module.
本発明のシリコーン感圧接着剤組成物、それを硬化してなる硬化物の用途としては、上記に開示した他に何ら制約はなく、当該組成物を硬化してなる硬化物を備えてなる感圧接着フィルムはテレビ受像機、コンピューター用モニター、携帯情報端末用モニター、監視用モニター、ビデオカメラ、デジタルカメラ、携帯電話、携帯情報端末、自動車などの計器盤用ディスプレイ、種々の設備・装置・機器の計器盤用ディスプレイ、自動券売機、現金自動預け払い機、車載用表示装置、車載用透過型スクリーンなど、文字や記号、画像を表示するための種々の表示装置に利用可能である。このような表示装置の表面形状は、平面ではなく曲面状ないし湾曲した形状であってもよく、各種フラットパネルディスプレイ(FPD)のほか、自動車(電気自動車含む)や航空機等に利用される曲面ディスプレイまたは曲面透過型スクリーンが例示される。さらに、これらの表示装置は、スクリーンやディスプレイ上に機能またはプログラムを実行するためのアイコンや、電子メール・プログラム等の通知表示、カーナビゲーション装置、スピーカー用のメンブレン、オーディオ装置、空調装置などの各種装置の操作ボタンを表示することができ、これらのアイコンや通知表示、操作ボタンに指を触れることで、入力操作が可能となるタッチパネル機能が付加されていてもよい。装置としては、CRTディスプレイ、液晶ディスプレイ、プラズマディスプレイ、有機ELディスプレイ、無機ELディスプレイ、LEDディスプレイ、表面電解ディスプレイ(SED)、電界放出型ディスプレイ(FED)などの表示装置や、これらを利用したタッチパネルに応用が可能である。また、当該組成物を硬化してなる硬化物は、接着性と粘弾性特性に優れるため、スピーカー用のメンブレン等のトランスデューサー用部材(センサ、スピーカー、アクチュエーター、およびジェネレーター用を含む)であるフィルム又はシート状部材として利用できるほか、さらに、二次電池、燃料電池または太陽電池モジュールに用いる封止層または接着剤層として利用することができる。 There are no restrictions on the use of the silicone pressure-sensitive adhesive composition of the present invention and the cured product obtained by curing the composition, other than those disclosed above, and the feeling that the cured product obtained by curing the composition is provided. Pressure-bonded film is used for TV receivers, computer monitors, mobile information terminal monitors, surveillance monitors, video cameras, digital cameras, mobile phones, mobile information terminals, instrument panel displays for automobiles, and various equipment / devices / equipment. It can be used for various display devices for displaying characters, symbols, and images, such as a display for an instrument panel, an automatic ticket vending machine, an automatic cash deposit / payment machine, an in-vehicle display device, and an in-vehicle transmissive screen. The surface shape of such a display device may be a curved shape or a curved shape instead of a flat surface, and is used for various flat panel displays (FPDs), automobiles (including electric vehicles), aircraft, and the like. Alternatively, a curved transparent screen is exemplified. In addition, these display devices include icons for executing functions or programs on screens and displays, notification displays such as e-mail programs, car navigation devices, speaker membranes, audio devices, air conditioners, and the like. The operation buttons of the device can be displayed, and a touch panel function that enables input operations by touching these icons, notification displays, and operation buttons may be added. Devices include display devices such as CRT displays, liquid crystal displays, plasma displays, organic EL displays, inorganic EL displays, LED displays, surface electrolytic displays (SED), field emission displays (FED), and touch panels using these. It can be applied. Further, since the cured product obtained by curing the composition has excellent adhesiveness and viscoelastic properties, it is a film that is a transducer member (including for a sensor, a speaker, an actuator, and a generator) such as a membrane for a speaker. Alternatively, it can be used as a sheet-like member, and can also be used as a sealing layer or an adhesive layer used for a secondary battery, a fuel cell, or a solar cell module.
本発明のシリコーン感圧接着剤組成物を硬化してなる感圧接着層は、実質的に透明であってよく、硬化不良や硬化性の低下の問題を生じることなく、かつ、各種表示デバイス等の基材への密着性に優れることから、長期間にわたって表示内容の視認性および操作性が良好な車両用表示装置、特に、曲面スクリーンまたは曲面ディスプレイを備え、任意でタッチパネル機能を有する車両用表示装置に好適に利用できる。例えば、特開2017-047767号公報、特開2014-182335号公報、特開2014-063064号公報、特開2013-233852号公報等には曲面状の表示面を備えた車両用表示装置が開示されているが、本発明にかかる感圧接着層は、これらの文献中の透明性が求められる接着層または粘着層の一部又は全部として好適に適用乃至置き換えが可能である。さらに、本発明のシリコーン感圧接着剤組成物は、他の公知の曲面状の表示装置についても、現在使用されている透明性が求められる接着層または粘着層を置き換えて利用できることは言うまでもなく、本発明の感圧接着剤の利点をさらに活用するために表示装置の設計や部材の厚みを公知の手法により調整することが好ましい。 The pressure-sensitive adhesive layer obtained by curing the silicone pressure-sensitive adhesive composition of the present invention may be substantially transparent, does not cause problems of poor curing or deterioration of curability, and various display devices and the like. A vehicle display device that has good visibility and operability of the displayed contents for a long period of time, particularly a curved screen or a curved display, and optionally has a touch panel function because of its excellent adhesion to the base material. It can be suitably used for an apparatus. For example, JP-A-2017-047767, JP-A-2014-182335, JP-A-2014-063064, JP-A-2013-233852, etc. disclose vehicle display devices having a curved display surface. However, the pressure-sensitive adhesive layer according to the present invention can be suitably applied or replaced as a part or all of the adhesive layer or the adhesive layer for which transparency is required in these documents. Further, it goes without saying that the silicone pressure-sensitive adhesive composition of the present invention can be used for other known curved display devices by replacing the currently used adhesive layer or adhesive layer that requires transparency. In order to further utilize the advantages of the pressure-sensitive adhesive of the present invention, it is preferable to adjust the design of the display device and the thickness of the member by a known method.
なお、本発明の感圧接着層を備えた透明なフィルム状基材を、これらの、ディスプレイ表面の傷つき防止、汚れ防止、指紋付着防止、帯電防止、反射防止、のぞき見防止などの目的で使用してもよい。 The transparent film-like base material provided with the pressure-sensitive adhesive layer of the present invention is used for the purposes of preventing scratches, stains, fingerprint adhesion, antistatic, antireflection, and peep prevention on the display surface. You may.
(実施例1〜11、比較例1〜3)
以下に、本発明の実施例及び比較例を記す。なお、各実施例、比較例において「硬化させた」とは、各々の硬化条件により、各組成物が完全に硬化したことを意味するものである。(Examples 1 to 11, Comparative Examples 1 to 3)
Examples and comparative examples of the present invention will be described below. In addition, in each Example and Comparative Example, "cured" means that each composition was completely cured under each curing condition.
(シリコーン感圧接着剤組成物の調製)
表1(実施例1〜11)、表2(比較例1〜3)に示す各成分を用いて、各実施例・比較例に示すシリコーン感圧接着剤組成物を調製した。なお、表1および表2における%は全て質量%であり、各成分において、Meはメチル基であり、Viはビニル基を各々表すものである。さらに、当該組成物は、実質的に無溶剤型の組成物である。(Preparation of Silicone Pressure Sensitive Adhesive Composition)
Using each component shown in Table 1 (Examples 1 to 11) and Table 2 (Comparative Examples 1 to 3), the silicone pressure-sensitive adhesive composition shown in each Example / Comparative Example was prepared. In addition,% in Table 1 and Table 2 is all mass%, and in each component, Me represents a methyl group and Vi represents a vinyl group, respectively. Further, the composition is a substantially solvent-free composition.
(オルガノポリシロキサン成分の分子量の測定)
Waters社製ゲルパーミエーションクロマトグラフィー(GPC)を用い、テトラヒドロフラン(THF)を溶媒として、標準ポリスチレン換算で、オルガノポリシロキサンレジン等のオルガノポリシロキサン成分の重量平均分子量(Mw)、数平均分子量(Mn)を求めた。(Measurement of molecular weight of organopolysiloxane component)
Using Gel Permeation Chromatography (GPC) manufactured by Waters, using tetrahydrofuran (THF) as a solvent, in terms of standard polystyrene, weight average molecular weight (Mw) and number average molecular weight (Mn) of organopolysiloxane components such as organopolysiloxane resin. ) Was asked.
(粘着力測定、膜表面)
各組成物を、PETフィルム(株式会社東レ製、製品名ルミラー(登録商標)S10、厚さ50μm)に硬化後の厚みが40μmとなるように塗工し、150℃で3分間硬化させた。1日放置後、同試料を幅20mmに切断し、粘着層面をSUS板(パルテック製)にローラーを用いて貼り合せて試験片とした。試験片は、オリエンテック社製RTC−1210引っ張り試験機を用いてJIS Z0237に準じて180°引き剥がし試験方法を用いて引張速度300mm/minにて粘着力(20mm幅での測定を表示単位gf/インチに換算)を測定した。また、引き剥がした際の、膜表面について観察し、SUS板に粘着剤が残っている組成を、糊残り有りと判断した。(Adhesive strength measurement, film surface)
Each composition was applied to a PET film (manufactured by Toray Industries, Inc., product name Lumirror (registered trademark) S10, thickness 50 μm) so that the cured thickness was 40 μm, and cured at 150 ° C. for 3 minutes. After leaving for 1 day, the sample was cut to a width of 20 mm, and the adhesive layer surface was bonded to a SUS plate (manufactured by Paltek) using a roller to prepare a test piece. The test piece has an adhesive force (measurement at a width of 20 mm is displayed as a display unit gf) at a tensile speed of 300 mm / min using a 180 ° peeling test method according to JIS Z0237 using an RTC-1210 tensile tester manufactured by Orientec. / Converted to inches) was measured. In addition, the surface of the film when peeled off was observed, and the composition in which the adhesive remained on the SUS plate was judged to have adhesive residue.
(高温保持力)
シリコーン感圧接着剤剤組成物を、ポリイミド樹脂フィルム上に、40μmの厚さになるように塗工した後、150℃で3分間乾燥し、接着剤フィルムを作成した。感圧接着剤面側をSUS板に貼り付け、SUS板の下部に200g重りをつるし、200℃のオーブンで30分間エージングした。エージング後にポリイミド樹脂フィルムに対してSUS板が移動している距離を測定した。(High temperature holding power)
The silicone pressure-sensitive adhesive composition was applied onto a polyimide resin film to a thickness of 40 μm, and then dried at 150 ° C. for 3 minutes to prepare an adhesive film. The pressure-sensitive adhesive surface side was attached to a SUS plate, a 200 g weight was hung on the lower part of the SUS plate, and the product was aged in an oven at 200 ° C. for 30 minutes. The distance that the SUS plate was moving with respect to the polyimide resin film after aging was measured.
(組成物の全体粘度)
[粘度]
粘度(mPa・s)は、JIS K7117−1に準拠した回転粘度計を使用して測定した値であり、動粘度(mm2/s)は、JIS Z8803に準拠したウベローデ型粘度計によって測定した値である。(Overall viscosity of composition)
[viscosity]
The viscosity (mPa · s) was measured using a rotational viscometer compliant with JIS K7117-1, and the kinematic viscosity (mm 2 / s) was measured using a Ubbelohde viscometer compliant with JIS Z8803. The value.
(ボールタック)
[粘着力:ボールタック値]上記と同様に作成した粘着シートを、水平方向からの角度が30°である斜面に設置し、規定のステンレス製ボールを上方から3回転がした。3回中2回以上、粘着シート上の転がり距離が10cm以内であったボール番号のうち、最大のものをボールタック値とした。(Ball tack)
[Adhesive strength: Ball tack value] The adhesive sheet prepared in the same manner as above was placed on a slope having an angle of 30 ° from the horizontal direction, and the specified stainless steel ball was rotated three times from above. Among the ball numbers in which the rolling distance on the adhesive sheet was within 10 cm two or more times out of three times, the largest ball number was defined as the ball tack value.
表1に無溶剤型シリコーン感圧接着剤組成物の材料を示す。なお、各成分の粘度は以下の方法により、室温(25℃)において測定した。
[粘度]
粘度(mPa・s)は、JIS K7117−1に準拠した回転粘度計を使用して測定した値である。Table 1 shows the materials of the solvent-free silicone pressure-sensitive adhesive composition. The viscosity of each component was measured at room temperature (25 ° C.) by the following method.
[viscosity]
The viscosity (mPa · s) is a value measured using a rotational viscometer conforming to JIS K7117-1.
表1の各成分として、次のシリコーンを使用した。(A)成分〜(B)成分をあらかじめ混合したものに(C)成分のシリコーンレジンのキシレン溶液を添加し、減圧下でキシレンを留去したものを用いた。 The following silicones were used as each component in Table 1. A xylene solution of the silicone resin of the component (C) was added to a mixture of the components (A) to (B) in advance, and xylene was distilled off under reduced pressure.
(A1成分)
下式で表されるアルケニル基含有ポリシロキサン(ビニル基含有量:6.3質量%)(A1 component)
Alkenyl group-containing polysiloxane represented by the following formula (vinyl group content: 6.3% by mass)
(A2成分)
下式で表されるアルケニル基含有ポリシロキサン(ビニル基含有量:0.44質量%)(A2 component)
Alkenyl group-containing polysiloxane represented by the following formula (vinyl group content: 0.44% by mass)
(B1成分)
下式で表されるSiH基含有ポリシロキサン(ケイ素原子結合水素原子含有量:0.124質量%)(B1 component)
SiH group-containing polysiloxane represented by the following formula (silicon atom-bonded hydrogen atom content: 0.124% by mass)
(B2成分)
下式で表されるSiH基含有ポリシロキサン(ケイ素原子結合水素原子含有量:0.072質量%)(B2 component)
SiH group-containing polysiloxane represented by the following formula (silicon atom-bonded hydrogen atom content: 0.072% by mass)
(C1成分)
(CH3)3SiO1/2単位とSiO4/2単位および水酸基からなるMQシリコーン樹脂、ポリスチレン換算による重量平均分子量(Mw) 6500、OH含有量4.5モル%(1.0質量%)、キシレン溶液(固形分70質量%)(C1 component)
(CH 3 ) MQ silicone resin consisting of 3 SiO 1/2 unit, SiO 4/2 unit and hydroxyl group, polystyrene-equivalent weight average molecular weight (Mw) 6500, OH content 4.5 mol% (1.0% by mass) , Xylene solution (solid content 70% by mass)
(C2成分)
(CH3)3SiO1/2単位とSiO4/2単位および水酸基からなるMQシリコーン樹脂、Mw 3300、OH含有量3.5モル%(0.8質量%)、キシレン溶液(固形分75.5質量%)(C2 component)
(CH 3 ) MQ silicone resin consisting of 3 SiO 1/2 unit, SiO 4/2 unit and hydroxyl group, Mw 3300, OH content 3.5 mol% (0.8 mass%), xylene solution (solid content 75. 5% by mass)
(D1成分)
分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルハイドロジェンシロキサン共重合体、ケイ素原子結合水素原子含有量1.58質量%(D1 component)
Methylhydrogensiloxane copolymer having both ends of the molecular chain sealed with a trimethylsiloxy group, silicon atom-bonded hydrogen atom content 1.58% by mass
(D2成分)
分子鎖両末端がトリメチルシロキシ基で封鎖されたジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、ケイ素原子結合水素原子含有量0.70質量%(D2 component)
Dimethylsiloxane / methylhydrogensiloxane copolymer with both ends of the molecular chain sealed with a trimethylsiloxy group, silicon atom-bonded hydrogen atom content 0.70% by mass
(D3成分)
分子鎖両末端がトリメチルシロキシ基で封鎖されたジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、ポリスチレン換算による重量平均分子量(Mw)1600、ケイ素原子結合水素原子含有量0.73質量%(D3 component)
Dimethylsiloxane / methylhydrogensiloxane copolymer with both ends of the molecular chain sealed with trimethylsiloxy groups, weight average molecular weight (Mw) 1600 in terms of polystyrene, silicon atom-bonded hydrogen atom content 0.73% by mass
[総括]
実施例1〜11にかかるシリコーン感圧接着剤組成物は、実質的に無溶剤型であるが、実用上、塗工可能な粘度範囲にあり、かつ、得られる粘着剤層の硬化性および粘着特性において実用上十分に優れるものであった。一方、(B)成分に対するSiH/Vi比が本発明の下限未満である比較例1、2においては、硬化物の被着体に対する糊残りが発生した。さらに、組成物全体のSiH/Vi比が本発明の上限を超える比較例3においては、十分な粘着力を実現できないものであった。[Summary]
The silicone pressure-sensitive adhesive compositions according to Examples 1 to 11 are substantially solvent-free, but are practically within a coatable viscosity range, and the obtained pressure-sensitive adhesive layer has curability and adhesion. The characteristics were sufficiently excellent for practical use. On the other hand, in Comparative Examples 1 and 2 in which the SiH / Vi ratio with respect to the component (B) was less than the lower limit of the present invention, adhesive residue was generated on the adherend of the cured product. Further, in Comparative Example 3 in which the SiH / Vi ratio of the entire composition exceeds the upper limit of the present invention, sufficient adhesive strength could not be realized.
Claims (11)
(B)分子鎖両末端のみにケイ素結合水素原子を有する直鎖状オルガノハイドロジェンポリシロキサン、
(C)分子内にR3SiO1/2(式中、Rは互いに独立して一価有機基を表す)で表されるシロキサン単位(M単位)、及び、SiO4/2で表されるシロキサン単位(Q単位)を含むオルガノポリシロキサン樹脂、
(D)分子内に少なくとも3個のケイ素結合水素原子を有するオルガノハイドロジェンポリシロキサン、および
(E)ヒドロシリル化反応触媒
を含有し、
(B)成分中のケイ素結合水素原子のモル数の(A)成分中の脂肪族不飽和炭素−炭素結合含有基のモル数に対する比が、0.90〜1.30の範囲にあり、
(B)成分と(D)成分を合わせたケイ素結合水素原子のモル数の(A)成分中の脂肪族不飽和炭素−炭素結合含有基のモル数に対する比が、0.95〜1.35の範囲であり、
25℃における組成物全体の粘度が1,000〜300,000mPa・sの範囲であり、かつ、
有機溶媒の含有量が組成物全体の20質量%未満である、
シリコーン感圧接着剤組成物。(A) A linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule and having a siloxane degree of polymerization in the range of 5 to 250.
(B) A linear organohydrogenpolysiloxane having a silicon-bonded hydrogen atom only at both ends of the molecular chain,
(C) Intramolecularly represented by R 3 SiO 1/2 (in the formula, R represents a monovalent organic group independently of each other) in siloxane units (M units) and SiO 4/2. Organopolysiloxane resin containing siloxane units (Q units),
It contains (D) an organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule, and (E) a hydrosilylation reaction catalyst.
The ratio of the number of moles of the silicon-bonded hydrogen atom in the component (B) to the number of moles of the aliphatic unsaturated carbon-carbon bond-containing group in the component (A) is in the range of 0.99 to 1.30.
The ratio of the number of moles of silicon-bonded hydrogen atoms including the components (B) and (D) to the number of moles of aliphatic unsaturated carbon-carbon bond-containing groups in the component (A) is 0.95-1.35. Is in the range of
The viscosity of the entire composition at 25 ° C. is in the range of 1,000 to 300,000 mPa · s, and
The content of the organic solvent is less than 20% by weight of the total composition.
Silicone pressure sensitive adhesive composition.
(A)成分および(B)成分の合計量が、10〜80質量部の範囲であり、
(C)成分の量が10〜80質量部の範囲であり、
(D)成分の量が、0.01〜10質量部の範囲であることを特徴とする、
請求項1に記載のシリコーン感圧接着剤組成物。When the total amount of the components (A) to (D) is 100 parts by mass,
The total amount of the component (A) and the component (B) is in the range of 10 to 80 parts by mass.
The amount of the component (C) is in the range of 10 to 80 parts by mass.
The amount of the component (D) is in the range of 0.01 to 10 parts by mass.
The silicone pressure-sensitive adhesive composition according to claim 1.
(D1)分子内に少なくとも3個のケイ素結合水素原子を有する環状オルガノハイドロジェンポリシロキサン、および
(D2)分子鎖末端にケイ素結合水素原子を有さず、分子内に少なくとも3個のケイ素結合水素原子を有する直鎖状または分岐鎖状のオルガノハイドロジェンポリシロキサン
からなる群から選ばれる少なくとも1種類以上である、
請求項1または請求項2に記載のシリコーン感圧接着剤組成物。The component (D) is
(D1) Cyclic organohydrogenpolysiloxane having at least 3 silicon-bonded hydrogen atoms in the molecule, and (D2) Silicon-bonded hydrogen having no silicon-bonded hydrogen atom at the end of the molecular chain and having at least 3 silicon-bonded hydrogen atoms in the molecule. At least one selected from the group consisting of linear or branched organohydrogenpolysiloxane having atoms.
The silicone pressure-sensitive adhesive composition according to claim 1 or 2.
該フィルム状基材上に形成された第1剥離層、
該剥離層上に請求項1乃至5のいずれか1項に記載のシリコーン感圧接着剤組成物を塗工し硬化させて形成された感圧接着層、及び
該感圧接着層上に積層された第2剥離層
を含む、請求項8に記載の積層体。Film-like substrate,
The first release layer formed on the film-like substrate,
A pressure-sensitive adhesive layer formed by applying and curing the silicone pressure-sensitive adhesive composition according to any one of claims 1 to 5 on the release layer, and laminated on the pressure-sensitive adhesive layer. The laminate according to claim 8, which includes a second release layer.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201862779231P | 2018-12-13 | 2018-12-13 | |
US62/779,231 | 2018-12-13 | ||
PCT/JP2019/047623 WO2020121939A1 (en) | 2018-12-13 | 2019-12-05 | Pressure-sensitive silicone adhesive composition and use thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2020121939A1 true JPWO2020121939A1 (en) | 2021-11-11 |
JP7491655B2 JP7491655B2 (en) | 2024-05-28 |
Family
ID=71076454
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2020560005A Active JP7491655B2 (en) | 2018-12-13 | 2019-12-05 | Silicone pressure sensitive adhesive composition and uses thereof |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP7491655B2 (en) |
KR (1) | KR20210102358A (en) |
CN (1) | CN113302255A (en) |
WO (1) | WO2020121939A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102525733B1 (en) * | 2018-08-10 | 2023-04-27 | 다우 도레이 캄파니 리미티드 | Pressure-sensitive adhesive layer-forming organopolysiloxane composition and use thereof |
CN116134093A (en) * | 2020-06-30 | 2023-05-16 | 陶氏东丽株式会社 | Curable silicone composition and cured product thereof |
KR20230125248A (en) | 2020-12-25 | 2023-08-29 | 다우 도레이 캄파니 리미티드 | Silicone adhesive composition and use thereof |
CN114196374B (en) * | 2022-01-13 | 2023-05-30 | 万华化学集团股份有限公司 | High AF screen adhesive force organic silicon pressure-sensitive adhesive applicable to TPU film general curing, preparation method and application thereof |
CN114921192B (en) * | 2022-06-24 | 2023-03-21 | 江西昊泽光学膜科技有限公司 | Organic silicon pressure-sensitive adhesive for lithium battery adhesive tape and preparation process thereof |
WO2024075661A1 (en) * | 2022-10-05 | 2024-04-11 | ダウ・東レ株式会社 | Curable organopolysiloxane composition for transducers, cured product of same, and transducer and others each provided with said cured product |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006160923A (en) * | 2004-12-08 | 2006-06-22 | Shin Etsu Chem Co Ltd | Solvent-free silicone adhesive composition |
JP2006335899A (en) * | 2005-06-02 | 2006-12-14 | Shin Etsu Chem Co Ltd | Adhesive for addition reaction curing type silicone rubber |
JP2008274251A (en) * | 2007-03-30 | 2008-11-13 | Shin Etsu Chem Co Ltd | Solventless silicone pressure-sensitive adhesive composition |
JP2012041505A (en) * | 2010-08-23 | 2012-03-01 | Shin-Etsu Chemical Co Ltd | Solventless addition-curable pressure sensitive silicone adhesive composition and adhesive article |
JP2017206594A (en) * | 2016-05-17 | 2017-11-24 | 信越化学工業株式会社 | Silicone composition for forming different release agent for silicone adhesive, and double-sided different releasing paper or film |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5130995B1 (en) | 1971-04-09 | 1976-09-03 | ||
JPH0684494A (en) | 1992-09-01 | 1994-03-25 | Hitachi Ltd | Ion implanter |
-
2019
- 2019-12-05 WO PCT/JP2019/047623 patent/WO2020121939A1/en active Application Filing
- 2019-12-05 JP JP2020560005A patent/JP7491655B2/en active Active
- 2019-12-05 KR KR1020217021499A patent/KR20210102358A/en not_active Application Discontinuation
- 2019-12-05 CN CN201980089314.4A patent/CN113302255A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006160923A (en) * | 2004-12-08 | 2006-06-22 | Shin Etsu Chem Co Ltd | Solvent-free silicone adhesive composition |
JP2006335899A (en) * | 2005-06-02 | 2006-12-14 | Shin Etsu Chem Co Ltd | Adhesive for addition reaction curing type silicone rubber |
JP2008274251A (en) * | 2007-03-30 | 2008-11-13 | Shin Etsu Chem Co Ltd | Solventless silicone pressure-sensitive adhesive composition |
JP2012041505A (en) * | 2010-08-23 | 2012-03-01 | Shin-Etsu Chemical Co Ltd | Solventless addition-curable pressure sensitive silicone adhesive composition and adhesive article |
JP2017206594A (en) * | 2016-05-17 | 2017-11-24 | 信越化学工業株式会社 | Silicone composition for forming different release agent for silicone adhesive, and double-sided different releasing paper or film |
Also Published As
Publication number | Publication date |
---|---|
CN113302255A (en) | 2021-08-24 |
WO2020121939A1 (en) | 2020-06-18 |
KR20210102358A (en) | 2021-08-19 |
JP7491655B2 (en) | 2024-05-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102515709B1 (en) | Organopolysiloxane composition for forming pressure-sensitive adhesive layer and its use | |
JP7046196B2 (en) | Pressure-sensitive adhesive layer-forming organopolysiloxane composition and its use | |
JP7469232B2 (en) | Silicone pressure sensitive adhesive composition and its uses | |
JP7046198B2 (en) | Pressure-sensitive adhesive layer-forming organopolysiloxane composition and its use | |
JP7046197B2 (en) | Pressure-sensitive adhesive layer-forming organopolysiloxane composition and its use | |
JP7491655B2 (en) | Silicone pressure sensitive adhesive composition and uses thereof | |
JPWO2018186161A1 (en) | Curing-reactive organopolysiloxane composition, pressure-sensitive adhesive composition using the same, and use thereof | |
WO2022138913A1 (en) | Pressure sensitive adhesive layer-forming organopolysiloxane composition, use of same, and composition design method for same | |
WO2022030120A1 (en) | Curable silicone composition and cured product of same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20221108 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230816 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20231005 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20231211 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240306 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240424 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20240515 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240515 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7491655 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |