JPH0236234A - Silicone resin composition and production thereof - Google Patents
Silicone resin composition and production thereofInfo
- Publication number
- JPH0236234A JPH0236234A JP18744988A JP18744988A JPH0236234A JP H0236234 A JPH0236234 A JP H0236234A JP 18744988 A JP18744988 A JP 18744988A JP 18744988 A JP18744988 A JP 18744988A JP H0236234 A JPH0236234 A JP H0236234A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- group
- general formula
- mtq
- resin composition
- 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
- 229920002050 silicone resin Polymers 0.000 title claims description 22
- 239000011342 resin composition Substances 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- -1 alkyl silicate Chemical compound 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims 2
- 229920002379 silicone rubber Polymers 0.000 abstract description 12
- 239000004945 silicone rubber Substances 0.000 abstract description 12
- 239000012744 reinforcing agent Substances 0.000 abstract description 11
- 125000000962 organic group Chemical group 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 93
- 229920005989 resin Polymers 0.000 description 87
- 239000011347 resin Substances 0.000 description 87
- 229920001296 polysiloxane Polymers 0.000 description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 14
- 239000004205 dimethyl polysiloxane Substances 0.000 description 12
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 12
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 229910052799 carbon Chemical group 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 125000000118 dimethyl group Chemical class [H]C([H])([H])* 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DFJDZTPFNSXNAX-UHFFFAOYSA-N ethoxy(triethyl)silane Chemical compound CCO[Si](CC)(CC)CC DFJDZTPFNSXNAX-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- ACXIAEKDVUJRSK-UHFFFAOYSA-N methyl(silyloxy)silane Chemical compound C[SiH2]O[SiH3] ACXIAEKDVUJRSK-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- OTNVGWMVOULBFZ-UHFFFAOYSA-N sodium;hydrochloride Chemical compound [Na].Cl OTNVGWMVOULBFZ-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LGSAOJLQTXCYHF-UHFFFAOYSA-N tri(propan-2-yl)-tri(propan-2-yl)silyloxysilane Chemical compound CC(C)[Si](C(C)C)(C(C)C)O[Si](C(C)C)(C(C)C)C(C)C LGSAOJLQTXCYHF-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- WILBTFWIBAOWLN-UHFFFAOYSA-N triethyl(triethylsilyloxy)silane Chemical compound CC[Si](CC)(CC)O[Si](CC)(CC)CC WILBTFWIBAOWLN-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はシリコーン樹脂組成物、特には１官能性オルガ
ノシロキサン単位（Ｍ単位）と３官能性シロキサン単位
（Ｔ単位）および４官能性シロキサン単位（Ｑ単位）と
からなる、２官能性シロキサン単位（Ｄ単位）からなる
オルガノポリシロキサンとの相溶性にすぐれていること
からシリコーン系感圧接着剤、シリコーンゴムの補強剤
として有用とされるＭＴＱ単位からなるシリコーン樹脂
組成物およびこの製造方法に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to silicone resin compositions, particularly monofunctional organosiloxane units (M units), trifunctional siloxane units (T units), and tetrafunctional siloxane units. MTQ is useful as a reinforcing agent for silicone pressure-sensitive adhesives and silicone rubber because of its excellent compatibility with organopolysiloxanes consisting of bifunctional siloxane units (D units) consisting of (Q units). The present invention relates to a silicone resin composition consisting of units and a method for producing the same.
（従来の技術）
従来からオルガノシロキサン樹脂については各種のもの
が知られており、例えば１官能性シロキサン単位（以下
Ｍ単位と略記する）と４官能性シロキサン単位（以下Ｑ
単位と略記する）とからなる共重合体はＭＱレジンと呼
ばれており、このものはシリコーン感圧接着剤の原料と
して、または特に透明性を必要とするシリコーンゴム、
なかでも常温硬化性（以下ＲＴＶと略記する）シリコー
ンゴムの強度補強剤として使用されており、またこのＭ
Ｑにさらに２官能性シロキサン単位（以下り単位と略記
する）を導入した共重合体もＭＤＱレジンと呼ばれてお
り、これもＭＱレジンに優れるとも劣らない効果をもつ
ものであることが知られている。(Prior Art) Various types of organosiloxane resins have been known, such as monofunctional siloxane units (hereinafter abbreviated as M units) and tetrafunctional siloxane units (hereinafter referred to as Q units).
A copolymer consisting of units (hereinafter abbreviated as ``units'') is called MQ resin, and this resin is used as a raw material for silicone pressure-sensitive adhesives, or as a material for silicone rubbers that particularly require transparency.
Among these, it is used as a strength reinforcing agent for room temperature curable (hereinafter abbreviated as RTV) silicone rubber, and this
A copolymer in which a bifunctional siloxane unit (hereinafter abbreviated as a unit) is further introduced into Q is also called MDQ resin, and it is known that this resin has an effect that is as good as that of MQ resin. ing.
しかし、このＭＱレジンに３官能性シロキサン単位（以
下Ｔ単位と略記する）を導入したＭＴＱレジンはこのＴ
単位のシロキサンが特に加水分解時においてゲル化し易
いためにその製造が難しく、得られたものもゲル化物を
含有していたり、収率が極度にわるく、さらにこのＭＴ
Ｑレジンは相手材料との相溶性に乏しく、感圧接着剤に
応用した場合には粘着力が低くなり、またシリコーンゴ
ムの補強剤としての補強効果も殆ど認められず、したが
ってこのものは工業的に実用化されていない。However, MTQ resin in which trifunctional siloxane units (hereinafter abbreviated as T units) are introduced into this MQ resin is
Since the siloxane unit is easily gelled, especially during hydrolysis, it is difficult to manufacture, and the obtained product also contains gelled products, the yield is extremely low, and furthermore, this MT
Q-resin has poor compatibility with the mating material, resulting in low adhesive strength when applied to pressure-sensitive adhesives, and hardly any reinforcing effect as a reinforcing agent for silicone rubber, so this material is not suitable for industrial use. It has not been put into practical use.
（発明の構成）
本発明はこのような不利を解決したＭＴＱレジンおよび
製造方法に関するものであり、これは１）一般式Ｒ１，
ｌ５ｉＯヨ（こ＼にＲ１は非置換または置換の同種また
は異種の１価炭化水素基、ａは２．６〜３．０の正数）
で示されるシロキサン単位と、２）一般式Ｓｉ○２で示
されるシロキサン単位、および３）一般式Ｒ”ｌ）Ｓ
ｉ Ｏ付（こ＼にＲ２はその３０モル％以上が炭素数２
以上の基である、非置換または置換の同種または異種の
１価炭化水素基、ｂは０．９５〜１．０５の正数）で示
されるシロキサン単位、とからなることを特徴とするシ
リコーン樹脂組成物、および１）一般式Ｒ１ａＳｉ（Ｏ
Ｒ３）−−ａ （Ｒ１は非置換または置換の同種または
異種の１価炭化水素基、Ｒ３は水素原子または炭素数１
〜５のアルキル基、ａは２．６〜３．０の正数）で示さ
れるオルガノハイドロキシシラン、オルガノアルコキシ
シランおよび／または一般式（Ｒ１８Ｓｉ）２０＋−ａ
（Ｒ’、ａは前記に同じ）で示されるオルガノシロキサ
ンと、２）一般式５ｉ（ＯＲ４）４（こ＼にＲ４は炭素
数１〜５のアルキル基）で示されるアルキルシリケート
および／またはその部分加水分解線金物、および３）一
般式Ｒ”ｌ）Ｓ ｉ （ＯＲ’Ｌ−ｂ （Ｒ２はその３
０モル％以上が炭素数２以上の基である、非置換または
置換の同種または異種の１価炭化水素基、Ｒ４は前記に
同じ）で示されるオルガノアルコキシシランおよび／ま
たはその加水分解線金物を混合し、これを共加水分解、
重縮合反応させることを特徴とするシリコーン樹脂組成
物の製造方法に関するものである。(Structure of the Invention) The present invention relates to an MTQ resin and a manufacturing method that solve the above-mentioned disadvantages.
l5iOyo (where R1 is an unsubstituted or substituted same or different monovalent hydrocarbon group, a is a positive number from 2.6 to 3.0)
2) a siloxane unit represented by the general formula Si○2, and 3) a siloxane unit represented by the general formula R''l)S
i O attached (R2 has 2 carbon atoms or more at least 30 mol%)
A silicone resin characterized by comprising a siloxane unit represented by an unsubstituted or substituted same or different monovalent hydrocarbon group, b being a positive number of 0.95 to 1.05, which is the above group. composition, and 1) having the general formula R1aSi(O
R3) --a (R1 is an unsubstituted or substituted same or different monovalent hydrocarbon group, R3 is a hydrogen atom or a carbon number 1
~5 alkyl group, a is a positive number of 2.6 to 3.0) organohydroxysilane, organoalkoxysilane and/or general formula (R18Si)20+-a
2) an alkyl silicate represented by the general formula 5i(OR4)4 (where R4 is an alkyl group having 1 to 5 carbon atoms) and/or its partially hydrolyzed wire hardware, and 3) general formula R"l)S i (OR'L-b (R2 is the 3
An organoalkoxysilane represented by an unsubstituted or substituted same or different monovalent hydrocarbon group in which 0 mol% or more is a group having 2 or more carbon atoms (R4 is the same as above) and/or its hydrolyzable wire metal. Mix and co-hydrolyze this,
The present invention relates to a method for producing a silicone resin composition characterized by carrying out a polycondensation reaction.
すなわち１本発明者らは工業的な有用性の高いＭＴＱレ
ジンを開発すべく種々検討した結果、このＭＴＱレジン
についてはそのＴ単位を構成する一般式Ｒ２ｂＳｉＯ４
−ｂで示されるシロキサン中における１価炭化水素基が
すべてメチル基である場合にはこれが一般式Ｒ’ ＣＳ
ｉ Ｏ己（こ＼にＲ５は非置換または置換の同種また
は異種の１価炭化水素基、Ｃは１．８〜２．１の正数）
で示される２官能性シロキサン単位（Ｄ単位）からなる
オルガノポリシロキサンとの相溶性が全くなく、シリコ
ーン感圧接着剤に応用した場合には粘着力が低くて実用
性がなく、シリコーンゴムの補強剤として使用する場合
も補強効果が殆ど認められず、前記したＭＱレジン、Ｍ
ＤＱレジンにくらべて性能面で著しく劣るものであるけ
れども、このＴ単位を構成する上記した一般式Ｒ”ｌ）
Ｓ ｉ Ｏ＝上で示されるシロキサン中における１価炭
化水素基Ｒ２をその３０モル％以上が炭素数２以上の１
価炭化水素基であるものとすると、このＭＴＱレジンは
上記したＤ単位のシロキサンからなるオルガノポリシロ
キサンとの相溶性のすぐれたものとなり、シリコーン感
圧接着剤に応用した場合にすぐれた接着性を示すし、シ
リコーンゴム補強剤として応用した場合にはすぐれた補
強効果を示すようになるということを見出すと共に、こ
のものはオルガノポリシロキサンをベースとする消泡剤
に添加すると消泡効果の向上、消泡性持続の効果を示し
、各種プラスチックに配合すると成形時の発泡防止、フ
ロー性（流れ特性）、離形性を改善すると共に成形品の
印刷性向上、表面光沢の改良、機械的特性を向上させ、
さらにはエポキシ樹脂と各種無機質充填剤とからなるモ
ールディングコンパウンドに配合するとその耐湿性、耐
水性、耐熱性を向上させるという効果をもつものである
ことを確認し、こへに使用する各成分の種類、配合量お
よびこの製造方法についての研究を進めて本発明を完成
させた。 以下これを詳述する。Namely, as a result of various studies in order to develop an MTQ resin with high industrial utility, the present inventors found that the general formula R2bSiO4 constituting the T unit of this MTQ resin is
When all the monovalent hydrocarbon groups in the siloxane represented by -b are methyl groups, this is represented by the general formula R' CS
i Oself (here, R5 is an unsubstituted or substituted same or different monovalent hydrocarbon group, C is a positive number from 1.8 to 2.1)
It has no compatibility with organopolysiloxanes consisting of bifunctional siloxane units (D units) represented by When used as an agent, almost no reinforcing effect was observed, and the above-mentioned MQ resin, M
Although it is significantly inferior in performance compared to DQ resin, the above general formula R''l) that constitutes this T unit
S i O = 30 mol% or more of the monovalent hydrocarbon group R2 in the siloxane shown above is 1 having a carbon number of 2 or more
Assuming that the MTQ resin is a valent hydrocarbon group, this MTQ resin has excellent compatibility with the above-mentioned organopolysiloxane consisting of D unit siloxane, and exhibits excellent adhesive properties when applied to silicone pressure-sensitive adhesives. We have found that when applied as a silicone rubber reinforcing agent, it shows an excellent reinforcing effect, and when added to an organopolysiloxane-based antifoaming agent, it improves the antifoaming effect. It exhibits the effect of maintaining defoaming properties, and when mixed with various plastics, it prevents foaming during molding, improves flow properties (flow characteristics), and mold release properties, as well as improves printability of molded products, improves surface gloss, and improves mechanical properties. improve,
Furthermore, it was confirmed that when mixed into a molding compound consisting of an epoxy resin and various inorganic fillers, it has the effect of improving the moisture resistance, water resistance, and heat resistance of the molding compound. The present invention was completed by conducting research on the amount to be added and the manufacturing method. This will be explained in detail below.
本発明のシリコーン樹脂組成物を構成する第１成分であ
るＭ単位としてのシロキサン単位は一般弐Ｒ”ＢＳ ｉ
Ｏヨで示され Ｒ１はメチル基、エチル基、プロピル基
、ブチル基などのアルキル基、シクロヘキシル基などの
シクロアルキル基、ビニル基、アリル基などのアルケニ
ル基、フェニル基、トリル基などのアリール基、または
これらの基の炭素原子に結合した水素原子の一部または
全部をハロゲン原子、シアノ基などで置換したクロロメ
チル基、トリフルオロプロピル基、シアノエチル基など
から構成される非置換または置換の同種または異種の１
価炭化水素基であるものとされるが、このａ値について
はこれが２．６より小さいと目的とするＭＴＱレジンが
他のオルガノシロキサンやシリコーン以外の有機樹脂と
の相溶性のわるいものとなり、３．０より大きくすると
無官能のシロキサン単位からなるオルガノシラン類が混
入することになって目的とするＭＴＱレジン中にこれら
の無官能オルガノシラン類が混在して好ましくない結果
を招くので、これは２．６〜３．０の正数とされる。The siloxane unit as the M unit which is the first component constituting the silicone resin composition of the present invention is a general 2R"BS i
R1 is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group or a tolyl group. , or unsubstituted or substituted homologs consisting of chloromethyl groups, trifluoropropyl groups, cyanoethyl groups, etc. in which some or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. or a dissimilar one
However, if this a value is less than 2.6, the target MTQ resin will have poor compatibility with other organosiloxanes and organic resins other than silicone, and If it is larger than 0, organosilanes made of non-functional siloxane units will be mixed in, and these non-functional organosilanes will be mixed in the target MTQ resin, leading to undesirable results. It is assumed to be a positive number between .6 and 3.0.
また、本発明のシリコーン樹脂組成物を構成する第２成
分としてのＱ単位であるシロキサン単位は一般式Ｓｉ○
２で示されるものとすればよい。Further, the siloxane unit which is the Q unit as the second component constituting the silicone resin composition of the present invention has the general formula Si○
2 may be used.
しかし、これは一般に言われているＳｉＯ□（シリカ）
なる組成の石英ではなく、第１成分、第３成分の出発原
料と共重合し得る形態の組成が好ましく、共重合してか
ら、最終的にはＳｉ○２単位の形態に変り得るものとす
ることが必要であり、これには例えば、アルキルシリケ
ート、一般式Ｓ ｉ （ＯＲ’）４（Ｒ’は炭素数１〜
５のアルキル基）で示されるものが第２成分の出発原料
として最適である。However, this is commonly referred to as SiO□ (silica).
Rather than using quartz with a composition of This requires, for example, alkyl silicate, general formula S i (OR')4 (R' has 1 to 1 carbon atoms)
The alkyl group shown in No. 5) is most suitable as the starting material for the second component.
本発明のシリコーン樹脂を構成する第３成分としてのＴ
単位であるシロキサン単位は一般式Ｒ２ｂＳｉＯので示
され、Ｒ２は前記したＲ１について例示したものと同じ
非置換また置換の同種または異種の１価炭化水素基であ
るが、このＲ２についてはそのすべてがメチル基である
と目的とするＭＴＱレジンがＤ単位のシロキサン単位か
らなるオルガノポリシロキサンに相溶しなくなってこの
ＭＴＱレジンがシリコーン感圧接着剤、シリコーンゴム
の補強剤として使用できなくなる。従って、これは炭素
数２以上の基が３０モル％以上、換言すればメチル基以
外の基が３０モル％以上のＭＴＱレジンでないと、Ｄ単
位のシロキサン単位からなるオルガノポリシロキサンと
の相溶性が悪くなり、シリコーン感圧接着剤の原料、シ
リコーンゴムの補強剤として不適格となる。このものは
好ましくは、６０モル％以上が炭素数２以上の基である
ことが良いが、炭素数が多くなればなる程、また、その
モル％が大きくなればなる程、有機性が増すため、シリ
コーン以外の有機樹脂との親和性が良くなるといった利
点があるので、これについてはＲ２の３０モル％以上が
メチル基以外の基。T as the third component constituting the silicone resin of the present invention
The siloxane unit is represented by the general formula R2bSiO, and R2 is the same unsubstituted or substituted monovalent hydrocarbon group as exemplified above for R1, but all of R2 are methyl. If it is a base, the target MTQ resin becomes incompatible with the organopolysiloxane composed of D-unit siloxane units, and this MTQ resin cannot be used as a silicone pressure-sensitive adhesive or a reinforcing agent for silicone rubber. Therefore, unless the MTQ resin contains 30 mol% or more of groups having 2 or more carbon atoms, in other words, 30 mol% or more of groups other than methyl groups, it will not be compatible with the organopolysiloxane consisting of D-unit siloxane units. This makes it unsuitable as a raw material for silicone pressure-sensitive adhesives or as a reinforcing agent for silicone rubber. Preferably, 60 mol% or more of this substance is a group having 2 or more carbon atoms, but as the number of carbon atoms increases and the mol% increases, the organicity increases. , since it has the advantage of improved affinity with organic resins other than silicone, in this case, 30 mol% or more of R2 is a group other than a methyl group.
すなわち炭素数が２以上の基とする必要がある。That is, it is necessary to use a group having 2 or more carbon atoms.
また、このｂ値についてはこれが０．９５より小さいと
目的とするＭＴＱレジンが他のオルガノポリシロキサン
、シリコーン以外の有機樹脂との相溶性、分散性のわる
いものとなり、１．０５より大きくすると得られたＭＴ
Ｑレジンを他のオルガノポリシロキサン、シリコーン以
外の有機樹脂に配合したときにその機械的特性、その他
の物性の向上に期待する程の効果が得られず、むしろ助
効果となる傾向を示すので、これは０．９５〜１．０５
の正数とする必要がある。Regarding this b value, if it is smaller than 0.95, the target MTQ resin will have poor compatibility and dispersibility with other organopolysiloxanes and organic resins other than silicone, and if it is larger than 1.05, it will not be good. MT
When Q-Resin is blended with other organopolysiloxanes and organic resins other than silicone, the desired effect of improving mechanical properties and other physical properties is not obtained, but rather tends to be an auxiliary effect. This is 0.95 to 1.05
Must be a positive number.
本発明のシリコーン樹脂組成物は上記した第１〜第３成
分のシロキサン単位からなるものとされるが、これらの
配合割合はこのシリコーン樹脂組成物の用途、目的に応
じて定められるべきものであるので特に限定されるべき
ものではないが、第１成分であるＭ単位としてのシロキ
サン単位が極端に小さい場合にはこのＭＴＱレジンに添
加されるオルガノポリシロキサンやシリコーン以外の有
機樹脂に対する相溶性、分散性がわるくなるので、この
Ｍ単位としてのシロキサン単位とＱ単位としてのシロキ
サン単位とのモル比（Ｍ／Ｑ）が０゜４以上とすること
がよく、これはまたＭ単位に対するＱ単位が少なすぎる
と他のオルガノポリシロキサン、シリコーン以外の有機
樹脂との配合物の機械的強度、その他の物性の向上効果
がむしろマイナスとなるのでこれは２．０を上限とする
ことがよい。また、このシリコーン樹脂組成物中におけ
るＴ単位としてのシロキサン単位の配合割合はこれが１
モル％より少ないとシリコーン感圧接着剤に応用した場
合、その性能、特に粘着力において著しい効果は認めら
れず、またシリコーンゴムの補強剤としての効果もＭＱ
レジンを使用した場合と殆ど変らない結果となり、２０
モル％より多くすると、ＭＴＱレジン自体が不安定な状
態となるし、さらに、ＭＴＱレジンの製造過程において
増粘、ゲル化する場合も生ずる。またこのように増粘し
て、高分子化し、ゲル化に至るため、Ｄ単位のシロキサ
ン単位からなるオルガノポリシロキサンに対する相溶性
が悪くなるといった結果となるのでこれは１〜２０モル
％の範囲とすればよいが、これはこのＴ単位の配合に伴
う効果が最大限に発揮される範囲とすればよい。The silicone resin composition of the present invention is composed of the siloxane units of the first to third components described above, and the proportions of these components should be determined depending on the use and purpose of the silicone resin composition. Therefore, there are no particular limitations, but if the siloxane unit as the first component M unit is extremely small, the compatibility and dispersion with organic resins other than organopolysiloxane and silicone added to this MTQ resin may be affected. Therefore, the molar ratio (M/Q) between the siloxane units as M units and the siloxane units as Q units is preferably set to 0°4 or more. If it is too high, the effect of improving the mechanical strength and other physical properties of the blend with other organopolysiloxanes and organic resins other than silicone will be rather negative, so the upper limit is preferably 2.0. In addition, the blending ratio of siloxane units as T units in this silicone resin composition is 1.
If it is less than mol%, when applied to silicone pressure-sensitive adhesives, no significant effect is observed on its performance, especially on adhesive strength, and its effectiveness as a reinforcing agent for silicone rubber also exceeds MQ.
The result was almost the same as when resin was used, and 20
If the amount exceeds mol %, the MTQ resin itself becomes unstable, and furthermore, thickening and gelation may occur during the manufacturing process of the MTQ resin. In addition, as the viscosity increases, polymerization, and gelation occur, the D unit becomes less compatible with organopolysiloxane composed of siloxane units, so this should be in the range of 1 to 20 mol%. However, this may be within a range where the effects associated with the combination of this T unit are maximized.
このように配合されて作られた本発明のＭＴＱレジンと
してのシリコーン樹脂組成物は二＼に配合されるＴ単位
としてのシロキサン単位がメチル基だけでなく、炭素数
が２以上の１価炭化水素基を３０モル％以上含有するも
のであるので、例えばＤ単位としてのシロキサン単位か
らなるオルガノポリシロキサンやシリコーン以外の有機
樹脂とよく相溶し、このものはシリコーン感圧接着剤と
したときにすぐれた接着力を示すし、シリコーンゴムの
補強剤として使用したときにもすぐれた補強効果を示し
、さらに他の有機樹脂に添加したときにはその成形性、
成形物の物性向上に効果を示す。In the silicone resin composition as the MTQ resin of the present invention, which is blended in this way, the siloxane unit as the T unit blended in the second is not only a methyl group but also a monovalent hydrocarbon having 2 or more carbon atoms. Since it contains 30 mol% or more of groups, it is well compatible with, for example, organopolysiloxanes consisting of siloxane units as D units and organic resins other than silicone, and this material is excellent when used as a silicone pressure-sensitive adhesive. It also exhibits excellent reinforcing effect when used as a reinforcing agent for silicone rubber, and also improves moldability when added to other organic resins.
Effective in improving the physical properties of molded products.
なお、本発明のシリコーン樹脂組成物は従来公知のＭＱ
レジンにＴ単位としてシロキサン基を導スしたものであ
るが、このＴ単位のシロキサン単位からなるオルガノポ
リシロキサンは前記したＲ”ｂＳ ｉ Ｏユ上で示され
るものであるけれども、このオルガノポリシロキサンを
脂肪族不飽和基、例えば
基を含有するものとしてこのＭＴＱレジンを有機過酸化
物を触媒として加硫させると、ＣＨ２＝ＣＨ−の２重結
合部とシリコーンゴムの有機基との架橋度がさらに増加
するので補強性が向上し。In addition, the silicone resin composition of the present invention is a conventionally known MQ.
This is a resin in which a siloxane group is introduced as a T unit, and the organopolysiloxane composed of the siloxane unit of this T unit is shown above in the above R"bS i O, but this organopolysiloxane is When this MTQ resin containing an aliphatic unsaturated group, such as a group, is vulcanized using an organic peroxide as a catalyst, the degree of crosslinking between the CH2=CH- double bond and the organic group of the silicone rubber is further increased. This increases the reinforcing properties.
これをシリコーン感圧接着剤として使用するときには凝
集力がよくなり１体質改善の効果がさらに増加するし、
これにオルガノハイドロジエンポリシロキサンと白金ま
たはパラジウム系の触媒を配合すると、その２重結合部
とけい素原子に結合し７た水素原子との付加反応によっ
てその諸物性が向上するという有利性が与えられる。ま
た、従来公知のＭＱレジンについてはこのＭ単位として
式と（ＣＨ３） ３Ｓ Ｉ Ｏ１／２で示されるオルガ
ノシロキサンを使用して分子鎖末端にビニル基を導入し
たものも知られていて、このジメチルビニルシロキサン
単位の原料としては高価なテトラメチルジビニルジシロ
キサン、ジメチルビニルアルコキシシラン、ジメチルビ
ニルクロロシランが使用されているために、このＭＱレ
ジンは高価なものとなり、したがってその応用範囲も限
定されていたのであるが、本発明のシリコーン樹脂組成
物はこのＭＴＱレジンを作るときのＴ単位をシロキサン
単位として安価なビニルトリクロロシラン、ビニルトリ
アルコキシシランなどを使用することができるので、こ
れを安価に得ることができ、したがって今までに限定さ
れていた応用範囲外にも広く使用できるという有利性が
与えられる。When this is used as a silicone pressure-sensitive adhesive, the cohesive force is improved and the effect of improving the physical constitution is further increased.
When organohydrodiene polysiloxane is blended with a platinum or palladium catalyst, it has the advantage of improving its physical properties through an addition reaction between its double bond and the hydrogen atom bonded to the silicon atom. . In addition, conventionally known MQ resins are known to have a vinyl group introduced at the end of the molecular chain using an organosiloxane represented by the formula (CH3) 3S I O1/2 as the M unit, and this dimethyl Because expensive tetramethyldivinyldisiloxane, dimethylvinylalkoxysilane, and dimethylvinylchlorosilane are used as raw materials for the vinylsiloxane unit, this MQ resin is expensive and its range of application is therefore limited. However, in the silicone resin composition of the present invention, when making this MTQ resin, the T unit is a siloxane unit and inexpensive vinyltrichlorosilane, vinyltrialkoxysilane, etc. can be used, so it can be obtained at low cost. This gives them the advantage of being widely usable beyond the hitherto limited range of applications.
本発明のシリコーン樹脂組成物は上記したように前記し
た第１〜第３成分の共重合体からなるものとされるが、
このものの製造は例えば下記の方法で行なえばよい、す
なわち、この製造方法における第１成分を構成すべきシ
ロキサン単位としては構成材として一般式Ｒ’ａＳ ｉ
（ＯＲ３）４−８で示され、Ｒ１，ａは前記の通りで
あり、Ｒ′″は水素原子または炭素数１〜５のアルキル
基であるトリオルガノシラノール、トリオルガノアルコ
キシシランおよび／または一般式（Ｒ’ａＳ ｌ ）ｚ
ｏ４−ａで示され Ｒ１、ａは前記の通りであるヘキ
サオルガノジシロキサン、具体的にはトリメチルシラノ
ール、トリメチルメトキシシラン、トリメチルエトキシ
シラン、トリエチルメトキシシラン、トリエチルエトキ
シシラン、トリエチルシラノール、ヘキサメチルジシロ
キサン、ヘキサエチルジシロキサン、ヘキサイソプロピ
ルジシロキサンおよびこれらの混合物を使用すればよい
。As mentioned above, the silicone resin composition of the present invention is made of a copolymer of the first to third components described above,
This product may be manufactured, for example, by the following method. That is, the siloxane unit to constitute the first component in this manufacturing method has the general formula R'aS i as a constituent material.
(OR3) triorganosilanol, triorganoalkoxysilane and/or triorganoalkoxysilane represented by 4-8, R1 and a are as described above, and R'' is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and/or the general formula (R'aS l )z
o4-a, R1 and a are as described above, hexaorganodisiloxane, specifically trimethylsilanol, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylsilanol, hexamethyldisiloxane , hexaethyldisiloxane, hexaisopropyldisiloxane and mixtures thereof.
つぎに、この第２成分としてのＱ単位であるシロキサン
単位構成材は一般式Ｓ ｉ （ＯＲ’）４で示され、Ｒ
４は炭素数１〜５のアルキル基であるアルキルシリケー
ト、例えばメチルシリケート、エチルシリケート、プロ
ピルシリケート、ブチルシリケートおよび／またはこれ
らの部分加水分解縮合物とすればよい６
また、この第３成分としてのＴ単位のシロキサン単位構
成材は一般式Ｒ”ｂＳ ｉ （○Ｒ’）、−ｂで示され
、Ｒ２、Ｒ，、ｂは前記の通りのものであるオルガノト
リアルコキシシラン、例えばメチルトリメトキシシラン
、メチルトリエトキシシラン、エチルトリメトキシシラ
ン、ビニルトリメトキシシラン、プロピルトリメトキシ
シラン、ブチルトリメトキシシラン、エチルトリエトキ
シシラン、ビニルトリエトキシシラン、プロピルトリエ
トキシシラン、ブチルトリエトキシシラン、ヘキシルト
リメトキシシラン、オクチルトリメトキシシラン、フェ
ニルトリメトキシシランなど、またはこれらの部分加水
分解縮合物が例示されるが、この第３成分についてはこ
のシロキサン単位がその３０モル％以上が炭素数２以上
の１価炭化水素基であることが必要とされるのでこれは
上記のものから適宜選択組合せて使用することが必要と
される。Next, the siloxane unit constituent material which is the Q unit as the second component is represented by the general formula S i (OR')4, and R
4 may be an alkyl silicate which is an alkyl group having 1 to 5 carbon atoms, such as methyl silicate, ethyl silicate, propyl silicate, butyl silicate and/or a partially hydrolyzed condensate thereof6. The siloxane unit constituent material of the T unit is an organotrialkoxysilane, such as methyltrimethoxysilane, having the general formula R"bS i (○R'), -b, where R2, R,, b are as described above. , methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane , octyltrimethoxysilane, phenyltrimethoxysilane, etc., or partially hydrolyzed condensates thereof; however, for the third component, 30 mol% or more of this siloxane unit is monovalent carbonized with a carbon number of 2 or more. Since it is required to be a hydrogen group, it is necessary to use an appropriate combination of the above-mentioned groups.
本発明のシリコーン樹脂組成物は上記した第１〜第３成
分を構成するためのオルガノシランおよび／またはオル
ガノシロキサンを混合し、共加水分解、重縮合させるこ
とによって得られることができるが、これらの配合比は
目的とするシリコーン樹脂組成物中における第１〜第３
成分の配合比となるように配合すればよく、したがって
前記したようにＭ／Ｑ （モル比）が０．４〜２．０で
Ｔ単位が１〜２０モル％となるようにすればよい、しか
し、これらの各成分を混合し、これを従来公知の加水分
解、重縮合方法、例えば必要に応じ添加されるアルキル
アルコールの存在下に無機酸と必要量の水を添加して加
水分解し、中和水洗する方法で加水分解、重結合させる
と、得られるＭＴＱレジンは他のオルガノポリシロキサ
ン、シリコーン以外の有機樹脂との相溶性、分散性のわ
るいものとなり、これを添加した各樹脂の物性向上をも
雅しくなるので、この加水分解、重縮合は上記した各成
分の混合物に必要に応じアルキルアルコール、芳香族系
の溶剤を加え、塩酸、硫酸などの無機酸を添加して十分
に攪拌したのち、加水分解に必要な水量を加えて加水分
解を行ない、縮合したアルコール類を通常の方法で除去
し、非極性の溶媒例えばトルエン、キシレンなどに置換
してから酸を中和するために必要とする量以上のアルカ
リを添加して中和し、ついで温度を上げて過剰に加えた
アルカリを触媒として重縮合させ、つぎにアルカリを中
和するのに必要な量以上の酸を加えて中和後、酸性下に
温度を２０〜１４０℃として過剰に加えた酸を触媒とし
て再び重縮合を行なったのち、酸分をアルカリで中和す
るか水洗によって除去して中性にするという方法で行な
えばよいが、これはこのアルカリによる重縮合と酸によ
る重縮合の順序を逆にしてもよい。このようにして得ら
れたＭＴＱレジンであるシリコーン樹脂組成物は他のオ
ルガノポリシロキサン、シリコーン以外の有機樹脂との
相溶性、分散性にすぐれているし、これをシリコーン感
圧接着剤として使用するとすぐれた接着性を示すし、シ
リコーンゴムの補強剤として使用する場合にはすぐれた
補強効果を示し、さらにこのものは他種の合成樹脂に添
加すればその樹脂の成形性を向上させ、得られる成形品
の強度その他の物性を改善するという有利性をもつもの
となる。The silicone resin composition of the present invention can be obtained by mixing organosilanes and/or organosiloxanes for constituting the first to third components described above, and cohydrolyzing and polycondensing them. The blending ratio is 1st to 3rd in the target silicone resin composition.
The components may be blended in such a manner that the blending ratio is such that the M/Q (molar ratio) is 0.4 to 2.0 and the T unit is 1 to 20 mol%, as described above. However, these components are mixed and then hydrolyzed using conventionally known hydrolysis and polycondensation methods, for example, by adding an inorganic acid and a required amount of water in the presence of an alkyl alcohol added as necessary. When hydrolyzed and polymerized by neutralization and washing with water, the resulting MTQ resin will have poor compatibility and dispersibility with other organopolysiloxanes and organic resins other than silicone, and the physical properties of each resin to which it is added will deteriorate. This hydrolysis and polycondensation are carried out by adding alkyl alcohol and aromatic solvent as necessary to the mixture of the above components, adding an inorganic acid such as hydrochloric acid or sulfuric acid, and stirring thoroughly. After that, hydrolysis is carried out by adding the amount of water necessary for hydrolysis, the condensed alcohol is removed by the usual method, and the alcohol is replaced with a non-polar solvent such as toluene or xylene, and then the acid is neutralized. Neutralize by adding more alkali than the required amount, then raise the temperature and use the excess alkali as a catalyst to cause polycondensation, and then add more acid than necessary to neutralize the alkali. After neutralization, polycondensation is carried out again using excess acid as a catalyst under acidic conditions at a temperature of 20 to 140°C, and then the acid content is neutralized with alkali or removed by water washing to make it neutral. However, the order of polycondensation with alkali and polycondensation with acid may be reversed. The silicone resin composition that is the MTQ resin thus obtained has excellent compatibility and dispersibility with other organopolysiloxanes and organic resins other than silicone, and when used as a silicone pressure-sensitive adhesive. It exhibits excellent adhesion and has an excellent reinforcing effect when used as a reinforcing agent for silicone rubber.Furthermore, when added to other types of synthetic resins, it improves the moldability of the resin and can be obtained. This has the advantage of improving the strength and other physical properties of the molded product.
つぎに本発明の実施例をあげるが、例中の部は重量部を
、また粘度、比重はいずれも２５℃での測定値を示した
ものであり、参考例にあげたシリコーン感圧接着剤の物
性は下記の測定方法による測定結果を示したものである
。Next, examples of the present invention will be given. Parts in the examples are parts by weight, and viscosity and specific gravity are both measured values at 25°C. The physical properties are the results of measurement using the following measurement method.
ステンレス板（ＳＵＳ２７ｃｐ、２８０グリツド）の沖
央に試験片の粘着剤層側を下側にして軽く貼り、この上
から厚さ約６ｍｍのゴム層で被覆された重さ２，０００
±５０ｇ、直径８０ｍの金属製のローラーを圧着速度３
００ｍ／分で１往復させて試験片を圧着し、ついでこの
試験片を２３±２℃、６０±５％ＲＨの恒温恒湿室内に
１６時間放置したのち、遊びの部分を角度１８０°に折
返し、３００＋ｍ／分の速度で連続し、て引き剥がした
ときの剥離力で測定した。The test piece was lightly attached to the center of a stainless steel plate (SUS27cp, 280 grid) with the adhesive layer facing down, and then covered with a rubber layer approximately 6 mm thick and weighing 2,000 mm.
±50g, 80m diameter metal roller crimping speed 3
The test piece was crimped by making one reciprocation at 00 m/min, and then left in a constant temperature and humidity room at 23 ± 2°C and 60 ± 5% RH for 16 hours, and then the loose part was folded back at an angle of 180°. It was measured by the peeling force when the film was continuously peeled off at a speed of 300+ m/min.
傾斜角３０″の斜面で助走距離１０■のところから鋼球
（ＪＩＳ Ｇ４８０５の５ＵＪ２）を転がして、粘着剤
層の１０ａ＋＋の範囲内で停止する鋼球の最大の直径の
Ｎαで示した（傾斜式ポールタック潤定法）。A steel ball (JIS G4805 5UJ2) is rolled from a run-up distance of 10cm on a slope with an inclination angle of 30'', and the maximum diameter of the steel ball that stops within 10a++ of the adhesive layer is indicated by Nα (inclination (Pole tuck water method).
なお、Ｎ（１３２は１インチ、ＮＱ２４は２４／３２イ
ンチであり、測定は２３±２℃、６０±５％ＲＨ恒温恒
湿室内で行なわれた。Note that N(132 is 1 inch, NQ24 is 24/32 inches, and the measurement was performed in a constant temperature and humidity room at 23±2° C. and 60±5% RH.
前記したステンレス板に長さ２０ｍｎ＋、巾１０国の面
積で試験片を貼付し、荷重１．０００±１０ｇを懸垂さ
せ、２３±２℃、６ｏ±５％ＲＨの恒温恒湿室内に３０
分間放置したのちのズレ距離をもって示した。A test piece with a length of 20 mm + and a width of 10 mm was attached to the stainless steel plate described above, a load of 1.000 ± 10 g was suspended, and the test piece was placed in a constant temperature and humidity room at 23 ± 2 ° C. and 6 o ± 5% RH for 30 minutes.
The deviation distance after being left for a minute is shown.
実施例１
温度計、還流冷却器、攪拌機を取りつけた１Ｑの四ツロ
フラスコにオルソエチルシリケートの部分加水分解線金
物であるエチルボリシケート（ＳｉＯ□含有量４０％）
３７８ｇ、ヘキサメチールジシロキサン１２２．５ ｇ
、ビニルトリメトキシシラン６６．３ ｇおよびエタノ
ール２０ｇを仕込み、２０℃に保って３５％塩酸水Ｌｏ
ｇと水９０ｇを３０分間にわたって滴下し、７６℃で４
時間攪拌して加水分解させたのち、トルエン２００ｇと
炭酸水素ナトリウムＬｏｇを添加し、加熱によってエタ
ノールをストリップしながらトルエンを追加して不揮発
分が６０％であるトルエン溶液とした。Example 1 Partial hydrolysis of orthoethyl silicate, ethyl boricinate (SiO□ content: 40%), was placed in a 1Q four-way flask equipped with a thermometer, reflux condenser, and stirrer.
378g, hexamethyldisiloxane 122.5g
, 66.3 g of vinyltrimethoxysilane and 20 g of ethanol were added, kept at 20°C, and diluted with 35% hydrochloric acid (Lo).
g and 90 g of water were added dropwise over 30 minutes and heated at 76°C for 4 hours.
After stirring for a period of time for hydrolysis, 200 g of toluene and Log sodium bicarbonate were added, and toluene was added while stripping ethanol by heating to obtain a toluene solution with a nonvolatile content of 60%.
ついで過剰に添加した炭酸水素ナトリウムを触媒として
１１４℃で４時間アルカリ重合させ、冷却後に９５％硫
酸Ｌｏｇを加えて５０℃で４時間酸重合させ、これに炭
酸水素ナトリウムを添加して４０℃で３時間攪拌して硫
酸を中和し、さらに系内の水分を無水芒硝で脱水したの
ちび過したところ、不揮発分６０．３％、粘度１７．２
ｃＳ、比重１．０５０、水酸基含有量０．０２ モ／Ｌ
／／ １００ｇレジンである無色透明なトルエン溶液が
得られ。Next, alkaline polymerization was carried out at 114°C for 4 hours using excess added sodium hydrogen carbonate as a catalyst, and after cooling, 95% sulfuric acid Log was added and acid polymerization was carried out at 50°C for 4 hours. After stirring for 3 hours to neutralize the sulfuric acid and further dehydrating the water in the system with anhydrous sodium sulfate, the non-volatile content was 60.3% and the viscosity was 17.2.
cS, specific gravity 1.050, hydroxyl group content 0.02 mo/L
// A colorless and transparent toluene solution containing 100 g of resin was obtained.
このものは分析の結果、Ｍ／Ｑモル比が０．６でＴ単位
としてＣＨ＝ＣＨ８ｉＯ３／２を１０モル％含有するＭ
ＴＱレジン（以下ＭＴＱ−１と略記する）であることが
確認され、このものはトルエンを留去したところ無色透
明の固形レジンとなった。As a result of analysis, this product has an M/Q molar ratio of 0.6 and contains 10 mol% of CH=CH8iO3/2 as T units.
It was confirmed that the resin was TQ resin (hereinafter abbreviated as MTQ-1), and when toluene was distilled off, a colorless and transparent solid resin was obtained.
つぎにこのＭＴＱ−１１００部と分子鎖末端が水酸基で
封鎖されている平均重合度が４，０００であるジメチル
ポリシロキサン１００部とをミキサーで十分混合し、減
圧で脱泡したのちガラスシャーレに厚さ８肩となるよう
に採取し、溶剤を揮発させたあとの混合物の透明性をし
らへたところ、このものは完全に透明であり、このＭＴ
Ｑ−■がジオルガノポリシロキサンと相溶性をもつもの
であることが確認された。Next, 1100 parts of this MTQ-1 and 100 parts of dimethylpolysiloxane whose molecular chain ends are blocked with hydroxyl groups and whose average degree of polymerization is 4,000 are thoroughly mixed in a mixer, defoamed under reduced pressure, and then placed in a glass Petri dish in a thick layer. When we checked the transparency of the mixture after evaporating the solvent, we found that it was completely transparent.
It was confirmed that Q-■ is compatible with diorganopolysiloxane.
実施例２
実施例１におけるエチルポリシリケート３７８ｇに対す
るヘキサメチルジシロキサン、ビニルトリメトキシシラ
ン、エタノールの添加量をヘキサメチルジシロキサン１
５３ ｇ、ビニルトリメトキシシラン７３．１ ｇ、エ
タノール１５ｇとしたほかは実施例１と同様に処理した
ところ、不揮発分６０．０％粘度１１．８ｃＳ、比重１
，０５１、水酸基含有量０．０３モル／ １００ ｇレ
ジンである無色透明の６０％トルエン溶液が得られ、こ
のものは分析の結果、Ｍ／Ｑモル比が０．７５でＴ単位
としてＣＨ２＝ＣＨ８１Ｏ３／２を１０モル％含有する
ＭＴＱレジン（以下ＭＴＱ−１１と略記する）であるこ
とが確認され、このものはトルエンを揮発させたところ
無色透明の固体レジンとなった。Example 2 The amount of hexamethyldisiloxane, vinyltrimethoxysilane, and ethanol added to 378 g of ethyl polysilicate in Example 1 was changed to 1 part of hexamethyldisiloxane.
When treated in the same manner as in Example 1 except that 53 g, vinyltrimethoxysilane 73.1 g, and ethanol 15 g were used, the nonvolatile content was 60.0%, the viscosity was 11.8 cS, and the specific gravity was 1.
, 051, a colorless and transparent 60% toluene solution with a hydroxyl group content of 0.03 mol/100 g resin was obtained, and as a result of analysis, the M/Q molar ratio was 0.75 and the T unit was CH2=CH81O3. It was confirmed that the resin was an MTQ resin (hereinafter abbreviated as MTQ-11) containing 10 mol % of /2, and when toluene was volatilized, this resin became a colorless and transparent solid resin.
また、このＭＴＱ−ｎについてはこれを実施例１と同様
にジメチルポリシロキサンと混合したところ、このもの
はジメチルシロキサンとの相溶性のすぐれたものである
ことが確認された。Further, when this MTQ-n was mixed with dimethylpolysiloxane in the same manner as in Example 1, it was confirmed that this product had excellent compatibility with dimethylsiloxane.
実施例３
実施例１におけるエチルポリシリケート３７８ｇに対す
るヘキサメチルジシロキサン、ビニルトリメトキシシラ
ン、エタノールの添加量をヘキサメチルジシロキサン１
６３．３ ｇ、ビニルトリメトキシシラン７４．６ｇ、
エタノール１０ｇとしたほかは実施例１と同様に処理し
たところ、不揮発分６０．８％、粘度１１．５ｃＳ、比
重１，０５０、水酸基含有量０．０２モル／ １００
ｇレジンである無色透明の６０％トルエン溶液が得られ
、このものは分析の結果、Ｍ／Ｑモル比が０．８５でＴ
単位としてＣＨ−ＣＨ３１○３／２を１０モル％含有す
るＭＴＱレジン（以下ＭＴＱ−ｍと略記する）であるこ
とが確認され、このものはトルエンを揮発させたところ
無色透明の固形レジンとなつた・
また、このＭＴＱ−ＩＩＩについては実施例１と同様の
方法でジメチルポリシロキサンとの相溶性をしらべたと
ころ、このものはすぐれた相溶性を示した。Example 3 The amount of hexamethyldisiloxane, vinyltrimethoxysilane, and ethanol added to 378 g of ethyl polysilicate in Example 1 was changed to 1 part of hexamethyldisiloxane.
63.3 g, vinyltrimethoxysilane 74.6 g,
When treated in the same manner as in Example 1 except that 10 g of ethanol was used, the nonvolatile content was 60.8%, the viscosity was 11.5 cS, the specific gravity was 1,050, and the hydroxyl group content was 0.02 mol/100.
A colorless and transparent 60% toluene solution of g resin was obtained, and as a result of analysis, it was found that the M/Q molar ratio was 0.85 and T
It was confirmed to be an MTQ resin (hereinafter abbreviated as MTQ-m) containing 10 mol% of CH-CH31○3/2 as a unit, and when toluene was evaporated, this resin became a colorless and transparent solid resin. - Furthermore, when this MTQ-III was examined for compatibility with dimethylpolysiloxane in the same manner as in Example 1, it was found to have excellent compatibility.
実施例４
実施例１におけるエチルポリシリケート３７８ｇに対す
るヘキサメチルジシロキサン、ビニルトリメトキシシラ
ン、エタノールの添加量をヘキサメチルジシロキサン２
０４．１ｇ、ビニルトリメトキシシラン８２．９ｇ、エ
タノールＬｏｇとしたほかは実施例１と同様に処理した
ところ、不揮発分５９．８％、粘度１０．２ ｃ Ｓ、
比重１，０５１、水酸基含有量０．０２モル／ １００
ｇレジンである無色透明の６０％トルエン溶液が得ら
れ、このものは分析の結果、Ｍ・７０モル比が１．００
でＴ単位としてＣＨＣＨ３１○３／２を１０モル％含有
するＭＴＱレジン（以下ＭＴＱ−ＩＶと略記する）であ
ることが確認され、このものはトルエンを揮発させたと
ころ無色透明でや＼粘着性を帯びた固形レジンとなった
。Example 4 The amount of hexamethyldisiloxane, vinyltrimethoxysilane, and ethanol added to 378 g of ethyl polysilicate in Example 1 was changed to 2
04.1 g, vinyltrimethoxysilane 82.9 g, and ethanol Log were treated in the same manner as in Example 1. Nonvolatile content was 59.8%, viscosity was 10.2 cS,
Specific gravity 1,051, hydroxyl group content 0.02 mol/100
A colorless and transparent 60% toluene solution of g resin was obtained, and as a result of analysis, the molar ratio of M.70 was 1.00.
It was confirmed that this is an MTQ resin (hereinafter abbreviated as MTQ-IV) containing 10 mol% of CHCH31○3/2 as T units, and when toluene was evaporated, this resin was colorless and transparent and had no adhesive properties. It became a solid resin with a tinge.
また、このＭＴＱ−ＩＶについては実施例１と同じ方法
でジメチルポリシロキサンとの相溶性をしらべたところ
、すぐれた相溶性を示した。Further, when this MTQ-IV was examined for compatibility with dimethylpolysiloxane in the same manner as in Example 1, it was found to have excellent compatibility.
実施例５
実施例１におけるエチルポリシリケート３７８ｇに対す
るヘキサメチルジシロキサン、ビニルトリメトキシシラ
ン、エタノールの添加量をヘキサメチルジシロキサン２
２４．５ｇ、ビニルトルメトキシシラン８７ｇ、エタノ
ール１０ｇとしたほかは実施例１と同様に処理したとこ
ろ、不揮発分６１．９％、粘度９．８ｃＳ、比重１．０
５２、水酸基含有量０．０３モル／１００ｇレジンであ
る無色透明の６０％トルエン溶液が得られ、このものは
分析の結果、Ｍ／Ｑモル比が１．１０でＴ単位としてＣ
Ｈ２＝ＣＨ８１○３／２を１Ｏ−Ｔ−ル％含有するＭＴ
Ｑレジン（以下ＭＴ−Ｖと略記する）であることが確認
され、このものはトルエンを揮発させたところ無色透明
の粘稠な固溶体レジンとなった。Example 5 The amount of hexamethyldisiloxane, vinyltrimethoxysilane, and ethanol added to 378 g of ethyl polysilicate in Example 1 was changed to 2
When treated in the same manner as in Example 1 except that 24.5 g, vinyltormethoxysilane 87 g, and ethanol 10 g were used, the nonvolatile content was 61.9%, the viscosity was 9.8 cS, and the specific gravity was 1.0.
52. A colorless and transparent 60% toluene solution with a hydroxyl group content of 0.03 mol/100 g of resin was obtained, and as a result of analysis, the M/Q molar ratio was 1.10 and the T unit was C.
MT containing 1O-T-le% of H2=CH81○3/2
It was confirmed that the resin was Q resin (hereinafter abbreviated as MT-V), and when toluene was volatilized, this resin became a colorless and transparent viscous solid solution resin.
また、このＭＴＱ−Ｖについては実施例１と同じ方法で
ジメチルポリシロキサンとの相溶性をしらべたところ、
すぐれた相溶性を示した。In addition, when this MTQ-V was examined for compatibility with dimethylpolysiloxane in the same manner as in Example 1, it was found that
It showed excellent compatibility.
実施例６〜９
温度計、還流冷却器、攪拌機を取りつけたＩＱの四ツロ
フラスコに、オルソメチルシリケートの部分加水分解結
合物であるメチルポリシリケート（Ｓ ｉ Ｏ２含有量
５１％）とヘキサメチルジシロキサンおよびイソブチル
トリメトキシシランを第１表に示した配合割合で添加し
、さらにイソプロピルアルコール２０ｇを添加し、系内
の温度を４０℃に保ち、こ＼に３５％塩酸水５ｇと第１
表に示した量の水を滴下して加水分解させ、７０℃で３
時間熟成させたのち、水１００ｇ、トルエン２００ｇを
加えてトルエン樹脂層とメタノール・イソプロピルアル
コール・水・塩酸層に分液分前し、トルエン樹脂層にト
ルエンを加えてその不揮発分を６０％とし、炭酸水素ナ
トリウム２ｇを添加してから１１４℃で４時間アルカリ
重合を行ない、ついで３５％塩酸水を８ｇ添加して９０
℃で６時間酸重合を行なわせ、水洗して塩酸分を除去し
てから無水芒硝で脱水して不揮発分を６０％に調整した
ところ、無色透明な液体が得られた。これらは第２表に
示したとおりの性状を示した。Examples 6-9 Methyl polysilicate (51% SiO2 content), which is a partially hydrolyzed combination of orthomethylsilicate, and hexamethyldisiloxane were added to an IQ four-way flask equipped with a thermometer, reflux condenser, and stirrer. and isobutyltrimethoxysilane in the proportions shown in Table 1, further added 20 g of isopropyl alcohol, kept the temperature in the system at 40°C, and added 5 g of 35% hydrochloric acid water and
Hydrolyze by adding the amount of water shown in the table dropwise.
After aging for a time, 100 g of water and 200 g of toluene were added to separate the toluene resin layer and the methanol/isopropyl alcohol/water/hydrochloric acid layer, and toluene was added to the toluene resin layer to make the nonvolatile content 60%. After adding 2 g of sodium hydrogen carbonate, alkaline polymerization was carried out at 114°C for 4 hours, and then 8 g of 35% hydrochloric acid was added to
Acid polymerization was carried out at .degree. C. for 6 hours, washed with water to remove hydrochloric acid, and then dehydrated with anhydrous sodium sulfate to adjust the non-volatile content to 60%, yielding a colorless and transparent liquid. These exhibited properties as shown in Table 2.
なお、こ−に得られた組成物はいずれもＭＴＱレジンで
あるが、これらについては実施例１と同じ方法でジメチ
ルポリシロキサンとの相溶性をしらべたところ、いずれ
もすぐれた相溶性を示した。The compositions obtained here are all MTQ resins, and when they were examined for compatibility with dimethylpolysiloxane in the same manner as in Example 1, they all showed excellent compatibility. .
第
表
実施例１０〜１３
温度計、還流冷却器、攪拌機を取りつけたＩＱの四ツロ
フラスコに、オルソメチルシリケートの部分加水分解締
金物であるメチルポリシリケート（Ｓ ｉ Ｏ２含有量
５１％）とへキサメチルジシロキサン、メチルトリメト
キシシランおよびイソブチルトリメトキシシランを第３
表に示した配合割合で添加し、さらにインプロピルアル
コール２０ｇを添加し、系内の温度を１０℃に保ち、こ
ンに３５％塩酸水５ｇと第１表に示した量の水を滴下し
て加水分解させ、７０℃で３時間熟成させたのち、水１
００ｇ、 トルエン２００ｇを加えてトルエン樹脂層
とメタノール・イソプロピルアルコール・水・塩酸層に
分液分離し、トルエン樹脂層にトルエンを加えてその不
揮発分を６０％とし、炭酸水素ナトリウム２ｇを添加し
てから１１４℃で４時間アルカリ重合を行ない、ついで
３５％塩酸水を８ｇ添加して９０℃で６時間酸重合を行
なわせ、水洗して塩酸分を除去してから無水芒硝で脱水
して不揮発分を６０％にＷＲＵｔ、たところ、無色透明
な液体が得られ、これらは第４表に示したとおりの性状
を示した。Table Examples 10 to 13 Methyl polysilicate (S i O 2 content 51%), which is a partially hydrolyzed clamp of orthomethyl silicate, was added to an IQ four-way flask equipped with a thermometer, reflux condenser, and stirrer. Methyldisiloxane, methyltrimethoxysilane and isobutyltrimethoxysilane as the third
Add in the proportions shown in the table, further add 20 g of inpropyl alcohol, keep the temperature in the system at 10°C, and dropwise add 5 g of 35% hydrochloric acid water and the amount of water shown in Table 1. After hydrolyzing and aging at 70°C for 3 hours, 1
00g, 200g of toluene was added to separate the toluene resin layer and methanol/isopropyl alcohol/water/hydrochloric acid layer, toluene was added to the toluene resin layer to make the nonvolatile content 60%, and 2g of sodium hydrogen carbonate was added. Then, 8 g of 35% hydrochloric acid solution was added and acid polymerization was carried out at 90°C for 6 hours. The hydrochloric acid content was removed by washing with water, and then dehydrated with anhydrous sodium sulfate to remove non-volatile matter. When WRUt was increased to 60%, a colorless and transparent liquid was obtained, which exhibited properties as shown in Table 4.
なお、こ＼に得られた組成物はいずれもＭＴＱレジンで
あるが、これらについて実施例１と同じ方法でジメチル
ポリシロキサンとの相溶性をしらべたところ、これらは
いずれもすぐれた相溶性を示した。The compositions obtained here are all MTQ resins, and when they were examined for compatibility with dimethylpolysiloxane in the same manner as in Example 1, they all showed excellent compatibility. Ta.
実施例１４〜１７
メチルポリシリケート、ヘキサメチルジシロキサン、メ
チルトリメトキシシラン、イソブチルトリメトキシシラ
ンの配合割合および加水分解用水の添加量を実施例１０
〜１３における第３表と同一にし、実施例１０〜１３と
同じ方法で加水分解し、熟成し、トルエンを添加して得
たトルエン樹脂層に、３５％塩酸水５，５ｇを添加し９
０℃で６時間酸重合を行なわせたのち、５０℃まで冷却
してから炭酸水素ナトリウム６．５を徐々に添加して中
和し、ついで過剰の炭酸水素ナトリウムを触媒として１
１５℃でアルカリ重合を４時間行なわせ、３５％塩酸水
３．７ｇを含む水１００ｇを６０℃に冷却してから徐々
に加え８０℃に１時間加熱して中和し、水洗して余分の
塩酸分と生成した塩酸ナトリウム分を除去したのち、無
水芒硝で脱水し、トルエンを添加して濾過して不揮発分
が６０％となるように調整してＭＴＱレジンを作ったと
ころ、このものは第５表に示したとおりの結果を示した
。Examples 14 to 17 The blending ratios of methyl polysilicate, hexamethyldisiloxane, methyltrimethoxysilane, and isobutyltrimethoxysilane and the amount of water for hydrolysis added were determined as in Example 10.
13, 5.5 g of 35% hydrochloric acid water was added to the toluene resin layer obtained by hydrolyzing, aging and toluene in the same manner as in Examples 10 to 13.
After acid polymerization was carried out at 0°C for 6 hours, it was cooled to 50°C and neutralized by gradually adding 6.5% of sodium hydrogen carbonate.
Alkaline polymerization was carried out at 15°C for 4 hours, and 100g of water containing 3.7g of 35% hydrochloric acid was cooled to 60°C, then gradually added, heated to 80°C for 1 hour to neutralize, and washed with water to remove the excess. After removing the hydrochloric acid content and the generated sodium hydrochloride content, it was dehydrated with anhydrous sodium sulfate, and toluene was added and filtered to adjust the nonvolatile content to 60% to make MTQ resin. The results were shown in Table 5.
なお、こぎに得られたＭＴＱレジンについては実施例１
と同じ方法でジメチルポリシロキサンとの相溶性をしら
べたところ、これらはいずれもすぐれた相溶性を示した
。Regarding the MTQ resin obtained in Example 1,
When the compatibility with dimethylpolysiloxane was examined in the same manner as above, both showed excellent compatibility.
第 ５ 表
比較例
温度計、還流冷却器、攪拌機を取りつけたＩＱの四ツロ
フラスコに、実施例１で使用したエチルシリケート３７
８ｇ、ヘキサメチルジシロキサン１５３ｇおよびエタノ
ール１５ｇを仕込み、こ＼に３５％塩酸水Ｌｏｇと水９
０ｇを滴下して加水分解させ、７６℃で４時間熟成して
からトルエン２０３ｇを加えて溶解し、水洗を数回行な
って塩酸分を除去し、無水芒硝で脱水し濾過したところ
、無色透明で不揮発分６０．１％、粘度４．３ ｃ Ｓ
、比重１．０５０、水酸基量１．８モル／ １００ ｇ
レジンである液体が得られたが、このものは分析の結果
、Ｍ／Ｑモル比が０．７５であるＭＱレジンであること
が確認されたが、このもののジメチルポリシロキサンと
の相溶性を実施例１と同じ方法でしらべたところ、この
混合物は微白濁の様相を生じていたので、ジメチルポリ
シロキサンとの相溶性がよくないものであることが判っ
た。Table 5 Comparative Examples Ethyl silicate 37 used in Example 1 was placed in an IQ four-way flask equipped with a thermometer, reflux condenser, and stirrer.
8g, hexamethyldisiloxane 153g and ethanol 15g, and 35% hydrochloric acid water Log and water 9g.
0 g was added dropwise to hydrolyze it, and after aging at 76°C for 4 hours, 203 g of toluene was added to dissolve it, washed with water several times to remove the hydrochloric acid content, dehydrated with anhydrous sodium sulfate, and filtered. Nonvolatile content 60.1%, viscosity 4.3 cS
, specific gravity 1.050, hydroxyl group amount 1.8 mol/100 g
A liquid resin was obtained, which was analyzed and confirmed to be an MQ resin with an M/Q molar ratio of 0.75, but compatibility with dimethylpolysiloxane was investigated. When examined in the same manner as in Example 1, this mixture had a slightly cloudy appearance, indicating that it had poor compatibility with dimethylpolysiloxane.
参考例１
実施例３で得られたＭＴＱ−ｍの固形分１２５部に分子
鎖両末端が水酸基で封鎖された、平均重合度が６，５０
０であるジメチルポリシロキサン生ゴム１００部を添加
し、トルエンを加えて固形分が６０％になるようにうす
め、１０時間にわたり、温度を１００℃に保って攪拌を
行ない、シリコーン感圧接着剤を製造したところ、この
ものは無色透明で不揮発分６０．１％、粘度１３６，０
００ｃＳの物性を示した。Reference Example 1 The solid content of MTQ-m obtained in Example 3 was 125 parts, both ends of the molecular chain were blocked with hydroxyl groups, and the average degree of polymerization was 6.50.
Add 100 parts of dimethylpolysiloxane raw rubber of 0.0%, dilute with toluene to make the solid content 60%, and stir for 10 hours while keeping the temperature at 100°C to produce a silicone pressure-sensitive adhesive. As a result, this product was colorless and transparent, had a non-volatile content of 60.1%, and a viscosity of 136.0%.
It showed physical properties of 00cS.
ついでこのシリコーン感圧接着剤１００ 部に過酸化ベ
ンゾイル２部とトルエン５０部を添加してよく攪拌して
得た試料を巾２５ｎ＋ｍ、厚さ０．０２５ｍのポリイミ
ドフィルムにアプリケーターを用いて４０μｍの厚さに
塗布し、５分間風乾後に１８０℃で３分間焼き付けて試
験片を作り、これについての粘着力、ポールタック、凝
集力を測定したところ第６表に示したとおりの結果が得
られた。Next, 2 parts of benzoyl peroxide and 50 parts of toluene were added to 100 parts of this silicone pressure-sensitive adhesive, and the sample obtained by stirring well was applied to a 40 μm thick polyimide film with a width of 25 nm+m and a thickness of 0.025 m using an applicator. The test piece was prepared by applying the test piece to the surface, air-drying it for 5 minutes, and then baking it at 180°C for 3 minutes.The adhesion, pole tack, and cohesive force of the test piece were measured, and the results shown in Table 6 were obtained.
また、このシリコーン感圧接着剤１００部にけい素原子
に結合した水素原子を２０モル％含有する粘度が５５ｃ
Ｓのメチルハイドロジエンポリシロキサン５部と付加反
応用触媒としての白金触媒を白金量で３Ｑｐｐｍおよび
トルエン５０部を添加してよく攪拌して得た試料を上記
と同様のポリイミドフィルムにアプリケーターを用いて
厚さ４０Ｉ＃に塗布し、５分間風乾後に１００℃で５分
間加硫して試験片を作り、これについての粘着力。In addition, when 100 parts of this silicone pressure-sensitive adhesive contains 20 mol% of hydrogen atoms bonded to silicon atoms, the viscosity is 55c.
A sample obtained by adding 5 parts of methylhydrodiene polysiloxane of S, 3 Qppm of platinum catalyst as an addition reaction catalyst, and 50 parts of toluene and stirring well was applied to the same polyimide film as above using an applicator. Coating to a thickness of 40I#, air-drying for 5 minutes, and vulcanizing at 100°C for 5 minutes to prepare a test piece, and the adhesion strength thereof.
ポールタック、凝集力を測定したところ、第６表に併記
したとおりの結果が得られた。When pole tack and cohesive force were measured, the results shown in Table 6 were obtained.
しかし、比較のために上記で使用したＭＴＱ−■の代わ
りに、Ｍ／Ｑモル比が０．８で有機基がメチル基であり
、不揮発分が６０．５％、粘度が９．３ ｃ Ｓ、水酸
基含有量が０．０４モル／１００ｇレジンであるＭＱレ
ジンを使用して上記と同じ方法でシリコーン感圧接着剤
を作ったところ、このものは不揮発分６０．４％、粘度
１０２，０００ｃＳの無色透明で粘稠なトルエン溶液で
あったが。However, instead of MTQ-■ used above for comparison, the M/Q molar ratio was 0.8, the organic group was a methyl group, the nonvolatile content was 60.5%, and the viscosity was 9.3 c S When a silicone pressure-sensitive adhesive was made in the same manner as above using MQ resin with a hydroxyl content of 0.04 mol/100 g resin, it had a non-volatile content of 60.4% and a viscosity of 102,000 cS. It was a clear, colorless and viscous toluene solution.
このものを上記と同じように過酸化ベンゾイルで加硫し
たのちポリイミドフィルムに塗布し、風乾し焼き付けた
ものの粘着力、ポールタック、凝集力は第６表に併記し
たとおりであった。This product was vulcanized with benzoyl peroxide in the same manner as above, then applied to a polyimide film, air-dried and baked, and the adhesive strength, pole tack, and cohesive strength were as shown in Table 6.
第 ６ 表
参考例２
実施例２で得られたＭＴＱレジン（ＭＴＱ−１１）と比
較例１で得られたＭＱレジンの各々１００部に、両末端
がビニルジメチルシリル基で封鎖され、主鎖のけい素原
子に結合したビニル基が１分子中に平均２ヶ結合された
平均重合度が１，０００の直鎖状のビニル基含有ジメチ
ルポリシロキサン１００部を各々に混合し、溶剤である
トルエンをストリップしたものに、両末端がハイドロジ
エンジメチルシリル基で封鎖され、主鎖のけい素原子に
結合した水素原子が１分子中に平均２０ケ含有されてい
る直鎖状のハイドロジエンメチルポリシロキサンを３５
部づつ混合し、さらに白金触媒を白金量として混合物に
対して３Ｑｐｐｍ加えて混合し、減圧脱泡してから１０
０℃で２時間硬化させて、厚さ１閣のゴムシートを作っ
た。ついで、このシートを所定のサイズに切断して引張
り試験を行なった結果、ＭＴＱ−ｎを配合したゴムシー
トは引張り強度が３５ｋｇ／ｃｄで透明なゴムシートで
あった。Table 6 Reference Example 2 100 parts each of the MTQ resin (MTQ-11) obtained in Example 2 and the MQ resin obtained in Comparative Example 1 were added to 100 parts each of the MTQ resin (MTQ-11) obtained in Example 2 and the MQ resin obtained in Comparative Example 1. 100 parts of linear vinyl group-containing dimethylpolysiloxane with an average degree of polymerization of 1,000, in which an average of two vinyl groups bonded to silicon atoms are bonded to each molecule, were mixed with each, and toluene as a solvent was added to each. The stripped product contains a linear hydrogen methylpolysiloxane whose both ends are capped with hydrogen dimethylsilyl groups and which contains an average of 20 hydrogen atoms bonded to silicon atoms in the main chain in one molecule. 35
3 Qppm of platinum catalyst was added to the mixture, and the mixture was degassed under reduced pressure.
It was cured at 0°C for 2 hours to produce a rubber sheet with a thickness of one inch. This sheet was then cut into a predetermined size and subjected to a tensile test. As a result, the rubber sheet containing MTQ-n had a tensile strength of 35 kg/cd and was transparent.
しかし、比較例１で作ったＭＱレジンを配合したものは
引張り強度が２０ｋｇ／ｃｄで乳白色の不透明なゴムシ
ートであり、このことがらＭＴＱ−１１はシリコーンゴ
ムの補強剤として優れた性能を示すものであることが確
認された。However, the product blended with the MQ resin made in Comparative Example 1 has a tensile strength of 20 kg/cd and is a milky white opaque rubber sheet, which indicates that MTQ-11 has excellent performance as a reinforcing agent for silicone rubber. It was confirmed that
Claims (1)
２）（こゝにＲ＾１は非置換または置換の同種または異
種の１価炭化水素基、ａは２．６〜３．０の正数）で示
されるシロキサン単位と、 ２）一般式ＳｉＯ＿２で示されるシロキサン単位、およ
び ３）一般式Ｒ＾２＿ＳｉＯ（＿４＿−＿ｂ＿／＿２）（
こゝにＲ＾２はその３０モル％以上が炭素数２以上の基
である、非置換または置換の同種または異種の１価炭化
水素基、ｂは０．９５〜１．０５の正数）で示されるシ
ロキサン単位、 とからなることを特徴とするシリコーン樹脂組成物。 ２、１）一般式Ｒ＾１′＿ａＳｉ（ＯＲ＾３）＿４＿−
＿ａ（Ｒ＾１は非置換または置換の同種または異種の１
価炭化水素基、Ｒ＾３は水素原子または炭素数１〜５の
アルキル基、ａは２．６〜３．０の正数）で示されるオ
ルガノハイドロキシシラン、オルガノアルコキシシラン
および／または一般式（Ｒ＾１＿ａＳｉ）＿２Ｏ＿４＿
−＿ａ（Ｒ＾１、ａは前記に同じ）で示されるオルガノ
シロキサンと、 ２）一般式Ｓｉ（ＯＲ＾４）＿４（こゝにＲ＾４は炭素
数１〜５のアルキル基）で示されるアルキルシリケート
および／またはその部分加水分解縮合物、および ３）一般式Ｒ＾２＿ｂＳｉ（ＯＲ＾４）＿４＿−＿ｂ（
Ｒ＾２はその３０モル％以上が炭素数２以上の基である
、非置換または置換の同種または異種の１価炭化水素基
、Ｒ＾４は前記に同じ）で示されるオルガノアルコキシ
シランおよび／またはその加水分解縮合物を混合し、こ
れを共加水分解、重縮合反応させることを特徴とする請
求項１に記載のシリコーン樹脂組成物の製造方法。 ３、共加水分解、重縮合反応を第１成分〜第３成分の混
合物を無機酸と水を加えて加水分解したのち、アルカリ
触媒の存在下で重縮合したのち酸触媒の存在下で重縮合
するか、または酸触媒の存在下で重縮合したのちアルカ
リ触媒の存在下で重縮合させる、請求項２に記載のシリ
コーン樹脂組成物の製造方法。[Claims] 1,1) General formula R^1_aSiO(_4_-_a_/_
2) A siloxane unit represented by (where R^1 is an unsubstituted or substituted same or different monovalent hydrocarbon group, a is a positive number from 2.6 to 3.0), and 2) a general formula SiO_2 and 3) general formula R^2_SiO(_4_-_b_/_2)(
Here, R^2 is an unsubstituted or substituted monovalent hydrocarbon group of the same or different kind, of which 30 mol% or more is a group having 2 or more carbon atoms, and b is a positive number from 0.95 to 1.05) A silicone resin composition comprising a siloxane unit represented by: 2, 1) General formula R^1'_aSi(OR^3)_4_-
_a (R^1 is unsubstituted or substituted same or different 1
a valent hydrocarbon group, R^3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is a positive number of 2.6 to 3.0); R^1_aSi)_2O_4_
-_a (R^1, a is the same as above), and 2) an organosiloxane represented by the general formula Si(OR^4)_4 (where R^4 is an alkyl group having 1 to 5 carbon atoms). and 3) an alkyl silicate and/or a partially hydrolyzed condensate thereof, and 3) having the general formula R^2_bSi(OR^4)_4_-_b(
R^2 is an unsubstituted or substituted monovalent hydrocarbon group of the same or different kind, of which 30 mol% or more is a group having 2 or more carbon atoms; R^4 is the same as above); 2. The method for producing a silicone resin composition according to claim 1, further comprising mixing a hydrolyzed condensate thereof and subjecting the mixture to a cohydrolysis and polycondensation reaction. 3. Co-hydrolysis and polycondensation reaction: After hydrolyzing the mixture of the first to third components by adding an inorganic acid and water, polycondensation is carried out in the presence of an alkali catalyst, and then polycondensation is carried out in the presence of an acid catalyst. 3. The method for producing a silicone resin composition according to claim 2, wherein the silicone resin composition is polycondensed in the presence of an acid catalyst and then polycondensed in the presence of an alkali catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63187449A JPH0813888B2 (en) | 1988-07-27 | 1988-07-27 | Silicone resin and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63187449A JPH0813888B2 (en) | 1988-07-27 | 1988-07-27 | Silicone resin and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0236234A true JPH0236234A (en) | 1990-02-06 |
| JPH0813888B2 JPH0813888B2 (en) | 1996-02-14 |
Family
ID=16206269
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63187449A Expired - Fee Related JPH0813888B2 (en) | 1988-07-27 | 1988-07-27 | Silicone resin and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JPH0813888B2 (en) |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60262151A (en) * | 1984-06-11 | 1985-12-25 | Nippon Telegr & Teleph Corp <Ntt> | Intermediate layer for 3-layer resist material and method for using it |
-
1988
- 1988-07-27 JP JP63187449A patent/JPH0813888B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60262151A (en) * | 1984-06-11 | 1985-12-25 | Nippon Telegr & Teleph Corp <Ntt> | Intermediate layer for 3-layer resist material and method for using it |
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|---|---|
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