WO2024038795A1 - Photo-cationically curable silicone composition, silicone cured product, and optical device - Google Patents
Photo-cationically curable silicone composition, silicone cured product, and optical device Download PDFInfo
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- WO2024038795A1 WO2024038795A1 PCT/JP2023/028843 JP2023028843W WO2024038795A1 WO 2024038795 A1 WO2024038795 A1 WO 2024038795A1 JP 2023028843 W JP2023028843 W JP 2023028843W WO 2024038795 A1 WO2024038795 A1 WO 2024038795A1
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- silicone composition
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 230000003287 optical effect Effects 0.000 title claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 32
- 239000004593 Epoxy Substances 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000001424 substituent group Chemical group 0.000 claims abstract description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 6
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- -1 siloxane units Chemical group 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 93
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000003921 oil Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- OGFPIZPNFPWPOO-UHFFFAOYSA-H C(=C)[Si](O[Si](C=C)(C)C)(C)C.[Pt](Cl)(Cl)(Cl)(Cl)(Cl)Cl Chemical compound C(=C)[Si](O[Si](C=C)(C)C)(C)C.[Pt](Cl)(Cl)(Cl)(Cl)(Cl)Cl OGFPIZPNFPWPOO-UHFFFAOYSA-H 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000002096 quantum dot Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 238000013006 addition curing Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention relates to a photocationically curable silicone composition, a cured product thereof, and an optical device using the same.
- a light emitting diode (LED) lamp known as an optical semiconductor device, has a structure in which an LED mounted on a substrate is sealed with a sealing material made of transparent resin. Addition-curing silicone compositions are widely used.
- quantum dot displays that utilize quantum dots with excellent wavelength conversion efficiency and are characterized by low power consumption and high definition.
- quantum dots contain sulfur and act as addition catalyst poisons, there is a problem in that curing inhibition occurs in general addition-curing silicones.
- quantum dots have low heat resistance and are not suitable for manufacturing processes that require heat curing.
- Patent Document 1 a radical-curable silicone composition that can be cured at low temperatures has been proposed (Patent Document 1), but its mechanical properties were insufficient for applications that require high hardness and high strength. .
- the present invention was made in view of the above circumstances, and an object of the present invention is to provide a silicone composition that has a high refractive index, is curable by ultraviolet irradiation, and provides a cured product with excellent hardness and strength. do.
- the present invention provides a cationically curable silicone composition
- a cationically curable silicone composition comprising:
- Me is a methyl group
- Ph is a phenyl group
- R E is each independently a monovalent substituent containing an epoxy group having 2 to 16 carbon atoms
- R 1 is each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond
- R 2 is each independently a methyl group or a phenyl group
- 3 is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms or an oxygen atom
- h is an integer of 1 to 10
- i is an integer of 0 to 10
- j is an integer of 0 to 10
- k is an integer of 1 to 100.
- the arrangement of the siloxane units in the parentheses with h and i is arbitrary.
- (B) a photocationic polymerization initiator It contains A photocation in which the content of phenyl groups bonded to silicon atoms in component (A) is 40 mol% or more based on the total number of monovalent substituents bonded to silicon atoms in component (A).
- a curable silicone composition is provided.
- the photocationically curable silicone composition of the present invention has a high refractive index, can be cured by ultraviolet irradiation, and provides a cured product with excellent hardness and strength.
- R 2 is a phenyl group
- R 3 is an alkylene group having 1 to 3 carbon atoms
- i is 0, j is 1, and k is 1. It is preferable.
- Such a photo-cationically curable silicone composition has a higher refractive index and provides a cured product with superior hardness and strength.
- (C) may contain an epoxy silicone other than the component (A).
- the present invention also provides a cured silicone product that is a cured product of the above-mentioned photo-cationically curable silicone composition.
- the present invention provides an optical device having the above-mentioned cured silicone product.
- the cured silicone product of the present invention has excellent properties such as high refractive index, high hardness, and high strength, and is therefore suitable for optical device applications such as encapsulants, lens materials, and coating materials.
- the photocationically curable silicone composition of the present invention can be cured by ultraviolet irradiation, and the cured product has excellent properties such as high refractive index, high hardness, and high strength, so it can be used as a sealing material, a lens material, Suitable for optical device applications such as coating materials.
- the present invention is a cationically curable silicone composition
- Me is a methyl group
- Ph is a phenyl group
- R E is each independently a monovalent substituent containing an epoxy group having 2 to 16 carbon atoms
- R 1 is each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond
- R 2 is each independently a methyl group or a phenyl group
- 3 is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms or an oxygen atom
- h is an integer of 1 to 10
- i is an integer of 0 to 10
- j is an integer of 0 to 10
- k is an integer of 1 to 100.
- the arrangement of the siloxane units in the parentheses with h and i is arbitrary.
- the photocationically curable silicone composition of the present invention contains components (A) and (B) described below as essential components. This composition may further contain optional components in addition to the above-mentioned essential components, if necessary. Each component will be explained in detail below.
- Component (A) is (A) epoxy silicone represented by the following general formula (1).
- Me is a methyl group
- Ph is a phenyl group
- R E is each independently a monovalent substituent containing an epoxy group having 2 to 16 carbon atoms
- R 1 is each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond
- R 2 is each independently a methyl group or a phenyl group
- 3 is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms or an oxygen atom
- h is an integer of 1 to 10
- i is an integer of 0 to 10
- j is an integer from 0 to 10
- k is an integer from 1 to 100.
- the arrangement of the siloxane units in the parentheses with h and i is arbitrary.
- R E Specific examples of the monovalent substituent containing an epoxy group represented by R E include groups represented by the following formula (2) and the following formula (3), but are limited to these: isn't it.
- the monovalent hydrocarbon group represented by R 1 includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, Alkyl groups having 1 to 12 carbon atoms such as n-decyl, cyclopentyl, and cyclohexyl groups; Aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl groups; tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, and pentyl.
- alkylaryl groups having 7 to 12 carbon atoms such as phenyl and hexylphenyl groups
- aralkyl groups having 7 to 12 carbon atoms such as benzyl and phenethyl groups, and methyl or phenyl groups are preferred.
- divalent hydrocarbon group represented by R 3 examples include methylene, ethylene, trimethylene, tetramethylene, and pentamethylene groups, with methylene, ethylene, and trimethylene groups being preferred.
- O (oxygen) may be present in these divalent hydrocarbon groups, for example, a portion may be an -O- ether group.
- the content of phenyl groups bonded to silicon atoms in component (A) is 40 mol% or more and 50 mol% based on the total number of monovalent substituents bonded to silicon atoms in component (A). It is preferable that it is above. If the content of phenyl groups is less than 40 mol%, the refractive index, hardness, strength, etc. may decrease.
- component (A) there is no particular restriction on the upper limit of the content of phenyl groups bonded to silicon atoms relative to the total number of monovalent substituents bonded to silicon atoms in component (A), but for example, less than 100 mol%, preferably 90 It can be mol % or less, more preferably 80 mol % or less, still more preferably 70 mol % or less, and extremely preferably 60 mol % or less.
- h is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 3.
- i is an integer from 0 to 10, preferably 0.
- j is an integer of 0 to 10, preferably an integer of 1 to 10, and more preferably 1.
- k is an integer of 1 to 100, preferably an integer of 1 to 10, and more preferably 1.
- component (A) has general formula (1), R 2 is a phenyl group, R 3 is an alkylene group having 1 to 3 carbon atoms, i is 0, and j is 1. and k is preferably 1.
- component (A) Suitable examples of component (A) are shown below, but are not limited thereto.
- component (A) may be used alone or in combination of two or more.
- Component (B) is a photocationic polymerization initiator that generates cationic species upon irradiation with ultraviolet rays, and any compound having such a function can be used without particular limitation.
- Y - is an anion such as SbF 6 - , AsF 6 - , PF 6 - , BF 4 - , HSO 4 - , ClO 4 - ;
- Examples include lylselenonium salts, tetraarylphosphonium salts, aryldiazonium salts, and the like.
- the blending amount of component (B) is preferably 0.1 parts by mass to 20.0 parts by mass, more preferably 0.1 parts by mass to 5.0 parts by mass of component (B) per 100 parts by mass of component (A). Part by mass. If the amount of component (B) is 0.1 part by mass or more, sufficient curability can be reliably obtained.
- the photocationically curable silicone composition of the present invention may contain, as the (C) component, an epoxy silicone other than the (A) component.
- epoxy silicones include, but are not limited to, those represented by the following general formulas (4) to (6).
- R E , R 1 , and R 2 are the same as R E , R 1 , and R 2 in the general formula (1) mentioned above for component (A).
- p is 1 to 5
- r is an integer from 1 to 5
- s is an integer from 4 to 82
- t is an integer from 1 to 40.
- the blending amount is preferably 1 to 50 parts by weight per 100 parts by weight of component (A).
- the photocationically curable silicone composition of the present invention may optionally contain an epoxy diluent, an organic solvent, silicone, an antioxidant, a light stabilizer, an adhesion aid, Reinforcing fillers, dyes, pigments, etc. may also be added.
- the photocationically curable silicone composition of the present invention can be cured by irradiating it with light such as ultraviolet rays.
- UV light source examples include UV LED lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and xenon lamps.
- the amount of UV irradiation is preferably 100 to 18,000 mJ/cm 2 , more preferably 3,000 to 18,000 mJ/cm 2 for a sheet formed from the composition of the present invention to a thickness of about 2.0 mm. cm2 . That is, when using ultraviolet rays with an illuminance of 100 mW/cm 2 , curing can be achieved by irradiating the ultraviolet rays for about 1 to 180 seconds.
- curing may be accelerated by heating at 40° C. to 200° C. after irradiating with light such as ultraviolet rays.
- the present invention also provides a cured silicone product, which is a cured product of the photocationically curable silicone composition, and an optical device containing the cured silicone product.
- the photocationically curable silicone composition of the present invention can be cured by ultraviolet irradiation, and the cured product has excellent properties such as high refractive index, high hardness, and high strength, so it can be used as a sealing material, a lens material, Suitable for optical device applications such as coating materials.
- the viscosity is a value at 25° C. measured using a B-type rotational viscometer.
- organopolysiloxane 545 represented by the following formula (8)
- a solution of .5 g and 450 g of toluene was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was stirred at 90°C for 2.5 hours.
- Toluene was distilled off under reduced pressure to obtain 926 g of a colorless and transparent oily organohydrogenpolysiloxane represented by the following formula (9) (viscosity at 25° C.: 11,820 mPa ⁇ s).
- a solution of 250 g of organohydrogenpolysiloxane represented by the above formula (9) and 130 g of toluene was added dropwise to this over 1 hour. After the dropwise addition was completed, the mixture was stirred at 80°C for 2 hours. Toluene was distilled off under reduced pressure to obtain 281 g of epoxy silicone (A-1) in the form of a colorless and transparent oil (viscosity at 25° C.: 16,040 mPa ⁇ s). In the epoxy silicone (A-1), the content of phenyl groups bonded to silicon atoms was 50 mol% based on the total number of monovalent substituents bonded to silicon atoms.
- organohydrogendisiloxane represented by the above structural formula (11) and 260 g of toluene to a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, It was heated to 85°C using an oil bath.
- organohydrogenpolysiloxane represented by the following formula (13) was added dropwise over 2 hours. After the dropwise addition was completed, the mixture was stirred at 80°C for 3 hours. Toluene was distilled off under reduced pressure to obtain 169 g of epoxy silicone (C-2) in the form of a colorless and transparent oil (viscosity at 25° C.: 330 mPa ⁇ s).
- organohydrogensiloxane represented by the above formula (7) 100 g was added dropwise to this over 2 hours. After the dropwise addition was completed, the mixture was stirred at 80°C for 3 hours. Toluene was distilled off under reduced pressure to obtain 169 g of epoxy silicone (C-3) in the form of a colorless and transparent oil (viscosity at 25° C.: 330 mPa ⁇ s).
- organohydrogensiloxane represented by the following formula (14) was added dropwise to this over 1 hour. After the dropwise addition was completed, the mixture was stirred at 75°C for 15 hours. Toluene was distilled off under reduced pressure to obtain 356 g of epoxy silicone (C-4) in the form of a colorless and transparent oil (viscosity at 25° C.: 54 mPa ⁇ s).
- Examples 1 to 5 and Comparative Examples 1 and 2 The components shown below were mixed in the composition (parts by mass) shown in Table 1 to prepare a photo-cationically curable silicone composition.
- the refractive index (nD25) of the photocation-curable silicone composition was measured using a digital refractometer (model RX-9000i) manufactured by Atago Co., Ltd. at 25° C. using sodium D line as a light source.
- the photocation-curable silicone composition was irradiated with ultraviolet light with a wavelength of 365 nm to 18,000 mJ/cm 2 using an i-UV electronic control device (model UBX0601-01) manufactured by i-Graphics Co., Ltd.
- the Type A hardness of a 2 mm thick cured product that was cured by irradiating ultraviolet rays at 25° C. in the atmosphere was measured in accordance with JIS K6253.
- a photo-cationically curable silicone composition in which (A) an epoxy silicone represented by the following general formula (1) (In the formula, Me is a methyl group, Ph is a phenyl group, R E is each independently a monovalent substituent containing an epoxy group having 2 to 16 carbon atoms, and R 1 is each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond; R 2 is each independently a methyl group or a phenyl group; 3 is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms or an oxygen atom, h is an integer of 1 to 10, i is an integer of 0 to 10, j is an integer of 0 to 10, k is an integer of 1 to 100.
- an epoxy silicone represented by the following general formula (1) In the formula, Me is a methyl group, Ph is a phenyl group, R E is each independently a monovalent substituent containing
- a photocationically curable silicone composition characterized in that the cationic photocurable silicone composition is mol% or more.
- R 2 is a phenyl group
- R 3 is an alkylene group having 1 to 3 carbon atoms
- i is 0, j is 1, and k is 1
- a cured silicone product which is a cured product of the photocationically curable silicone composition described in [1], [2], or [3] above.
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Abstract
The present invention is a photo-cationically curable silicone composition comprising (A) an epoxy silicone represented by general formula (1) (where Me is a methyl group, Ph is a phenyl group, RE is a monovalent substituent containing a C2-16 epoxy group, R1 is a C1-12 monovalent hydrocarbon group having no aliphatic unsaturated bond, R2 is a methyl group or a phenyl group, R3 is a C1-5 divalent hydrocarbon group or an oxygen atom, h is an integer of 1-10, I is an integer of 0-10, j is an integer of 0-10, and k is an integer of 1-100) and (B) a photocationic polymerization initiator, wherein the content of phenyl groups bonded to silicon atoms in the component (A) is not less than 40 mol% with respect to the total number of monovalent substituents bonded to silicon atoms in the component (A). Thus, provided is a silicone composition that has a high refractive index, that can be cured with ultraviolet irradiation, and that provides a cured product having excellent hardness and strength.
Description
本発明は、光カチオン硬化型シリコーン組成物及びその硬化物、並びに、それを用いた光デバイスに関する。
The present invention relates to a photocationically curable silicone composition, a cured product thereof, and an optical device using the same.
光半導体装置として知られる発光ダイオード(LED)ランプは、基板に実装されたLEDを透明な樹脂からなる封止材料で封止した構成であり、封止材料としては、優れた耐熱性を有する観点から付加硬化型シリコーン組成物が広く使用されている。
A light emitting diode (LED) lamp, known as an optical semiconductor device, has a structure in which an LED mounted on a substrate is sealed with a sealing material made of transparent resin. Addition-curing silicone compositions are widely used.
近年、電子機器の小型化、薄型化、高機能化などにより、光学材料に要求される性能がより高いものとなっている。例えば、光学通信関係で広く使用されるマイクロレンズ材料では、効率的な集光、拡散を実現するために、高硬度、高屈折率、高強度であるといった性能が要求される。また、省エネルギー化の目的で、材料を硬化させる際の加熱工程を極力少なくするため、紫外線等の光照射により低温で硬化可能な光硬化型樹脂のニーズが高まっている。
In recent years, as electronic devices have become smaller, thinner, and more sophisticated, the performance required of optical materials has become even higher. For example, microlens materials widely used in optical communications require performance such as high hardness, high refractive index, and high strength in order to achieve efficient light collection and diffusion. Furthermore, in order to minimize the heating process required for curing materials for the purpose of energy saving, there is an increasing need for photocurable resins that can be cured at low temperatures by irradiation with light such as ultraviolet rays.
更に、ディスプレイ分野では、優れた波長変換効率を有する量子ドットを利用した、低消費電力、高精細が特徴の量子ドットディスプレイの開発が進められている。しかしながら、このような量子ドットは硫黄を含み、付加触媒毒となるため、一般的な付加硬化型シリコーンでは硬化阻害が発生するという問題がある。加えて、量子ドットは耐熱性が低く、加熱硬化が必要な製造工程には適していない。
Furthermore, in the field of displays, progress is being made in the development of quantum dot displays that utilize quantum dots with excellent wavelength conversion efficiency and are characterized by low power consumption and high definition. However, since such quantum dots contain sulfur and act as addition catalyst poisons, there is a problem in that curing inhibition occurs in general addition-curing silicones. In addition, quantum dots have low heat resistance and are not suitable for manufacturing processes that require heat curing.
このような問題に対し、低温で硬化可能なラジカル硬化型シリコーン組成物が提案されている(特許文献1)が、高硬度及び高強度が求められる用途においては、機械特性が不十分であった。
To address these problems, a radical-curable silicone composition that can be cured at low temperatures has been proposed (Patent Document 1), but its mechanical properties were insufficient for applications that require high hardness and high strength. .
本発明は、上記事情に鑑みなされたものであって、高い屈折率を有し、紫外線照射により硬化可能であり、硬度及び強度に優れた硬化物を与えるシリコーン組成物を提供することを目的とする。
The present invention was made in view of the above circumstances, and an object of the present invention is to provide a silicone composition that has a high refractive index, is curable by ultraviolet irradiation, and provides a cured product with excellent hardness and strength. do.
上記課題を解決するために、本発明では、カチオン硬化型シリコーン組成物であって、
(A)下記一般式(1)で表されるエポキシシリコーン
(式中、Meはメチル基であり、Phはフェニル基であり、REは、それぞれ独立に、炭素原子数2~16のエポキシ基を含有する1価の置換基であり、R1は、それぞれ独立に、脂肪族不飽和結合を有しない、置換又は非置換の炭素原子数1~12の1価炭化水素基であり、R2は、それぞれ独立に、メチル基又はフェニル基であり、R3は、それぞれ独立に、置換又は非置換の炭素原子数1~5の2価炭化水素基又は酸素原子であり、hは1~10の整数であり、iは0~10の整数であり、jは0~10の整数であり、kは1~100の整数である。hおよびiが付された括弧内のシロキサン単位の配列は任意である。)、及び
(B)光カチオン重合開始剤
を含有するものであり、
前記(A)成分中のケイ素原子に結合したフェニル基の含有量が、前記(A)成分中のケイ素原子に結合した1価の置換基の合計数に対して40モル%以上である光カチオン硬化型シリコーン組成物を提供する。 In order to solve the above problems, the present invention provides a cationically curable silicone composition comprising:
(A) Epoxy silicone represented by the following general formula (1)
(In the formula, Me is a methyl group, Ph is a phenyl group, R E is each independently a monovalent substituent containing an epoxy group having 2 to 16 carbon atoms, and R 1 is each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond; R 2 is each independently a methyl group or a phenyl group; 3 is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms or an oxygen atom, h is an integer of 1 to 10, i is an integer of 0 to 10, j is an integer of 0 to 10, k is an integer of 1 to 100. The arrangement of the siloxane units in the parentheses with h and i is arbitrary.), and (B) a photocationic polymerization initiator It contains
A photocation in which the content of phenyl groups bonded to silicon atoms in component (A) is 40 mol% or more based on the total number of monovalent substituents bonded to silicon atoms in component (A). A curable silicone composition is provided.
(A)下記一般式(1)で表されるエポキシシリコーン
(B)光カチオン重合開始剤
を含有するものであり、
前記(A)成分中のケイ素原子に結合したフェニル基の含有量が、前記(A)成分中のケイ素原子に結合した1価の置換基の合計数に対して40モル%以上である光カチオン硬化型シリコーン組成物を提供する。 In order to solve the above problems, the present invention provides a cationically curable silicone composition comprising:
(A) Epoxy silicone represented by the following general formula (1)
A photocation in which the content of phenyl groups bonded to silicon atoms in component (A) is 40 mol% or more based on the total number of monovalent substituents bonded to silicon atoms in component (A). A curable silicone composition is provided.
本発明の光カチオン硬化型シリコーン組成物であれば、高い屈折率を有し、紫外線照射により硬化可能であり、硬度及び強度に優れた硬化物を与える。
The photocationically curable silicone composition of the present invention has a high refractive index, can be cured by ultraviolet irradiation, and provides a cured product with excellent hardness and strength.
また、前記一般式(1)において、R2がフェニル基であり、R3が炭素原子数1~3のアルキレン基であり、iが0であり、jが1であり、kが1であることが好ましい。
Further, in the general formula (1), R 2 is a phenyl group, R 3 is an alkylene group having 1 to 3 carbon atoms, i is 0, j is 1, and k is 1. It is preferable.
このような光カチオン硬化型シリコーン組成物であれば、より高い屈折率を有し、硬度及び強度により優れた硬化物を与える。
Such a photo-cationically curable silicone composition has a higher refractive index and provides a cured product with superior hardness and strength.
更に、(C)前記(A)成分以外のエポキシシリコーンを含有するものであってもよい。
Furthermore, (C) may contain an epoxy silicone other than the component (A).
このような(C)成分を用いることによって、得られる硬化物の物性を容易に調整することができる。
By using such component (C), the physical properties of the resulting cured product can be easily adjusted.
また本発明では、上記の光カチオン硬化型シリコーン組成物の硬化物であるシリコーン硬化物を提供する。
The present invention also provides a cured silicone product that is a cured product of the above-mentioned photo-cationically curable silicone composition.
さらに本発明では、上記のシリコーン硬化物を有するものである光デバイスを提供する。
Furthermore, the present invention provides an optical device having the above-mentioned cured silicone product.
本発明のシリコーン硬化物は、高屈折率、高硬度、高強度等の特性に優れるものであるため、封止材、レンズ材料、コーティング材料等の光デバイス用途に好適である。
The cured silicone product of the present invention has excellent properties such as high refractive index, high hardness, and high strength, and is therefore suitable for optical device applications such as encapsulants, lens materials, and coating materials.
本発明の光カチオン硬化型シリコーン組成物は、紫外線照射により硬化可能であり、その硬化物は高屈折率、高硬度、高強度等の特性に優れるものであるため、封止材、レンズ材料、コーティング材料等の光デバイス用途に好適である。
The photocationically curable silicone composition of the present invention can be cured by ultraviolet irradiation, and the cured product has excellent properties such as high refractive index, high hardness, and high strength, so it can be used as a sealing material, a lens material, Suitable for optical device applications such as coating materials.
上述のように、高い屈折率を有し、紫外線照射により硬化可能であり、硬度及び強度に優れた硬化物を与えるシリコーン組成物の開発が求められていた。
As mentioned above, there has been a need to develop a silicone composition that has a high refractive index, is curable by ultraviolet irradiation, and provides a cured product with excellent hardness and strength.
本発明者らは、上記目的を達成するために鋭意検討した結果、後述する(A)及び(B成分を含むシリコーン樹脂組成物であれば、上記課題を解決できることを見出し、本発明を完成させた。
As a result of intensive studies to achieve the above object, the present inventors discovered that the above problems could be solved by using a silicone resin composition containing components (A) and (B) described below, and completed the present invention. Ta.
即ち、本発明は、カチオン硬化型シリコーン組成物であって、
(A)下記一般式(1)で表されるエポキシシリコーン
(式中、Meはメチル基であり、Phはフェニル基であり、REは、それぞれ独立に、炭素原子数2~16のエポキシ基を含有する1価の置換基であり、R1は、それぞれ独立に、脂肪族不飽和結合を有しない、置換又は非置換の炭素原子数1~12の1価炭化水素基であり、R2は、それぞれ独立に、メチル基又はフェニル基であり、R3は、それぞれ独立に、置換又は非置換の炭素原子数1~5の2価炭化水素基又は酸素原子であり、hは1~10の整数であり、iは0~10の整数であり、jは0~10の整数であり、kは1~100の整数である。hおよびiが付された括弧内のシロキサン単位の配列は任意である。)、及び
(B)光カチオン重合開始剤
を含有するものであり、
前記(A)成分中のケイ素原子に結合したフェニル基の含有量が、前記(A)成分中のケイ素原子に結合した1価の置換基の合計数に対して40モル%以上である光カチオン硬化型シリコーン組成物である。 That is, the present invention is a cationically curable silicone composition,
(A) Epoxy silicone represented by the following general formula (1)
(In the formula, Me is a methyl group, Ph is a phenyl group, R E is each independently a monovalent substituent containing an epoxy group having 2 to 16 carbon atoms, and R 1 is each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond; R 2 is each independently a methyl group or a phenyl group; 3 is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms or an oxygen atom, h is an integer of 1 to 10, i is an integer of 0 to 10, j is an integer of 0 to 10, k is an integer of 1 to 100. The arrangement of the siloxane units in the parentheses with h and i is arbitrary.), and (B) a photocationic polymerization initiator It contains
A photocation in which the content of phenyl groups bonded to silicon atoms in component (A) is 40 mol% or more based on the total number of monovalent substituents bonded to silicon atoms in component (A). It is a curable silicone composition.
(A)下記一般式(1)で表されるエポキシシリコーン
(B)光カチオン重合開始剤
を含有するものであり、
前記(A)成分中のケイ素原子に結合したフェニル基の含有量が、前記(A)成分中のケイ素原子に結合した1価の置換基の合計数に対して40モル%以上である光カチオン硬化型シリコーン組成物である。 That is, the present invention is a cationically curable silicone composition,
(A) Epoxy silicone represented by the following general formula (1)
A photocation in which the content of phenyl groups bonded to silicon atoms in component (A) is 40 mol% or more based on the total number of monovalent substituents bonded to silicon atoms in component (A). It is a curable silicone composition.
以下、本発明について詳細に説明するが、本発明はこれらに限定されるものではない。
Hereinafter, the present invention will be explained in detail, but the present invention is not limited thereto.
[光カチオン硬化型シリコーン組成物]
本発明の光カチオン硬化型シリコーン組成物は、後述する(A)および(B)成分を必須成分として含有するものである。この組成物は、前記必須成分以外に必要に応じて任意の成分を更に含むことができる。以下、各成分について詳細に説明する。 [Photocation-curable silicone composition]
The photocationically curable silicone composition of the present invention contains components (A) and (B) described below as essential components. This composition may further contain optional components in addition to the above-mentioned essential components, if necessary. Each component will be explained in detail below.
本発明の光カチオン硬化型シリコーン組成物は、後述する(A)および(B)成分を必須成分として含有するものである。この組成物は、前記必須成分以外に必要に応じて任意の成分を更に含むことができる。以下、各成分について詳細に説明する。 [Photocation-curable silicone composition]
The photocationically curable silicone composition of the present invention contains components (A) and (B) described below as essential components. This composition may further contain optional components in addition to the above-mentioned essential components, if necessary. Each component will be explained in detail below.
[(A)成分]
(A)成分は、(A)下記一般式(1)で表されるエポキシシリコーンである。
(式中、Meはメチル基であり、Phはフェニル基であり、REは、それぞれ独立に、炭素原子数2~16のエポキシ基を含有する1価の置換基であり、R1は、それぞれ独立に、脂肪族不飽和結合を有しない、置換又は非置換の炭素原子数1~12の1価炭化水素基であり、R2は、それぞれ独立に、メチル基又はフェニル基であり、R3は、それぞれ独立に、置換又は非置換の炭素原子数1~5の2価炭化水素基又は酸素原子であり、hは1~10の整数であり、iは0~10の整数であり、jは0~10の整数であり、kは1~100の整数である。hおよびiが付された括弧内のシロキサン単位の配列は任意である。)
[(A) Component]
Component (A) is (A) epoxy silicone represented by the following general formula (1).
(In the formula, Me is a methyl group, Ph is a phenyl group, R E is each independently a monovalent substituent containing an epoxy group having 2 to 16 carbon atoms, and R 1 is each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond; R 2 is each independently a methyl group or a phenyl group; 3 is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms or an oxygen atom, h is an integer of 1 to 10, i is an integer of 0 to 10, j is an integer from 0 to 10, and k is an integer from 1 to 100. The arrangement of the siloxane units in the parentheses with h and i is arbitrary.)
(A)成分は、(A)下記一般式(1)で表されるエポキシシリコーンである。
Component (A) is (A) epoxy silicone represented by the following general formula (1).
REで表されるエポキシ基を含有する1価の置換基としては、具体的には下記式(2)および下記式(3)で表される基が挙げられるが、これらに限定されるものではない。
Specific examples of the monovalent substituent containing an epoxy group represented by R E include groups represented by the following formula (2) and the following formula (3), but are limited to these: isn't it.
R1で表される1価炭化水素基としては、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、sec-ブチル、tert-ブチル、n-ペンチル、n-ヘキシル、n-オクチル、n-デシル、シクロペンチル、シクロヘキシル基等の炭素原子数1~12のアルキル基;フェニル、ナフチル基等の炭素原子数6~12のアリール基;トリル、キシリル、エチルフェニル、プロピルフェニル、ブチルフェニル、ペンチルフェニル、ヘキシルフェニル基等の炭素原子数7~12のアルキルアリール基;ベンジル、フェネチル基等の炭素原子数7~12のアラルキル基などが挙げられ、メチル基又はフェニル基が好ましい。
The monovalent hydrocarbon group represented by R 1 includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, Alkyl groups having 1 to 12 carbon atoms such as n-decyl, cyclopentyl, and cyclohexyl groups; Aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl groups; tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, and pentyl. Examples include alkylaryl groups having 7 to 12 carbon atoms such as phenyl and hexylphenyl groups; aralkyl groups having 7 to 12 carbon atoms such as benzyl and phenethyl groups, and methyl or phenyl groups are preferred.
R3で表される2価炭化水素基としては、メチレン、エチレン、トリメチレン、テトラメチレン、ペンタメチレン基などが挙げられ、メチレン、エチレン、トリメチレン基が好ましい。これらの2価炭化水素基にはO(酸素)が介在してもよく、例えば一部が-O-のエーテル基となっていてもよい。
Examples of the divalent hydrocarbon group represented by R 3 include methylene, ethylene, trimethylene, tetramethylene, and pentamethylene groups, with methylene, ethylene, and trimethylene groups being preferred. O (oxygen) may be present in these divalent hydrocarbon groups, for example, a portion may be an -O- ether group.
(A)成分中のケイ素原子に結合したフェニル基の含有率が、(A)成分中のケイ素原子に結合した1価の置換基の合計数に対して40モル%以上であり、50モル%以上であることが好ましい。フェニル基の含有率が40モル%未満であると、屈折率、硬度、強度等の低下を引き起こす場合がある。一方、(A)成分中におけるケイ素原子に結合した1価の置換基の合計数に対するケイ素原子に結合したフェニル基の含有率の上限に特に制限はないが、例えば100モル%未満、好ましくは90モル%以下、より好ましくは80モル%以下、さらに好ましくは70モル%以下、きわめて好ましくは60モル%以下とすることができる。
The content of phenyl groups bonded to silicon atoms in component (A) is 40 mol% or more and 50 mol% based on the total number of monovalent substituents bonded to silicon atoms in component (A). It is preferable that it is above. If the content of phenyl groups is less than 40 mol%, the refractive index, hardness, strength, etc. may decrease. On the other hand, there is no particular restriction on the upper limit of the content of phenyl groups bonded to silicon atoms relative to the total number of monovalent substituents bonded to silicon atoms in component (A), but for example, less than 100 mol%, preferably 90 It can be mol % or less, more preferably 80 mol % or less, still more preferably 70 mol % or less, and extremely preferably 60 mol % or less.
hは、1~10の整数であり、1~5の整数であることが好ましく、3であることがより好ましい。iは、0~10の整数であり、0であることが好ましい。jは、0~10の整数であり、1~10の整数であることが好ましく、1であることがより好ましい。kは、1~100の整数であり、1~10の整数であることが好ましく、1であることがより好ましい。
h is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 3. i is an integer from 0 to 10, preferably 0. j is an integer of 0 to 10, preferably an integer of 1 to 10, and more preferably 1. k is an integer of 1 to 100, preferably an integer of 1 to 10, and more preferably 1.
以上のことから、(A)成分は、一般式(1)において、R2がフェニル基であり、R3が炭素原子数1~3のアルキレン基であり、iが0であり、jが1であり、kが1であることが好ましい。
From the above, component (A) has general formula (1), R 2 is a phenyl group, R 3 is an alkylene group having 1 to 3 carbon atoms, i is 0, and j is 1. and k is preferably 1.
(A)成分の好適な例を以下に示すが、これらに限定されるものではない。
Suitable examples of component (A) are shown below, but are not limited thereto.
なお、(A)成分は、一種単独で用いても、二種以上併用してもよい。
Note that component (A) may be used alone or in combination of two or more.
[(B)成分]
(B)成分は、紫外線照射によりカチオン種を発生する光カチオン重合開始剤であり、このような機能を有する化合物であれば特に限定はなく、いずれでも使用することができる。例えば、R4 2I+Y-、R4 3S+Y-、R4 3Se+Y-、R4 4P+Y-、R4N+Y-(R4はアルキル基で置換されていてもよいアリール基、Y-はSbF6 -、AsF6 -、PF6 -、BF4 -、HSO4 -、ClO4 -などの陰イオン)で示されるジアリールヨードニウム塩、トリアリールスルホニウム塩、トリアリールセレノニウム塩、テトラアリールホスホニウム塩、アリールジアゾニウム塩などが挙げられる。 [(B) Component]
Component (B) is a photocationic polymerization initiator that generates cationic species upon irradiation with ultraviolet rays, and any compound having such a function can be used without particular limitation. For example, R 4 2 I + Y - , R 4 3 S + Y - , R 4 3 Se + Y - , R 4 4 P + Y - , R 4 N + Y - (R 4 is substituted with an alkyl group) aryl group, Y - is an anion such as SbF 6 - , AsF 6 - , PF 6 - , BF 4 - , HSO 4 - , ClO 4 - ; Examples include lylselenonium salts, tetraarylphosphonium salts, aryldiazonium salts, and the like.
(B)成分は、紫外線照射によりカチオン種を発生する光カチオン重合開始剤であり、このような機能を有する化合物であれば特に限定はなく、いずれでも使用することができる。例えば、R4 2I+Y-、R4 3S+Y-、R4 3Se+Y-、R4 4P+Y-、R4N+Y-(R4はアルキル基で置換されていてもよいアリール基、Y-はSbF6 -、AsF6 -、PF6 -、BF4 -、HSO4 -、ClO4 -などの陰イオン)で示されるジアリールヨードニウム塩、トリアリールスルホニウム塩、トリアリールセレノニウム塩、テトラアリールホスホニウム塩、アリールジアゾニウム塩などが挙げられる。 [(B) Component]
Component (B) is a photocationic polymerization initiator that generates cationic species upon irradiation with ultraviolet rays, and any compound having such a function can be used without particular limitation. For example, R 4 2 I + Y - , R 4 3 S + Y - , R 4 3 Se + Y - , R 4 4 P + Y - , R 4 N + Y - (R 4 is substituted with an alkyl group) aryl group, Y - is an anion such as SbF 6 - , AsF 6 - , PF 6 - , BF 4 - , HSO 4 - , ClO 4 - ; Examples include lylselenonium salts, tetraarylphosphonium salts, aryldiazonium salts, and the like.
なかでも、下記式で表されるビス[4-n-アルキルフェニル]ヨードニウムヘキサフルオロアンチモン酸塩が好ましい。
Among these, bis[4-n-alkylphenyl]iodonium hexafluoroantimonate represented by the following formula is preferred.
(B)成分の配合量は、(A)成分100質量部に対して、(B)成分0.1質量部~20.0質量部が好ましく、より好ましくは0.1質量部~5.0質量部である。(B)成分の配合量が0.1質量部以上であれば、十分な硬化性を確実に得ることができる。
The blending amount of component (B) is preferably 0.1 parts by mass to 20.0 parts by mass, more preferably 0.1 parts by mass to 5.0 parts by mass of component (B) per 100 parts by mass of component (A). Part by mass. If the amount of component (B) is 0.1 part by mass or more, sufficient curability can be reliably obtained.
[(C)成分]
本発明の光カチオン硬化型シリコーン組成物は、(C)成分として、(A)成分以外のエポキシシリコーンを含有していても良い。 [(C) Component]
The photocationically curable silicone composition of the present invention may contain, as the (C) component, an epoxy silicone other than the (A) component.
本発明の光カチオン硬化型シリコーン組成物は、(C)成分として、(A)成分以外のエポキシシリコーンを含有していても良い。 [(C) Component]
The photocationically curable silicone composition of the present invention may contain, as the (C) component, an epoxy silicone other than the (A) component.
このようなエポキシシリコーンの例としては、下記一般式(4)~(6)で表されるものが挙げられるが、これらに限定されるものではない。
Examples of such epoxy silicones include, but are not limited to, those represented by the following general formulas (4) to (6).
(C)成分を使用する場合の配合量は、(A)成分100質量部に対して1~50質量部が好ましい。
When using component (C), the blending amount is preferably 1 to 50 parts by weight per 100 parts by weight of component (A).
[その他の成分]
本発明の光カチオン硬化型シリコーン組成物は、上記(A)~(C)成分以外に、必要に応じてエポキシ系希釈剤、有機溶剤、シリコーン、酸化防止剤、光安定剤、接着助剤、補強性充填剤、染料、顔料などを添加してもよい。 [Other ingredients]
In addition to the above-mentioned components (A) to (C), the photocationically curable silicone composition of the present invention may optionally contain an epoxy diluent, an organic solvent, silicone, an antioxidant, a light stabilizer, an adhesion aid, Reinforcing fillers, dyes, pigments, etc. may also be added.
本発明の光カチオン硬化型シリコーン組成物は、上記(A)~(C)成分以外に、必要に応じてエポキシ系希釈剤、有機溶剤、シリコーン、酸化防止剤、光安定剤、接着助剤、補強性充填剤、染料、顔料などを添加してもよい。 [Other ingredients]
In addition to the above-mentioned components (A) to (C), the photocationically curable silicone composition of the present invention may optionally contain an epoxy diluent, an organic solvent, silicone, an antioxidant, a light stabilizer, an adhesion aid, Reinforcing fillers, dyes, pigments, etc. may also be added.
[硬化方法および硬化条件]
本発明の光カチオン硬化型シリコーン組成物は、紫外線等の光を照射することで硬化させることができる。 [Curing method and curing conditions]
The photocationically curable silicone composition of the present invention can be cured by irradiating it with light such as ultraviolet rays.
本発明の光カチオン硬化型シリコーン組成物は、紫外線等の光を照射することで硬化させることができる。 [Curing method and curing conditions]
The photocationically curable silicone composition of the present invention can be cured by irradiating it with light such as ultraviolet rays.
紫外線の光源としては、UVLEDランプ、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアークランプ、及びキセノンランプ等が挙げられる。紫外線の照射量(積算光量)は、例えば、本発明の組成物を2.0mm程度の厚みに成形したシートに対して、好ましくは100~18000mJ/cm2であり、より好ましくは3000~18000mJ/cm2である。即ち、照度100mW/cm2の紫外線を用いた場合、1~180秒程度紫外線を照射することで硬化させることができる。
Examples of the ultraviolet light source include UV LED lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and xenon lamps. The amount of UV irradiation (cumulative amount of light) is preferably 100 to 18,000 mJ/cm 2 , more preferably 3,000 to 18,000 mJ/cm 2 for a sheet formed from the composition of the present invention to a thickness of about 2.0 mm. cm2 . That is, when using ultraviolet rays with an illuminance of 100 mW/cm 2 , curing can be achieved by irradiating the ultraviolet rays for about 1 to 180 seconds.
また、紫外線等の光を照射した後に、40℃~200℃で加熱することで硬化を促進してもよい。
Furthermore, curing may be accelerated by heating at 40° C. to 200° C. after irradiating with light such as ultraviolet rays.
[シリコーン硬化物および光デバイス]
また本発明では、上記の光カチオン硬化型シリコーン組成物の硬化物であるするシリコーン硬化物、および該シリコーン硬化物を有するものである光デバイスを提供する。 [Silicone cured product and optical device]
The present invention also provides a cured silicone product, which is a cured product of the photocationically curable silicone composition, and an optical device containing the cured silicone product.
また本発明では、上記の光カチオン硬化型シリコーン組成物の硬化物であるするシリコーン硬化物、および該シリコーン硬化物を有するものである光デバイスを提供する。 [Silicone cured product and optical device]
The present invention also provides a cured silicone product, which is a cured product of the photocationically curable silicone composition, and an optical device containing the cured silicone product.
本発明の光カチオン硬化型シリコーン組成物は、紫外線照射により硬化可能であり、その硬化物は高屈折率、高硬度、高強度等の特性に優れるものであるため、封止材、レンズ材料、コーティング材料等の光デバイス用途に好適である。
The photocationically curable silicone composition of the present invention can be cured by ultraviolet irradiation, and the cured product has excellent properties such as high refractive index, high hardness, and high strength, so it can be used as a sealing material, a lens material, Suitable for optical device applications such as coating materials.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明はこれによって限定されるものではない。なお、粘度はB型回転粘度計を用いて測定した25℃における値である。
Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Note that the viscosity is a value at 25° C. measured using a B-type rotational viscometer.
[合成例1]
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、下記構造式(7)で表されるオルガノハイドロジェントリシロキサン400g、および、トルエン450gを加え、オイルバスを用いて85℃に加熱した。 [Synthesis example 1]
400 g of organohydrogentrisiloxane represented by the following structural formula (7) and 450 g of toluene were added to a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, and the mixture was heated in an oil bath. and heated to 85°C.
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、下記構造式(7)で表されるオルガノハイドロジェントリシロキサン400g、および、トルエン450gを加え、オイルバスを用いて85℃に加熱した。 [Synthesis example 1]
400 g of organohydrogentrisiloxane represented by the following structural formula (7) and 450 g of toluene were added to a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, and the mixture was heated in an oil bath. and heated to 85°C.
これに六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)を0.57g添加し、攪拌しながら下記式(8)で表されるオルガノポリシロキサン545.5gとトルエン450gとの溶液を1時間かけて滴下した。滴下終了後、90℃で2.5時間攪拌した。トルエンを減圧留去して、無色透明なオイル状の下記式(9)で表されるオルガノハイドロジェンポリシロキサン(25℃における粘度:11,820mPa・s)926gを得た。
To this was added 0.57 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and while stirring, organopolysiloxane 545 represented by the following formula (8) A solution of .5 g and 450 g of toluene was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was stirred at 90°C for 2.5 hours. Toluene was distilled off under reduced pressure to obtain 926 g of a colorless and transparent oily organohydrogenpolysiloxane represented by the following formula (9) (viscosity at 25° C.: 11,820 mPa·s).
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、1,2-エポキシ-4-ビニルシクロヘキサン(商品名:CEL2000、(株)ダイセル製)37.6g、トルエン70g、イソプロピルアルコール70g、六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)0.115g、および、アセトニトリル0.201gを加え、オイルバスを用いて80℃に加熱した。
In a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, 37.6 g of 1,2-epoxy-4-vinylcyclohexane (trade name: CEL2000, manufactured by Daicel Corporation) was added. Add 70 g of toluene, 70 g of isopropyl alcohol, 0.115 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and 0.201 g of acetonitrile, and use an oil bath. Heated to 80°C.
これに、上記式(9)で表されるオルガノハイドロジェンポリシロキサン250gとトルエン130gとの溶液を1時間かけて滴下した。滴下終了後、80℃で2時間攪拌した。トルエンを減圧留去して、無色透明なオイル状(25℃における粘度:16,040mPa・s)のエポキシシリコーン(A-1)281gを得た。なお、エポキシシリコーン(A-1)中、ケイ素原子に結合したフェニル基の含有量は、ケイ素原子に結合した1価の置換基の合計数に対して50モル%であった。
A solution of 250 g of organohydrogenpolysiloxane represented by the above formula (9) and 130 g of toluene was added dropwise to this over 1 hour. After the dropwise addition was completed, the mixture was stirred at 80°C for 2 hours. Toluene was distilled off under reduced pressure to obtain 281 g of epoxy silicone (A-1) in the form of a colorless and transparent oil (viscosity at 25° C.: 16,040 mPa·s). In the epoxy silicone (A-1), the content of phenyl groups bonded to silicon atoms was 50 mol% based on the total number of monovalent substituents bonded to silicon atoms.
[合成例2]
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、1-アリルオキシ-2,3-エポキシプロパン(商品名:アリルグリシジルエーテル、東京化成工業(株)製)34.6g、および、トルエン140gを加え、85℃に加熱した。 [Synthesis example 2]
1-allyloxy-2,3-epoxypropane (trade name: allyl glycidyl ether, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was placed in a four-necked flask equipped with a stirring device, cooling tube, reflux condenser, dropping funnel, and thermometer. 34.6 g and 140 g of toluene were added and heated to 85°C.
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、1-アリルオキシ-2,3-エポキシプロパン(商品名:アリルグリシジルエーテル、東京化成工業(株)製)34.6g、および、トルエン140gを加え、85℃に加熱した。 [Synthesis example 2]
1-allyloxy-2,3-epoxypropane (trade name: allyl glycidyl ether, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was placed in a four-necked flask equipped with a stirring device, cooling tube, reflux condenser, dropping funnel, and thermometer. 34.6 g and 140 g of toluene were added and heated to 85°C.
これに六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)を0.171g添加し、攪拌しながら上記式(9)で表されるオルガノハイドロジェンポリシロキサン250gとトルエン130gとの溶液を1時間かけて滴下した。滴下終了後、85℃で2時間攪拌した。トルエンを減圧留去して、無色透明なオイル状(25℃における粘度:7,960mPa・s)のエポキシシリコーン(A-2)266gを得た。なお、エポキシシリコーン(A-2)中、ケイ素原子に結合したフェニル基の含有量は、ケイ素原子に結合した1価の置換基の合計数に対して50モル%であった。
To this was added 0.171 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and while stirring, the organohydrogen polyamide expressed by the above formula (9) was added. A solution of 250 g of siloxane and 130 g of toluene was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was stirred at 85° C. for 2 hours. Toluene was distilled off under reduced pressure to obtain 266 g of epoxy silicone (A-2) in the form of a colorless and transparent oil (viscosity at 25° C.: 7,960 mPa·s). In the epoxy silicone (A-2), the content of phenyl groups bonded to silicon atoms was 50 mol% based on the total number of monovalent substituents bonded to silicon atoms.
[合成例3]
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、下記構造式(10)で表されるオルガノハイドロジェンジシロキサン191g、および、トルエン145gを加え、オイルバスを用いて85℃に加熱した。 [Synthesis example 3]
191 g of organohydrogendisiloxane represented by the following structural formula (10) and 145 g of toluene were added to a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, and the mixture was placed in an oil bath. The mixture was heated to 85°C using a .
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、下記構造式(10)で表されるオルガノハイドロジェンジシロキサン191g、および、トルエン145gを加え、オイルバスを用いて85℃に加熱した。 [Synthesis example 3]
191 g of organohydrogendisiloxane represented by the following structural formula (10) and 145 g of toluene were added to a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, and the mixture was placed in an oil bath. The mixture was heated to 85°C using a .
これに六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)を0.084g添加し、攪拌しながら1,2-エポキシ-4-ビニルシクロヘキサン(商品名:CEL2000、(株)ダイセル製)88.2gを1時間かけて滴下した。滴下終了後、85℃で3時間攪拌した。トルエンを減圧留去して、下記構造式(11)で表されるオルガノハイドロジェンジシロキサン174gを得た。
To this was added 0.084 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and while stirring, 1,2-epoxy-4-vinylcyclohexane (trade name) 88.2 g of CEL2000 (manufactured by Daicel Corporation) was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was stirred at 85° C. for 3 hours. Toluene was distilled off under reduced pressure to obtain 174 g of organohydrogendisiloxane represented by the following structural formula (11).
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、上記構造式(11)で表されるオルガノハイドロジェンジシロキサン12.5g、および、トルエン260gを加え、オイルバスを用いて85℃に加熱した。
Add 12.5 g of organohydrogendisiloxane represented by the above structural formula (11) and 260 g of toluene to a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, It was heated to 85°C using an oil bath.
これに六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)を0.158g添加し、攪拌しながら下記式(12)で表されるオルガノポリシロキサン250gとトルエン100gとの溶液を1時間かけて滴下した。滴下終了後、85℃で3時間攪拌した。トルエンを減圧留去して、無色透明なオイル状(25℃における粘度:10,690mPa・s)のエポキシシリコーン(C-1)253gを得た。なお、エポキシシリコーン(C-1)中、ケイ素原子に結合したフェニル基の含有量は、ケイ素原子に結合した1価の置換基の合計数に対して28モル%であった。
To this was added 0.158 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and while stirring, 250 g of organopolysiloxane represented by the following formula (12). A solution of 100 g of toluene was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was stirred at 85° C. for 3 hours. Toluene was distilled off under reduced pressure to obtain 253 g of epoxy silicone (C-1) in the form of a colorless and transparent oil (viscosity at 25° C.: 10,690 mPa·s). In the epoxy silicone (C-1), the content of phenyl groups bonded to silicon atoms was 28 mol% based on the total number of monovalent substituents bonded to silicon atoms.
[合成例4]
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、1,2-エポキシ-4-ビニルシクロヘキサン(商品名:CEL2000、(株)ダイセル製)28.3g、トルエン160g、イソプロピルアルコール28g、六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)0.112g、および、アセトニトリル0.112gを加え、オイルバスを用いて80℃に加熱した。 [Synthesis example 4]
In a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, 28.3 g of 1,2-epoxy-4-vinylcyclohexane (trade name: CEL2000, manufactured by Daicel Corporation), Add 160 g of toluene, 28 g of isopropyl alcohol, 0.112 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and 0.112 g of acetonitrile, and use an oil bath. Heated to 80°C.
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、1,2-エポキシ-4-ビニルシクロヘキサン(商品名:CEL2000、(株)ダイセル製)28.3g、トルエン160g、イソプロピルアルコール28g、六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)0.112g、および、アセトニトリル0.112gを加え、オイルバスを用いて80℃に加熱した。 [Synthesis example 4]
In a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, 28.3 g of 1,2-epoxy-4-vinylcyclohexane (trade name: CEL2000, manufactured by Daicel Corporation), Add 160 g of toluene, 28 g of isopropyl alcohol, 0.112 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and 0.112 g of acetonitrile, and use an oil bath. Heated to 80°C.
これに下記式(13)で表されるオルガノハイドロジェンポリシロキサン100gを2時間かけて滴下した。滴下終了後、80℃で3時間攪拌した。トルエンを減圧留去して、無色透明なオイル状(25℃における粘度:330mPa・s)のエポキシシリコーン(C-2)169gを得た。
To this, 100 g of organohydrogenpolysiloxane represented by the following formula (13) was added dropwise over 2 hours. After the dropwise addition was completed, the mixture was stirred at 80°C for 3 hours. Toluene was distilled off under reduced pressure to obtain 169 g of epoxy silicone (C-2) in the form of a colorless and transparent oil (viscosity at 25° C.: 330 mPa·s).
[合成例5]
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、1,2-エポキシ-4-ビニルシクロヘキサン(商品名:CEL2000、(株)ダイセル製)82.0g、およびトルエン127g、イソプロピルアルコール39g、六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)0.072g、アセトニトリル0.126gを加え、オイルバスを用いて80℃に加熱した。 [Synthesis example 5]
In a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, 82.0 g of 1,2-epoxy-4-vinylcyclohexane (trade name: CEL2000, manufactured by Daicel Corporation) was added. Then, 127 g of toluene, 39 g of isopropyl alcohol, 0.072 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and 0.126 g of acetonitrile were added, and the mixture was heated to 80 g using an oil bath. heated to ℃.
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、1,2-エポキシ-4-ビニルシクロヘキサン(商品名:CEL2000、(株)ダイセル製)82.0g、およびトルエン127g、イソプロピルアルコール39g、六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)0.072g、アセトニトリル0.126gを加え、オイルバスを用いて80℃に加熱した。 [Synthesis example 5]
In a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, 82.0 g of 1,2-epoxy-4-vinylcyclohexane (trade name: CEL2000, manufactured by Daicel Corporation) was added. Then, 127 g of toluene, 39 g of isopropyl alcohol, 0.072 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and 0.126 g of acetonitrile were added, and the mixture was heated to 80 g using an oil bath. heated to ℃.
これに前記式(7)で表されるオルガノハイドロジェンシロキサン100gを2時間かけて滴下した。滴下終了後、80℃で3時間攪拌した。トルエンを減圧留去して、無色透明なオイル状(25℃における粘度:330mPa・s)のエポキシシリコーン(C-3)169gを得た。
100 g of organohydrogensiloxane represented by the above formula (7) was added dropwise to this over 2 hours. After the dropwise addition was completed, the mixture was stirred at 80°C for 3 hours. Toluene was distilled off under reduced pressure to obtain 169 g of epoxy silicone (C-3) in the form of a colorless and transparent oil (viscosity at 25° C.: 330 mPa·s).
[合成例6]
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、1,2-エポキシ-4-ビニルシクロヘキサン(商品名:CEL2000、(株)ダイセル製)219.3g、トルエン307g、イソプロピルアルコール44g、六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)0.219g、および、アセトニトリル0.219gを加え、オイルバスを用いて80℃に加熱した。 [Synthesis example 6]
In a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, 219.3 g of 1,2-epoxy-4-vinylcyclohexane (trade name: CEL2000, manufactured by Daicel Corporation), Add 307 g of toluene, 44 g of isopropyl alcohol, 0.219 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and 0.219 g of acetonitrile, and use an oil bath. Heated to 80°C.
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、1,2-エポキシ-4-ビニルシクロヘキサン(商品名:CEL2000、(株)ダイセル製)219.3g、トルエン307g、イソプロピルアルコール44g、六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)0.219g、および、アセトニトリル0.219gを加え、オイルバスを用いて80℃に加熱した。 [Synthesis example 6]
In a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, 219.3 g of 1,2-epoxy-4-vinylcyclohexane (trade name: CEL2000, manufactured by Daicel Corporation), Add 307 g of toluene, 44 g of isopropyl alcohol, 0.219 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and 0.219 g of acetonitrile, and use an oil bath. Heated to 80°C.
これに下記式(14)で表されるオルガノハイドロジェンシロキサン160gを1時間かけて滴下した。滴下終了後、75℃で15時間攪拌した。トルエンを減圧留去して、無色透明なオイル状(25℃における粘度:54mPa・s)のエポキシシリコーン(C-4)356gを得た。
160 g of organohydrogensiloxane represented by the following formula (14) was added dropwise to this over 1 hour. After the dropwise addition was completed, the mixture was stirred at 75°C for 15 hours. Toluene was distilled off under reduced pressure to obtain 356 g of epoxy silicone (C-4) in the form of a colorless and transparent oil (viscosity at 25° C.: 54 mPa·s).
[合成例7]
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、1,2-エポキシ-4-ビニルシクロヘキサン(商品名:CEL2000、(株)ダイセル製)190.1g、およびトルエン340gを加え、オイルバスを用いて85℃に加熱した。 [Synthesis example 7]
In a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, 190.1 g of 1,2-epoxy-4-vinylcyclohexane (trade name: CEL2000, manufactured by Daicel Corporation) was added. Then, 340 g of toluene was added thereto, and the mixture was heated to 85° C. using an oil bath.
撹拌装置、冷却管、還流冷却器、滴下ロートおよび温度計を備えた4つ口フラスコに、1,2-エポキシ-4-ビニルシクロヘキサン(商品名:CEL2000、(株)ダイセル製)190.1g、およびトルエン340gを加え、オイルバスを用いて85℃に加熱した。 [Synthesis example 7]
In a four-necked flask equipped with a stirring device, a cooling tube, a reflux condenser, a dropping funnel, and a thermometer, 190.1 g of 1,2-epoxy-4-vinylcyclohexane (trade name: CEL2000, manufactured by Daicel Corporation) was added. Then, 340 g of toluene was added thereto, and the mixture was heated to 85° C. using an oil bath.
これに六塩化白金1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度0.5質量%)を0.204g添加し、攪拌しながら下記式(15)で表されるオルガノハイドロジェンポリシロキサン150gを1時間かけて滴下した。滴下終了後、85℃で5時間攪拌した。トルエンを減圧留去して、無色透明なオイル状(25℃における粘度:16,640mPa・s)のエポキシシリコーン(C-5)304gを得た。
To this was added 0.204 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass), and while stirring, the organohydrogen polyamide expressed by the following formula (15) was added. 150 g of siloxane was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was stirred at 85° C. for 5 hours. Toluene was distilled off under reduced pressure to obtain 304 g of epoxy silicone (C-5) in the form of a colorless and transparent oil (viscosity at 25° C.: 16,640 mPa·s).
[実施例1~5および比較例1,2]
下記に示す各成分を表1に示す組成(質量部)でそれぞれ混合し、光カチオン硬化型シリコーン組成物を調製した。 [Examples 1 to 5 and Comparative Examples 1 and 2]
The components shown below were mixed in the composition (parts by mass) shown in Table 1 to prepare a photo-cationically curable silicone composition.
下記に示す各成分を表1に示す組成(質量部)でそれぞれ混合し、光カチオン硬化型シリコーン組成物を調製した。 [Examples 1 to 5 and Comparative Examples 1 and 2]
The components shown below were mixed in the composition (parts by mass) shown in Table 1 to prepare a photo-cationically curable silicone composition.
(B)成分:
(B-1)下記式で表されるビス[4-n-アルキルフェニル]ヨードニウムヘキサフルオロアンチモン酸塩92質量%、アセトニトリル8質量%の混合物
(B) Component:
(B-1) A mixture of 92% by mass of bis[4-n-alkylphenyl]iodonium hexafluoroantimonate represented by the following formula and 8% by mass of acetonitrile
(B-1)下記式で表されるビス[4-n-アルキルフェニル]ヨードニウムヘキサフルオロアンチモン酸塩92質量%、アセトニトリル8質量%の混合物
(B-1) A mixture of 92% by mass of bis[4-n-alkylphenyl]iodonium hexafluoroantimonate represented by the following formula and 8% by mass of acetonitrile
(C)成分
(C-1)合成例3で得られたエポキシシリコーン
(式中、括弧内のシロキサン単位の配列順は不定である。)
(C) Component (C-1) Epoxy silicone obtained in Synthesis Example 3
(In the formula, the arrangement order of the siloxane units in parentheses is undefined.)
(C-1)合成例3で得られたエポキシシリコーン
実施例1~5および比較例1,2で得られた光カチオン硬化型シリコーン組成物を以下の方法で評価し、結果を表2に示した。
The photocationically curable silicone compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated by the following method, and the results are shown in Table 2.
[屈折率]
光カチオン硬化型シリコーン組成物を(株)アタゴ製デジタル屈折計(型式RX-9000i)を用い、25℃におけるナトリウムのD線を光源とした屈折率(nD25)を測定した。 [Refractive index]
The refractive index (nD25) of the photocation-curable silicone composition was measured using a digital refractometer (model RX-9000i) manufactured by Atago Co., Ltd. at 25° C. using sodium D line as a light source.
光カチオン硬化型シリコーン組成物を(株)アタゴ製デジタル屈折計(型式RX-9000i)を用い、25℃におけるナトリウムのD線を光源とした屈折率(nD25)を測定した。 [Refractive index]
The refractive index (nD25) of the photocation-curable silicone composition was measured using a digital refractometer (model RX-9000i) manufactured by Atago Co., Ltd. at 25° C. using sodium D line as a light source.
[硬さ]
光カチオン硬化型シリコーン組成物に、アイグラフィックス(株)製アイUV電子制御装置(型式UBX0601-01)を用い、波長365nmの紫外光での照射量が18,000mJ/cm2となるように大気中25℃で紫外線を照射し、硬化させた2mm厚の硬化物の硬度について、TypeA硬度をJIS K6253に準拠して測定した。 [Hardness]
The photocation-curable silicone composition was irradiated with ultraviolet light with a wavelength of 365 nm to 18,000 mJ/cm 2 using an i-UV electronic control device (model UBX0601-01) manufactured by i-Graphics Co., Ltd. The Type A hardness of a 2 mm thick cured product that was cured by irradiating ultraviolet rays at 25° C. in the atmosphere was measured in accordance with JIS K6253.
光カチオン硬化型シリコーン組成物に、アイグラフィックス(株)製アイUV電子制御装置(型式UBX0601-01)を用い、波長365nmの紫外光での照射量が18,000mJ/cm2となるように大気中25℃で紫外線を照射し、硬化させた2mm厚の硬化物の硬度について、TypeA硬度をJIS K6253に準拠して測定した。 [Hardness]
The photocation-curable silicone composition was irradiated with ultraviolet light with a wavelength of 365 nm to 18,000 mJ/cm 2 using an i-UV electronic control device (model UBX0601-01) manufactured by i-Graphics Co., Ltd. The Type A hardness of a 2 mm thick cured product that was cured by irradiating ultraviolet rays at 25° C. in the atmosphere was measured in accordance with JIS K6253.
[引張強さ]
上記硬さ試験と同様の条件で作製した2mm厚の硬化物について、東陽精機(株)製ストログラフ(型式VG1-E)を用い23℃で引張方向の力に対する最大破断力を測定した。 [Tensile strength]
For a 2 mm thick cured product produced under the same conditions as the hardness test above, the maximum breaking force against force in the tensile direction was measured at 23° C. using a Strograph (model VG1-E) manufactured by Toyo Seiki Co., Ltd.
上記硬さ試験と同様の条件で作製した2mm厚の硬化物について、東陽精機(株)製ストログラフ(型式VG1-E)を用い23℃で引張方向の力に対する最大破断力を測定した。 [Tensile strength]
For a 2 mm thick cured product produced under the same conditions as the hardness test above, the maximum breaking force against force in the tensile direction was measured at 23° C. using a Strograph (model VG1-E) manufactured by Toyo Seiki Co., Ltd.
表2に示されるように、本発明の光カチオン硬化型シリコーン組成物を用いた実施例1~5では、得られた硬化物は高屈折率であり、硬化物の硬さ、強度に優れる。一方、(A)成分をフェニル基の含有率が低く、長鎖のエポキシシリコーン(C-1)に変更した比較例1では硬さおよび引張強さが劣っていた。また、(A)成分をフェニル基を有しないエポキシシリコーン(C-2)に変更した比較例2では引張強さが劣っていた。
As shown in Table 2, in Examples 1 to 5 using the photocationically curable silicone composition of the present invention, the obtained cured products had a high refractive index and were excellent in hardness and strength. On the other hand, in Comparative Example 1, in which component (A) was changed to a long-chain epoxy silicone (C-1) with a low content of phenyl groups, the hardness and tensile strength were poor. Furthermore, in Comparative Example 2 in which component (A) was changed to epoxy silicone (C-2) having no phenyl group, the tensile strength was poor.
本明細書は、以下の発明を包含する。
This specification includes the following inventions.
[1]:光カチオン硬化型シリコーン組成物であって、(A)下記一般式(1)で表されるエポキシシリコーン
(式中、Meはメチル基であり、Phはフェニル基であり、REは、それぞれ独立に、炭素原子数2~16のエポキシ基を含有する1価の置換基であり、R1は、それぞれ独立に、脂肪族不飽和結合を有しない、置換又は非置換の炭素原子数1~12の1価炭化水素基であり、R2は、それぞれ独立に、メチル基又はフェニル基であり、R3は、それぞれ独立に、置換又は非置換の炭素原子数1~5の2価炭化水素基又は酸素原子であり、hは1~10の整数であり、iは0~10の整数であり、jは0~10の整数であり、kは1~100の整数である。hおよびiが付された括弧内のシロキサン単位の配列は任意である。)、及び(B)光カチオン重合開始剤を含有するものであり、前記(A)成分中のケイ素原子に結合したフェニル基の含有量が、前記(A)成分中のケイ素原子に結合した1価の置換基の合計数に対して40モル%以上であることを特徴とする光カチオン硬化型シリコーン組成物。
[1]: A photo-cationically curable silicone composition, in which (A) an epoxy silicone represented by the following general formula (1)
(In the formula, Me is a methyl group, Ph is a phenyl group, R E is each independently a monovalent substituent containing an epoxy group having 2 to 16 carbon atoms, and R 1 is each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms without an aliphatic unsaturated bond; R 2 is each independently a methyl group or a phenyl group; 3 is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 5 carbon atoms or an oxygen atom, h is an integer of 1 to 10, i is an integer of 0 to 10, j is an integer of 0 to 10, k is an integer of 1 to 100. The arrangement of the siloxane units in the parentheses with h and i is arbitrary.), and (B) a photocationic polymerization initiator and the content of phenyl groups bonded to silicon atoms in component (A) is 40% relative to the total number of monovalent substituents bonded to silicon atoms in component (A). 1. A photocationically curable silicone composition characterized in that the cationic photocurable silicone composition is mol% or more.
[2]:前記一般式(1)において、R2がフェニル基であり、R3が炭素原子数1~3のアルキレン基であり、iが0であり、jが1であり、kが1であることを特徴とする上記[1]に記載の光カチオン硬化型シリコーン組成物。
[2]: In the general formula (1), R 2 is a phenyl group, R 3 is an alkylene group having 1 to 3 carbon atoms, i is 0, j is 1, and k is 1 The photocationically curable silicone composition according to item [1] above.
[3]:更に、(C)前記(A)成分以外のエポキシシリコーンを含有するものであることを特徴とする上記[1]又は上記[2]に記載の光カチオン硬化型シリコーン組成物。
[3]: The photocationically curable silicone composition as described in [1] or [2] above, further comprising (C) an epoxy silicone other than the component (A).
[4]:上記[1]、上記[2]、又は上記[3]に記載の光カチオン硬化型シリコーン組成物の硬化物であることを特徴とするシリコーン硬化物。
[4]: A cured silicone product, which is a cured product of the photocationically curable silicone composition described in [1], [2], or [3] above.
[5]:上記[4]に記載のシリコーン硬化物を有するものであることを特徴とする光デバイス。
[5]: An optical device comprising the cured silicone product described in [4] above.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。
Note that the present invention is not limited to the above embodiments. The above-mentioned embodiments are illustrative, and any embodiment that has substantially the same configuration as the technical idea stated in the claims of the present invention and has similar effects is the present invention. covered within the technical scope of.
Claims (5)
- 光カチオン硬化型シリコーン組成物であって、
(A)下記一般式(1)で表されるエポキシシリコーン
(B)光カチオン重合開始剤
を含有するものであり、
前記(A)成分中のケイ素原子に結合したフェニル基の含有量が、前記(A)成分中のケイ素原子に結合した1価の置換基の合計数に対して40モル%以上であることを特徴とする光カチオン硬化型シリコーン組成物。 A photocationically curable silicone composition, comprising:
(A) Epoxy silicone represented by the following general formula (1)
The content of phenyl groups bonded to silicon atoms in component (A) is 40 mol% or more based on the total number of monovalent substituents bonded to silicon atoms in component (A). A photo-cationically curable silicone composition. - 前記一般式(1)において、R2がフェニル基であり、R3が炭素原子数1~3のアルキレン基であり、iが0であり、jが1であり、kが1であることを特徴とする請求項1に記載の光カチオン硬化型シリコーン組成物。 In the general formula (1), R 2 is a phenyl group, R 3 is an alkylene group having 1 to 3 carbon atoms, i is 0, j is 1, and k is 1. The photocationically curable silicone composition according to claim 1.
- 更に、(C)前記(A)成分以外のエポキシシリコーンを含有するものであることを特徴とする請求項1に記載の光カチオン硬化型シリコーン組成物。 The photo-cationically curable silicone composition according to claim 1, further comprising (C) an epoxy silicone other than the component (A).
- 請求項1から請求項3のいずれか一項に記載の光カチオン硬化型シリコーン組成物の硬化物であることを特徴とするシリコーン硬化物。 A cured silicone product, which is a cured product of the photocationically curable silicone composition according to any one of claims 1 to 3.
- 請求項4に記載のシリコーン硬化物を有するものであることを特徴とする光デバイス。 An optical device comprising the cured silicone product according to claim 4.
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2007100005A (en) * | 2005-10-07 | 2007-04-19 | Shin Etsu Chem Co Ltd | Light curable coating composition for forming rigid protecting film and article |
JP2012001668A (en) * | 2010-06-18 | 2012-01-05 | Shin-Etsu Chemical Co Ltd | Silphenylene-containing photocurable composition, method for forming pattern using the same, and optical semiconductor element obtained using the method |
WO2012117929A1 (en) * | 2011-02-28 | 2012-09-07 | 新日鐵化学株式会社 | Epoxy silicone resin and hardening resin composition using same |
JP2017508008A (en) * | 2014-01-28 | 2017-03-23 | エルジー・ケム・リミテッド | Cured body |
WO2021127246A1 (en) * | 2019-12-18 | 2021-06-24 | Dow Silicones Corporation | Curable silicone composition and cured product thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2007100005A (en) * | 2005-10-07 | 2007-04-19 | Shin Etsu Chem Co Ltd | Light curable coating composition for forming rigid protecting film and article |
JP2012001668A (en) * | 2010-06-18 | 2012-01-05 | Shin-Etsu Chemical Co Ltd | Silphenylene-containing photocurable composition, method for forming pattern using the same, and optical semiconductor element obtained using the method |
WO2012117929A1 (en) * | 2011-02-28 | 2012-09-07 | 新日鐵化学株式会社 | Epoxy silicone resin and hardening resin composition using same |
JP2017508008A (en) * | 2014-01-28 | 2017-03-23 | エルジー・ケム・リミテッド | Cured body |
WO2021127246A1 (en) * | 2019-12-18 | 2021-06-24 | Dow Silicones Corporation | Curable silicone composition and cured product thereof |
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