WO2015083446A1 - Composition de résine de silicone de type durcissement par réaction d'addition, résine de silicone durcie de type durcissement par réaction d'addition, et élément photo-semi-conducteur étanche - Google Patents
Composition de résine de silicone de type durcissement par réaction d'addition, résine de silicone durcie de type durcissement par réaction d'addition, et élément photo-semi-conducteur étanche Download PDFInfo
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- WO2015083446A1 WO2015083446A1 PCT/JP2014/077513 JP2014077513W WO2015083446A1 WO 2015083446 A1 WO2015083446 A1 WO 2015083446A1 JP 2014077513 W JP2014077513 W JP 2014077513W WO 2015083446 A1 WO2015083446 A1 WO 2015083446A1
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- WIPO (PCT)
- Prior art keywords
- group
- silicone resin
- addition
- formula
- curable silicone
- Prior art date
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- 229920002050 silicone resin Polymers 0.000 title claims abstract description 128
- 239000011342 resin composition Substances 0.000 title claims abstract description 66
- 238000013006 addition curing Methods 0.000 title abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 125000003118 aryl group Chemical group 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 20
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 74
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 24
- 230000003287 optical effect Effects 0.000 claims description 17
- 239000004065 semiconductor Substances 0.000 claims description 15
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 10
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- 239000007809 chemical reaction catalyst Substances 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 4
- 238000003860 storage Methods 0.000 abstract description 11
- 239000002318 adhesion promoter Substances 0.000 abstract description 6
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 abstract 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 abstract 2
- -1 addition curing type Chemical compound 0.000 description 65
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 25
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- 239000000463 material Substances 0.000 description 13
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- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 description 5
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- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000004980 phosphorus peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011995 wilkinson's catalyst Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Definitions
- the present invention relates to an addition-curable silicone resin composition excellent in interfacial adhesion, storage stability, and transparency. Moreover, this invention relates to the addition curable silicone resin hardened
- a transparent resin is used as a sealing material for light emitting elements.
- the transparent resin include epoxy resins and silicone resins such as addition curing type, condensation curing type, and UV curing type.
- addition-curable silicone resins are white because a by-product is not generated by a hydrosilylation reaction between a vinylsilyl group and a hydrosilyl group, and a cured product having excellent characteristics such as weather resistance and heat resistance is formed. It is used for sealing materials for high-luminance and high-power optical semiconductor elements such as LEDs.
- these addition-curable silicone resins have low adhesion to semiconductor material components.
- PCT poly (1,4- Cyclohexyldimethylene terephthalate
- PCT poly (1,4- Cyclohexyldimethylene terephthalate
- the adhesiveness is also insufficient for noble metals such as silver which are widely used as electrodes.
- the adhesiveness is lowered due to heat generation from the light emitting element and temperature cycle, and peeling is likely to occur between the base material such as PCT or the noble metal electrode and the silicone resin.
- Patent Document 1 discloses an addition-curable silicone resin composition containing an isocyanuric acid ester having an epoxy group as an adhesion-imparting agent
- Patent Document 2 discloses an adhesive silicone resin.
- a reactive modified silicone resin containing a vinyl group and a carbamate group in the same molecule and having an alkoxy group or an OH group bonded to a silicon atom at the end of the molecule is disclosed.
- the method of blending an isocyanuric acid ester as disclosed in Patent Document 1 is not sufficient in improving the adhesion to the substrate. Furthermore, since isocyanuric acid esters are not easily compatible with silicone resins, transparency may not be sufficiently obtained. Moreover, since the modified silicone resin as disclosed in Patent Document 2 has a vinyl group imparting curability and a carbamate group imparting adhesiveness in the same molecule, it is uniform throughout the cured resin of the carbamate group. In some cases, the carbamate group concentration in the vicinity of the adhesive interface decreases and the effect of improving the adhesiveness is not sufficient.
- the carbamate group content in the molecule is increased in order to increase the carbamate group concentration in the vicinity of the adhesive interface, the physical properties and durability of the silicone resin may be adversely affected.
- it since it is excellent in the effect of improving the adhesiveness, it may be possible to use a silicone resin containing an alkoxy group or an OH group bonded to a silicon atom, but such a resin has a problem of poor storage stability. there were.
- An object of the present invention is to provide an addition-curable silicone resin composition excellent in interfacial adhesion, storage stability, and transparency. Moreover, an object of this invention is to provide the addition curable silicone resin hardened
- the present invention is an addition curable silicone resin composition
- an addition curable silicone resin mixture comprising an addition curable silicone resin mixture and an adhesion-imparting agent, wherein the addition curable silicone resin mixture has a refractive index of 1.45 to 1.60.
- the adhesion-imparting agent is represented by the following formula (1-3) between the structural unit represented by the following formula (1-1) and the structural unit represented by the following formula (1-2).
- An addition-curable silicone resin composition comprising a structural unit represented by formula (1-4) below and / or a compound having a refractive index of 1.45 to 1.60. .
- R 1a independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
- R 1b independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
- m is an integer of 1 to 50
- n is an integer of 1 to 1500.
- each A is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or the following formula (2): It is a group. However, in formulas (1-1) to (1-3), at least one A is a group represented by formula (2).
- R 2a represents an alkylene group having 1 to 8 carbon atoms in which some of the carbon atoms except for the carbon atom bonded to the silicon atom may be substituted with an oxygen atom
- R 2b represents Each independently represents an alkylene group having 1 to 3 carbon atoms
- each R 3 independently represents an alkylene group having 1 to 3 carbon atoms
- each R 4 independently represents a hydrogen atom or one having 3 to 3 carbon atoms. It represents an alkyl group, an alkyl group having 1 to 3 carbon atoms having an OH group, or a halogeno group.
- x is an integer of 0-2.
- the present inventors blended an addition-curable silicone resin mixture with a compound having a specific structure as an adhesion-imparting agent, and specified a refractive index as the addition-curable silicone resin mixture and the adhesion-imparting agent. It was found that an addition curable silicone resin composition having extremely excellent interfacial adhesiveness, storage stability, and transparency can be obtained by using a material in the above range, and the present invention has been completed.
- FIGS. 1A and 1B show a case where a conventional addition-curable silicone resin composition is used, and a conventional addition-curable silicone resin composition of the present invention is used.
- FIGS. 1A and 1B show a case where the adherend 1 is bonded with a conventional addition-curable silicone resin composition having poor interfacial adhesion to the adherend 1, the addition-curable silicone resin is cured. Interfacial destruction occurs at the interface between the object 2 and the adherend 1.
- FIG. 1A and 1B shows a case where the adherend 1 is bonded with a conventional addition-curable silicone resin composition having poor interfacial adhesion to the adherend 1.
- the addition-curable silicone resin composition of the present invention includes, as an adhesiveness-imparting agent, between the structural unit represented by the formula (1-1) and the structural unit represented by the formula (1-2), A compound having a structural unit represented by the formula (1-3) and / or a structural unit represented by the formula (1-4) and having a refractive index of 1.45 to 1.60 (hereinafter referred to as “ It is also referred to as “adhesion imparting agent according to the present invention”.
- the structural units represented by the formulas (1-1) and (1-2) mean the molecular ends.
- the adhesiveness imparting agent according to the present invention may be a block copolymer or a random copolymer.
- the adhesiveness imparting agent according to the present invention exhibits a sufficient effect only by blending a small amount. This is because the adhesion-imparting agent according to the present invention does not contain a functional group having curability such as a vinyl group in its molecular structure, and thus gradually during the curing reaction of the addition-curable silicone resin composition. This is considered to be due to segregation at the adhesive interface with the substrate and increase in the concentration of the adhesion-imparting agent according to the present invention at the adhesive interface. Moreover, since the adhesiveness imparting agent according to the present invention does not contain an alkoxy group or OH group bonded to a silicon atom in its molecular structure, it has excellent storage stability. The adhesiveness imparting agent according to the present invention may be used alone or in combination of two or more.
- R 1a independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
- “independently” means “may be the same or different”.
- Examples of the alkyl group having 1 to 18 carbon atoms represented by R 1a include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and an n-pentyl group.
- Group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n-nonyl group, n-decyl group, n- A dodecyl group etc. are mentioned. Of these, a methyl group is preferable.
- Examples of the cycloalkyl group represented by R 1a include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a methylcyclohexyl group, and the like.
- Examples of the aryl group represented by R 1a include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group. Of these, a phenyl group is preferred.
- Examples of the aralkyl group represented by R 1a include a benzyl group, an ⁇ -phenethyl group, a ⁇ -phenethyl group, and the like.
- R 1a is preferably an alkyl group having 1 to 18 carbon atoms or an aryl group, and more preferably a methyl group or a phenyl group.
- R 1b independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
- Examples of the alkyl group having 1 to 18 carbon atoms represented by R 1b include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and an n-pentyl group.
- Group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n-nonyl group, n-decyl group, n- A dodecyl group etc. are mentioned. Of these, a methyl group is preferable.
- Examples of the cycloalkyl group represented by R 1b include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.
- Examples of the aryl group represented by R 1b include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group. Of these, a phenyl group is preferred.
- Examples of the aralkyl group represented by R 1b include a benzyl group, an ⁇ -phenethyl group, a ⁇ -phenethyl group, and the like.
- R 1b is preferably an alkyl group having 1 to 18 carbon atoms or an aryl group, and more preferably a methyl group or a phenyl group.
- m is an integer of 1 to 50, preferably an integer of 2 to 45.
- n is an integer of 1 to 1500, preferably an integer of 2 to 1400.
- each R 1b in the repeating unit may be the same or different.
- each A is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or the formula (2). It is a group. However, in formulas (1-1) to (1-3), at least one A is a group represented by formula (2). Examples of the alkyl group having 1 to 18 carbon atoms, the cycloalkyl group, the aryl group, and the aralkyl group represented by A include those similar to R 1a and R 1b , respectively.
- the formula (1-1) and the formula A in (1-2) is preferably a group represented by the formula (2). Further, from the viewpoint of refractive index, R 1b in the formula (1-3) and / or the formula (1-4) preferably has at least one aryl group.
- R 2a represents an alkylene group having 1 to 8 carbon atoms in which some of the carbon atoms excluding the carbon atom bonded to the silicon atom may be substituted with an oxygen atom.
- the alkylene group having 1 to 8 carbon atoms represented by R 2a include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-octylene. And groups in which some carbon atoms of these alkylene groups are substituted with oxygen atoms.
- an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and a group in which some of these alkylene groups are substituted with an oxygen atom are preferable.
- R 2b independently represents an alkylene group having 1 to 3 carbon atoms.
- Examples of the alkylene group having 1 to 3 carbon atoms represented by R 2b include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.
- x in Formula (2) is 2, two R ⁇ 2b> may be the same and may differ.
- each R 3 independently represents an alkylene group having 1 to 3 carbon atoms.
- Examples of the alkylene group having 1 to 3 carbon atoms represented by R 3 include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.
- each R 3 may be the same or different.
- each R 4 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms having an OH group, or a halogeno group.
- the alkyl group having 1 to 3 carbon atoms represented by R 4 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
- the alkyl group having 1 to 3 carbon atoms and having an OH group represented by R 4 include a hydroxymethyl group and a hydroxyethyl group.
- each R 4 may be the same or different.
- x is an integer of 0-2.
- the x is preferably an integer of 0 or 1.
- the case where x is 0 means the case where R 2a and NH group are directly bonded.
- R 3 in the formula (2) is a methylene group and R 4 is each from the viewpoint of compatibility with the addition-curable silicone resin mixture and availability of raw materials. Independently, a hydrogen atom or a hydroxymethyl group is preferable.
- the functional group of the adhesion-imparting agent according to the present invention is a carbamate group (N—CO—O). More specifically, the functional group equivalent of the adhesion-imparting agent is defined by (molecular weight of the adhesion-imparting agent) / (number of moles of carbamate groups), and depends on the ratio of m and n.
- the minimum with a preferable functional group equivalent of the said Formula (2) of the adhesiveness imparting agent concerning this invention is 300, and a preferable upper limit is 15000.
- the adhesive property corresponding to the functional group equivalent of the group represented by the formula (2) is not exhibited, and the formula If the functional group equivalent of (2) exceeds 15000, the resulting addition-curable silicone resin composition may have insufficient adhesion.
- the more preferable lower limit of the functional group equivalent of the formula (2) of the adhesiveness imparting agent according to the present invention is 400, the more preferable upper limit is 12000, the still more preferable lower limit is 500, and the more preferable upper limit is 10,000.
- the refractive index of the adhesiveness imparting agent according to the present invention is 1.45 to 1.60. When the refractive index of the adhesiveness imparting agent according to the present invention is within this range, the transparency of the cured product obtained from the addition-curable silicone resin composition obtained is good.
- the refractive index of the adhesiveness imparting agent according to the present invention is preferably more than 1.45, more preferably 1.46 or more, and further preferably 1.48 or more. Moreover, it is preferable that the refractive index of the adhesiveness imparting agent concerning this invention is 1.58 or less.
- the “refractive index” means a value measured using a digital Abbe refractometer (manufactured by Atago Co., Ltd.) at 25 ° C. and a wavelength of 589 nm.
- Examples of the method for producing the adhesion-imparting agent according to the present invention include, for example, the following formula between a structural unit represented by the following formula (3-1) and a structural unit represented by the following formula (3-2).
- a silicone compound having a structural unit represented by (3-3) and / or a structural unit represented by the following formula (3-4) (hereinafter also referred to as “silicone compound having an amino group”), And a method of reacting the cyclic carbonate compound represented by 4) (hereinafter also simply referred to as “cyclic carbonate compound”).
- R 1a independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
- R 1b independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
- m is an integer of 1 to 50
- n is an integer of 1 to 1500.
- each B independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or the following formula (5). Group.
- at least one B is a group represented by formula (5). Note that the R 1a of the formula (3-1) and (3-2) in R 1a and formula (1-1) and formula (1-2), respectively be the same group, the formula (3-3 ) and a R 1b of the formula (3-4) in the R 1b and formula (1-3) and formula (1-4), respectively at the same group.
- R 3 represents an alkylene group having 1 to 3 carbon atoms
- R 4 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms having an OH group, Or, it represents a halogeno group.
- the R 3 of R 3 and the formula (2) in formula (4) respectively be the same group
- the R 4 in R 4 and equation (2) in formula (4) respectively the same group It becomes.
- R 2a represents an alkylene group having 1 to 8 carbon atoms in which a part of carbon atoms excluding a carbon atom bonded to a silicon atom may be substituted with an oxygen atom
- R 2b represents Independently, it represents an alkylene group having 1 to 3 carbon atoms.
- x is an integer of 0-2.
- two R 2b may be the same or different. Note that the R 2a in the formula (5) in R 2a and Equation (2), respectively be the same group, the R 2b of R 2b and equation (2) in formula (5), respectively the same group It becomes.
- the amino group equivalent of the silicone compound having an amino group corresponds to the functional group equivalent of the adhesiveness-imparting agent according to the present invention.
- the functional group of the adhesiveness imparting agent according to the present invention is a carbamate group (N—CO—O).
- the method for measuring the amino group equivalent of the silicone compound having an amino group include methods such as non-aqueous neutralization titration using perchloric acid. From the value of the amino group equivalent of the silicone compound having an amino group, the number of moles of the carbamate group (N—CO—O) group, which is a functional group contained in the adhesion-imparting agent according to the present invention, that is, the functional group equivalent is Can be calculated.
- Examples of a method for synthesizing the silicone compound having an amino group include dialkoxy having an alkylamino group disclosed in US Pat. No. 3,355,424, US Pat. No. 2,947,771, US Pat. No. 3,890,269, and the like.
- a method using a polycondensation reaction that leads to an alkylsilane unit being inserted into the siloxane chain can be used. This reaction is usually performed in the presence of an acidic or alkaline catalyst. This reaction can also be carried out as a polymerization reaction using dialkoxyalkylsilane and cyclic siloxane.
- silicone compounds having an amino group examples include X-22-1660B-3 and X-22-9409 (both terminal amines, side chain phenyl type) (both are Shin-Etsu Chemical Co., Ltd.). Etc.).
- both terminal amines and side chain phenyl types X-22-1660B-3 (refractive index 1.497), X-22-9409 (refractive index 1.500) (both Shin-Etsu Chemical Co., Ltd.) are preferably used.
- Examples of the cyclic carbonate compound represented by the formula (4) include a compound represented by the following formula (6). Among these, from the viewpoint of ease of reaction and performance, those in which R 3 in the formula (4) is a methylene group are preferable, and ethylene carbonate and glycerol carbonate are more preferable.
- the amount of the cyclic carbonate compound used in the reaction between the silicone compound having an amino group and the cyclic carbonate compound is 0.5 to 10 mol with respect to 1 mol of the amino group of the silicone compound having an amino group. Is preferable, and 0.8 to 5 mol is more preferable.
- the amino group here is an amino group capable of reacting with the cyclic carbonate compound, and specifically, a primary amino group and a secondary amino group.
- the reaction of the silicone compound having an amino group and the cyclic carbonate compound may be performed in the presence of a solvent.
- a solvent a silicone compound having an amino group is easily dissolved and a solvent having an appropriate polarity is preferable, for example, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, dichloromethane, chloroform, diethyl ether, diisopropyl ether, Acetone, ethyl methyl ketone, methyl isobutyl ketone, isopropanol, butanol and the like can be mentioned.
- the reaction between the silicone compound having an amino group and the cyclic carbonate compound is preferably carried out at a temperature within the range of 40 to 180 ° C. depending on the solvent used, but the solvent at a temperature within the range of 80 to 160 ° C. It is more preferable to carry out without using.
- the minimum with preferable content of the adhesiveness imparting agent concerning this invention in the addition-curable silicone resin composition of this invention is 0.01 mass%, and a preferable upper limit is 15 mass%. There exists a possibility that the effect which improves adhesiveness may not fully be exhibited as content of the adhesive provision agent concerning this invention is less than 0.01 mass%.
- the content of the adhesion-imparting agent according to the present invention exceeds 15% by mass, the hardness of the cured product may be adversely affected.
- the more preferable lower limit of the content of the adhesiveness imparting agent according to the present invention is 0.1% by mass, the more preferable upper limit is 10% by mass, the still more preferable lower limit is 0.3% by mass, and the still more preferable upper limit is 5% by mass.
- a preferable minimum is 0.01 mass part and a preferable upper limit is 20 mass parts with respect to 100 mass parts of addition-curable silicone resin mixture. If the blending amount of the adhesion-imparting agent according to the present invention is less than 0.01 parts by mass, the effect of improving the adhesion may not be sufficiently exhibited. When the compounding amount of the adhesion-imparting agent exceeds 20 parts by mass, the hardness of the cured product may be adversely affected.
- the more preferable lower limit of the compounding amount of the adhesiveness imparting agent according to the present invention is 0.1 parts by mass
- the more preferable upper limit is 10 parts by mass
- the still more preferable lower limit is 0.3 parts by mass
- the more preferable upper limit is 5 parts by mass.
- the addition-curable silicone resin composition of the present invention may contain other adhesiveness-imparting agents in addition to the adhesiveness-imparting agent according to the present invention as long as the object of the present invention is not impaired.
- the addition-curable silicone resin composition of the present invention contains an addition-curable silicone resin mixture.
- the addition-curable silicone resin mixture is a mixture containing an addition-curable silicone resin that is cured by a hydrosilylation reaction between a silyl group having a carbon-carbon double bond and a hydrosilyl group.
- the addition-curable silicone resin mixture is a polyorganosiloxane having at least two substituents having a carbon-carbon double bond bonded to a silicon atom (hereinafter also referred to as “carbon-carbon double bond-containing polyorganosiloxane”).
- polyorganohydrogensiloxane having at least two hydrogen atoms bonded to silicon atoms
- hydrosilylation reaction catalyst a polyorganohydrogensiloxane having at least two hydrogen atoms bonded to silicon atoms
- the carbon-carbon double bond-containing polyorganosiloxane and polyorganohydrogensiloxane preferably have an aryl group from the viewpoint of refractive index.
- Examples of the molecular structure of the carbon-carbon double bond-containing polyorganosiloxane include linear and cyclic structures, and the structure may have a branch. Among these, a linear structure in which the main chain is composed of repeating diorganosiloxane units and both ends are blocked with triorganosiloxy groups is preferable.
- the substituent having a carbon-carbon double bond bonded to a silicon atom is preferably one having 2 to 8 carbon atoms, specifically, for example, a vinyl group Allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, acryloyl group, methacryloyl group and the like.
- a vinyl group, an acryloyl group, or a methacryloyl group is preferable, and a vinyl group is more preferable.
- the substituent having a carbon-carbon double bond is bonded to a silicon atom only at either the molecular chain end or the middle. It may be bonded to the silicon atom both at the molecular chain end and in the middle.
- Examples of the organic group bonded to the silicon atom other than the substituent having a carbon-carbon double bond in the carbon-carbon double bond-containing polyorganosiloxane include, for example, methyl group, ethyl group, n-propyl group, n- Alkyl groups having 1 to 12 carbon atoms such as butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, phenyl group, tolyl group, C6-C14 aryl group such as xylyl group and naphthyl group, aralkyl group such as benzyl group, phenethyl group and phenylpropyl group, chloromethyl group, 3-chloropropyl group, bromoethyl group, 3, 3, 3 -An unsubstituted or halogen-substit
- the preferred lower limit of the viscosity of the carbon-carbon double bond-containing polyorganosiloxane is 100 mPa ⁇ s, and the preferred upper limit is 100,000 mPa ⁇ s.
- the viscosity of the carbon-carbon double bond-containing polyorganosiloxane is within this range, the workability of the resulting addition-curable silicone resin composition is good and the addition-curable silicone resin composition is The resulting cured product has good physical properties.
- the more preferable lower limit of the viscosity of the carbon-carbon double bond-containing polyorganosiloxane is 500 mPa ⁇ s, and the more preferable upper limit is 10,000 mPa ⁇ s.
- the “viscosity” means a value measured at 25 ° C. using a rotational viscometer (BM type).
- carbon-carbon double bond-containing polyorganosiloxane examples include, for example, a trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer at both molecular chain terminals, and a trimethylsiloxy group-capped methylvinylpolysiloxane at both molecular chain terminals.
- R 5 examples include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n -C1-C12 alkyl group such as decyl group, C3-C8 cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group, tolyl group, xylyl group, naphthyl group, etc.
- Aryl groups having 6 to 14 carbon atoms such as benzyl group, phenethyl group, phenylpropyl group, chloromethyl group, 3-chloropropyl group, bromoethyl group, 3,3,3-trifluoropropyl group, etc.
- Examples include halogenated alkyl groups.
- R 5 is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group.
- R 6 preferably has 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an acryloyl group, and a methacryloyl group.
- a vinyl group, an acryloyl group, or a methacryloyl group is preferable, and a vinyl group is more preferable.
- the polyorganohydrogensiloxane reacts with the carbon-carbon double bond-containing polyorganosiloxane and acts as a crosslinking component.
- polyorganohydrogensiloxane for example, various polyorganohydrogensiloxanes having a molecular structure such as linear, cyclic, branched, and three-dimensional network structure (resinous) can be used.
- the polyorganohydrogensiloxane has 2 or more, preferably 3 or more, hydrogen atoms bonded to silicon atoms in one molecule, that is, hydrosilyl groups (Si—H groups).
- Si—H groups hydrosilyl groups
- these Si—H groups may be located only in either one of the molecular chain terminal or the middle part, or in both of them. It may be.
- the number (degree of polymerization) of silicon atoms in one molecule of the polyorganohydrogensiloxane is preferably 2 to 1000, and more preferably 3 to 100.
- Examples of the polyorganohydrogensiloxane include R 7 a H b SiO (4-ab / 2) (R 7 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 14 carbon atoms. The number of carbon atoms of R 7 is preferably 1 to 10.
- a and b are 0.7 ⁇ a ⁇ 2.1, 0.001 ⁇ b ⁇ 1.0, and 0.8 ⁇ a + b ⁇ 3.0 is preferable, and a positive number satisfying 1.0 ⁇ a + b ⁇ 2.5 is more preferable).
- R 7 examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n- C1-C12 alkyl groups such as octyl group, n-nonyl group and n-decyl group, C3-C8 cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, phenyl group and tolyl Groups, xylyl groups, naphthyl groups and other aryl groups having 6 to 14 carbon atoms, benzyl groups, phenethyl groups, phenylpropyl groups and other aralkyl groups, vinyl groups, allyl groups and other alkenyl groups, and hydrocarbon groups thereof.
- R 7 is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group.
- the R 7 may be the same hydrocarbon group or different.
- polyorganohydrogensiloxane examples include, for example, molecular chain both-end trimethylsiloxy group-blocked methylhydrogen polysiloxane, molecular chain both-end trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain Both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, Molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane / methylhydrogensiloxane copolymer, (R 5 ) 3 SiO 0.5 (R 5 is as described above) ), A polyorganohydrogensiloxane copolymer comprising a siloxy unit represented by (R 5 ) 2 HSiO 0.5 and a siloxy unit represented by SiO 2 , (R 5 ) 2 HSiO represented by 0.5 Proxy unit polyorganohydrogensiloxane copolymers
- the content of the polyorganohydrogensiloxane is the effective amount of curing of the carbon-carbon double bond-containing polyorganosiloxane.
- the Si—H group of the polyorganohydrogensiloxane contains a carbon-carbon double bond.
- the ratio is preferably 0.1 to 4.0 per substituent having a carbon-carbon double bond in the polyorganosiloxane.
- the number of Si—H groups exceeds 4.0 per substituent having a carbon-carbon double bond, a large amount of unreacted Si—H groups remain in the cured product, so that the physical properties of the cured product are deteriorated over time. May change. More preferably, the number of Si—H groups is 1.0 to 3.0 per substituent having a carbon-carbon double bond.
- platinum group metals such as platinum (including platinum black), rhodium and palladium, H 2 PtCl 4 ⁇ yH 2 O, H 2 PtCl 6 ⁇ yH 2 O, NaHPtCl 6 ⁇ yH 2 O, KHPtCl 6 ⁇ yH 2 O, Na 2 PtCl 6 ⁇ yH 2 O, K 2 PtCl 4 ⁇ yH 2 O, PtCl 4 ⁇ yH 2 O, PtCl 2 , Na 2 HPtCl 4 ⁇ yH 2 O (where, y Is an integer of 0 to 6, preferably an integer of 0 or 6, such as platinum chloride, chloroplatinic acid and chloroplatinate, alcohol-modified chloroplatinic acid (see US Pat.
- platinum group metals such as platinum (including platinum black), rhodium and palladium
- H 2 PtCl 4 ⁇ yH 2 O H 2 PtCl 6 ⁇ yH 2 O
- the content of the hydrosilylation reaction catalyst is not particularly limited as long as it is an effective amount as a catalyst for the hydrosilylation reaction, but is 0.1 to 1000 ppm in terms of a metal element such as platinum in the addition-curable silicone resin mixture. It is preferable that When the content of the hydrosilylation reaction catalyst is within this range, the addition reaction is sufficiently accelerated, so that the resulting addition-curable silicone resin composition can be sufficiently cured and economically. It is advantageous.
- the content of the hydrosilylation reaction catalyst is more preferably 1 to 500 ppm, still more preferably 1 to 20 ppm.
- the addition-curable silicone resin mixture has a refractive index of 1.45 to 1.60. When the refractive index of the addition curable silicone resin mixture is within this range, the transparency of the cured product obtained from the resulting addition curable silicone resin composition becomes good.
- the refractive index of the addition curable silicone resin mixture is preferably more than 1.45, more preferably 1.46 or more, and still more preferably 1.48 or more.
- the refractive index of the addition curable silicone resin mixture is preferably 1.58 or less.
- thermosetting type addition-curable silicone resin mixture known ones can be used, and a two-component thermosetting type is preferable from the viewpoint of availability.
- Commercially available products of the two-component thermosetting type addition-curable silicone resin mixture include, for example, SCR-1011, SCR-1012, SCR-1016, KER-6000, KER-6100, KER-6110, KER- 6200, ASP-1031, ASP-1111, ASP-1120 (all manufactured by Shin-Etsu Chemical Co., Ltd.), OE-6450, OE-6520, OE-6550, OE-6663, OE-6636, OE-6635, OE-6630 OE-6665N, SR7010 (all manufactured by Toray Dow Corning), XE14-C2860, XE14-C3450, and IVS5854 (all manufactured by Momentive Performance Materials).
- the addition-curable silicone resin composition of the present invention contains additives as necessary within the range that does not impair the purpose and effect of the present invention. You may contain.
- the additive examples include an inorganic filler, an antioxidant, an inorganic phosphor, a lubricant, an ultraviolet absorber, a thermal light stabilizer, a dispersant, an antistatic agent, a polymerization inhibitor, an antifoaming agent, a curing accelerator, and a solvent.
- Anti-aging agent radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocking agent, nucleating agent, coupling agent, Examples include conductivity imparting agents, phosphorus peroxide decomposing agents, pigments, metal deactivators, and property modifiers.
- the inorganic filler is not particularly limited, and examples thereof include fine particles that do not deteriorate optical properties. Specific examples include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine powder amorphous silica, hydrophobic ultrafine silica, talc, calcium carbonate, barium sulfate and the like.
- Examples of the inorganic phosphor include yttrium, aluminum, garnet-based YAG phosphor, ZnS phosphor, Y 2 O 2 S phosphor, red light-emitting phosphor, and blue light emission, which are widely used in LEDs. Examples thereof include phosphors and green light emitting phosphors.
- an addition-curable silicone resin composition of the present invention for example, an addition-curable silicone resin mixture, an adhesion-imparting agent according to the present invention, and an additive used as necessary are mixed.
- an addition-curable silicone resin mixture, an adhesion-imparting agent according to the present invention, and an additive used as necessary are mixed.
- the addition-curable silicone resin composition of the present invention can be a one-component type or a two-component type.
- the addition-curable silicone resin composition of the present invention can be used after being applied to a substrate such as an optical semiconductor element and cured.
- Examples of the method for applying the addition-curable silicone resin composition of the present invention to a substrate include a method using a dispenser, a potting method, screen printing, transfer molding, injection molding, and the like.
- the addition-curable silicone resin composition of the present invention can be cured at room temperature or by heating.
- the addition-curable silicone resin cured product obtained by curing the addition-curable silicone resin composition of the present invention is also one aspect of the present invention.
- the final heating temperature when the addition-curable silicone resin composition of the present invention is cured by heating is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 120 to 200 ° C. Preferably, it is 120 to 180 ° C.
- Examples of the use of the addition-curable silicone resin composition of the present invention include a sealing material composition for electronic materials, a sealing agent composition for buildings, a sealing agent composition for automobiles, and an adhesive composition.
- Examples of the electronic material include a lead frame, a wired tape carrier, a wiring board, glass, a support member such as a silicon wafer, an optical semiconductor element, an active element such as a semiconductor chip, a transistor, a diode, and a thyristor, and a capacitor. And passive elements such as resistors and coils. Especially, it can use suitably as a sealing material of an optical semiconductor element.
- the sealed optical semiconductor element sealed with the cured addition-curable silicone resin of the present invention is also one aspect of the present invention.
- the addition-curable silicone resin composition of the present invention is used for display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, semiconductor integrated circuit peripheral materials, etc. Can be used for
- the addition curable silicone resin composition excellent in interfacial adhesiveness, storage stability, and transparency can be provided.
- cured material and optical semiconductor element sealing body which use this addition curable silicone resin composition can be provided.
- 1 (a) to 1 (c) are schematic diagrams showing destruction modes when adherends are bonded using various addition-curable silicone resin compositions.
- the mixture was stirred for 15 hours using a tic stirrer.
- the residual amino group was confirmed to be less than 1% by neutralization titration.
- the reaction liquid is transferred to a 200 mL four-necked flask equipped with a stirrer, a thermometer, and a cooler, 50 g of chlorobenzene and 50 g of water are added to separate the liquid, and the organic layer is concentrated to obtain a transparent liquid (adhesiveness). 4.1 g of imparting agent A) was obtained.
- the adhesion-imparting agent A is a structural unit represented by the formula (1-1) (R 1a is a methyl group, and A is a formula (2).
- R 2a is an n-propylene group, x is 0, R 3 is a methylene group, and R 4 is hydrogen
- the structural unit represented by the formula (1-2) (R 1a is methyl)
- R 2a is an n-propylene group, x is 0, R 3 is a methylene group, and R 4 is hydrogen
- the formula (1-4) And having a structural unit (R 1b is a methyl group, a phenyl group).
- the adhesion-imparting agent B was found to be a structural unit represented by the formula (1-1) (R 1a is a methyl group, A is a formula (2) R 2a is an n-propylene group, x is 0, R 3 is a methylene group, and R 4 is a hydroxymethyl group), and a structural unit (R 1a Is a methyl group, A is a group represented by the formula (2), R 2a is an n-propylene group, x is 0, R 3 is a methylene group, and R 4 is a hydroxymethyl group), and the formula (1- It was confirmed that the structural unit represented by 4) (R 1b is a methyl group, a phenyl group).
- the refractive index of the adhesion-imparting agent B measured in the same manner as the adhesion-imparting agent A was 1.502.
- the adhesion-imparting agent C is a structural unit represented by the formula (1-1) (R 1a is a methyl group, A is a formula (2).
- R 2a is an n-propylene group, x is 0, R 3 is a methylene group, and R 4 is hydrogen), and the structural unit represented by the formula (1-2) (R 1a is methyl) A group represented by the formula (2), R 2a is an n-propylene group, x is 0, R 3 is a methylene group, and R 4 is hydrogen), and the formula (1-4) And having a structural unit (R 1b is a methyl group, a phenyl group).
- the refractive index of the adhesion-imparting agent C measured in the same manner as the adhesion-imparting agent A was 1.509.
- the adhesion-imparting agent D was found to be a structural unit represented by the above formula (1-1) (R 1a is a methyl group, A is a formula (2) R 2a is an n-propylene group, x is 0, R 3 is a methylene group, and R 4 is a hydroxymethyl group), and a structural unit (R 1a Is a methyl group, A is a group represented by the formula (2), R 2a is an n-propylene group, x is 0, R 3 is a methylene group, and R 4 is a hydroxymethyl group), and the formula (1- It was confirmed that the structural unit represented by 4) (R 1b is a methyl group, a phenyl group).
- the refractive index of the adhesion imparting agent D measured in the same manner as the adhesion imparting agent A was 1.508.
- Examples 1 to 9, Comparative Examples 1 to 5 Each component was uniformly mixed with the compounding quantity described in Table 1, and then an addition-curable silicone resin composition was prepared by sufficiently degassing.
- addition-curable silicone resin mixture A-1 in Table 1 liquids A and B (1: 4 mixture) of OE-6630 (manufactured by Dow Corning Toray) were used. OE-6630 is an addition-curable silicone resin mixture having a refractive index of 1.535.
- a liquid and B liquid (3: 7 mixture) of KER-6110 manufactured by Shin-Etsu Chemical Co., Ltd.
- KER-6110 is an addition curable silicone resin mixture having a refractive index of 1.526.
- addition-curable silicone resin mixture C-1 in Table 1 liquid A and liquid B (1: 1 mixture) of KER-6150 (manufactured by Shin-Etsu Chemical Co., Ltd.) were used.
- KER-6150 is an addition curable silicone resin mixture having a refractive index of 1.441.
- adhesion-imparting agent E in Table 1 glycidoxypropyltrimethoxylane (manufactured by Toray Dow Corning, “Z-6040”, refractive index 1.427) is used, and the adhesion-imparting agent F is used. Used is triglycidyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd., and the refractive index cannot be measured because it is solid).
- the obtained adhesion test piece was subjected to a tensile shear adhesion test using a tensile tester (manufactured by Shimadzu Corporation, “AGS-X”) under the conditions of a distance between grips of 100 mm and a test speed of 5 mm / min.
- the adhesive strength was measured.
- the fracture surface after the tensile shear adhesion test was visually observed.
- the fracture mode was FIG. 1 (a) or FIG. 1 (b)
- AF and when the fracture mode was FIG. 1 (c)
- CF The interfacial adhesion was evaluated.
- the obtained adhesion test piece was subjected to a tensile shear adhesion test using a tensile tester (manufactured by Shimadzu Corporation, “AGS-X”) under the conditions of a distance between grips of 100 mm and a test speed of 5 mm / min.
- the adhesive strength was measured.
- the fracture surface after the tensile shear adhesion test was visually observed.
- the fracture mode was FIG. 1 (a) or FIG. 1 (b)
- AF and when the fracture mode was FIG. 1 (c)
- CF The interfacial adhesion was evaluated.
- Example 10 to 18, Comparative Examples 6 to 10 Each component was uniformly mixed with the compounding amount described in Table 2, and then sufficiently deaerated to prepare an addition-curable silicone resin composition.
- a liquid of OE-6630 manufactured by Dow Corning Toray
- B-2 in Table 2 A liquid of KER-6110 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used.
- KER-6150 manufactured by Shin-Etsu Chemical Co., Ltd.
- KER-6150 manufactured by Shin-Etsu Chemical Co., Ltd.
- adhesion-imparting agent E in Table 2 glycidoxypropyltrimethoxylane (manufactured by Toray Dow Corning, “Z-6040”, refractive index 1.427) was used, and the adhesion-imparting agent F was used. Used is triglycidyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd., and the refractive index cannot be measured because it is solid).
- the addition curable silicone resin composition excellent in interfacial adhesiveness, storage stability, and transparency can be provided.
- cured material and optical semiconductor element sealing body which use this addition curable silicone resin composition can be provided.
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Abstract
Le but de la présente invention est de fournir une composition de résine de silicone de type durcissement par réaction d'addition qui est excellente en termes d'adhésion interfaciale, de stabilité au stockage, et de transparence. Un autre but est de fournir une résine de silicone durcie de type durcissement par réaction d'addition et un élément photo-semi-conducteur étanche qui sont obtenus à partir de ou en utilisant la composition de résine de silicone de type durcissement par réaction d'addition. Cette composition de résine de silicone de type durcissement par réaction d'addition comprend un mélange de résine de silicone de type durcissement par réaction d'addition et un promoteur d'adhésion, le mélange de résine de silicone de type durcissement par réaction d'addition ayant un indice de réfraction de 1,45 à 1,60 et le promoteur d'adhésion comprenant un composé ayant un motif structurel représenté par la formule suivante (1-3) et/ou un motif structurel représenté par la formule suivante (1-4) entre un motif structurel représenté par la formule suivante (1-1) et un motif structurel représenté par la formule suivante (1-2) et qui a un indice de réfraction de 1,45 à 1,60. Dans les formules (1-1) et (1-2), les fractions R1a représentent chacune indépendamment un groupe alkyle en C1-18, un groupe cycloalkyle, un groupe aryle, ou un groupe aralkyle. Dans les formules (1-3) et (1-4), les fractions R1b représentent chacune indépendamment un groupe alkyle en C1-18, un groupe cycloalkyle, un groupe aryle, ou un groupe aralkyle. Dans la formule (1-3), m est un nombre entier d'une valeur de 1 à 50. Dans la formule (1-4), n est un nombre entier d'une valeur de 1 à 1500. Dans les formules (1-1) à (1-3), les fractions A sont chacune indépendamment un groupe alkyle en C1-18, un groupe cycloalkyle, un groupe aryle, un groupe aralkyle, ou un groupe représenté par la formule suivante (2), au moins l'une des fractions A dans les formules (1-1) à (1-3) étant un groupe représenté par la formule (2). Dans la formule (2), R2a représente un groupe alkylène en C1-8 dans lequel certains des atomes de carbone à l'exclusion de l'atome de carbone lié à l'atome de silicium peuvent avoir été remplacés par un atome d'oxygène; les fractions R2b représentent chacune indépendamment un groupe alkylène en C1-3; les fractions R3 représentent chacune indépendamment un groupe alkylène en C1-3; et les fractions R4 représentent chacune indépendamment un atome d'hydrogène, un groupe alkyle en C1-3, un groupe alkyle en C1-3 contenant un groupe OH, ou un groupe halogéno. Dans la formule (2), x est un nombre entier d'une valeur allant de 0 à 2.
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