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WO2016017344A1 - Composition de résine de silicone, produit durci de résine de silicone et corps étanche pour élément optique à semi-conducteur - Google Patents

Composition de résine de silicone, produit durci de résine de silicone et corps étanche pour élément optique à semi-conducteur Download PDF

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Publication number
WO2016017344A1
WO2016017344A1 PCT/JP2015/068773 JP2015068773W WO2016017344A1 WO 2016017344 A1 WO2016017344 A1 WO 2016017344A1 JP 2015068773 W JP2015068773 W JP 2015068773W WO 2016017344 A1 WO2016017344 A1 WO 2016017344A1
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Prior art keywords
group
carbon atoms
silicone resin
formula
carbon
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English (en)
Japanese (ja)
Inventor
翔平 眞田
矩章 福田
山本　勝政
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Sumitomo Seika Chemicals Co Ltd
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Sumitomo Seika Chemicals Co Ltd
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Priority to JP2016538227A priority Critical patent/JP6592438B2/ja
Publication of WO2016017344A1 publication Critical patent/WO2016017344A1/fr
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    • 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
    • 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
    • H10W74/00—
    • H10W74/10—
    • H10W74/40—

Definitions

  • the present invention relates to a silicone resin composition that is excellent in interfacial adhesion and moisture and heat resistance. Moreover, this invention relates to the 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. Since these silicone resins form a cured product having excellent properties such as weather resistance and heat resistance, they are used for sealing materials for high-luminance and high-output optical semiconductor elements such as white LEDs. However, these silicone resins generally have a problem of low adhesion to semiconductor material components.
  • PCT poly (1,4- Cyclohexyldimethylene terephthalate
  • PCT does not have a hydrogen-bonding donor in the molecule. Therefore, when a general silicone resin is used as a sealing material, it is sufficiently sufficient for the PCT. Cannot be glued.
  • the silicone resin has insufficient adhesion to noble metals such as silver, which are widely used as electrodes. Furthermore, after adhesion, there is a problem that adhesion is reduced due to heat generation from the light emitting element or temperature cycle, and peeling is likely to occur between a base material such as PCT or a noble metal electrode and the silicone resin.
  • Patent Document 1 discloses a silicone resin composition in which an isocyanuric acid ester having an epoxy group is blended as an adhesiveness imparting agent other than a silane coupling agent.
  • An object of this invention is to provide the silicone resin composition excellent in interfacial adhesiveness and heat-and-moisture resistance. Moreover, an object of this invention is to provide the silicone resin hardened
  • the present invention is a silicone resin composition
  • a silicone resin composition comprising a silicone resin mixture and an adhesion promoter, wherein the adhesion promoter is a structural unit represented by the following formula (1-1) and the following formula (1- 2)
  • the adhesion promoter is a structural unit represented by the following formula (1-1) and the following formula (1- 2)
  • R 1a independently represents a carbon atom of which some carbon atoms except for carbon atoms bonded to silicon atoms may be substituted with oxygen atoms.
  • R 1a alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group having 2 to 9 carbon atoms, (meth) acryloyloxyalkyl group, (meth) acryloyloxy group, or alkoxy group having 1 to 4 carbon atoms Represents.
  • R 1b is each independently a carbon atom of which some carbon atoms except for carbon atoms bonded to silicon atoms may be substituted with oxygen atoms -18 alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group having 2 to 9 carbon atoms, (meth) acryloyloxyalkyl group, (meth) acryloyloxy group, or alkoxy group having 1 to 4 carbon atoms Represents.
  • m is an integer of 1 to 50
  • n is an integer of 1 to 1500.
  • each A independently represents a carbon number of 1 to 18 in which some of the carbon atoms excluding the carbon atom bonded to the silicon atom may be substituted with an oxygen atom.
  • the group represented by Formula (2) is represented. 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 a linear or branched alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or cycloalkyl.
  • x is an integer of 0 to 2
  • Y represents an oxygen atom or NH.
  • the present inventors have found that a silicone resin composition having extremely excellent interfacial adhesiveness and moist heat resistance can be obtained by blending a compound having a specific structure as an adhesion promoter in the silicone resin mixture, The present invention has been completed.
  • the adhesiveness imparting agent according to the present invention exhibits a sufficient effect only by blending a small amount. This is because the adhesiveness imparting agent according to the present invention gradually segregates at the adhesive interface with the substrate during the curing reaction of the silicone resin composition, and the concentration of the adhesiveness imparting agent according to the present invention at the adhesive interface increases. This is thought to be due to
  • the silicone resin composition of the present invention has, as an adhesion-imparting agent, between the structural unit represented by the formula (1-1) and the structural unit represented by the formula (1-2), -3) and / or a compound having the structural unit represented by the formula (1-4) (hereinafter also referred to as “adhesion imparting agent according to the present invention”).
  • the structural unit represented by the formula (1-1), the structural unit represented by the formula (1-3), and other structural units in the structural unit represented by the formula (1-4) An oxygen atom related to the bond to the silicon atom in the other structural unit, the structural unit represented by the formula (1-2), the structural unit represented by the formula (1-3), and the A silicon atom related to a bond with another structural unit in the structural unit represented by the formula (1-4) is bonded to an oxygen atom in the other structural unit.
  • 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 may be used alone or in combination of two or more.
  • R 1a is each independently carbon in which a part of carbon atoms excluding a carbon atom bonded to a silicon atom may be substituted with an oxygen atom.
  • An alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group having 2 to 9 carbon atoms, a (meth) acryloyloxyalkyl group, a (meth) acryloyloxy group, or an alkyl group having 1 to 4 carbon atoms Represents an alkoxy group.
  • Two R 1a in the formula (1-1) in and, the two R 1a in the formula (1-2) in may each be the same or may be different.
  • “independently” means “may be the same or different”.
  • the “(meth) acryloyl” means acryloyl or methacryloyl.
  • 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.
  • 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- Examples include a dodecyl group and a group in which a part of carbon atoms excluding a carbon atom bonded to a silicon atom of these alkyl groups is substituted with an oxygen atom.
  • the alkyl group having 1 to 18 carbon atoms represented by R 1a 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.
  • the cycloalkyl group represented by R 1a may have a substituent.
  • substituents examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, C1-C8 alkyl groups such as tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group And an alkoxy group having 1 to 4 carbon atoms such as an n-butoxy group, a halogeno group such as a fluoro group, a chloro group and a bromo group, and a hydroxy group.
  • 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.
  • the aryl group represented by R 1a may have a substituent. Examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert group.
  • an alkyl group having 1 to 8 carbon atoms such as -butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group
  • Examples thereof include an alkoxy group having 1 to 4 carbon atoms such as an n-butoxy group, a halogeno group such as a fluoro group, a chloro group and a bromo group, and a hydroxy group.
  • the aryl group represented by R 1a is preferably a phenyl group.
  • Examples of the aralkyl group represented by R 1a include a benzyl group, an ⁇ -phenethyl group, a ⁇ -phenethyl group, and the like.
  • the aralkyl group represented by R 1a may have a substituent. Examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert group.
  • An alkyl group having 1 to 8 carbon atoms such as -butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, Examples thereof include an alkoxy group having 1 to 4 carbon atoms such as an n-butoxy group, a halogeno group such as a fluoro group, a chloro group and a bromo group, and a hydroxy group.
  • Examples of the alkenyl group having 2 to 9 carbon atoms represented by R 1a include a vinyl group, an allyl group, and a butenyl group.
  • Examples of the (meth) acryloyloxyalkyl group represented by R 1a include a (meth) acryloyloxymethyl group, a (meth) acryloyloxyethyl group, a (meth) acryloyloxypropyl group, and a (meth) acryloyloxybutyl group. Etc.
  • Examples of the (meth) acryloyloxy group represented by R 1a include an acryloyloxy group and a methacryloyloxy group.
  • Examples of the alkoxy group having 1 to 4 carbon atoms represented by R 1a include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group.
  • 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 is each independently carbon in which a part of carbon atoms excluding a carbon atom bonded to a silicon atom may be substituted with an oxygen atom.
  • An alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group having 2 to 9 carbon atoms, a (meth) acryloyloxyalkyl group, a (meth) acryloyloxy group, or an alkyl group having 1 to 4 carbon atoms Represents an alkoxy group.
  • Two R 1b in the formula (1-4) may be the same or different.
  • each R 1b in each repeating unit may be the same or different.
  • each R 1b in each repeating unit may be the same or different.
  • 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.
  • 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- Examples include a dodecyl group and a group in which a part of carbon atoms excluding a carbon atom bonded to a silicon atom of these alkyl groups is substituted with an oxygen atom.
  • the alkyl group having 1 to 18 carbon atoms represented by R 1b is preferably a methyl group.
  • Examples of the cycloalkyl group represented by R 1b include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.
  • the cycloalkyl group represented by R 1b may have a substituent.
  • substituents examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, C1-C8 alkyl groups such as tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group And an alkoxy group having 1 to 4 carbon atoms such as an n-butoxy group, a halogeno group such as a fluoro group, a chloro group and a bromo group, and a hydroxy 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.
  • the aryl group represented by R 1b may have a substituent. Examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert group.
  • an alkyl group having 1 to 8 carbon atoms such as -butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group
  • Examples thereof include an alkoxy group having 1 to 4 carbon atoms such as an n-butoxy group, a halogeno group such as a fluoro group, a chloro group and a bromo group, and a hydroxy group.
  • the aryl group represented by R 1b is preferably a phenyl group.
  • Examples of the aralkyl group represented by R 1b include a benzyl group, an ⁇ -phenethyl group, a ⁇ -phenethyl group, and the like.
  • the aralkyl group represented by R 1b may have a substituent, and examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert group, An alkyl group having 1 to 8 carbon atoms such as -butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, Examples thereof include an alkoxy group having 1 to 4 carbon atoms such as an n-butoxy group, a halogeno group such as a fluoro group, a chloro
  • Examples of the alkenyl group having 2 to 9 carbon atoms represented by R 1b include a vinyl group, an allyl group, and a butenyl group.
  • Examples of the (meth) acryloyloxyalkyl group represented by R 1b include a (meth) acryloyloxymethyl group, a (meth) acryloyloxyethyl group, a (meth) acryloyloxypropyl group, and a (meth) acryloyloxybutyl group.
  • Examples of the (meth) acryloyloxy group represented by R 1b include an acryloyloxy group and a methacryloyloxy group.
  • Examples of the alkoxy group having 1 to 4 carbon atoms represented by R 1b include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group.
  • R 1b is an alkyl group having 1 to 18 carbon atoms, an aryl group, or 2 to 9 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.
  • An alkenyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 to 18 carbon atoms and an aryl group are more preferable, and a methyl group and a phenyl group are still more preferable.
  • 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 A independently represents a carbon number of 1 to 1 in which some of the carbon atoms excluding the carbon atom bonded to the silicon atom may be substituted with an oxygen atom.
  • the group represented by the formula (2) is represented. However, in formulas (1-1) to (1-3), at least one A is a group represented by formula (2).
  • a part of carbon atoms other than the carbon atom bonded to the silicon atom represented by A may be substituted with an oxygen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, carbon Examples of the alkenyl group having 2 to 9 carbon atoms, (meth) acryloyloxyalkyl group, (meth) acryloyloxy group, and alkoxy group having 1 to 4 carbon atoms are the same as those for R 1a and R 1b , respectively. It is done.
  • each A in each repeating unit may be the same or different.
  • the above formula (1-1) and the above formula ( A in 1-2) is preferably a group represented by the formula (2).
  • 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.
  • alkylene group having 1 to 8 carbon atoms represented by R 2a examples include ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and alkylene thereof.
  • a group in which part of the carbon atoms of the group is substituted with an oxygen atom is preferred.
  • each R 2a in the groups represented by all the formulas (2) is: They may be the same or different.
  • 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.
  • the adhesiveness imparting agent according to the present invention when two or more A are groups represented by the above formula (2) in which x is 1 or more, all the groups represented by the above formula (2). Each R 2b in may be the same or different.
  • each R 3 independently represents a linear or branched alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, a cycloalkyl group, an aryl group, or Represents an aralkyl group.
  • x in Formula (2) is 1 or more, each R 3 may be the same or different.
  • each R 3 in the groups represented by all the formulas (2) is: They may be the same or different.
  • Examples of the linear or branched alkyl group having 1 to 30 carbon atoms represented by R 3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, tert-butyl, n-pentyl, neopentyl, tert-pentyl, n-hexyl, n-heptyl, 2,2,4-trimethylpentyl, n-octyl, isooctyl, n-nonyl N-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl
  • hydrogen atoms may be substituted. Specifically, one or more hydrogen atoms may be substituted with a halogeno group such as a fluoro group, a chloro group, or a bromo group.
  • a halogeno group such as a fluoro group, a chloro group, or a bromo group.
  • Examples of the linear or branched alkyl group having 1 to 30 carbon atoms represented by R 3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n- A hexyl group, n-heptyl group, n-dodecyl group and n-octadecyl group are preferred, and a methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group and n-heptyl group are more preferred.
  • Examples of the alkenyl group having 2 to 7 carbon atoms represented by R 3 include a vinyl group, an allyl group, and a butenyl group. As the alkenyl group having 2 to 7 carbon atoms represented by R 3 , among them, a vinyl group and an allyl group are preferable.
  • Examples of the cycloalkyl group represented by R 3 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.
  • the cycloalkyl group represented by R 3 may have a substituent.
  • the substituent examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, C1-C8 alkyl groups such as tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group And an alkoxy group having 1 to 4 carbon atoms such as an n-butoxy group, a halogeno group such as a fluoro group, a chloro group and a bromo group, and a hydroxy group.
  • the cycloalkyl group represented by R 3 is preferably a cyclopentyl group or a cyclohexyl group, and more preferably a cyclohexyl group.
  • Examples of the aryl group represented by R 3 include a phenyl group, a naphthyl group, and a biphenyl group.
  • the aryl group represented by R 3 may have a substituent.
  • Examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group.
  • aryl group represented by R 3 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • Examples of the aralkyl group represented by R 3 include a benzyl group, an ⁇ -phenethyl group, a ⁇ -phenethyl group, and the like.
  • the aralkyl group represented by R 3 may have a substituent. Examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert group.
  • An alkyl group having 1 to 8 carbon atoms such as -butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, Examples thereof include an alkoxy group having 1 to 4 carbon atoms such as an n-butoxy group, a halogeno group such as a fluoro group, a chloro group and a bromo group, and a hydroxy group.
  • R 3 As the aralkyl group represented by R 3 , among them, a benzyl group and a ⁇ -phenethyl group are preferable.
  • R 3 is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group, and is preferably a linear or branched chain.
  • An alkyl group having 1 to 30 carbon atoms, an aryl group, and an aralkyl group are more preferable.
  • x is an integer of 0 to 2
  • Y represents an oxygen atom or NH.
  • the x is preferably an integer of 0 or 1.
  • the case where x is 0 means the case where R 2a and Y are directly bonded.
  • R 3 in the formula (2) is independently a linear or branched chain from the viewpoint of compatibility with the silicone resin mixture and availability of raw materials.
  • the alkyl group having 1 to 30 carbon atoms, cycloalkyl group, aryl group or aralkyl group is preferred.
  • the amide group (N—C ⁇ O) or the ester group (O—C ⁇ O) contained in the formula (2) is defined as “the adhesiveness imparting agent according to the present invention. It is called “functional group”. More specifically, the functional group equivalent of the adhesion-imparting agent according to the present invention is defined by (molecular weight of adhesion-imparting agent) / (number of moles of amide group or ester group), and depends on the ratio of m to n. It will be.
  • the minimum with a preferable functional group equivalent of the adhesiveness imparting agent concerning this invention is 100, and a preferable upper limit is 12000.
  • the functional group equivalent of the adhesiveness imparting agent according to the present invention is less than 100, the adhesiveness corresponding to the functional group equivalent of the adhesiveness imparting agent according to the present invention is not exhibited, or compatibility with the silicone resin mixture is exhibited. It may be inferior.
  • the functional group equivalent of the adhesiveness imparting agent according to the present invention exceeds 12,000, the resulting silicone resin composition may have insufficient adhesiveness.
  • the more preferable lower limit of the functional group equivalent of the adhesiveness imparting agent according to the present invention is 200, the more preferable upper limit is 9000, the still more preferable lower limit is 300, and the further preferable upper limit is 8000.
  • 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). 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 / or a hydroxy group”) And a method of reacting a compound represented by the following formula (4) or a compound represented by the following formula (5).
  • R 1a independently represents a carbon atom of which some carbon atoms other than the carbon atom bonded to the silicon atom may be substituted with an oxygen atom.
  • R 1b independently represents a carbon atom of which some carbon atoms except for carbon atoms bonded to silicon atoms may be substituted with oxygen atoms.
  • each B independently represents a carbon number of 1 to 18 in which some of the carbon atoms except for the carbon atom bonded to the silicon atom may be substituted with an oxygen atom.
  • at least one B is a group represented by formula (6).
  • R 1a of the formula (3-1) and (3-2) in R 1a and formula (1-1) and formula (1-2) are each the same It becomes group
  • R 1b of the formula (3-3) and (3-4) in the R 1b and formula (1-3) and formula (1-4) is respectively the same groups.
  • R 3 represents a linear or branched alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group
  • Z represents a hydroxy group, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms.
  • R 3 represents a linear or branched alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
  • R ⁇ 3 > in Formula (5) and R ⁇ 3 > in Formula (2) become the same group.
  • R 2a represents an alkylene group having 1 to 8 carbon atoms in which a part of carbon atoms excluding the carbon atom bonded to the 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 to 2
  • Y represents an oxygen atom or NH.
  • the amino group equivalent and / or hydroxy group equivalent of the silicone compound having an amino group and / or hydroxy group corresponds to the functional group equivalent of the adhesion-imparting agent according to the present invention.
  • the functional group of the adhesiveness imparting agent according to the present invention is an amide group (N—C ⁇ O) in the case of producing an adhesiveness imparting agent using a silicone compound having an amino group as a raw material.
  • a silicone compound having a group is used as a raw material, it is an ester group (O—C ⁇ O).
  • Examples of 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.
  • the hydroxy group equivalent of the silicone compound having a hydroxy group can be calculated from the hydroxyl value of the silicone compound having a hydroxy group.
  • Examples of the method for determining the hydroxyl value of the silicone compound having a hydroxy group include the method described in JIS K 5601-2-1.
  • 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, etc.
  • 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 carried out 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.
  • polyorganosiloxane having a silicon atom-bonded hydrogen atom and an organic compound having an aliphatic unsaturated hydrocarbon group disclosed in Japanese Patent Application Laid-Open No. 04-88024 are disclosed.
  • a method of adding a silicon compound in the presence of a platinum-based catalyst can be used. In this method, first, polyorganosiloxane having a silicon atom-bonded hydrogen atom is added to an organosilicon compound having an aliphatic unsaturated hydrocarbon group by hydrosilylation using a platinum-based catalyst.
  • the trialkylsilyl group at the molecular chain end of the polyorganosiloxane produced by the addition reaction is removed by desilylation, and the molecular chain terminal is converted to a hydroxy group to obtain a hydroxy group-containing polyorganosiloxane.
  • silicone compounds having an amino group examples include KF-864, KF-865, KF-868 (monoamine type), KF-859, KF-393, KF-860, KF-880.
  • silicone compounds having a hydroxy group examples include X-22-4039, X-22-4015 (side chain carbinol type), X-22-160AS, KF-6001, KF- 6002, KF-6003 (both ends carbinol type), X-22-170BX, X-22-170DX (single end carbinol type) (all manufactured by Shin-Etsu Chemical Co., Ltd.), SF8428 (side chain carbinol type), SF8427, BY16-201, BY16-004 (both ends carbinol type) (all manufactured by Toray Dow Corning) and the like.
  • R 3 is a linear or branched alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, a cycloalkyl group, an aryl group, or Represents an aralkyl group.
  • a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group are preferable, and a linear or branched alkyl group having 1 to 30 carbon atoms and an aryl group are preferable.
  • Group and aralkyl group are more preferred.
  • Z represents a hydroxy group, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms.
  • the halogen atom represented by Z in the formula (4) include a chlorine atom and a bromine atom.
  • a chlorine atom is preferable.
  • the alkoxy group having 1 to 4 carbon atoms represented by Z in the formula (4) include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group.
  • Z in the formula (4) is preferably a hydroxy group, a chlorine atom or an alkoxy group having 1 to 4 carbon atoms, more preferably a hydroxy group, a chlorine atom, a methoxy group or an ethoxy group.
  • the compound represented by the formula (4) or the compound represented by the formula (5) is not particularly limited, but preferably acetic acid, propionic acid, acrylic acid, butanoic acid, 3-methylbutanoic acid, 3-butene Acid, methacrylic acid, pentanoic acid, 2-methylpentanoic acid, 4-methylpentanoic acid, 2,2-dimethylpentanoic acid, nonafluoropentanoic acid, 2-propylpentanoic acid, 5-phenylpentanoic acid, 4-pentenoic acid, 2-methyl-4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, hexanoic acid, 2-methylhexanoic acid, 5-methylhexanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid , 6-phenylhexanoic acid, undecafluorohexanoic acid, 5-hexenoic acid, heptanoic acid
  • the amount of the compound represented by the formula (5) is as follows.
  • x in the formula (6) is 0 and Y is NH
  • the amount of the amino group of the silicone compound having an amino group is 1 mol.
  • 0.8 to 5 mol is preferable, and 0.9 to 3 mol is more preferable.
  • x in the formula (6) is 0 and Y is an oxygen atom, it is preferably 0.8 to 5 mol with respect to 1 mol of the hydroxy group of the silicone compound having a hydroxy group. It is more preferably 0.9 to 3 mol.
  • x in the formula (6) is 1 or 2 and Y is NH, it is preferably 0.8 to 5 moles relative to 1 mole of amino groups of the silicone compound having an amino group. More preferably, it is 9 to 3 mol.
  • x in formula (6) is 1 or 2 and Y is an oxygen atom
  • the amount of O.O is 0. 0 with respect to 1 mol in total of the amino group and hydroxy group of the silicone compound having an amino group and a hydroxy group.
  • the amount is preferably 8 to 5 mol, more preferably 0.9 to 3 mol.
  • the amino group here is an amino group capable of reacting with the compound represented by the formula (4) or the compound represented by the formula (5), and more specifically, a primary amino group and a secondary amino group. It is a group.
  • the reaction of the silicone compound having an amino group and / or a hydroxy group with the compound represented by the formula (4) or the compound represented by the formula (5) may be performed in the presence of a solvent.
  • a solvent As the solvent to be used, the silicone compound having an amino group and / or hydroxy group is easily dissolved, and the silicone compound having the amino group and / or hydroxy group and the compound represented by the formula (4) or the formula (5) ) Is not particularly limited as long as it does not inhibit the reaction with the compound represented by, for example, hexane, heptane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, dichloromethane, chloroform, diethyl ether, diisopropyl ether, Acetone, ethyl methyl ketone, methyl isobutyl ketone and the like can be mentioned.
  • the reaction of the silicone compound having an amino group and / or hydroxy group with the compound represented by the formula (4) or the compound represented by the formula (5) may be performed at ⁇ 20 ° C. or higher depending on the solvent used.
  • the reaction is preferably carried out at a temperature in the range of 150 ° C., but more preferably using a solvent at a temperature in the range of 0 ° C. to 140 ° C.
  • the minimum with preferable content of the adhesiveness imparting agent concerning this invention in the silicone resin composition of this invention is 0.01 mass%, and a preferable upper limit is 15 mass%.
  • a preferable upper limit is 15 mass%.
  • the content of the adhesiveness imparting agent according to the present invention is less than 0.01% by mass, the effect of improving the adhesiveness may not be sufficiently exhibited. If 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 adhesion-imparting agent according to the present invention is 0.05% by mass, the more preferable upper limit is 10% by mass, the still more preferable lower limit is 0.1% by mass, and the still more preferable upper limit is 5% by mass.
  • a preferable minimum is 0.01 mass part with respect to 100 mass parts of silicone resin mixtures, and a preferable upper limit is 20 mass parts. If the content 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. If the content of the adhesion-imparting agent according to the present invention exceeds 20 parts 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 0.05 parts by mass, the more preferable upper limit is 13 parts by mass, the still more preferable lower limit is 0.1 parts by mass, and the still more preferable upper limit is 6 parts by mass. .
  • the silicone resin composition of this invention may contain the other adhesive imparting agent in addition to the adhesive imparting agent concerning this invention.
  • the silicone resin composition of the present invention contains a silicone resin mixture.
  • a silicone resin mixture according to the present invention an addition-curable silicone resin mixture or a condensation-curable silicone resin mixture is mainly used.
  • the addition-curable silicone resin mixture used in the present invention 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”).
  • a polyorganohydrogensiloxane having at least two hydrogen atoms bonded to silicon atoms hereinafter also simply referred to as “polyorganohydrogensiloxane” and a hydrosilylation reaction catalyst.
  • 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 An allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a (meth) acryloyloxyalkyl group, and the like.
  • the substituent having a carbon-carbon double bond bonded to a silicon atom is preferably a vinyl group or a (meth) acryloyloxyalkyl group. More preferred.
  • 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- An alkyl group 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, cyclopentyl group, cyclohexyl group, A cycloalkyl group having 3 to 8 carbon atoms such as cycloheptyl group, an aryl group having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenethyl group, phenylpropyl group, etc.
  • Non-aralkyl groups, halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, bromoethyl group, 3,3,3-trifluoropropyl group, etc. ⁇ can be mentioned monovalent hydrocarbon groups of halogen-substituted.
  • the organic group bonded to the silicon atom other than the substituent having a carbon-carbon double bond is preferably an alkyl group or an aryl group. Groups are more preferred.
  • 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 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.
  • a polyorganosiloxane copolymer comprising a siloxy unit represented by (R 4 ) 2 SiO, and a siloxy unit represented by SiO 2 ; and siloxy units represented by 4) 3 SiO 0.5, and siloxy units represented by (R 4) 2 R 5 SiO 0.5, represented by SiO 2
  • a polyorganosiloxane copolymer consisting of a siloxy unit, a siloxy unit represented by (R 4 ) 2 SiO, a siloxy unit represented by R 4 R 5 SiO, and (R 4 ) And a polyorganosiloxane copolymer composed of a siloxy unit represented by 4 Si 2 R 6 O.
  • These may be used individually by 1 type and may be used in combination of 2 or more type.
  • Examples of the unsubstituted or substituted monovalent hydrocarbon group having no alkenyl group represented by R 4 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n Alkyl groups having 1 to 12 carbon atoms such as -hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group, and 3 to 3 carbon atoms such as cyclopentyl group, cyclohexyl group and cycloheptyl group 8 cycloalkyl groups, aryl groups having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group and naphthyl group, aralkyl groups such as benzyl group, phenethyl group and phenylpropyl group, chloromethyl group, 3
  • the alkenyl group represented by R 5 or a group having an alkenyl group is preferably one having 2 to 8 carbon atoms, for example, vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, (Meth) acryloyloxyalkyl group and the like can be mentioned.
  • a vinyl group and a (meth) acryloyloxyalkyl group are preferable, and a vinyl group is more preferable.
  • Examples of the divalent hydrocarbon group represented by R 6 include a phenylene group, an ethylene group, a hexylene group, and an octylene group. As the divalent hydrocarbon group represented by R 6 , a phenylene group is particularly preferable.
  • Examples of commercially available carbon-carbon double bond-containing polyorganosiloxanes include DMS-V21, DMS-V22, DMS-V25, DMS-V31, DMS-V33, DMS-V35, and DMS-V41.
  • DMS-V42, DMS-V46, DMS-V25R, DMS-V35R dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of molecular chain
  • VDT- 123, VDT 127, VDT-131, VDT-431, VDT-731 trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer
  • PMV-9925 molecular chain both ends dimethylvinylsiloxy group-blocked phenylmethylpol
  • 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).
  • Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 14 carbon atoms represented by R 7 include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl.
  • the unsubstituted or substituted monovalent hydrocarbon group having 1 to 14 carbon atoms represented by R 7 is preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group.
  • the R 7 may be the same hydrocarbon group or different.
  • polyorganohydrogensiloxanes specific examples include blocking of trimethylsiloxy groups at both molecular chains.
  • Methylhydrogenpolysiloxane, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer with both ends of molecular chain trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer
  • molecular chain Both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane
  • Hydrogensiloxane siloxane copolymer, (R 4 ) 2 HSiO A polyorganohydrogensiloxane copolymer consisting of a siloxy unit represented by 0.5 and a siloxy unit represented by SiO 2 , represented by R 4 HSiO siloxy represented by siloxy units and R 4 SiO 1.5 Position or polyorganohydrogensiloxane copolymers comprising a siloxy unit represented by HSiO 1.5 and the like.
  • Specific examples of the polyorganohydrogensiloxane other than the polyorganohydrogensiloxane represented by R 7 a H b SiO (4-ab / 2) include (R 4 ) 3 SiO 0.
  • a siloxy unit represented by (R 4 ) 2 HSiO 0.5 , a siloxy unit represented by (R 4 ) 2 SiO, and R 4 SiO 1.5 A polyorganohydrogensiloxane copolymer comprising a siloxy unit and a siloxy unit represented by (R 4 ) 4 Si 2 R 6 O (R 6 is as described above), (R 4 ) 3 SiO 0.5 A siloxy unit represented by (R 4 ) 2 HSiO 0.5 , a siloxy unit represented by (R 4 ) 2 SiO, a siloxy unit represented by (R 4 ) 2 SiO, and R 5 SiO 1.5 (R 5 Street In a siloxy unit represented, (R 4) 4 Si 2 R 6 O consisting of siloxy units represented by polyorganohydrogensiloxane copolymers, siloxy represented by (R 4) 3 SiO 0.5 A polyorganohydro consisting of a unit, a siloxy unit represented by (R 4 )
  • polyorganohydrogensiloxanes include, for example, DMS-H03, DMS-H11, DMS-H21, DMS-H25, DMS-H31, DMS-H41, (dimethylhydrogen at both ends of molecular chain) Siloxy group-capped dimethylpolysiloxane), HMS-013, HMS-031, HMS-064, HMS-071, HMS-082, HMS-151, HMS-301, HMS-501 (trimethylsiloxy group-capped dimethylsiloxane at both molecular chains) ⁇ Methylhydrogensiloxane copolymer), HMS-991, HMS-992, HMS-993 (trimethylsiloxy group-blocked methylhydrogenpolysiloxane blocked at both molecular chains), HMS-H271 (dimethylhydrogensiloxy group at both ends of molecular chain) Seal Dimethylsiloxane / methylhydrogensiloxane copolymer), HP
  • 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 , Y is an integer of 0 to 6, preferably 0 or 6, and chloroplatinic acid and chloroplatinate, and alcohol-modified chloroplatinic acid (see US Pat.
  • Pt 2 (((CH 2 ⁇ CH) Me 2 Si ) 2 O) 3 , HPt 2 (((CH 2 ⁇ CH) Me 2 Si 2 ) O) 2 , PtCO (CH 2 ⁇ CH (Me) SiO) 4 , Pt (CH 2 ⁇ CH (Me) SiO) 4
  • Platinum group metal catalysts such as a vinyl siloxane complex of platinum such as JP-A-11-152337.
  • 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 silicone resin composition can be sufficiently cured and is economically advantageous. .
  • the content of the hydrosilylation reaction catalyst is more preferably 1 to 500 ppm, still more preferably 1 to 20 ppm.
  • 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.
  • examples of commercially available two-component thermosetting type addition-curable silicone resin mixtures include IVS4312, XE14-C2042, IVS4542, IVS4546, IVS4622, IVS4632, IVS4742, IVS4752, XE14-C2860, XE14-C3450, IVS5854 (all manufactured by Momentive Performance Materials), KER-2500, KER-2500N, KER-2600, KER-2700, KER-6150, KER-6075F, KER-6020F, SCR-1011, SCR -1012, SCR-1016, KER-6000, KER-6100, KER-6110, KER-6200, ASP-1031, ASP-1111, ASP-1120 (Izu Manufactured by Shin-Etsu Chemical Co., Ltd.), OE-6351, OE-6336,
  • the condensation curable silicone resin mixture used in the present invention means a silicone resin that is in a liquid state before being cured and becomes a rubber elastic body by being cured while generating a reaction byproduct.
  • hydrolyzable groups such as alkoxysilyl groups and acetoxysilyl groups exist in the polysiloxane, and these groups are hydrolyzed to silanol groups by moisture in the air, and the silanol groups are condensed with each other. As a result, a stable siloxane bond is formed and crosslinked.
  • condensation-curable silicone resin mixture a generally known one-component type or two-component type can be used.
  • the one-component type include an oxime type, an alcohol type, an acetone type, and an acetic acid type.
  • an alcohol type and an acetone type that do not corrode metal are preferable.
  • the two-component type include an alcohol type and an acetone type.
  • tin, titanium, or an amine compound may be used as a catalyst, if necessary.
  • condensation-curable silicone resin mixtures include, for example, KE-3490, KE-3493, KE-3494, KE-3497, KE-3466, KE-, as one-component condensed acetone types. 3412, KE-3421, KE-3423, KE-3495 (all manufactured by Shin-Etsu Chemical Co., Ltd.), KE-4806-W, KE-4901-W, KE-4920T, KE- 4920, KE-4921-B, KE-4921-W (all manufactured by Shin-Etsu Chemical Co., Ltd.), KE-200, KE-210 (all manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Can be mentioned.
  • the silicone resin composition of the present invention may contain additives as necessary within the range not impairing the purpose and effect of the present invention, in addition to the silicone resin mixture and the adhesiveness imparting agent according to the present invention.
  • 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.
  • the silicone resin composition of the present invention for example, it can be produced by mixing the silicone resin mixture, the adhesiveness imparting agent according to the present invention, and the additive used as necessary. .
  • the silicone resin composition of the present invention can be a one-component type or a two-component type.
  • the 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 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 silicone resin composition of the present invention can be cured at room temperature or by heating.
  • a cured silicone resin obtained by curing the silicone resin composition of the present invention is also one aspect of the present invention.
  • the final heating temperature when the 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., more preferably 120 ° C. More preferably, it is ⁇ 180 ° C.
  • the use of the silicone resin composition of the present invention includes, for example, a sealing material composition for electronic materials, a sealing agent composition for buildings, a sealing agent composition for automobiles, and an adhesive composition.
  • 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.
  • passive elements such as resistors and coils.
  • a sealed optical semiconductor element in which the optical semiconductor element is sealed with the cured silicone resin of the present invention is also one aspect of the present invention.
  • the silicone resin composition of the present invention is used for applications such as 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, and the like. be able to.
  • the silicone resin composition excellent in interfacial adhesiveness and heat-and-moisture resistance can be provided.
  • cured material and optical semiconductor element sealing body which use this silicone resin composition can be provided.
  • 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, Y is NH, and R 3 is a phenyl group), and the structural unit represented by the formula (1-2) (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, Y is NH, and R 3 is a phenyl group), and is represented by the above formula (1-4) It was confirmed that it had a structural unit (R 1b was a methyl group or a phenyl group).
  • the adhesion-imparting agent B was found to be a structural unit represented by the above formula (1-1) (R 1a is a methyl group, and A is R 2a is an n-propylene group, x is 0, Y is NH, and R 3 is a phenyl group), and the structural unit represented by the formula (1-2) (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, Y is NH, and R 3 is a phenyl group), and is represented by the above formula (1-4) It was confirmed that it had a structural unit (R 1b was a methyl group or a phenyl group).
  • 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, Y is NH, and R 3 is a phenethyl group), and the structural unit represented by the formula (1-2) (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, Y is NH, and R 3 is a phenethyl group), and is represented by the above formula (1-4) It was confirmed that it had a structural unit (R 1b was a methyl group or a phenyl group).
  • the adhesion-imparting agent D is 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, Y is NH, and R 3 is a phenethyl group), and the structural unit represented by the formula (1-2) (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, Y is NH, and R 3 is a phenethyl group), and is represented by the above formula (1-4) It was confirmed that it had a structural unit (R 1b was a methyl group or a phenyl group).
  • the adhesion-imparting agent E is a structural unit represented by the formula (1-1) (R 1a is a methyl group, A is a methyl group), The structural unit represented by the formula (1-2) (R 1a is a methyl group, A is a methyl group), the formula (1-3) (R 1b is a methyl group, and A is represented by the formula (2).
  • R 2a is an n-propylene group, x is 0, Y is NH, and R 3 is a phenyl group), and the structural unit represented by the formula (1-4) (R 1b is a methyl group) It was confirmed that it has.
  • Examples 1 to 18, Comparative Examples 1 to 8 Each silicone resin composition was prepared by mixing each component uniformly in the compounding amounts shown in Tables 1 to 3 and then thoroughly degassing.
  • additional-curable silicone resin mixture A in Tables 1 to 3, OE-6630 (manufactured by Dow Corning Toray) A liquid and B liquid (1: 4 mixture) were used.
  • the addition-curable silicone resin mixture A is a mixture containing a polyorganosiloxane component containing a carbon-carbon double bond and a polyorganohydrogensiloxane component.
  • addition-curable silicone resin mixture B in Tables 1 to 3, OE-6370M (manufactured by Dow Corning Toray) A liquid and B liquid (1: 1 mixture) were used.
  • the addition-curable silicone resin mixture B is a mixture containing a polyorganosiloxane component containing a carbon-carbon double bond and a polyorganohydrogensiloxane component.
  • condensation curable silicone resin mixture C a two-component condensation acetone type silicone resin mixture (“KE-200” manufactured by Shin-Etsu Chemical Co., Ltd.) was used.
  • adhesion-imparting agent F in Tables 1 to 3 glycidoxypropyltrimethoxysilane (manufactured by Dow Corning Toray, “Z-6040”) was used, and the adhesion-imparting agents in Tables 1 to 3 were used.
  • G triglycidyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
  • Hardness (Type D, Type A) Each addition-curable silicone resin composition (Examples 1 to 12 and Comparative Examples 1 to 3) containing the addition-curable silicone resin mixture A is poured into a resin mold and heated at 150 ° C. for 2 hours to perform addition-curable silicone. The resin composition was cured. The obtained cured product was released from the mold to obtain a cured product having a radius of 20 mm and a thickness of 6 mm, which was a test piece for hardness measurement. About the obtained test piece for hardness measurement, hardness (type D) was measured using the rubber hardness meter (The product made by ASKER, D type).
  • each addition-curable silicone resin composition (Examples 13 to 15 and Comparative Examples 4 to 6) containing the addition-curable silicone resin mixture B was poured into a resin mold and heated at 150 ° C. for 4 hours to perform addition curing.
  • the type silicone resin composition was cured.
  • the obtained cured product was released from the mold to obtain a cured product having a radius of 20 mm and a thickness of 6 mm, which was a test piece for hardness measurement.
  • the hardness (type A) of the obtained specimen for measuring hardness was measured using a rubber / plastic hardness meter (manufactured by Furusato Seiki Seisakusho, “KR-24A”).
  • each condensation curable silicone resin composition (Examples 16 to 18 and Comparative Examples 7 and 8) containing the condensation curable silicone resin mixture C was poured into a resin mold and allowed to stand at room temperature for 1 week, followed by condensation curing.
  • the type silicone resin composition was cured.
  • the obtained cured product was released from the mold to obtain a cured product having a radius of 20 mm and a thickness of 6 mm, which was a test piece for hardness measurement.
  • the hardness (type A) of the obtained specimen for measuring hardness was measured using a rubber / plastic hardness meter (manufactured by Furusato Seiki Seisakusho, “KR-24A”).
  • the silicone resin compositions obtained in Examples 16 to 18 and Comparative Examples 7 and 8 were allowed to stand for 1 week at room temperature and cured), and were used as tensile shear adhesion test pieces.
  • the silver-plated copper plate that is the adhesive substrate was dried at 150 ° C. for 1 hour.
  • the obtained tensile shear 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. Tensile shear bond strength was measured.
  • Example 1 to 18 and Comparative Examples 1 to 8 were filled in 10 LED packages, and then each silicone resin composition was cured (Examples 1 to 12 and Comparative Examples 1 to 3 were cured by heating at 150 ° C. for 2 hours, and the respective silicone resin compositions obtained in Examples 13 to 15 and Comparative Examples 4 to 6 were 150 ° C. And heated for 4 hours to cure, and each silicone resin composition obtained in Examples 16 to 18 and Comparative Examples 7 and 8 was allowed to stand at room temperature for 1 week to cure), and a humidified reflow test encapsulant was produced. did. Each produced sealing body was allowed to stand in an atmosphere of 85 ° C.
  • each sealed body was immersed in red ink for 24 hours. The state of the sealed body after immersion was visually observed to confirm the presence or absence of peeling or cracks. As an evaluation standard, the case where the red ink penetrates between the LED package and the cured silicone resin was rejected, and the case where the red ink was not penetrated was accepted. “ ⁇ ” if there are 0 failures, “ ⁇ ” if there is 1 failure, “ ⁇ ” if there are 2 to 3 failures, and “ ⁇ ” if there are more than 4 failures. As evaluated.
  • the silicone resin composition excellent in interfacial adhesiveness and heat-and-moisture resistance can be provided.
  • cured material and optical semiconductor element sealing body which use this silicone resin composition can be provided.

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  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
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Abstract

La présente invention a pour objet une composition de résine de silicone ayant d'excellentes adhérence interfaciale et résistance à la chaleur humide et, également, un produit durci de résine de silicone et un corps étanche de dispositif optique à semi-conducteur, qui sont formés à l'aide de ladite composition de résine de silicone. La composition de résine de silicone selon la présente invention contient un mélange de résine de silicone et d'un agent conférant de l'adhérence, l'agent conférant de l'adhérence contenant un composé ayant un motif structural représenté par la formule (1-3) suivante et/ou un motif structural représenté par la formule (1-4) suivante entre un motif structural représenté par la formule (1-1) suivante et un motif structural représenté par la formule (1-2) suivante. Dans les formules (1-1) et (1-2), les R1a représentent chacun indépendamment un groupe alkyle, cycloalkyle, aryle ou aralkyle ayant de 1 à 18 atomes de carbone; un groupe alcényle, (méth)acryloyloxyalkyle ou (méth)acryloyloxy ayant de 2 à 9 atomes de carbone; ou un groupe alcoxy ayant de 1 à 4 atomes de carbone, certains atomes de carbone autres qu'un atome de carbone lié à un atome de silicium pouvant être remplacés par des atomes d'oxygène. Dans les formules (1-3) et (1-4), les R1b représentent chacun indépendamment un groupe alkyle, cycloalkyle, aryle ou aralkyle ayant 1 à 18 atomes de carbone; un groupe alcényle, (méth)acryloyloxyalkyle ou (méth)acryloyloxy ayant 2 à 9 atomes de carbone; ou un groupe alcoxy ayant de 1 à 4 atomes de carbone, certains atomes de carbone autres qu'un atome de carbone lié à un atome de silicium pouvant être remplacés par des atomes d'oxygène. Dans la formule (1-3), m représente un nombre entier de 1 à 50 et dans la formule (1-4), n représente un nombre entier de 1 à 1 500. Dans les formules (1-1) à (1-3), chaque A représente indépendamment un groupe alkyle, cycloalkyle, aryle ou aralkyle ayant 1 à 18 atomes de carbone; un groupe alcényle, (méth)acryloyloxyalkyle ou (méth)acryloyloxy ayant de 2 à 9 atomes de carbone; un groupe alcoxy ayant de 1 à 4 atomes de carbone; ou un groupe représenté par la formule (2) suivante, certains atomes de carbone autres qu'un atome de carbone lié à un atome de silicium pouvant être remplacés par des atomes d'oxygène. Cependant, au moins un A dans les formules (1-1) à (1-3) représente un groupe représenté par la formule (2). Dans la formule (2), R2a représente un groupe alkylène ayant de 1 à 8 atomes de carbone, certains atomes de carbone autres qu'un atome de carbone lié à un atome de silicium pouvant être remplacés par des atomes d'oxygène, les R2b représentent chacun indépendamment un groupe alkylène ayant de 1 à 3 atomes de carbone et les R3 représentent chacun indépendamment un groupe alkyle linéaire ou ramifié ayant de 1 à 30 atomes de carbone; ou un groupe alcényle, cycloalkyle, aryle ou aralkyle ayant de 2 à 7 atomes de carbone. Dans la formule (2), x représente un nombre entier de 0 à 2 et Y représente un atome d'oxygène ou un groupe NH.
PCT/JP2015/068773 2014-07-30 2015-06-30 Composition de résine de silicone, produit durci de résine de silicone et corps étanche pour élément optique à semi-conducteur Ceased WO2016017344A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114450352A (zh) * 2019-10-04 2022-05-06 三键有限公司 导电性树脂组合物

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173789A (ja) * 2008-01-25 2009-08-06 Momentive Performance Materials Inc 光半導体封止用シリコーン組成物及びそれを用いた光半導体装置
JP2011178983A (ja) * 2010-01-26 2011-09-15 Yokohama Rubber Co Ltd:The シリコーン樹脂組成物およびその使用方法、シリコーン樹脂、シリコーン樹脂含有構造体、ならびに光半導体素子封止体
JP2012012434A (ja) * 2010-06-29 2012-01-19 Dow Corning Toray Co Ltd 硬化性オルガノポリシロキサン組成物および光半導体装置
JP2012149131A (ja) * 2011-01-17 2012-08-09 Shin-Etsu Chemical Co Ltd シリコーン樹脂組成物及び当該組成物を使用した光半導体装置
WO2014073341A1 (fr) * 2012-11-09 2014-05-15 住友精化株式会社 Composition de résine de silicone, résine de silicone durcie et élément semi-conducteur optique scellé
WO2015025617A1 (fr) * 2013-08-19 2015-02-26 住友精化株式会社 Composition de résine de silicone à réticulation par addition, produit de durcissement de résine de silicone réticulée par addition, et corps d'étanchéité d'élément semi-conducteur optique
WO2015025577A1 (fr) * 2013-08-20 2015-02-26 住友精化株式会社 Composition de résine de silicone durcissable par condensation, produit durci en résine de silicone durcissable par condensation, et corps de scellement pour élément semi-conducteur optique
WO2015083446A1 (fr) * 2013-12-06 2015-06-11 住友精化株式会社 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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8193295B2 (en) * 2007-08-22 2012-06-05 Sony Chemical & Information Device Corporation Amide group-containing siloxane amine compound
JP2010006956A (ja) * 2008-06-27 2010-01-14 Nof Corp 光半導体封止用熱硬化性樹脂組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173789A (ja) * 2008-01-25 2009-08-06 Momentive Performance Materials Inc 光半導体封止用シリコーン組成物及びそれを用いた光半導体装置
JP2011178983A (ja) * 2010-01-26 2011-09-15 Yokohama Rubber Co Ltd:The シリコーン樹脂組成物およびその使用方法、シリコーン樹脂、シリコーン樹脂含有構造体、ならびに光半導体素子封止体
JP2012012434A (ja) * 2010-06-29 2012-01-19 Dow Corning Toray Co Ltd 硬化性オルガノポリシロキサン組成物および光半導体装置
JP2012149131A (ja) * 2011-01-17 2012-08-09 Shin-Etsu Chemical Co Ltd シリコーン樹脂組成物及び当該組成物を使用した光半導体装置
WO2014073341A1 (fr) * 2012-11-09 2014-05-15 住友精化株式会社 Composition de résine de silicone, résine de silicone durcie et élément semi-conducteur optique scellé
WO2015025617A1 (fr) * 2013-08-19 2015-02-26 住友精化株式会社 Composition de résine de silicone à réticulation par addition, produit de durcissement de résine de silicone réticulée par addition, et corps d'étanchéité d'élément semi-conducteur optique
WO2015025577A1 (fr) * 2013-08-20 2015-02-26 住友精化株式会社 Composition de résine de silicone durcissable par condensation, produit durci en résine de silicone durcissable par condensation, et corps de scellement pour élément semi-conducteur optique
WO2015083446A1 (fr) * 2013-12-06 2015-06-11 住友精化株式会社 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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114450352A (zh) * 2019-10-04 2022-05-06 三键有限公司 导电性树脂组合物
CN114450352B (zh) * 2019-10-04 2023-12-26 三键有限公司 导电性树脂组合物

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