WO2016017344A1 - Silicone resin composition, silicone resin cured product, and optical semiconductor device sealed body - Google Patents

Silicone resin composition, silicone resin cured product, and optical semiconductor device sealed body 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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group
carbon atoms
silicone resin
formula
carbon
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PCT/JP2015/068773
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French (fr)
Japanese (ja)
Inventor
翔平 眞田
矩章 福田
山本　勝政
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住友精化株式会社
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Priority to JP2016538227A priority Critical patent/JP6592438B2/en
Publication of WO2016017344A1 publication Critical patent/WO2016017344A1/en

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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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Abstract

The purpose of the present invention is to provide a silicone resin composition having excellent interfacial adhesion and moist-heat resistance, and also, to provide a silicone resin cured product and an optical semiconductor device sealed body, which are formed using said silicone resin composition. The present invention relates to a silicone resin composition containing a silicone resin mixture and an adhesion-imparting agent, wherein the adhesion-imparting agent contains a compound having a structural unit represented by following formula (1-3) and/or a structural unit represented by following formula (1-4) between a structural unit represented by following formula (1-1) and a structural unit represented by following formula (1-2). In formulae (1-1) and (1-2), R1a each independently represents an alkyl, cycloalkyl, aryl, or aralkyl group having 1-18 carbon atoms; an alkenyl, (meth)acryloyloxyalkyl, or (meth)acryloyloxy group having 2-9 carbon atoms; or an alkoxy group having 1-4 carbon atoms, in which some carbon atoms other than a carbon atom bonded to a silicon atom may be substituted with oxygen atoms. In formulae (1-3) and (1-4), R1b each independently represents an alkyl, cycloalkyl, aryl, or aralkyl group having 1-18 carbon atoms; an alkenyl, (meth)acryloyloxyalkyl, or (meth)acryloyloxy group having 2-9 carbon atoms; or an alkoxy group having 1-4 carbon atoms, in which some carbon atoms other than a carbon atom bonded to a silicon atom may be substituted with oxygen atoms. In formula (1-3), m is an integer from 1 to 50, and in formula (1-4), n is an integer from 1 to 1,500. In formulae (1-1) to (1-3), each A independently represents an alkyl, cycloalkyl, aryl, or aralkyl group having 1-18 carbon atoms; an alkenyl, (meth)acryloyloxyalkyl, or (meth)acryloyloxy group having 2-9 carbon atoms; an alkoxy group having 1-4 carbon atoms; or a group represented by following formula (2), in which some carbon atoms other than a carbon atom bonded to a silicon atom may be substituted with oxygen atoms. However, at least one A in formulae (1-1) to (1-3) is a group represented by formula (2). In formula (2), R2a represents an alkylene group having 1-8 carbon atoms in which some carbon atoms other than a carbon atom bonded to a silicon atom may be substituted with oxygen atoms, R2b each independently represents an alkylene group having 1-3 carbon atoms, and R3 each independently represents a linear or branched alkyl group having 1-30 carbon atoms; or an alkenyl, cycloalkyl, aryl, or aralkyl group having 2-7 carbon atoms. In formula (2), x is an integer from 0 to 2, and Y represents an oxygen atom or an NH group.

Description

シリコーン樹脂組成物、シリコーン樹脂硬化物、及び、光半導体素子封止体Silicone resin composition, cured silicone resin, and sealed optical semiconductor element
本発明は、界面接着性及び耐湿熱性に優れるシリコーン樹脂組成物に関する。また、本発明は、該シリコーン樹脂組成物を用いてなるシリコーン樹脂硬化物及び光半導体素子封止体に関する。 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 | cured material and optical semiconductor element sealing body which use this silicone resin composition.
ＬＥＤや光半導体デバイスにおいて、透明な樹脂が発光素子の封止材料として用いられている。この透明な樹脂としては、エポキシ樹脂や付加硬化型・縮合硬化型・ＵＶ硬化型等のシリコーン樹脂がある。これらのシリコーン樹脂は、耐候性、耐熱性等の特性に優れた硬化物を形成することから、白色ＬＥＤ等の高輝度・高出力の光半導体素子の封止材料用途に使用されている。しかし、これらのシリコーン樹脂は、一般的に、半導体材料の構成部材に対する接着性が低いという問題がある。例えば、近年、リフレクター材料として、耐候性や耐湿性等の長期安定性に課題のあったＰＰＡ（ポリフタルアミド樹脂）に代わって、耐候性や耐湿性に優れたＰＣＴ（ポリ（１，４－シクロヘキシルジメチレンテレフタレート））が採用されているが、ＰＣＴは分子内に水素結合性ドナーを有していないため、封止材料として一般的なシリコーン樹脂を用いた場合、該ＰＣＴに対して充分に接着させることができない。また、シリコーン樹脂は、電極として広く使用されている銀等の貴金属に対しても接着性が不充分である。更に、接着後、発光素子からの発熱や温度サイクルにより接着性が低下し、ＰＣＴ等の基材や貴金属電極とシリコーン樹脂との間で剥離が生じやすいという問題があった。 In LEDs and optical semiconductor devices, a transparent resin is used as a sealing material for light emitting elements. Examples of 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. For example, in recent years, instead of PPA (polyphthalamide resin), which has been a problem in long-term stability such as weather resistance and moisture resistance, as a reflector material, PCT (poly (1,4- Cyclohexyldimethylene terephthalate)) is employed, but 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. In addition, 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.
これらの課題を解決するために、各種のシランカップリング剤等の接着性付与剤の添加により接着性の向上が図られている（例えば、特許文献１）。また、特許文献２には、シランカップリング剤以外の接着性付与剤としてエポキシ基を有するイソシアヌル酸エステルを配合したシリコーン樹脂組成物が開示されている。 In order to solve these problems, the adhesion is improved by the addition of an adhesion-imparting agent such as various silane coupling agents (for example, Patent Document 1). Patent Document 2 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.
特開２０１２－００７１２６号公報JP 2012-007126 A 特開２００６－１３７７９７号公報JP 2006-137797 A
しかしながら、特許文献１に開示されているような各種のシランカップリング剤等の接着性付与剤の添加では、効果が充分ではない。更に、硬度の低下や、シランカップリング剤中のアルコキシシリル基による著しい吸湿によって接着性が低下する等の耐久性に乏しいという欠点を有している。特に、高温・高湿下においてはその接着性の低下は著しい。また、特許文献２に開示されているようなイソシアヌル酸エステルを配合する方法は、基材に対する接着性を向上させる効果が充分ではなく、更に、イソシアヌル酸エステルがシリコーン樹脂に相溶し難いため、透明性が充分に得られないことがあった。 However, the addition of adhesiveness imparting agents such as various silane coupling agents as disclosed in Patent Document 1 is not sufficient in effect. Furthermore, there is a drawback that the durability is poor, such as a decrease in hardness and a decrease in adhesiveness due to significant moisture absorption by the alkoxysilyl group in the silane coupling agent. In particular, the adhesiveness is remarkably lowered at high temperatures and high humidity. In addition, the method of blending an isocyanuric acid ester as disclosed in Patent Document 2 is not sufficient in improving the adhesion to the base material, and further, the isocyanuric acid ester is hardly compatible with the silicone resin. Transparency could not be obtained sufficiently.
本発明は、界面接着性及び耐湿熱性に優れるシリコーン樹脂組成物を提供することを目的とする。また、本発明は、該シリコーン樹脂組成物を用いてなるシリコーン樹脂硬化物及び光半導体素子封止体を提供することを目的とする。 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 | cured material and optical semiconductor element sealing body which use this silicone resin composition.
本発明は、シリコーン樹脂混合物と接着性付与剤とを含有するシリコーン樹脂組成物であって、前記接着性付与剤は、下記式（１－１）で表される構造単位と下記式（１－２）で表される構造単位との間に、下記式（１－３）で表される構造単位及び／又は下記式（１－４）で表される構造単位を有する化合物を含有するシリコーン樹脂組成物である。 The present invention is 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) A silicone resin containing a compound having a structural unit represented by the following formula (1-3) and / or a structural unit represented by the following formula (1-4) between the structural unit represented by 2) It is a composition.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
式（１－１）及び式（１－２）中、Ｒ１ａは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、又は、炭素数１～４のアルコキシ基を表す。式（１－３）及び式（１－４）中、Ｒ１ｂは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、又は、炭素数１～４のアルコキシ基を表す。式（１－３）中、ｍは、１～５０の整数であり、式（１－４）中、ｎは、１～１５００の整数である。式（１－１）～（１－３）中、Ａは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、炭素数１～４のアルコキシ基、又は、下記式（２）で表される基を表す。ただし、式（１－１）～（１－３）中、少なくとも１つのＡは式（２）で表される基である。 In formulas (1-1) and (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. -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. In formulas (1-3) and (1-4), 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. In the formula (1-3), m is an integer of 1 to 50, and in the formula (1-4), n is an integer of 1 to 1500. In formulas (1-1) to (1-3), 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. An alkyl group, 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, an alkoxy group having 1 to 4 carbon atoms, or 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).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
式（２）中、Ｒ２ａは、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～８のアルキレン基を表し、Ｒ２ｂは、それぞれ独立に、炭素数１～３のアルキレン基を表し、Ｒ３は、それぞれ独立に、直鎖状若しくは分岐鎖状の炭素数１～３０のアルキル基、炭素数２～７のアルケニル基、シクロアルキル基、アリール基、又は、アラルキル基を表す。式（２）中、ｘは、０～２の整数であり、Ｙは、酸素原子又はＮＨを表す。
以下に本発明を詳述する。 In the 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, and R 2b represents Each independently represents an alkylene group having 1 to 3 carbon atoms, and 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. Represents a group, an aryl group, or an aralkyl group. In the formula (2), x is an integer of 0 to 2, and Y represents an oxygen atom or NH.
The present invention is described in detail below.
本発明者らは、シリコーン樹脂混合物に接着性付与剤として特定の構造を有する化合物を配合することにより、極めて優れた界面接着性及び耐湿熱性を有するシリコーン樹脂組成物を得ることができることを見出し、本発明を完成させるに至った。 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.
本発明にかかる接着性付与剤は、少量を配合するだけで充分な効果を発揮する。これは、本発明にかかる接着性付与剤が、シリコーン樹脂組成物の硬化反応中、徐々に基材との接着界面に偏析し、接着界面での本発明にかかる接着性付与剤の濃度が高まることによるものであると考えられる。 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
本発明のシリコーン樹脂組成物は、接着性付与剤として前記式（１－１）で表される構造単位と前記式（１－２）で表される構造単位との間に、前記式（１－３）で表される構造単位及び／又は前記式（１－４）で表される構造単位を有する化合物（以下、「本発明にかかる接着性付与剤」ともいう）を含有する。また、前記式（１－１）で表される構造単位、前記式（１－３）で表される構造単位、及び、前記式（１－４）で表される構造単位における他の構造単位との結合に係る酸素原子は、該他の構造単位におけるケイ素原子と結合し、前記式（１－２）で表される構造単位、前記式（１－３）で表される構造単位及び前記式（１－４）で表される構造単位における他の構造単位との結合に係るケイ素原子は、該他の構造単位における酸素原子と結合する。なお、式（１－１）及び式（１－２）で表される構造単位は分子末端を意味する。本発明にかかる接着性付与剤は、ブロック共重合体であってもよいし、ランダム共重合体であってもよい。
本発明にかかる接着性付与剤は、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 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”). In addition, 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.
前記式（１－１）及び前記式（１－２）中、Ｒ１ａは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、又は、炭素数１～４のアルコキシ基を表す。
前記式（１－１）中の２個のＲ１ａ、及び、前記式（１－２）中の２個のＲ１ａは、それぞれ同一であってもよいし、異なっていてもよい。
なお、本明細書において、「それぞれ独立に」とは、「同一であってもよいし、異なっていてもよい」ことを意味する。
また、前記「（メタ）アクリロイル」は、アクリロイル又はメタクリロイルを意味する。 In the formula (1-1) and the formula (1-2), 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.
In the present specification, “independently” means “may be the same or different”.
The “(meth) acryloyl” means acryloyl or methacryloyl.
前記Ｒ１ａで表される炭素数１～１８のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、２，２，４－トリメチルペンチル基、ｎ－オクチル基、イソオクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ドデシル基、及び、これらのアルキル基のケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されてなる基等が挙げられる。前記Ｒ１ａで表される炭素数１～１８のアルキル基としては、なかでも、メチル基が好ましい。 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- 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. As the alkyl group having 1 to 18 carbon atoms represented by R 1a , a methyl group is preferable.
前記Ｒ１ａで表されるシクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、メチルシクロヘキシル基等が挙げられる。また、前記Ｒ１ａで表されるシクロアルキル基は置換基を有していてもよく、該置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の炭素数１～８のアルキル基や、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基等の炭素数１～４のアルコキシ基や、フルオロ基、クロロ基、ブロモ基等のハロゲノ基や、ヒドロキシ基等が挙げられる。 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. Examples of the substituent 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.
前記Ｒ１ａで表されるアリール基としては、例えば、フェニル基、トリル基、キシリル基、エチルフェニル基、ナフチル基等が挙げられる。また、前記Ｒ１ａで表されるアリール基は置換基を有していてもよく、該置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の炭素数１～８のアルキル基や、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基等の炭素数１～４のアルコキシ基や、フルオロ基、クロロ基、ブロモ基等のハロゲノ基や、ヒドロキシ基等が挙げられる。前記Ｒ１ａで表されるアリール基としては、なかでも、フェニル基が好ましい。 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. Among them, the aryl group represented by R 1a is preferably a phenyl group.
前記Ｒ１ａで表されるアラルキル基としては、例えば、ベンジル基、α－フェネチル基、β－フェネチル基等が挙げられる。また、前記Ｒ１ａで表されるアラルキル基は置換基を有していてもよく、該置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の炭素数１～８のアルキル基や、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基等の炭素数１～４のアルコキシ基や、フルオロ基、クロロ基、ブロモ基等のハロゲノ基や、ヒドロキシ基等が挙げられる。 Examples of the aralkyl group represented by R 1a include a benzyl group, an α-phenethyl group, a β-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.
前記Ｒ１ａで表される炭素数２～９のアルケニル基としては、例えば、ビニル基、アリル基、ブテニル基等が挙げられる。 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.
前記Ｒ１ａで表される（メタ）アクリロイルオキシアルキル基としては、例えば、（メタ）アクリロイルオキシメチル基、（メタ）アクリロイルオキシエチル基、（メタ）アクリロイルオキシプロピル基、（メタ）アクリロイルオキシブチル基等が挙げられる。 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.
前記Ｒ１ａで表される（メタ）アクリロイルオキシ基としては、例えば、アクリロイルオキシ基、メタクリロイルオキシ基が挙げられる。 Examples of the (meth) acryloyloxy group represented by R 1a include an acryloyloxy group and a methacryloyloxy group.
前記Ｒ１ａで表される炭素数１～４のアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｎ－ブトキシ基等が挙げられる。 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.
前記Ｒ１ａは、これらの中でも、炭素数１～１８のアルキル基、アリール基が好ましく、メチル基、フェニル基がより好ましい。 Among these, 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.
前記式（１－３）及び前記式（１－４）中、Ｒ１ｂは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、又は、炭素数１～４のアルコキシ基を表す。
前記式（１－４）中の２個のＲ１ｂは、それぞれ同一であってもよいし、異なっていてもよい。また、前記式（１－３）で表される構造単位においてｍが２以上の場合、各繰り返し単位における各Ｒ１ｂは、同一であってもよいし、異なっていてもよい。更に、前記式（１－４）で表される構造単位において、ｎが２以上の場合、各繰り返し単位における各Ｒ１ｂは、同一であってもよいし、異なっていてもよい。 In the formula (1-3) and the formula (1-4), 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. When m is 2 or more in the structural unit represented by the formula (1-3), each R 1b in each repeating unit may be the same or different. Furthermore, in the structural unit represented by the formula (1-4), when n is 2 or more, each R 1b in each repeating unit may be the same or different.
前記Ｒ１ｂで表される炭素数１～１８のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、２，２，４－トリメチルペンチル基、ｎ－オクチル基、イソオクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ドデシル基、及び、これらのアルキル基のケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されてなる基等が挙げられる。前記Ｒ１ｂで表される炭素数１～１８のアルキル基としては、なかでも、メチル基が好ましい。 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- 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.
前記Ｒ１ｂで表されるシクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、メチルシクロヘキシル基等が挙げられる。また、前記Ｒ１ｂで表されるシクロアルキル基は置換基を有していてもよく、該置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の炭素数１～８のアルキル基や、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基等の炭素数１～４のアルコキシ基や、フルオロ基、クロロ基、ブロモ基等のハロゲノ基や、ヒドロキシ基等が挙げられる。 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. Examples of the substituent 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.
前記Ｒ１ｂで表されるアリール基としては、例えば、フェニル基、トリル基、キシリル基、エチルフェニル基、ナフチル基等が挙げられる。また、前記Ｒ１ｂで表されるアリール基は置換基を有していてもよく、該置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の炭素数１～８のアルキル基や、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基等の炭素数１～４のアルコキシ基や、フルオロ基、クロロ基、ブロモ基等のハロゲノ基や、ヒドロキシ基等が挙げられる。前記Ｒ１ｂで表されるアリール基としては、なかでも、フェニル基が好ましい。 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. Among them, the aryl group represented by R 1b is preferably a phenyl group.
前記Ｒ１ｂで表されるアラルキル基としては、例えば、ベンジル基、α－フェネチル基、β－フェネチル基等が挙げられる。また、前記Ｒ１ｂで表されるアラルキル基は置換基を有していてもよく、該置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の炭素数１～８のアルキル基や、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基等の炭素数１～４のアルコキシ基や、フルオロ基、クロロ基、ブロモ基等のハロゲノ基や、ヒドロキシ基等が挙げられる。 Examples of the aralkyl group represented by R 1b include a benzyl group, an α-phenethyl group, a β-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 group and a bromo group, and a hydroxy group.
前記Ｒ１ｂで表される炭素数２～９のアルケニル基としては、例えば、ビニル基、アリル基、ブテニル基等が挙げられる。 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.
前記Ｒ１ｂで表される（メタ）アクリロイルオキシアルキル基としては、例えば、（メタ）アクリロイルオキシメチル基、（メタ）アクリロイルオキシエチル基、（メタ）アクリロイルオキシプロピル基、（メタ）アクリロイルオキシブチル基等が挙げられる。 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. Etc.
前記Ｒ１ｂで表される（メタ）アクリロイルオキシ基としては、例えば、アクリロイルオキシ基、メタクリロイルオキシ基が挙げられる。 Examples of the (meth) acryloyloxy group represented by R 1b include an acryloyloxy group and a methacryloyloxy group.
前記Ｒ１ｂで表される炭素数１～４のアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｎ－ブトキシ基等が挙げられる。 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.
前記Ｒ１ｂは、これらの中でも、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、アリール基、炭素数２～９のアルケニル基、炭素数１～４のアルコキシ基が好ましく、炭素数１～１８のアルキル基、アリール基がより好ましく、メチル基、フェニル基が更に好ましい。 Among these, 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.
前記式（１－３）中、ｍは、１～５０の整数であり、好ましくは２～４５の整数である。前記式（１－４）中、ｎは、１～１５００の整数であり、好ましくは２～１４００の整数である。
本発明にかかる接着性付与剤が前記式（１－３）と前記式（１－４）との両方の構造単位を有する場合、ｍとｎとの比率は、ｍ：ｎ＝１：０．５～１：１６０であることが好ましく、ｍ：ｎ＝１：１～１：１２０であることがより好ましい。 In the formula (1-3), m is an integer of 1 to 50, preferably an integer of 2 to 45. In the formula (1-4), n is an integer of 1 to 1500, preferably an integer of 2 to 1400.
When the adhesiveness imparting agent according to the present invention has both structural units of the above formulas (1-3) and (1-4), the ratio of m to n is m: n = 1: 0. It is preferably 5 to 1: 160, and more preferably m: n = 1: 1 to 1: 120.
前記式（１－１）～（１－３）中、Ａは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、炭素数１～４のアルコキシ基、又は、前記式（２）で表される基を表す。ただし、式（１－１）～（１－３）中、少なくとも１つのＡは式（２）で表される基である。
前記Ａで表されるケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、及び、炭素数１～４のアルコキシ基としては、それぞれ前記Ｒ１ａや前記Ｒ１ｂと同様のものが挙げられる。
前記式（１－３）で表される構造単位においてｍが２以上の場合、各繰り返し単位における各Ａは、同一であってもよいし、異なっていてもよい。 In the formulas (1-1) to (1-3), 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. 18 alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups having 2 to 9 carbon atoms, (meth) acryloyloxyalkyl groups, (meth) acryloyloxy groups, alkoxy groups having 1 to 4 carbon atoms, or 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.
When m is 2 or more in the structural unit represented by the formula (1-3), each A in each repeating unit may be the same or different.
本発明の接着性付与剤が前記式（１－３）で表される構造単位を有さない場合、接着性を向上させる効果に優れること等から、前記式（１－１）及び前記式（１－２）中のＡは、いずれも式（２）で表される基であることが好ましい。 When the adhesiveness imparting agent of the present invention does not have the structural unit represented by the above formula (1-3), the above formula (1-1) and the above formula ( A in 1-2) is preferably a group represented by the formula (2).
前記式（２）中、Ｒ２ａは、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～８のアルキレン基を表す。
前記Ｒ２ａで表される炭素数１～８のアルキレン基としては、例えば、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ペンチレン基、ｎ－へキシレン基、ｎ－オクチレン基、及び、これらのアルキレン基の一部の炭素原子が酸素原子で置換されてなる基等が挙げられる。前記Ｒ２ａで表される炭素数１～８のアルキレン基としては、なかでも、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ペンチレン基、ｎ－へキシレン基、及び、これらのアルキレン基の一部の炭素原子が酸素原子で置換されてなる基が好ましい。
また、本発明にかかる接着性付与剤において、２つ以上のＡが前記式（２）で表される基である場合、全ての前記式（２）で表される基における各Ｒ２ａは、同一であってもよいし、異なっていてもよい。 In 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.
Examples of 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. Examples of the alkylene group having 1 to 8 carbon atoms represented by R 2a 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.
Moreover, in the adhesiveness imparting agent according to the present invention, when two or more A are groups represented by the formula (2), each R 2a in the groups represented by all the formulas (2) is: They may be the same or different.
前記式（２）中、Ｒ２ｂは、それぞれ独立に、炭素数１～３のアルキレン基を表す。
前記Ｒ２ｂで表される炭素数１～３のアルキレン基としては、メチレン基、エチレン基、ｎ－プロピレン基、及び、イソプロピレン基が挙げられる。
なお、式（２）中のｘが２である場合、２つのＲ２ｂは、同一であってもよいし、異なっていてもよい。
また、本発明にかかる接着性付与剤において、２つ以上のＡが、ｘが１以上の前記式（２）で表される基である場合、全ての前記式（２）で表される基における各Ｒ２ｂは、同一であってもよいし、異なっていてもよい。 In the formula (2), 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.
In addition, when x in Formula (2) is 2, two R <2b> may be the same and may differ.
Moreover, in 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.
前記式（２）中、Ｒ３は、それぞれ独立に、直鎖状若しくは分岐鎖状の炭素数１～３０のアルキル基、炭素数２～７のアルケニル基、シクロアルキル基、アリール基、又は、アラルキル基を表す。
なお、式（２）中のｘが１以上である場合、各Ｒ３は、同一であってもよいし、異なっていてもよい。
また、本発明にかかる接着性付与剤において、２つ以上のＡが前記式（２）で表される基である場合、全ての前記式（２）で表される基における各Ｒ３は、同一であってもよいし、異なっていてもよい。 In the formula (2), 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.
In addition, when x in Formula (2) is 1 or more, each R 3 may be the same or different.
Moreover, in the adhesiveness imparting agent according to the present invention, when two or more A are groups represented by the formula (2), each R 3 in the groups represented by all the formulas (2) is: They may be the same or different.
前記Ｒ３で表される直鎖状又は分岐鎖状の炭素数１～３０のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、２，２，４－トリメチルペンチル基、ｎ－オクチル基、イソオクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－ペンタデシル基、ｎ－ヘキサデシル基、ｎ－ヘプタデシル基、ｎ－オクタデシル基、ｎ－ノナデシル基、ｎ－ヘンエイコシル基、ｎ－トリコシル基、ｎ－ペンタコシル基、ｎ－ヘプタコシル基、ｎ－ノナコシル基等が挙げられる。なお、これらのアルキル基は、水素原子が置換されていてもよく、具体的には、１つ以上の水素原子がフルオロ基、クロロ基、ブロモ基等のハロゲノ基で置換されていてもよい。前記Ｒ３で表される直鎖状又は分岐鎖状の炭素数１～３０のアルキル基としては、なかでも、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－ドデシル基、ｎ－オクタデシル基が好ましく、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ヘキシル基、ｎ－ヘプチル基がより好ましい。 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 group, n-nonadecyl group N-heneicosyl group, n-tricosyl group, n-pentacosyl group, n-heptacosyl group, n-nonacosyl group and the like. In these alkyl groups, 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. 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.
前記Ｒ３で表される炭素数２～７のアルケニル基としては、例えば、ビニル基、アリル基、ブテニル基等が挙げられる。前記Ｒ３で表される炭素数２～７のアルケニル基としては、なかでも、ビニル基、アリル基が好ましい。 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.
前記Ｒ３で表されるシクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、メチルシクロヘキシル基等が挙げられる。また、前記Ｒ３で表されるシクロアルキル基は置換基を有していてもよく、該置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の炭素数１～８のアルキル基や、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基等の炭素数１～４のアルコキシ基や、フルオロ基、クロロ基、ブロモ基等のハロゲノ基や、ヒドロキシ基等が挙げられる。前記Ｒ３で表されるシクロアルキル基としては、なかでも、シクロペンチル基、シクロヘキシル基が好ましく、シクロヘキシル基がより好ましい。 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. Examples of the substituent 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. Among them, the cycloalkyl group represented by R 3 is preferably a cyclopentyl group or a cyclohexyl group, and more preferably a cyclohexyl group.
前記Ｒ３で表されるアリール基としては、例えば、フェニル基、ナフチル基、ビフェニル基等が挙げられる。前記Ｒ３で表されるアリール基は置換基を有していてもよく、該置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の炭素数１～８のアルキル基や、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基等の炭素数１～４のアルコキシ基や、フルオロ基、クロロ基、ブロモ基等のハロゲノ基や、ヒドロキシ基等が挙げられる。前記Ｒ３で表されるアリール基としては、なかでも、フェニル基、ナフチル基が好ましく、フェニル基が更に好ましい。 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. Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and other alkyl groups having 1 to 8 carbon atoms, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- Examples thereof include an alkoxy group having 1 to 4 carbon atoms such as a butoxy group, a halogeno group such as a fluoro group, a chloro group and a bromo group, and a hydroxy group. Among them, the aryl group represented by R 3 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
前記Ｒ３で表されるアラルキル基としては、例えば、ベンジル基、α－フェネチル基、β－フェネチル基等が挙げられる。また、前記Ｒ３で表されるアラルキル基は置換基を有していてもよく、該置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の炭素数１～８のアルキル基や、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基等の炭素数１～４のアルコキシ基や、フルオロ基、クロロ基、ブロモ基等のハロゲノ基や、ヒドロキシ基等が挙げられる。前記Ｒ３で表されるアラルキル基としては、なかでも、ベンジル基、β－フェネチル基が好ましい。 Examples of the aralkyl group represented by R 3 include a benzyl group, an α-phenethyl group, a β-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. As the aralkyl group represented by R 3 , among them, a benzyl group and a β-phenethyl group are preferable.
前記Ｒ３は、これらの中でも、それぞれ独立に、直鎖状又は分岐鎖状の炭素数１～３０のアルキル基、シクロアルキル基、アリール基、アラルキル基が好ましく、直鎖状又は分岐鎖状の炭素数１～３０のアルキル基、アリール基、アラルキル基がより好ましい。 Among these, 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.
前記式（２）中、ｘは、０～２の整数であり、Ｙは、酸素原子又はＮＨを表す。
前記ｘは、０又は１の整数であることが好ましい。
なお、ｘが０である場合とは、Ｒ２ａとＹとが直接結合している場合を意味する。 In the formula (2), x is an integer of 0 to 2, and 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.
本発明にかかる接着性付与剤としては、シリコーン樹脂混合物との相溶性や原料の入手性等の観点から、式（２）中のＲ３が、それぞれ独立に、直鎖状若しくは分岐鎖状の炭素数１～３０のアルキル基、シクロアルキル基、アリール基、又は、アラルキル基であるものが好ましい。 As the adhesion-imparting agent according to the present invention, 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.
本発明にかかる接着性付与剤において、前記式（２）中に含まれる、アミド基（Ｎ－Ｃ＝Ｏ）又はエステル基（Ｏ－Ｃ＝Ｏ）を「本発明にかかる接着性付与剤の官能基」という。より詳細には、本発明にかかる接着性付与剤の官能基当量とは、（接着性付与剤の分子量）／（アミド基又はエステル基のモル数）で定義され、ｍとｎの比率に応じたものとなる。 In the adhesiveness imparting agent according to the present invention, 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.
本発明にかかる接着性付与剤の官能基当量の好ましい下限は１００、好ましい上限は１２０００である。本発明にかかる接着性付与剤の官能基当量が１００未満であると、該本発明にかかる接着性付与剤の官能基当量に見合った接着性を示さなかったり、シリコーン樹脂混合物との相溶性に劣るものとなったりするおそれがある。本発明にかかる接着性付与剤の官能基当量が１２０００を超えると、得られるシリコーン樹脂組成物の接着性が不充分となるおそれがある。本発明にかかる接着性付与剤の官能基当量のより好ましい下限は２００、より好ましい上限は９０００、更に好ましい下限は３００、更に好ましい上限は８０００である。 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. When 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. When 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.
本発明にかかる接着性付与剤の製造方法としては、例えば、下記式（３－１）で表される構造単位と下記式（３－２）で表される構造単位との間に、下記式（３－３）で表される構造単位及び／又は下記式（３－４）で表される構造単位を有するシリコーン化合物（以下、「アミノ基及び／又はヒドロキシ基を有するシリコーン化合物」ともいう）と、下記式（４）で表される化合物又は下記式（５）で表される化合物とを反応させる方法等が挙げられる。 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).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
式（３－１）及び式（３－２）中、Ｒ１ａは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、又は、炭素数１～４のアルコキシ基を表す。式（３－３）及び式（３－４）中、Ｒ１ｂは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、又は、炭素数１～４のアルコキシ基を表す。式（３－３）中、ｍは、１～５０の整数であり、式（３－４）中、ｎは、１～１５００の整数である。式（３－１）～（３－３）中、Ｂは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、炭素数１～４のアルコキシ基、又は、下記式（６）で表される基である。ただし、式（３－１）～（３－３）中、少なくとも１つのＢは式（６）で表される基である。
なお、前記製造方法で製造した場合、式（３－１）及び式（３－２）中のＲ１ａと式（１－１）及び式（１－２）中のＲ１ａとは、それぞれ同じ基となり、式（３－３）及び式（３－４）中のＲ１ｂと式（１－３）及び式（１－４）中のＲ１ｂとは、それぞれ同じ基となる。 In formulas (3-1) and (3-2), 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. -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. In formulas (3-3) and (3-4), 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. -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. In the formula (3-3), m is an integer of 1 to 50, and in the formula (3-4), n is an integer of 1 to 1500. In formulas (3-1) to (3-3), 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. An alkyl group, 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, an alkoxy group having 1 to 4 carbon atoms, or It is group represented by Formula (6). However, in formulas (3-1) to (3-3), at least one B is a group represented by formula (6).
Incidentally, the case produced by the production method, and 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, and 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.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
式（４）中、Ｒ３は、直鎖状若しくは分岐鎖状の炭素数１～３０のアルキル基、炭素数２～７のアルケニル基、シクロアルキル基、アリール基、又は、アラルキル基を表し、Ｚは、ヒドロキシ基、ハロゲン原子、又は、炭素数１～４のアルコキシ基を表す。
なお、前記製造方法で製造した場合、式（４）中のＲ３と式（２）中のＲ３とは、それぞれ同じ基となる。 In the formula (4), 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.
Incidentally, when prepared by the above method, R 3 and Formula (2) R 3 in the formula (4), respectively at the same group.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
式（５）中、Ｒ３は、直鎖状若しくは分岐鎖状の炭素数１～３０のアルキル基、炭素数２～７のアルケニル基、シクロアルキル基、アリール基、又は、アラルキル基を表す。
なお、前記製造方法で製造した場合、式（５）中のＲ３と、式（２）中のＲ３はいずれも同じ基となる。 In formula (5), 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.
In addition, when it manufactures with the said manufacturing method, both R < 3 > in Formula (5) and R < 3 > in Formula (2) become the same group.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
式（６）中、Ｒ２ａは、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～８のアルキレン基を表し、Ｒ２ｂは、それぞれ独立に、炭素数１～３のアルキレン基を表す。式（６）中、ｘは、０～２の整数であり、Ｙは、酸素原子又はＮＨを表す。
なお、前記製造方法で製造した場合、式（６）中のＲ２ａと式（２）中のＲ２ａとは、それぞれ同じ基となり、式（６）中のＲ２ｂと式（２）中のＲ２ｂとは、それぞれ同じ基となり、式（６）中のＹと式（２）中のＹとは、それぞれ同じ原子又は基となる。 In the formula (6), 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, and R 2b represents Independently, it represents an alkylene group having 1 to 3 carbon atoms. In the formula (6), x is an integer of 0 to 2, and Y represents an oxygen atom or NH.
Incidentally, the case produced by the production method, the R 2a in the formula (6) R 2a and formula (2) in each be the same group, the formula (6) in R 2b and equation (2) in the R 2b is the same group, and Y in formula (6) and Y in formula (2) are the same atom or group, respectively.
前記製造方法で製造した場合、前記アミノ基及び／又はヒドロキシ基を有するシリコーン化合物のアミノ基当量及び／又はヒドロキシ基当量が、本発明にかかる接着性付与剤の官能基当量に相当する。なお、本発明にかかる接着性付与剤の官能基とは、アミノ基を有するシリコーン化合物を原料に用いて接着性付与剤を製造した場合は、アミド基（Ｎ－Ｃ＝Ｏ）であり、ヒドロキシ基を有するシリコーン化合物を原料に用いた場合はエステル基（Ｏ－Ｃ＝Ｏ）である。
前記アミノ基を有するシリコーン化合物のアミノ基当量を測定する方法としては、例えば、過塩素酸を用いた非水中和滴定等の方法が挙げられる。また、前記ヒドロキシ基を有するシリコーン化合物のヒドロキシ基当量は、前記ヒドロキシ基を有するシリコーン化合物の水酸基価より算出することができる。前記ヒドロキシ基を有するシリコーン化合物の水酸基価を求める方法としてはＪＩＳ　Ｋ　５６０１－２－１に記載された方法が挙げられる。 When produced by the production method, 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. When 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.
前記アミノ基を有するシリコーン化合物の合成方法としては、米国特許第３３５５４２４号明細書、米国特許第２９４７７７１号明細書、米国特許第３８９０２６９号明細書等に開示されている、アルキルアミノ基を有するジアルコキシアルキルシラン単位がシロキサンの鎖中に挿入されることへとつながる重縮合反応を用いた方法を用いることができる。この反応は通常、酸性又はアルカリ性触媒の存在下で行われる。この反応はジアルコキシアルキルシラン及び環状シロキサンを用いる重合反応として行うこともできる。
また、前記ヒドロキシ基を有するシリコーン化合物の合成方法としては、特開平０４－８８０２４号公報等に開示されている、ケイ素原子結合水素原子を有するポリオルガノシロキサンと脂肪族不飽和炭化水素基を有する有機ケイ素化合物とを白金系触媒の存在下で付加させる方法を用いることができる。この方法ではまず、白金系の触媒を用いたヒドロシリル化により、ケイ素原子結合水素原子を有するポリオルガノシロキサンを脂肪族不飽和炭化水素基を有する有機ケイ素化合物に付加させる。次に付加反応により生成したポリオルガノシロキサンの分子鎖末端のトリアルキルシリル基を脱シリル化により除去し、分子鎖末端をヒドロキシ基に変換して、ヒドロキシ基含有ポリオルガノシロキサンを得ている。 As a method for synthesizing the silicone compound having an amino group, 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.
In addition, as a method for synthesizing the silicone compound having a hydroxy group, 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. Next, 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.
前記アミノ基を有するシリコーン化合物のうち市販されているものとしては、例えば、ＫＦ－８６４、ＫＦ－８６５、ＫＦ－８６８（モノアミン型）、ＫＦ－８５９、ＫＦ－３９３、ＫＦ－８６０、ＫＦ－８８０、ＫＦ－８００４、ＫＦ－８００２、ＫＦ－８００５、ＫＦ－８６７、ＫＦ－８６９、ＫＦ－８６１（ジアミン型）、Ｘ－２２－１６６０Ｂ－３、Ｘ－２２－９４０９（両末端アミン、側鎖フェニル型）、ＰＡＭ－Ｅ、ＫＦ－８０１０、Ｘ－２２－１６１Ａ、Ｘ－２２－１６１Ｂ、ＫＦ－８０１２、ＫＦ－８００８（両末端アミン型）（いずれも信越化学工業社製）、ＢＹ１６－２０５、ＢＹ１６－８４９、ＦＺ－３７８５、ＢＹ１６－８７２、ＢＹ１６－２１３、ＦＺ－３７０５（側鎖アミン型）（いずれも東レ・ダウコーニング社製）等が挙げられる。 Examples of commercially available silicone compounds having an amino group include KF-864, KF-865, KF-868 (monoamine type), KF-859, KF-393, KF-860, KF-880. KF-8004, KF-8002, KF-8005, KF-867, KF-869, KF-861 (diamine type), X-22-1660B-3, X-22-9409 (both end amine, side chain phenyl) Type), PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008 (both end amine type) (all manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-205, BY16-849, FZ-3785, BY16-872, BY16-213, FZ-3705 (side chain amine type) (all are Toray Dow Corning Company, Ltd.), and the like.
前記ヒドロキシ基を有するシリコーン化合物のうち市販されているものとしては、例えば、Ｘ－２２－４０３９、Ｘ－２２－４０１５（側鎖カルビノール型）、Ｘ－２２－１６０ＡＳ、ＫＦ－６００１、ＫＦ－６００２、ＫＦ－６００３（両末端カルビノール型）、Ｘ－２２－１７０ＢＸ、Ｘ－２２－１７０ＤＸ（片末端カルビノール型）（いずれも信越化学工業社製）、ＳＦ８４２８（側鎖カルビノール型）、ＳＦ８４２７、ＢＹ１６－２０１、ＢＹ１６－００４（両末端カルビノール型）（いずれも東レ・ダウコーニング社製）等が挙げられる。 Examples of commercially available silicone compounds having a hydroxy group 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.
式（４）又は式（５）中、Ｒ３は、直鎖状若しくは分岐鎖状の炭素数１～３０のアルキル基、炭素数２～７のアルケニル基、シクロアルキル基、アリール基、又は、アラルキル基を表す。これらの中でも直鎖状又は分岐鎖状の炭素数１～３０のアルキル基、シクロアルキル基、アリール基、アラルキル基が好ましく、直鎖状又は分岐鎖状の炭素数１～３０のアルキル基、アリール基、アラルキル基がより好ましい。 In Formula (4) or Formula (5), 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. Among these, 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.
前記式（４）中、Ｚは、ヒドロキシ基、ハロゲン原子、又は、炭素数１～４のアルコキシ基を表す。
前記式（４）中のＺで表されるハロゲン原子としては、例えば、塩素原子、臭素原子等が挙げられる。前記式（４）中のＺで表されるハロゲン原子としては、なかでも、塩素原子が好ましい。
前記式（４）中のＺで表される炭素数１～４のアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｎ－ブトキシ基等が挙げられる。前記式（４）中のＺで表される炭素数１～４のアルコキシ基としては、なかでも、メトキシ基、エトキシ基が好ましく、メトキシ基がより好ましい。
前記式（４）中のＺは、これらの中でもヒドロキシ基、塩素原子、炭素数１～４のアルコキシ基が好ましく、ヒドロキシ基、塩素原子、メトキシ基、エトキシ基がより好ましい。 In the formula (4), Z represents a hydroxy group, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms.
Examples of the halogen atom represented by Z in the formula (4) include a chlorine atom and a bromine atom. As the halogen atom represented by Z in the formula (4), a chlorine atom is preferable.
Examples of 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. Among the alkoxy groups having 1 to 4 carbon atoms represented by Z in the formula (4), a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.
Among these, 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.
前記式（４）で表される化合物又は前記式（５）で表される化合物としては特に限定されないが、好ましくは、酢酸、プロピオン酸、アクリル酸、ブタン酸、３－メチルブタン酸、３－ブテン酸、メタクリル酸、ペンタン酸、２－メチルペンタン酸、４－メチルペンタン酸、２，２－ジメチルペンタン酸、ノナフルオロペンタン酸、２－プロピルペンタン酸、５－フェニルペンタン酸、４－ペンテン酸、２－メチル－４－ペンテン酸、２，２－ジメチル－４－ペンテン酸、ヘキサン酸、２－メチルヘキサン酸、５－メチルヘキサン酸、３，５，５－トリメチルヘキサン酸、２－エチルヘキサン酸、６－フェニルヘキサン酸、ウンデカフルオロヘキサン酸、５－ヘキセン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ウンデカン酸、ドデカン酸、トリデカン酸、テトラデカン酸、ペンタデカン酸、ヘキサデカン酸、ヘプタデカン酸、オクダデカン酸、ノナデカン酸、エイコ酸、ドコサン酸、テトラコサン酸、テトラコサン酸、ヘキサコサン酸、オクタコサン酸、トリアコンタン酸、シクロペンタンカルボン酸、シクロヘキサンカルボン酸、安息香酸、２－フェニル安息香酸、３－フェニル安息香酸、４－フェニル安息香酸、１－ナフトエ酸、２－ナフトエ酸、３－フェニルプロピオン酸、５－フェニルペンタン酸、６－フェニルヘキサン酸、アセチルクロリド、プロピオニルクロリド、３－フェニルプロピオニルクロリド、アクリロイルクロリド、ブチリルクロリド、２，２－ジメチルブチリルクロリド、３，３－ジメチルブチリルクロリド、イソブチリルクロリド、メタクリロイルクロリド、バレリルクロリド、イソバレリルクロリド、４－メチルバレリルクロリド、２－プロピルバレリルクロリド、ヘキサノイルクロリド、２－エチルヘキサノイルクロリド、３，５，５－トリメチルヘキサノイルクロリド、ヘプタノイルクロリド、オクタノイルクロリド、ノナノイルクロリド、デカノイルクロリド、ウンデカノイルクロリド、ラウロイルクロリド、ベンゾイルクロリド、ベンゾイルブロミド、３－フェニルプロピオニルクロリド、プロピオン酸メチル、プロピオン酸エチル、酪酸メチル、酪酸エチル、吉草酸メチル、吉草酸エチル、４－ペンテン酸エチル、２－メチル－４－ペンテン酸エチル、ヘキサン酸メチル、ヘキサン酸エチル、５－ヘキセン酸メチル、ヘプタン酸メチル、ヘプタン酸エチル、オクタン酸メチル、オクタン酸エチル、ノナン酸メチル、ノナン酸エチル、デカン酸メチル、デカン酸エチル、１－ナフトエ酸メチル、無水酢酸、プロピオン酸無水物、酪酸無水物、吉草酸無水物、ヘキサン酸無水物、ヘプタン酸無水物、オクタン酸無水物、ノナン酸無水物、デカン酸無水物等が挙げられる。 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, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dode Acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, okdadecanoic acid, nonadecanoic acid, eicoic acid, docosanoic acid, tetracosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, triacontanoic acid, cyclopentanecarboxylic acid Cyclohexanecarboxylic acid, benzoic acid, 2-phenylbenzoic acid, 3-phenylbenzoic acid, 4-phenylbenzoic acid, 1-naphthoic acid, 2-naphthoic acid, 3-phenylpropionic acid, 5-phenylpentanoic acid, 6- Phenylhexanoic acid, acetyl chloride, propionyl chloride, 3-phenylpropionyl chloride, acryloyl chloride, butyryl chloride, 2,2-dimethylbutyryl chloride, 3,3-dimethylbutyryl chloride, isobutyryl chloride, methacrylate Yl chloride, valeryl chloride, isovaleryl chloride, 4-methyl valeryl chloride, 2-propyl valeryl chloride, hexanoyl chloride, 2-ethylhexanoyl chloride, 3,5,5-trimethylhexanoyl chloride, heptanoyl chloride , Octanoyl chloride, nonanoyl chloride, decanoyl chloride, undecanoyl chloride, lauroyl chloride, benzoyl chloride, benzoyl bromide, 3-phenylpropionyl chloride, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl valerate Ethyl valerate, ethyl 4-pentenoate, ethyl 2-methyl-4-pentenoate, methyl hexanoate, ethyl hexanoate, methyl 5-hexenoate, methyl heptanoate, ethyl heptanoate, methyl octanoate Chill, ethyl octanoate, methyl nonanoate, ethyl nonanoate, methyl decanoate, ethyl decanoate, methyl 1-naphthoate, acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, Examples include heptanoic anhydride, octanoic anhydride, nonanoic anhydride, decanoic anhydride and the like.
前記アミノ基及び／又はヒドロキシ基を有するシリコーン化合物と、前記式（４）で表される化合物又は前記式（５）で表される化合物との反応における前記式（４）で表される化合物又は前記式（５）で表される化合物の使用量としては、前記式（６）のｘが０であり、ＹがＮＨである場合は、アミノ基を有するシリコーン化合物のアミノ基１モルに対して、０．８～５モルであることが好ましく、０．９～３モルであることがより好ましい。また、前記式（６）のｘが０であり、Ｙが酸素原子である場合は、ヒドロキシ基を有するシリコーン化合物のヒドロキシ基１モルに対して、０．８～５モルであることが好ましく、０．９～３モルであることがより好ましい。
前記式（６）のｘが１又は２であり、ＹがＮＨである場合は、アミノ基を有するシリコーン化合物のアミノ基１モルに対して、０．８～５モルであることが好ましく、０．９～３モルであることがより好ましい。また、式（６）のｘが１又は２であり、Ｙが酸素原子である場合は、アミノ基及びヒドロキシ基を有するシリコーン化合物のアミノ基とヒドロキシ基との合計１モルに対して、０．８～５モルであることが好ましく、０．９～３モルであることがより好ましい。
ここでいうアミノ基は、前記式（４）で表される化合物又は前記式（５）で表される化合物と反応し得るアミノ基であり、詳しくは、第一級アミノ基及び第二級アミノ基である。 The compound represented by the formula (4) in the reaction between the silicone compound having the amino group and / or hydroxy group and the compound represented by the formula (4) or the compound represented by the formula (5) or The amount of the compound represented by the formula (5) is as follows. When 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. When 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.
When 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. Further, when 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.
前記アミノ基及び／又はヒドロキシ基を有するシリコーン化合物と、前記式（４）で表される化合物又は前記式（５）で表される化合物との反応は、溶媒の存在下で行ってもよい。用いる溶媒としては前記アミノ基及び／又はヒドロキシ基を有するシリコーン化合物が溶解しやすく、前記アミノ基及び／又はヒドロキシ基を有するシリコーン化合物と、前記式（４）で表される化合物又は前記式（５）で表される化合物との反応を阻害しないものであれば特に限定されず、例えば、ヘキサン、ヘプタン、ベンゼン、トルエン、キシレン、クロロベンゼン、ジクロロベンゼン、シクロヘキサン、ジクロロメタン、クロロホルム、ジエチルエーテル、ジイソプロピルエーテル、アセトン、エチルメチルケトン、メチルイソブチルケトン等が挙げられる。 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. 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.
前記アミノ基及び／又はヒドロキシ基を有するシリコーン化合物と、前記式（４）で表される化合物又は前記式（５）で表される化合物との反応は、使用する溶媒に応じて－２０℃～１５０℃の範囲内の温度で行うことが好ましいが、０℃～１４０℃の範囲内の温度で溶媒を用いて行うことがより好ましい。 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.
本発明のシリコーン樹脂組成物中の本発明にかかる接着性付与剤の含有量の好ましい下限は０．０１質量％、好ましい上限は１５質量％である。本発明にかかる接着性付与剤の含有量が０．０１質量％未満であると、接着性を向上させる効果が充分に発揮されないことがある。本発明にかかる接着性付与剤の含有量が１５質量％を超えると、硬化物の硬度に悪影響を及ぼすことがある。本発明にかかる接着性付与剤の含有量のより好ましい下限は０．０５質量％、より好ましい上限は１０質量％、更に好ましい下限は０．１質量％、更に好ましい上限は５質量％である。 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%. When 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.
また、本発明にかかる接着性付与剤の含有量は、シリコーン樹脂混合物１００質量部に対して、好ましい下限が０．０１質量部、好ましい上限が２０質量部である。本発明にかかる接着性付与剤の含有量が０．０１質量部未満であると、接着性を向上させる効果が充分に発揮されないことがある。本発明にかかる接着性付与剤の含有量が２０質量部を超えると、硬化物の硬度に悪影響を及ぼすことがある。本発明にかかる接着性付与剤の含有量のより好ましい下限は、０．０５質量部、より好ましい上限は１３質量部、更に好ましい下限は０．１質量部、更に好ましい上限は６質量部である。 Moreover, as for content of the adhesive provision agent concerning this invention, 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. .
本発明のシリコーン樹脂組成物は、本発明の目的を阻害しない範囲において、本発明にかかる接着性付与剤に加えて、その他の接着性付与剤を含有していてもよい。 In the range which does not inhibit the objective of this invention, the silicone resin composition of this invention may contain the other adhesive imparting agent in addition to the adhesive imparting agent concerning this invention.
本発明のシリコーン樹脂組成物は、シリコーン樹脂混合物を含有する。本発明にかかるシリコーン樹脂混合物としては、主に付加硬化型シリコーン樹脂混合物又は縮合硬化型シリコーン樹脂混合物が用いられる。 The silicone resin composition of the present invention contains a silicone resin mixture. As the silicone resin mixture according to the present invention, an addition-curable silicone resin mixture or a condensation-curable silicone resin mixture is mainly used.
［付加硬化型シリコーン樹脂混合物］
本発明に用いられる付加硬化型シリコーン樹脂混合物は、炭素－炭素二重結合を有するシリル基とヒドロシリル基とのヒドロシリル化反応によって硬化する付加硬化型シリコーン樹脂を含有する混合物である。
前記付加硬化型シリコーン樹脂混合物は、ケイ素原子に結合した炭素－炭素二重結合を有する置換基を少なくとも２個有するポリオルガノシロキサン（以下、「炭素－炭素二重結合含有ポリオルガノシロキサン」ともいう）と、ケイ素原子に結合した水素原子を少なくとも２個有するポリオルガノハイドロジェンシロキサン（以下、単に「ポリオルガノハイドロジェンシロキサン」ともいう）と、ヒドロシリル化反応触媒とを含有することが好ましい。 [Addition-curing silicone resin mixture]
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”). And a polyorganohydrogensiloxane having at least two hydrogen atoms bonded to silicon atoms (hereinafter also simply referred to as “polyorganohydrogensiloxane”) and a hydrosilylation reaction catalyst.
前記炭素－炭素二重結合含有ポリオルガノシロキサンの分子構造としては、例えば、直鎖状、環状等の構造が挙げられ、構造中に分岐を有していてもよい。なかでも、主鎖がジオルガノシロキサン単位の繰り返しからなり、両末端がトリオルガノシロキシ基で封鎖された直鎖状の構造が好ましい。 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.
前記炭素－炭素二重結合含有ポリオルガノシロキサンにおける、ケイ素原子に結合した炭素－炭素二重結合を有する置換基としては、炭素数が２～８のものが好ましく、具体的には例えば、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、（メタ）アクリロイルオキシアルキル基等が挙げられる。前記炭素－炭素二重結合含有ポリオルガノシロキサンにおける、ケイ素原子に結合した炭素－炭素二重結合を有する置換基としては、なかでも、ビニル基、（メタ）アクリロイルオキシアルキル基が好ましく、ビニル基がより好ましい。 In the carbon-carbon double bond-containing polyorganosiloxane, 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. In the carbon-carbon double bond-containing polyorganosiloxane, 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.
前記炭素－炭素二重結合含有ポリオルガノシロキサンの分子構造が直鎖状である場合、炭素－炭素二重結合を有する置換基は、分子鎖末端と中間とのいずれか一方でのみケイ素原子に結合していてもよいし、分子鎖末端と中間との両方でケイ素原子に結合していてもよい。 When the molecular structure of the carbon-carbon double bond-containing polyorganosiloxane is linear, 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.
前記炭素－炭素二重結合含有ポリオルガノシロキサンにおける、炭素－炭素二重結合を有する置換基以外のケイ素原子に結合する有機基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基等の炭素数１～１２のアルキル基や、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の炭素数３～８のシクロアルキル基や、フェニル基、トリル基、キシリル基、ナフチル基等の炭素数６～１４のアリール基や、ベンジル基、フェネチル基、フェニルプロピル基等のアラルキル基や、クロロメチル基、３－クロロプロピル基、ブロモエチル基、３，３，３－トリフルオロプロピル基等のハロゲン化アルキル基等の、非置換又はハロゲン置換の１価の炭化水素基が挙げられる。前記炭素－炭素二重結合含有ポリオルガノシロキサンにおける、炭素－炭素二重結合を有する置換基以外のケイ素原子に結合する有機基としては、なかでも、アルキル基、アリール基が好ましく、メチル基、フェニル基がより好ましい。 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.換又 can be mentioned monovalent hydrocarbon groups of halogen-substituted. In the carbon-carbon double bond-containing polyorganosiloxane, 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.
前記炭素－炭素二重結合含有ポリオルガノシロキサンの粘度の好ましい下限は１００ｍＰａ・ｓ、好ましい上限は１０万ｍＰａ・ｓである。炭素－炭素二重結合含有ポリオルガノシロキサンの粘度がこの範囲内にある場合には、得られるシリコーン樹脂組成物の作業性が良好である上に、該シリコーン樹脂組成物から得られる硬化物の物理的特性が良好である。炭素－炭素二重結合含有ポリオルガノシロキサンの粘度のより好ましい下限は５００ｍＰａ・ｓ、より好ましい上限は１万ｍＰａ・ｓである。
なお、本明細書において、前記「粘度」は、回転粘度計（ＢＭ型）を用いて、２５℃の条件で測定される値を意味する。 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. When the viscosity of the carbon-carbon double bond-containing polyorganosiloxane is within this range, the workability of the resulting silicone resin composition is good and the physical properties of the cured product obtained from the silicone resin composition are good. Good mechanical 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.
In the present specification, the “viscosity” means a value measured at 25 ° C. using a rotational viscometer (BM type).
前記炭素－炭素二重結合含有ポリオルガノシロキサンとしては、具体的には例えば、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルビニルポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖メチルビニルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端トリビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン共重合体、（Ｒ４）３ＳｉＯ０．５（Ｒ４はアルケニル基を有しない非置換又は置換の１価の炭化水素基である。以下同じ）で表されるシロキシ単位と、（Ｒ４）２Ｒ５ＳｉＯ０．５（Ｒ５はアルケニル基又はアルケニル基を有する基である。以下同じ）で表されるシロキシ単位と、（Ｒ４）２ＳｉＯで表されるシロキシ単位と、ＳｉＯ２で表されるシロキシ単位とからなるポリオルガノシロキサン共重合体、（Ｒ４）３ＳｉＯ０．５で表されるシロキシ単位と、（Ｒ４）２Ｒ５ＳｉＯ０．５で表されるシロキシ単位と、ＳｉＯ２で表されるシロキシ単位とからなるポリオルガノシロキサン共重合体、（Ｒ４）２Ｒ５ＳｉＯ０．５で表されるシロキシ単位と、（Ｒ４）２ＳｉＯで表されるシロキシ単位と、ＳｉＯ２で表されるシロキシ単位とからなるポリオルガノシロキサン共重合体、Ｒ４Ｒ５ＳｉＯで表されるシロキシ単位と、Ｒ４ＳｉＯ１．５で表されるシロキシ単位、又は、Ｒ５ＳｉＯ１．５で表されるシロキシ単位とからなるポリオルガノシロキサン共重合体、（Ｒ４）３ＳｉＯ０．５で表されるシロキシ単位と、（Ｒ４）２ＳｉＯで表されるシロキシ単位と、Ｒ４Ｒ５ＳｉＯで表されるシロキシ単位と、Ｒ４ＳｉＯ１．５で表されるシロキシ単位と、（Ｒ４）４Ｓｉ２Ｒ６Ｏ（Ｒ６は２価の炭化水素基である。以下同じ）で表されるシロキシ単位とからなるポリオルガノシロキサン共重合体、（Ｒ４）２ＳｉＯで表されるシロキシ単位と、Ｒ４Ｒ５ＳｉＯで表されるシロキシ単位と、（Ｒ４）４Ｓｉ２Ｒ６Ｏで表されるシロキシ単位とからなるポリオルガノシロキサン共重合体等が挙げられる。これらは１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Specific examples of the carbon-carbon double bond-containing polyorganosiloxane 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. Molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylvinylpolysiloxane, Dimethylsiloxane / methylvinylsiloxane copolymer with dimethylvinylsiloxy group blocked at both ends of molecular chain, dimethylsiloxane / methylvinylsiloxane / methylphenylsilane with dimethylvinylsiloxy group blocked at both ends of molecular chain Hexane copolymer, both molecular chain terminals by trimethylsiloxy blocked with dimethylvinylsiloxy groups at both molecular chain terminals with dimethylvinylsiloxy groups dimethylsiloxane-diphenylsiloxane copolymer, (R 4) 3 SiO 0.5 (R 4 is alkenyl An unsubstituted or substituted monovalent hydrocarbon group having no group, the same shall apply hereinafter) and (R 4 ) 2 R 5 SiO 0.5 (R 5 represents an alkenyl group or an alkenyl group. 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 Polyorganosiloxane copolymer consisting of a proxy unit, represented by (R 4) 2 R 5 and siloxy units represented by SiO 0.5, (R 4) 2 and siloxy units represented by SiO, SiO 2 A polyorganosiloxane copolymer composed of siloxy units, a siloxy unit represented by R 4 R 5 SiO, a siloxy unit represented by R 4 SiO 1.5 , or a R 5 SiO 1.5 A polyorganosiloxane copolymer consisting of siloxy units, a siloxy unit represented by (R 4 ) 3 SiO 0.5 , a siloxy unit represented by (R 4 ) 2 SiO, and R 4 R 5 SiO A siloxy unit represented, a siloxy unit represented by R 4 SiO 1.5 , and (R 4 ) 4 Si 2 R 6 O (R 6 is a divalent hydrocarbon group. The same below), 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.
前記Ｒ４で表されるアルケニル基を有しない非置換又は置換の１価の炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基等の炭素数１～１２のアルキル基や、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の炭素数３～８のシクロアルキル基や、フェニル基、トリル基、キシリル基、ナフチル基等の炭素数６～１４のアリール基や、ベンジル基、フェネチル基、フェニルプロピル基等のアラルキル基や、クロロメチル基、３－クロロプロピル基、ブロモエチル基、３，３，３－トリフルオロプロピル基等のハロゲン化アルキル基等が挙げられる。前記Ｒ４で表されるアルケニル基を有しない非置換又は置換の１価の炭化水素基としては、なかでも、アルキル基、アリール基が好ましく、メチル基、フェニル基がより好ましい。 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 -Halogenated alkyl groups such as chloropropyl group, bromoethyl group and 3,3,3-trifluoropropyl group. The unsubstituted or substituted monovalent hydrocarbon group having no alkenyl group represented by R 4 is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group.
前記Ｒ５で表されるアルケニル基又はアルケニル基を有する基としては、炭素数が２～８のものが好ましく、例えば、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、へプテニル基、（メタ）アクリロイルオキシアルキル基等が挙げられる。前記Ｒ５で表されるアルケニル基又はアルケニル基を有する基としては、なかでも、ビニル基、（メタ）アクリロイルオキシアルキル基が好ましく、ビニル基がより好ましい。 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. As the alkenyl group represented by R 5 or a group having an alkenyl group, a vinyl group and a (meth) acryloyloxyalkyl group are preferable, and a vinyl group is more preferable.
前記Ｒ６で表される２価の炭化水素基としては、例えば、フェニレン基、エチレン基、ヘキシレン基、オクチレン基等が挙げられる。前記Ｒ６で表される２価の炭化水素基としては、なかでも、フェニレン基が好ましい。 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.
前記炭素－炭素二重結合含有ポリオルガノシロキサンのうち市販されているものとしては、例えば、ＤＭＳ－Ｖ２１、ＤＭＳ－Ｖ２２、ＤＭＳ－Ｖ２５、ＤＭＳ－Ｖ３１、ＤＭＳ－Ｖ３３、ＤＭＳ－Ｖ３５、ＤＭＳ－Ｖ４１、ＤＭＳ－Ｖ４２、ＤＭＳ－Ｖ４６、ＤＭＳ－Ｖ２５Ｒ、ＤＭＳ－Ｖ３５Ｒ（分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン）、ＰＤＶ－０３２５、ＰＤＶ－０３３１、ＰＤＶ－０３４１、ＰＤＶ－０３４６、ＰＤＶ－０５２５、ＰＤＶ－０５３５、ＰＤＶ－０５４１、ＰＤＶ－１６２５、ＰＤＶ－１６３１、ＰＤＶ－１６３５、ＰＤＶ－１６４１、ＰＤＶ－２３３１（分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン共重合体）、ＶＤＴ－１２３、ＶＤＴ－１２７、ＶＤＴ－１３１、ＶＤＴ－４３１、ＶＤＴ－７３１（分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体）、ＰＭＶ－９９２５（分子鎖両末端ジメチルビニルシロキシ基封鎖フェニルメチルポリシロキサン）、ＰＶＶ－３５２２（分子鎖両末端ビニルフェニルメチル基封鎖ビニルフェニルシロキサン・フェニルメチルシロキサン共重合体）（いずれもＧｅｌｅｓｔ，Ｉｎｃ．製）等が挙げられる。 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), PDV-0325, PDV-0331, PDV-0341, PDV-0346, PDV-0525 PDV-0535, PDV-0541, PDV-1625, PDV-1631, PDV-1635, PDV-1641, PDV-2331 (a dimethylvinylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer at both molecular chains), 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 phenylmethylpolysiloxane) ), PVV-3522 (vinylphenylmethyl group-blocked vinylphenylsiloxane / phenylmethylsiloxane copolymer) (both from Gelest, Inc.) and the like.
前記ポリオルガノハイドロジェンシロキサンは、前記炭素－炭素二重結合含有ポリオルガノシロキサンと反応し、架橋成分として作用する。 The polyorganohydrogensiloxane reacts with the carbon-carbon double bond-containing polyorganosiloxane and acts as a crosslinking component.
前記ポリオルガノハイドロジェンシロキサンとしては、例えば、直線状、環状、分岐状、三次元網状構造（樹脂状）等の分子構造を有する各種のポリオルガノハイドロジェンシロキサンを使用することができる。 As the polyorganohydrogensiloxane, for example, various polyorganohydrogensiloxanes having a molecular structure such as linear, cyclic, branched, and three-dimensional network structure (resinous) can be used.
前記ポリオルガノハイドロジェンシロキサンは、１分子中に２個以上、好ましくは３個以上のケイ素原子に結合した水素原子、即ち、ヒドロシリル基（Ｓｉ－Ｈ基）を有する。前記ポリオルガノハイドロジェンシロキサンの分子構造が直線状である場合、これらのＳｉ－Ｈ基は、分子鎖末端と中間部とのいずれか一方のみに位置していてもよいし、その両方に位置していてもよい。 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). In the case where the molecular structure of the polyorganohydrogensiloxane is linear, 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.
前記ポリオルガノハイドロジェンシロキサンの１分子中のケイ素原子の数（重合度）は、２～１０００であることが好ましく、３～１００であることがより好ましい。 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.
前記ポリオルガノハイドロジェンシロキサンとしては、例えば、Ｒ７ ａＨｂＳｉＯ（４－ａ－ｂ／２）（Ｒ７は、炭素数が１～１４の非置換又は置換の１価の炭化水素基である。Ｒ７の炭素数は、１～１０であることが好ましい。ａ及びｂは、０．７≦ａ≦２．１、０．００１≦ｂ≦１．０であり、かつ、０．８≦ａ＋ｂ≦３．０を満足する正数であることが好ましく、１．０≦ａ＋ｂ≦２．５を満足する正数であることがより好ましい）で表されるポリオルガノハイドロジェンシロキサンが用いられる。 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). .
前記Ｒ７で表される炭素数が１～１４の非置換又は置換の１価の炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｎ－ヘキシル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基等の炭素数１～１２のアルキル基や、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の炭素数３～８のシクロアルキル基や、フェニル基、トリル基、キシリル基、ナフチル基等の炭素数６～１４のアリール基や、ベンジル基、フェネチル基、フェニルプロピル基等のアラルキル基や、ビニル基、アリル基等のアルケニル基や、これらの炭化水素基中の水素原子の一部又は全部をハロゲン原子で置換した基、例えば、クロロメチル基、３－クロロプロピル基、ブロモエチル基、３，３，３－トリフルオロプロピル基等が挙げられる。前記Ｒ７で表される炭素数が１～１４の非置換又は置換の１価の炭化水素基としては、なかでも、アルキル基、アリール基が好ましく、メチル基、フェニル基がより好ましい。なお、前記Ｒ７は、同一の炭化水素基であってもよいし、異なっていてもよい。 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. Group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group and other alkyl groups having 1 to 12 carbon atoms, cyclopentyl group, cyclohexyl Group, cycloalkyl group having 3 to 8 carbon atoms such as cycloheptyl group, aryl group having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group and naphthyl group, benzyl group, phenethyl group and phenylpropyl group Aralkyl groups such as vinyl groups, alkenyl groups such as vinyl groups and allyl groups, and groups in which some or all of the hydrogen atoms in these hydrocarbon groups are substituted with halogen atoms, such as chloromethyl Group, 3-chloropropyl group, bromoethyl group, 3,3,3-trifluoropropyl group and the like. 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.
前記ポリオルガノハイドロジェンシロキサンのうち、Ｒ７ ａＨｂＳｉＯ（４－ａ－ｂ／２）で表されるポリオルガノハイドロジェンシロキサンとしては、具体的には例えば、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジエンシロキシ基封鎖メチルフェニルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖フェニル（ジメチルハイドロシロキシ）シロキサン）、（Ｒ４）３ＳｉＯ０．５（Ｒ４は前記の通り）で表されるシロキシ単位と（Ｒ４）２ＨＳｉＯ０．５で表されるシロキシ単位とＳｉＯ２で表されるシロキシ単位とからなるポリオルガノハイドロジェンシロキサン共重合体、（Ｒ４）２ＨＳｉＯ０．５で表されるシロキシ単位とＳｉＯ２で表されるシロキシ単位とからなるポリオルガノハイドロジェンシロキサン共重合体、Ｒ４ＨＳｉＯで表されるシロキシ単位とＲ４ＳｉＯ１．５で表されるシロキシ単位又はＨＳｉＯ１．５で表されるシロキシ単位とからなるポリオルガノハイドロジェンシロキサン共重合体等が挙げられる。
Ｒ７ ａＨｂＳｉＯ（４－ａ－ｂ／２）で表されるポリオルガノハイドロジェンシロキサン以外の、前記ポリオルガノハイドロジェンシロキサンとしては、具体的には例えば、（Ｒ４）３ＳｉＯ０．５で表されるシロキシ単位と、（Ｒ４）２ＨＳｉＯ０．５で表されるシロキシ単位と、（Ｒ４）２ＳｉＯで表されるシロキシ単位と、Ｒ４ＳｉＯ１．５で表されるシロキシ単位と、（Ｒ４）４Ｓｉ２Ｒ６Ｏ（Ｒ６は前記の通り）で表されるシロキシ単位とからなるポリオルガノハイドロジェンシロキサン共重合体、（Ｒ４）３ＳｉＯ０．５で表されるシロキシ単位と、（Ｒ４）２ＨＳｉＯ０．５で表されるシロキシ単位と、（Ｒ４）２ＳｉＯで表されるシロキシ単位と、Ｒ５ＳｉＯ１．５（Ｒ５は前記の通り）で表されるシロキシ単位と、（Ｒ４）４Ｓｉ２Ｒ６Ｏで表されるシロキシ単位とからなるポリオルガノハイドロジェンシロキサン共重合体、（Ｒ４）３ＳｉＯ０．５で表されるシロキシ単位と、（Ｒ４）２ＳｉＯで表されるシロキシ単位と、Ｒ４ＨＳｉＯで表されるシロキシ単位と、（Ｒ４）４Ｓｉ２Ｒ６Ｏで表されるシロキシ単位とからなるポリオルガノハイドロジェンシロキサン共重合体等が挙げられる。これらは１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Among the polyorganohydrogensiloxanes, specific examples of the polyorganohydrogensiloxane represented by R 7 a H b SiO (4-ab / 2) 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, Molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane / methylhydrogensiloxane copolymer, Molecular chain both ends dimethylhydrogen Siloxy group-blocked dimethylsiloxane-methylphenylsiloxane copolymers, dimethylpolysiloxane with both molecular chain terminals hydro diene siloxy groups at methylphenyl polysiloxane with both molecular chain terminals with dimethylhydrogensiloxy group-blocked phenyl (dimethyl hydrogen siloxy) siloxane), (R 4 3 ) Polysiloxane composed of a siloxy unit represented by 3 SiO 0.5 (R 4 is as described above), a siloxy unit represented by (R 4 ) 2 HSiO 0.5 and a siloxy unit represented by SiO 2. 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. 5 , 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 ) 2 SiO, a siloxy unit represented by R 4 HSiO, and a siloxy unit represented by (R 4 ) 4 Si 2 R 6 O Examples include a gen siloxane copolymer. These may be used individually by 1 type and may be used in combination of 2 or more type.
前記ポリオルガノハイドロジェンシロキサンのうち市販されているものとしては、例えば、ＤＭＳ－Ｈ０３、ＤＭＳ－Ｈ１１、ＤＭＳ－Ｈ２１、ＤＭＳ－Ｈ２５、ＤＭＳ－Ｈ３１、ＤＭＳ－Ｈ４１、（分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン）、ＨＭＳ－０１３、ＨＭＳ－０３１、ＨＭＳ－０６４、ＨＭＳ－０７１、ＨＭＳ－０８２、ＨＭＳ－１５１、ＨＭＳ－３０１、ＨＭＳ－５０１（分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体）、ＨＭＳ－９９１、ＨＭＳ－９９２、ＨＭＳ－９９３（分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン）、ＨＭＳ－Ｈ２７１（分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体）、ＨＰＭ－５０２（分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖フェニルメチルシロキサン・メチルハイドロジェンシロキサン共重合体）、ＨＤＰ－１１１（分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖フェニル（ジメチルハイドロシロキシ）シロキサン）（いずれもＧｅｌｅｓｔ，Ｉｎｃ．製）等が挙げられる。 Commercially available 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), HPM-502 (both ends of the molecular chain dimethylhydrogensiloxy group blocked phenylmethylsiloxane / methylhydrogensiloxane copolymer), HDP-111 (both ends of the molecular chain dimethylhydrogen) And siloxy group-blocked phenyl (dimethylhydrosiloxy) siloxane (both manufactured by Gelest, Inc.).
前記ポリオルガノハイドロジェンシロキサンの含有量は、前記炭素－炭素二重結合含有ポリオルガノシロキサンの硬化有効量であり、特に、ポリオルガノハイドロジェンシロキサンの有するＳｉ－Ｈ基が炭素－炭素二重結合含有ポリオルガノシロキサン中の炭素－炭素二重結合を有する置換基１個当たり０．１～４．０個となる割合となることが好ましい。Ｓｉ－Ｈ基が炭素－炭素二重結合を有する置換基１個当たり０．１個未満であると、硬化反応が進行せず、硬化物を得ることが困難になることがある。Ｓｉ－Ｈ基が炭素－炭素二重結合を有する置換基１個当たり４．０個を超えると、未反応のＳｉ－Ｈ基が硬化物中に多量に残存するため、硬化物の物性が経時的に変化するおそれがある。Ｓｉ－Ｈ基は、炭素－炭素二重結合を有する置換基１個当たり１．０～３．０個の割合となることがより好ましい。 The content of the polyorganohydrogensiloxane is the effective amount of curing of the carbon-carbon double bond-containing polyorganosiloxane. In particular, 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. When the number of Si—H groups is less than 0.1 per substituent having a carbon-carbon double bond, the curing reaction does not proceed and it may be difficult to obtain a cured product. If 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.
前記ヒドロシリル化反応触媒としては、従来公知のものを使用することができる。具体的には例えば、白金（白金黒を含む）、ロジウム、パラジウム等の白金族金属単体や、Ｈ２ＰｔＣｌ４・ｙＨ２Ｏ、Ｈ２ＰｔＣｌ６・ｙＨ２Ｏ、ＮａＨＰｔＣｌ６・ｙＨ２Ｏ、ＫＨＰｔＣｌ６・ｙＨ２Ｏ、Ｎａ２ＰｔＣｌ６・ｙＨ２Ｏ、Ｋ２ＰｔＣｌ４・ｙＨ２Ｏ、ＰｔＣｌ４・ｙＨ２Ｏ、ＰｔＣｌ２、Ｎａ２ＨＰｔＣｌ４・ｙＨ２Ｏ（ただし、これらの式中、ｙは０～６の整数であり、好ましくは０又は６の整数である）等の塩化白金、塩化白金酸及び塩化白金酸塩や、アルコール変性塩化白金酸（米国特許第３２２０９７２号明細書参照）や、塩化白金酸とオレフィンとのコンプレックス（米国特許第３１５９６０１号明細書、米国特許第３１５９６６２号明細書、米国特許第３７７５４５２号明細書参照）や、白金黒、パラジウム等の白金族金属をアルミナ、シリカ、カーボン等の担体に担持させたものや、ロジウム－オレフィンコンプレックスや、クロロトリス（トリフェニルフォスフィン）ロジウム（ウィルキンソン触媒）や、塩化白金、塩化白金酸又は塩化白金酸塩とビニル基含有シロキサンとのコンプレックスや、ジクロロジピリジン白金（ＩＩ）（特開平０９－１６５４５３号公報参照）や、Ｐｔ２（（（ＣＨ２＝ＣＨ）Ｍｅ２Ｓｉ）２Ｏ）３、ＨＰｔ２（（（ＣＨ２＝ＣＨ）Ｍｅ２Ｓｉ２）Ｏ）２、ＰｔＣＯ（ＣＨ２＝ＣＨ（Ｍｅ）ＳｉＯ）４、Ｐｔ（ＣＨ２＝ＣＨ（Ｍｅ）ＳｉＯ）４等の白金のビニルシロキサン錯体（特開平１１－１５２３３７号公報参照）等の白金族金属系触媒等が挙げられる。 A conventionally well-known thing can be used as said hydrosilylation reaction catalyst. Specifically, for example, 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. No. 3,220,972) ), And a complex of chloroplatinic acid and olefin (see US Pat. No. 3,159,601, US Pat. No. 3,159,662, and US Pat. No. 3,775,452). A platinum group metal such as platinum black or palladium supported on a carrier such as alumina, silica or carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), platinum chloride, Complexes of chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane, dichlorodipyridine platinum (II) (see Japanese Patent Application Laid-Open No. 09-165453), 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.
前記ヒドロシリル化反応触媒の含有量は、ヒドロシリル化反応の触媒として有効な量であれば特に限定されないが、付加硬化型シリコーン樹脂混合物中において、白金等の金属元素に換算して０．１～１０００ｐｐｍであることが好ましい。前記ヒドロシリル化反応触媒の含有量がこの範囲にある場合には、付加反応が充分に促進されるため、得られるシリコーン樹脂組成物を充分に硬化させることができ、かつ、経済的に有利である。前記ヒドロシリル化反応触媒の含有量は、１～５００ｐｐｍであることがより好ましく、１～２０ｐｐｍであることが更に好ましい。 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.
前記付加硬化型シリコーン樹脂混合物としては、公知のものを用いることができ、入手の容易性から２液型の熱硬化性タイプが好ましい。
前記２液型の熱硬化性タイプの付加硬化型シリコーン樹脂混合物のうち市販されているものとしては、例えば、ＩＶＳ４３１２、ＸＥ１４－Ｃ２０４２、ＩＶＳ４５４２、ＩＶＳ４５４６、ＩＶＳ４６２２、ＩＶＳ４６３２、ＩＶＳ４７４２、ＩＶＳ４７５２、ＸＥ１４－Ｃ２８６０、ＸＥ１４－Ｃ３４５０、ＩＶＳ５８５４（いずれもモメンティブ・パフォーマンス・マテリアル社製）、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（いずれも信越化学工業社製）、ＯＥ－６３５１、ＯＥ－６３３６、ＯＥ－６３７０Ｍ、ＥＧ－６３０１、ＪＣＲ－６１２５、ＪＣＲ－６１４０、ＯＥ－６４５０、ＯＥ－６５２０、ＯＥ－６５５０、ＯＥ－６６３１、ＯＥ－６６３６、ＯＥ－６６３５、ＯＥ－６６３０、ＯＥ－６６６５Ｎ、ＳＲ７０１０（いずれも東レ・ダウコーニング社製）等が挙げられる。 As the 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, OE-6370M, EG-6301, JCR-6125, JCR-6140, OE-6450, OE-6520, OE-6550, OE-6331, OE- 6636, OE-6635, OE-6630, OE-6665N, SR7010 (all manufactured by Toray Dow Corning).
［縮合硬化型シリコーン樹脂混合物］
本発明に用いられる縮合硬化型シリコーン樹脂混合物とは、硬化前は液状であり、反応副生成物を発生させながら硬化することでゴム弾性体となるシリコーン樹脂のことを意味する。具体的には、ポリシロキサン中に、アルコキシシリル基やアセトキシシリル基等の加水分解性基が存在し、空気中の水分でこれらの基がシラノール基に加水分解され、該シラノール基同士が縮合することで安定なシロキサン結合が形成され架橋する。
前記した付加硬化型シリコーン樹脂混合物は、副生成物はほとんど発生しないが、架橋剤として通常用いられる白金触媒が、硫黄、窒素、リン原子を含む化合物と接触すると硬化阻害を生じることがあるため、硬化条件を厳密に管理する必要がある。一方、前記縮合硬化型シリコーン樹脂混合物は、硬化条件を厳密に管理することなく硬化させることができる。 [Condensation-curable silicone resin mixture]
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. Specifically, 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.
In the addition-curable silicone resin mixture described above, by-products are hardly generated, but a platinum catalyst usually used as a crosslinking agent may cause curing inhibition when it comes into contact with a compound containing sulfur, nitrogen, or phosphorus atoms. It is necessary to strictly control the curing conditions. On the other hand, the condensation curable silicone resin mixture can be cured without strictly controlling the curing conditions.
前記縮合硬化型シリコーン樹脂混合物は、一般的に公知な１液型や２液型を用いることができる。１液型としてはオキシム型、アルコール型、アセトン型、酢酸型等が挙げられ、これらの中でも、金属への腐食がないアルコール型及びアセトン型が好ましい。
２液型としては、アルコール型、アセトン型等が挙げられる。 As the condensation-curable silicone resin mixture, a generally known one-component type or two-component type can be used. Examples of the one-component type include an oxime type, an alcohol type, an acetone type, and an acetic acid type. Among these, an alcohol type and an acetone type that do not corrode metal are preferable.
Examples of the two-component type include an alcohol type and an acetone type.
前記縮合硬化型シリコーン樹脂混合物の縮合硬化反応には、必要に応じて、スズ、チタン、アミン化合物を触媒として用いてもよい。 In the condensation curing reaction of the condensation curable silicone resin mixture, tin, titanium, or an amine compound may be used as a catalyst, if necessary.
前記縮合硬化型シリコーン樹脂混合物のうち市販されているものとしては、例えば、１液縮合アセトン型のものとして、ＫＥ－３４９０、ＫＥ－３４９３、ＫＥ－３４９４、ＫＥ－３４９７、ＫＥ－３４６６、ＫＥ－３４１２、ＫＥ－３４２１、ＫＥ－３４２３、ＫＥ－３４９５（いずれも信越化学工業社製）、１液縮合アルコール型のものとして、ＫＥ－４８０６－Ｗ、ＫＥ－４９０１－Ｗ、ＫＥ－４９２０Ｔ、ＫＥ－４９２０、ＫＥ－４９２１－Ｂ、ＫＥ－４９２１－Ｗ（いずれも信越化学工業社製）、２液縮合アセトン型のものとして、ＫＥ－２００、ＫＥ－２１０（いずれも信越化学工業社製）等が挙げられる。 Examples of commercially available 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.
本発明のシリコーン樹脂組成物は、シリコーン樹脂混合物及び本発明にかかる接着性付与剤に加えて、本発明の目的や効果を損なわない範囲で、必要に応じて添加剤を含有してもよい。 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.
前記添加剤としては、例えば、無機フィラー、酸化防止剤、無機蛍光体、滑剤、紫外線吸収剤、熱光安定剤、分散剤、帯電防止剤、重合禁止剤、消泡剤、硬化促進剤、溶剤、老化防止剤、ラジカル禁止剤、接着性改良剤、難燃剤、界面活性剤、保存安定性改良剤、オゾン老化防止剤、増粘剤、可塑剤、放射線遮断剤、核剤、カップリング剤、導電性付与剤、リン系過酸化物分解剤、顔料、金属不活性化剤、物性調整剤等が挙げられる。 Examples of the additive 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.
前記無機フィラーとしては特に限定されず、光学特性を低下させない微粒子状のものが挙げられる。具体的には例えば、アルミナ、水酸化アルミニウム、溶融シリカ、結晶性シリカ、超微粉無定型シリカ、疎水性超微粉シリカ、タルク、炭酸カルシウム、硫酸バリウム等が挙げられる。 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.
前記無機蛍光体としては、例えば、ＬＥＤに広く利用されている、イットリウム、アルミニウム、ガーネット系のＹＡＧ系蛍光体、ＺｎＳ系蛍光体、Ｙ２Ｏ２Ｓ系蛍光体、赤色発光蛍光体、青色発光蛍光体、緑色発光蛍光体等が挙げられる。 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.
本発明のシリコーン樹脂組成物を製造する方法としては、例えば、シリコーン樹脂混合物と、本発明にかかる接着性付与剤と、必要に応じて使用する添加剤とを混合することによって製造することができる。 As a method for producing 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. .
本発明のシリコーン樹脂組成物は、１液型又は２液型とすることできる。
本発明のシリコーン樹脂組成物は、例えば、光半導体素子等の基材に塗布し硬化させて使用することができる。 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.
本発明のシリコーン樹脂組成物を基材に塗布する方法としては、例えば、ディスペンサーを使用する方法、ポッティング法、スクリーン印刷、トランスファー成形、インジェクション成形等の方法が挙げられる。 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.
本発明のシリコーン樹脂組成物は、室温で又は加熱によって硬化させることができる。本発明のシリコーン樹脂組成物を硬化させることによって得られるシリコーン樹脂硬化物もまた、本発明の１つである。 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.
本発明のシリコーン樹脂組成物を加熱して硬化させる際の最終的な加熱温度は、通常１００℃以上であり、１２０℃以上であることが好ましく、１２０～２００℃であることがより好ましく、１２０～１８０℃であることが更に好ましい。 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.
本発明のシリコーン樹脂組成物の用途としては、例えば、電子材料用の封止材組成物、建築用シーリング剤組成物、自動車用シーリング剤組成物、接着剤組成物等が挙げられる。
前記電子材料としては、例えば、リードフレーム、配線済みのテープキャリア、配線板、ガラス、シリコンウエハ等の支持部材や、光半導体素子や、半導体チップ、トランジスタ、ダイオード、サイリスタ等の能動素子や、コンデンサ、抵抗体、コイル等の受動素子等が挙げられる。なかでも、光半導体素子の封止材として好適に用いることができる。
光半導体素子が本発明のシリコーン樹脂硬化物で封止されている光半導体素子封止体もまた、本発明の１つである。 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.
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.
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.
また、本発明のシリコーン樹脂組成物は、例えば、ディスプレイ材料、光記録媒体材料、光学機器材料、光部品材料、光ファイバー材料、光・電子機能有機材料、半導体集積回路周辺材料等の用途に使用することができる。 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.
本発明によれば、界面接着性及び耐湿熱性に優れるシリコーン樹脂組成物を提供することができる。また、本発明によれば、該シリコーン樹脂組成物を用いてなるシリコーン樹脂硬化物及び光半導体素子封止体を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the silicone resin composition excellent in interfacial adhesiveness and heat-and-moisture resistance can be provided. Moreover, according to this invention, the silicone resin hardened | cured material and optical semiconductor element sealing body which use this silicone resin composition can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（製造例１）
（アミノ基を有するシリコーン化合物とベンゾイルクロリドとの反応（接着性付与剤Ａの調製））
撹拌機、温度計及び冷却器を備え付けた２００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、アミノ基を有するシリコーン化合物（信越化学工業社製、「Ｘ－２２－１６６０Ｂ－３」、アミノ基当量２２００ｇ／ｍｏｌ）１０．０ｇ（アミノ基４．５７ｍｍｏｌ）、トルエン４８．２ｇ及びトリエチルアミン０．４９ｇ（４．８０ｍｍｏｌ）を混合し、更にベンゾイルクロリド０．６９ｇ（４．８０ｍｍｏｌ）を滴下し、２５℃で、２時間撹拌した。中和滴定により残存アミノ基が１％未満であることを確認した。その後、水２５ｇを加えて分液し、有機層を濃縮することで、透明液体（接着性付与剤Ａ）１０．０９ｇを取得した。
１Ｈ－ＮＭＲにより、接着性付与剤Ａを測定した結果、接着性付与剤Ａは、前記式（１－１）で表される構造単位（Ｒ１ａがメチル基、Ａが式（２）で表される基であり、Ｒ２ａがｎ－プロピレン基、ｘが０、ＹがＮＨ、Ｒ３がフェニル基）と、前記式（１－２）で表される構造単位（Ｒ１ａがメチル基、Ａが式（２）で表される基であり、Ｒ２ａがｎ－プロピレン基、ｘが０、ＹがＮＨ、Ｒ３がフェニル基）と、前記式（１－４）で表される構造単位（Ｒ１ｂがメチル基、フェニル基）とを有していることを確認した。 (Production Example 1)
(Reaction of silicone compound having amino group with benzoyl chloride (Preparation of adhesion promoter A))
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, a silicone compound having an amino group (“X-22-1660B-3”, manufactured by Shin-Etsu Chemical Co., Ltd.) (Equivalent 2200 g / mol) 10.0 g (4.57 mmol amino group), 48.2 g toluene and 0.49 g (4.80 mmol) triethylamine were mixed, and 0.69 g (4.80 mmol) benzoyl chloride was added dropwise. Stir at 2 ° C. for 2 hours. The residual amino group was confirmed to be less than 1% by neutralization titration. Thereafter, 25 g of water was added for liquid separation, and the organic layer was concentrated to obtain 10.09 g of a transparent liquid (adhesion imparting agent A).
As a result of measuring the adhesion-imparting agent A by 1 H-NMR, 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).
（製造例２）
（アミノ基を有するシリコーン化合物とベンゾイルクロリドとの反応（接着性付与剤Ｂの調製））
撹拌機、温度計及び冷却器を備え付けた２００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、アミノ基を有するシリコーン化合物（信越化学工業社製、「Ｘ－２２－９４０９」、アミノ基当量６７０ｇ／ｍｏｌ）１０．２ｇ（アミノ基１５．３ｍｍｏｌ）、トルエン（５０．０ｇ及びトリエチルアミン１．５９ｇ（１５．７ｍｍｏｌ）を混合し、更にベンゾイルクロリド２．２１ｇ（１５．７ｍｍｏｌ）を滴下し、２５℃で２時間撹拌した。中和滴定により残存アミノ基が１％未満であることを確認した。その後、水２５ｇを加えて分液し、有機層を濃縮することで、透明液体（接着性付与剤Ｂ）１０．８２ｇを取得した。
１Ｈ－ＮＭＲにより、接着性付与剤Ｂを測定した結果、接着性付与剤Ｂは、前記式（１－１）で表される構造単位（Ｒ１ａがメチル基、Ａが式（２）で表される基であり、Ｒ２ａがｎ－プロピレン基、ｘが０、ＹがＮＨ、Ｒ３がフェニル基）と、前記式（１－２）で表される構造単位（Ｒ１ａがメチル基、Ａが式（２）で表される基であり、Ｒ２ａがｎ－プロピレン基、ｘが０、ＹがＮＨ、Ｒ３がフェニル基）と、前記式（１－４）で表される構造単位（Ｒ１ｂがメチル基、フェニル基）とを有していることを確認した。 (Production Example 2)
(Reaction between silicone compound having amino group and benzoyl chloride (Preparation of adhesion promoter B))
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, under a nitrogen atmosphere, a silicone compound having an amino group (“X-22-9409” manufactured by Shin-Etsu Chemical Co., Ltd.), an amino group equivalent of 670 g / Mol) 10.2 g (15.3 mmol of amino group), toluene (50.0 g and 1.59 g (15.7 mmol) of triethylamine) were mixed, and 2.21 g (15.7 mmol) of benzoyl chloride was added dropwise, and 25 ° C. The residual amino group was confirmed to be less than 1% by neutralization titration, and then 25 g of water was added for liquid separation, and the organic layer was concentrated to give a transparent liquid (adhesiveness-imparting agent). B) 10.82 g was obtained.
As a result of measuring the adhesion-imparting agent B by 1 H-NMR, 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).
（製造例３）
（アミノ基を有するシリコーン化合物と３－フェニルプロピオニルクロリドとの反応（接着性付与剤Ｃの調製））
撹拌機、温度計及び冷却器を備え付けた２００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、アミノ基を有するシリコーン化合物（信越化学工業社製、「Ｘ－２２－１６６０Ｂ－３」、アミノ基当量２２００ｇ／ｍｏｌ）１０．１ｇ（アミノ基４．５９ｍｍｏｌ）、トルエン５１．０ｇ及びトリエチルアミン０．４９ｇ（４．８４ｍｍｏｌ）を混合し、更に３－フェニルプロピオニルクロリド０．８２ｇ（４．８４ｍｍｏｌ）を滴下し、２５℃で、５時間撹拌した。中和滴定により残存アミノ基が１％未満であることを確認した。その後、水２５ｇを加えて分液し、有機層を濃縮することで、透明液体（接着性付与剤Ｃ）８．３ｇを取得した。
１Ｈ－ＮＭＲにより、接着性付与剤Ｃを測定した結果、接着性付与剤Ｃは、前記式（１－１）で表される構造単位（Ｒ１ａがメチル基、Ａが式（２）で表される基であり、Ｒ２ａがｎ－プロピレン基、ｘが０、ＹがＮＨ、Ｒ３がフェネチル基）と、前記式（１－２）で表される構造単位（Ｒ１ａがメチル基、Ａが式（２）で表される基であり、Ｒ２ａがｎ－プロピレン基、ｘが０、ＹがＮＨ、Ｒ３がフェネチル基）と、前記式（１－４）で表される構造単位（Ｒ１ｂがメチル基、フェニル基）とを有していることを確認した。 (Production Example 3)
(Reaction of silicone compound having amino group with 3-phenylpropionyl chloride (Preparation of adhesion promoter C))
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, a silicone compound having an amino group (“X-22-1660B-3”, manufactured by Shin-Etsu Chemical Co., Ltd.) Equivalent 2200 g / mol) 10.1 g (4.59 mmol amino group), 51.0 g toluene and 0.49 g (4.84 mmol) triethylamine were mixed, and 0.82 g (4.84 mmol) 3-phenylpropionyl chloride was added dropwise. And stirred at 25 ° C. for 5 hours. The residual amino group was confirmed to be less than 1% by neutralization titration. Thereafter, 25 g of water was added for liquid separation, and the organic layer was concentrated to obtain 8.3 g of a transparent liquid (adhesion imparting agent C).
As a result of measuring the adhesion-imparting agent C by 1 H-NMR, 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).
（製造例４）
（アミノ基を有するシリコーン化合物と３－フェニルプロピオニルクロリドとの反応（接着性付与剤Ｄの調製））
撹拌機、温度計及び冷却器を備え付けた２００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、アミノ基を有するシリコーン化合物（信越化学工業社製、「Ｘ－２２－９４０９」、アミノ基当量６７０ｇ／ｍｏｌ）１０．１ｇ（アミノ基１５．１ｍｍｏｌ）、トルエン５０．０ｇ及びトリエチルアミン１．６１ｇ（１５．９ｍｍｏｌ）を混合し、更に３－フェニルプロピオニルクロリド２．６８ｇ（１５．９ｍｍｏｌ）を滴下し、２５℃で、５時間撹拌した。中和滴定により残存アミノ基が１％未満であることを確認した。その後、水２５ｇを加えて分液し、有機層を濃縮することで、透明液体（接着性付与剤Ｄ）９．７５ｇを取得した。
１Ｈ－ＮＭＲにより、接着性付与剤Ｄを測定した結果、接着性付与剤Ｄは、前記式（１－１）で表される構造単位（Ｒ１ａがメチル基、Ａが式（２）で表される基であり、Ｒ２ａがｎ－プロピレン基、ｘが０、ＹがＮＨ、Ｒ３がフェネチル基）と、前記式（１－２）で表される構造単位（Ｒ１ａがメチル基、Ａが式（２）で表される基であり、Ｒ２ａがｎ－プロピレン基、ｘが０、ＹがＮＨ、Ｒ３がフェネチル基）と、前記式（１－４）で表される構造単位（Ｒ１ｂがメチル基、フェニル基）とを有していることを確認した。 (Production Example 4)
(Reaction of silicone compound having amino group with 3-phenylpropionyl chloride (Preparation of adhesion promoter D))
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, under a nitrogen atmosphere, a silicone compound having an amino group (“X-22-9409” manufactured by Shin-Etsu Chemical Co., Ltd.), an amino group equivalent of 670 g / Mol) 10.1 g (amino group 15.1 mmol), toluene 50.0 g and triethylamine 1.61 g (15.9 mmol) were mixed, and further 3-phenylpropionyl chloride 2.68 g (15.9 mmol) was added dropwise, Stir at 25 ° C. for 5 hours. The residual amino group was confirmed to be less than 1% by neutralization titration. Thereafter, 25 g of water was added for liquid separation, and the organic layer was concentrated to obtain 9.75 g of a transparent liquid (adhesion imparting agent D).
As a result of measuring the adhesion-imparting agent D by 1 H-NMR, 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).
（製造例５）
（アミノ基を有するシリコーン化合物とベンゾイルクロリドとの反応（接着性付与剤Ｅの調製））
撹拌機、温度計及び冷却器を備え付けた２００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、アミノ基を有するシリコーン化合物（信越化学工業社製、「ＫＦ－８６４」、アミノ基当量３８００ｇ／ｍｏｌ）１０．０ｇ（アミノ基２．６３ｍｍｏｌ）、トルエン５０．０ｇ及びトリエチルアミン０．２８ｇ（２．７６ｍｍｏｌ）を混合し、更にベンゾイルクロリド０．３９ｇ（２．７６ｍｍｏｌ）を滴下し、２５℃で、２時間撹拌した。中和滴定により残存アミノ基が１％未満であることを確認した。その後、水２５ｇを加えて分液し、有機層を濃縮することで、透明液体（接着性付与剤Ｅ）８．７ｇを取得した。
１Ｈ－ＮＭＲにより、接着性付与剤Ｅを測定した結果、接着性付与剤Ｅは、前記式（１－１）で表される構造単位（Ｒ１ａがメチル基、Ａがメチル基）と、前記式（１－２）で表される構造単位（Ｒ１ａがメチル基、Ａがメチル基）と、前記式（１－３）（Ｒ１ｂがメチル基、Ａが式（２）で表される基であり、Ｒ２ａがｎ－プロピレン基、ｘが０、ＹがＮＨ、Ｒ３がフェニル基）と、前記式（１－４）で表される構造単位（Ｒ１ｂがメチル基）とを有していることを確認した。 (Production Example 5)
(Reaction of silicone compound having amino group with benzoyl chloride (Preparation of adhesion promoter E))
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, under a nitrogen atmosphere, a silicone compound having an amino group (“KF-864” manufactured by Shin-Etsu Chemical Co., Ltd., amino group equivalent: 3800 g / mol) ) 10.0 g (amino group 2.63 mmol), toluene 50.0 g and triethylamine 0.28 g (2.76 mmol) were mixed, and benzoyl chloride 0.39 g (2.76 mmol) was further added dropwise at 25 ° C. Stir for hours. The residual amino group was confirmed to be less than 1% by neutralization titration. Thereafter, 25 g of water was added for liquid separation, and the organic layer was concentrated to obtain 8.7 g of a transparent liquid (adhesion imparting agent E).
As a result of measuring the adhesion-imparting agent E by 1 H-NMR, 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.
（実施例１～１８、比較例１～８）
表１～３に記載した配合量で各成分を均一に混合し、その後、充分に脱気することで各シリコーン樹脂組成物を調製した。
なお、表１～３中の「付加硬化型シリコーン樹脂混合物Ａ」としては、ＯＥ－６６３０（東レ・ダウコーニング社製）Ａ液及びＢ液（１：４混合物）を用いた。付加硬化型シリコーン樹脂混合物Ａは炭素－炭素二重結合含有ポリオルガノシロキサン成分とポリオルガノハイドロジェンシロキサン成分を含有する混合物である。また、表１～３中の「付加硬化型シリコーン樹脂混合物Ｂ」としては、ＯＥ－６３７０Ｍ（東レ・ダウコーニング社製）Ａ液及びＢ液（１：１混合物）を用いた。付加硬化型シリコーン樹脂混合物Ｂは炭素－炭素二重結合含有ポリオルガノシロキサン成分とポリオルガノハイドロジェンシロキサン成分を含有する混合物である。更に、表１～３中の「縮合硬化型シリコーン樹脂混合物Ｃ」としては、２液縮合アセトン型シリコーン樹脂混合物（信越化学工業社製、「ＫＥ－２００」）を用いた。また、表１～３中の接着性付与剤Ｆとしては、グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング社製、「Ｚ－６０４０」）を用い、表１～３中の接着性付与剤Ｇとしてはイソシアヌル酸トリグリシジル（東京化成工業社製）を用いた。 (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.
As “addition-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. In addition, as “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. Further, as the “condensation curable silicone resin mixture C” in Tables 1 to 3, a two-component condensation acetone type silicone resin mixture (“KE-200” manufactured by Shin-Etsu Chemical Co., Ltd.) was used. In addition, as the 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. As G, triglycidyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
＜評価＞
実施例１～１８及び比較例１～８で得られた各シリコーン樹脂組成物について、以下の評価を行った。結果を表１～３に示した。 <Evaluation>
The following evaluations were performed on the silicone resin compositions obtained in Examples 1 to 18 and Comparative Examples 1 to 8. The results are shown in Tables 1-3.
（１）硬度（タイプＤ、タイプＡ）
付加硬化型シリコーン樹脂混合物Ａを含有する各付加硬化型シリコーン樹脂組成物（実施例１～１２及び比較例１～３）を樹脂製モールドに流し込み、１５０℃で２時間加熱し、付加硬化型シリコーン樹脂組成物を硬化させた。得られた硬化物をモールドから離型し、半径２０ｍｍ×厚さ６ｍｍの硬化物とし、硬度測定用試験片とした。得られた硬度測定用試験片について、ゴム硬度計（ＡＳＫＥＲ社製、Ｄ型）を用いて硬度（タイプＤ）を測定した。
また、付加硬化型シリコーン樹脂混合物Ｂを含有する各付加硬化型シリコーン樹脂組成物（実施例１３～１５及び比較例４～６）を樹脂製モールドに流し込み、１５０℃で４時間加熱し、付加硬化型シリコーン樹脂組成物を硬化させた。得られた硬化物をモールドから離型し、半径２０ｍｍ×厚さ６ｍｍの硬化物とし、硬度測定用試験片とした。得られた硬度測定用試験片について、ゴム・プラスチック硬度計（古里精機製作所社製、「ＫＲ－２４Ａ」）を用いて硬度（タイプＡ）を測定した。
更に、縮合硬化型シリコーン樹脂混合物Ｃを含有する各縮合硬化型シリコーン樹脂組成物（実施例１６～１８及び比較例７、８）を樹脂製モールドに流し込み、室温で１週間静置し、縮合硬化型シリコーン樹脂組成物を硬化させた。得られた硬化物をモールドから離型し、半径２０ｍｍ×厚さ６ｍｍの硬化物とし、硬度測定用試験片とした。得られた硬度測定用試験片について、ゴム・プラスチック硬度計（古里精機製作所社製、「ＫＲ－２４Ａ」）を用いて硬度（タイプＡ）を測定した。 (1) 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).
Also, 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”).
Further, 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”).
（２）銀メッキ銅板に対する引張せん断接着強度
実施例１～１８及び比較例１～８で得られた各シリコーン樹脂組成物を、接着部が幅２０ｍｍ、長さ２５ｍｍの長方形になるように２枚の銀メッキ銅板（厚さ２ｍｍ、幅２５ｍｍ、長さ１００ｍｍ）の間に２ｍｍ厚となるように流し込んだ後に、各シリコーン樹脂組成物の硬化を行い（実施例１～１２及び比較例１～３で得られた各シリコーン樹脂組成物は１５０℃で２時間加熱して硬化、実施例１３～１５及び比較例４～６で得られた各シリコーン樹脂組成物は１５０℃で４時間加熱して硬化、実施例１６～１８及び比較例７、８で得られた各シリコーン樹脂組成物は室温で１週間静置して硬化した）、引張せん断接着試験片とした。接着基材である銀メッキ銅板は、１５０℃で１時間乾燥させたものを使用した。得られた引張せん断接着試験片について、引張試験機（島津製作所社製、「ＡＧＳ－Ｘ」）を用いて、つかみ具間距離１００ｍｍ、試験速度５ｍｍ／ｍｉｎの条件で引張せん断接着試験を行い、引張せん断接着強度を測定した。 (2) Tensile shear adhesive strength to silver-plated copper plate 2 pieces of each silicone resin composition obtained in Examples 1 to 18 and Comparative Examples 1 to 8 so that the bonded part is a rectangle having a width of 20 mm and a length of 25 mm Each of the silicone resin compositions was cured after flowing into a silver-plated copper plate (thickness 2 mm, width 25 mm, length 100 mm) to a thickness of 2 mm (Examples 1 to 12 and Comparative Examples 1 to 3). Each silicone resin composition obtained in 1) was cured by heating at 150 ° C. for 2 hours, and each silicone resin composition obtained in Examples 13 to 15 and Comparative Examples 4 to 6 was cured by heating at 150 ° C. for 4 hours. 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.
表１～３より、本発明にかかる接着性付与剤を配合することで、銀メッキ銅板に対する接着性が向上していることがわかる。一方で、接着性付与剤を配合しなかった、又は、一般的に接着性を向上させる目的に用いられるグリシドキシプロピルトリメトキシシランやイソシアヌル酸トリグリシジルを配合した比較例１～８においては、接着性は不充分なものであった。 From Tables 1 to 3, it can be seen that the adhesiveness to the silver-plated copper plate is improved by blending the adhesiveness imparting agent according to the present invention. On the other hand, in Comparative Examples 1 to 8 in which no adhesion-imparting agent was blended or glycidoxypropyltrimethoxysilane or triglycidyl isocyanurate, which is generally used for the purpose of improving adhesion, Adhesion was insufficient.
（３）赤インク試験
実施例１～１８及び比較例１～８で得られた各シリコーン樹脂組成物をＬＥＤパッケージ１０個に充填した後に、各シリコーン樹脂組成物の硬化を行い（実施例１～１２及び比較例１～３で得られた各シリコーン樹脂組成物は１５０℃で２時間加熱して硬化、実施例１３～１５及び比較例４～６で得られた各シリコーン樹脂組成物は１５０℃で４時間加熱して硬化、実施例１６～１８及び比較例７、８で得られた各シリコーン樹脂組成物は室温で１週間静置して硬化した）、加湿リフロー試験用封止体を作製した。作製した各封止体を８５℃、８５ＲＨ％の雰囲気下に１６８時間放置し、充分に吸湿させた後、２６０℃のリフロー炉に１分間通した（加湿リフロー試験）。
作製直後（初期）及び加湿リフロー試験後の各封止体を赤インクに２４時間浸漬させた。浸漬後の封止体の状態を目視にて観察し、剥離やクラックの有無を確認した。
評価基準としてはＬＥＤパッケージとシリコーン樹脂硬化物との間に赤インクが浸透しているものを不合格とし、赤インクが浸透していないものを合格とした。不合格が０個の場合を「◎」、不合格が１個の場合を「○」、不合格が２～３個の場合を「△」、不合格が４個以上の場合を「×」として評価した。 (3) Red ink test Each silicone resin composition obtained in Examples 1 to 18 and Comparative Examples 1 to 8 was 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. and 85 RH% for 168 hours to absorb moisture sufficiently, and then passed through a reflow oven at 260 ° C. for 1 minute (humidified reflow test).
Immediately after production (initial stage) and after the humidification reflow test, 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.
表１～３より、本発明にかかる接着性付与剤を配合することで、高温・高湿下においても接着性の低下により剥離が生じていないことがわかる。一方で、接着性付与剤を配合しなかった、又は、一般的に接着性を向上させる目的に用いられるグリシドキシプロピルトリメトキシシランやイソシアヌル酸トリグリシジルを配合した比較例１～８においては、高温・高湿下において接着性が低下していることがわかる。 From Tables 1 to 3, it can be seen that, when the adhesion-imparting agent according to the present invention is blended, peeling does not occur due to a decrease in adhesion even under high temperature and high humidity. On the other hand, in Comparative Examples 1 to 8 in which no adhesion-imparting agent was blended or glycidoxypropyltrimethoxysilane or triglycidyl isocyanurate, which is generally used for the purpose of improving adhesion, It can be seen that the adhesiveness is lowered under high temperature and high humidity.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
本発明によれば、界面接着性及び耐湿熱性に優れるシリコーン樹脂組成物を提供することができる。また、本発明によれば、該シリコーン樹脂組成物を用いてなるシリコーン樹脂硬化物及び光半導体素子封止体を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the silicone resin composition excellent in interfacial adhesiveness and heat-and-moisture resistance can be provided. Moreover, according to this invention, the silicone resin hardened | cured material and optical semiconductor element sealing body which use this silicone resin composition can be provided.

Claims (7)

  1. シリコーン樹脂混合物と接着性付与剤とを含有するシリコーン樹脂組成物であって、
    前記接着性付与剤は、下記式（１－１）で表される構造単位と下記式（１－２）で表される構造単位との間に、下記式（１－３）で表される構造単位及び／又は下記式（１－４）で表される構造単位を有する化合物を含有することを特徴とするシリコーン樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     式（１－１）及び式（１－２）中、Ｒ１ａは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、又は、炭素数１～４のアルコキシ基を表す。式（１－３）及び式（１－４）中、Ｒ１ｂは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、又は、炭素数１～４のアルコキシ基を表す。式（１－３）中、ｍは、１～５０の整数であり、式（１－４）中、ｎは、１～１５００の整数である。式（１－１）～（１－３）中、Ａは、それぞれ独立に、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～１８のアルキル基、シクロアルキル基、アリール基、アラルキル基、炭素数２～９のアルケニル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルオキシ基、炭素数１～４のアルコキシ基、又は、下記式（２）で表される基を表す。ただし、式（１－１）～（１－３）中、少なくとも１つのＡは式（２）で表される基である。
    Figure JPOXMLDOC01-appb-C000002
     式（２）中、Ｒ２ａは、ケイ素原子に結合した炭素原子を除く一部の炭素原子が酸素原子で置換されていてもよい炭素数１～８のアルキレン基を表し、Ｒ２ｂは、それぞれ独立に、炭素数１～３のアルキレン基を表し、Ｒ３は、それぞれ独立に、直鎖状若しくは分岐鎖状の炭素数１～３０のアルキル基、炭素数２～７のアルケニル基、シクロアルキル基、アリール基、又は、アラルキル基を表す。式（２）中、ｘは、０～２の整数であり、Ｙは、酸素原子又はＮＨを表す。     A silicone resin composition containing a silicone resin mixture and an adhesion promoter,
    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). A silicone resin composition comprising a compound having a structural unit and / or a structural unit represented by the following formula (1-4).
    Figure JPOXMLDOC01-appb-C000001
     In formulas (1-1) and (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. -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. In formulas (1-3) and (1-4), 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. In the formula (1-3), m is an integer of 1 to 50, and in the formula (1-4), n is an integer of 1 to 1500. In formulas (1-1) to (1-3), 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. An alkyl group, 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, an alkoxy group having 1 to 4 carbon atoms, or 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).
    Figure JPOXMLDOC01-appb-C000002
     In the 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, and R 2b represents Each independently represents an alkylene group having 1 to 3 carbon atoms, and 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. Represents a group, an aryl group, or an aralkyl group. In the formula (2), x is an integer of 0 to 2, and Y represents an oxygen atom or NH.
  2. 式（２）において、Ｒ３が、それぞれ独立に、直鎖状若しくは分岐鎖状の炭素数１～３０のアルキル基、シクロアルキル基、アリール基、又は、アラルキル基である請求項１記載のシリコーン樹脂組成物。 2. The silicone according to claim 1, wherein in formula (2), each R 3 independently represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Resin composition.
  3. 接着性付与剤の含有量が０．０１～１５質量％である請求項１又は２記載のシリコーン樹脂組成物。 3. The silicone resin composition according to claim 1, wherein the content of the adhesiveness imparting agent is 0.01 to 15% by mass.
  4. シリコーン樹脂混合物は、ケイ素原子に結合した炭素－炭素二重結合を有する置換基を少なくとも２個有するポリオルガノシロキサンと、ケイ素原子に結合した水素原子を少なくとも２個有するポリオルガノハイドロジェンシロキサンと、ヒドロシリル化反応触媒とを含有する請求項１、２又は３記載のシリコーン樹脂組成物。 The silicone resin mixture includes a polyorganosiloxane having at least two substituents having a carbon-carbon double bond bonded to a silicon atom, a polyorganohydrogensiloxane having at least two hydrogen atoms bonded to a silicon atom, and hydrosilyl The silicone resin composition according to claim 1, 2, or 3, which comprises a fluorination reaction catalyst.
  5. ポリオルガノシロキサン中のケイ素原子に結合した炭素－炭素二重結合を有する置換基は、ビニル基である請求項４記載のシリコーン樹脂組成物。 5. The silicone resin composition according to claim 4, wherein the substituent having a carbon-carbon double bond bonded to a silicon atom in the polyorganosiloxane is a vinyl group.
  6. 請求項１、２、３、４又は５記載のシリコーン樹脂組成物を硬化させることによって得られるシリコーン樹脂硬化物。 A cured silicone resin obtained by curing the silicone resin composition according to claim 1, 2, 3, 4 or 5.
  7. 光半導体素子が請求項６記載のシリコーン樹脂硬化物で封止されている光半導体素子封止体。 A sealed optical semiconductor element in which the optical semiconductor element is sealed with the cured silicone resin according to claim 6.
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