WO2015163355A1 - Composition de résine durcissable, produit durci correspondant, dérivé du glycoluril et procédé de production correspondant - Google Patents

Composition de résine durcissable, produit durci correspondant, dérivé du glycoluril et procédé de production correspondant Download PDF

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Publication number
WO2015163355A1
WO2015163355A1 PCT/JP2015/062210 JP2015062210W WO2015163355A1 WO 2015163355 A1 WO2015163355 A1 WO 2015163355A1 JP 2015062210 W JP2015062210 W JP 2015062210W WO 2015163355 A1 WO2015163355 A1 WO 2015163355A1
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group
formula
represented
same
resin composition
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PCT/JP2015/062210
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English (en)
Japanese (ja)
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禿恵明
宝来晃
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株式会社ダイセル
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group
    • 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
    • C08L83/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item

Definitions

  • the present invention is obtained by sealing a curable resin composition and a cured product thereof, a sealing agent using the curable resin composition, and a semiconductor element (particularly an optical semiconductor element) using the sealing agent.
  • the present invention relates to a semiconductor device (especially an optical semiconductor device).
  • the present invention also relates to a glycoluril derivative particularly useful as a constituent of the curable resin composition and a method for producing the same.
  • sealing materials in optical semiconductor devices include barrier properties against corrosive gases such as SOx gas and thermal shock resistance (such as cracking or peeling of the sealing material even when a thermal shock such as a cold cycle is applied). (Characteristics that are less likely to cause malfunctions such as non-lighting of the semiconductor device) and reflow resistance (cracking or peeling of the sealing material even when extremely high temperature heat is applied during the reflow process) It is demanded that all of the above characteristics are satisfied at a high level at the same time.
  • phenylsilicone phenylsilicone-based encapsulant
  • phenylsilicone-based encapsulant which has a relatively good balance of barrier property against corrosive gas, thermal shock resistance, and reflow resistance
  • optical semiconductor devices for example, refer to Patent Document 1.
  • the phenyl silicone-based encapsulant has a higher barrier property against corrosive gas than the conventionally used methyl silicone-based encapsulant, its properties are still insufficient. Actually, even when a phenyl silicone-based sealing material is used, there has been a problem that the corrosion of the electrode by the corrosive gas progresses with time in the optical semiconductor device, and the energization characteristics deteriorate.
  • an object of the present invention is to provide a curable resin composition capable of forming a cured product (sealing material) excellent in all the characteristics of thermal shock resistance, reflow resistance, and barrier properties against corrosive gas (for example, SOx gas).
  • a material (cured product) excellent in all the characteristics of thermal shock resistance, reflow resistance, and barrier property against corrosive gas for example, SOx gas.
  • another object of the present invention is a quality obtained by sealing a sealing element using the curable resin composition, and sealing a semiconductor element (particularly an optical semiconductor element) using the sealing agent.
  • Another object of the present invention is to provide a semiconductor device (particularly an optical semiconductor device) having excellent durability.
  • the present inventors include a specific component having two or more alkenyl groups in the molecule, a specific component having two or more hydrosilyl groups in the molecule, and a glycoluril derivative having a specific structure as essential components. As a result, it was found that a cured product having excellent thermal shock resistance, reflow resistance, and barrier properties against corrosive gas (for example, SOx gas) can be formed. I let you.
  • corrosive gas for example, SOx gas
  • the present invention is selected from the group consisting of a polyorganosiloxane (A1) having two or more alkenyl groups in the molecule and a polyorganosiloxysilalkylene (A2) having two or more alkenyl groups in the molecule.
  • R e and R f are the same or different and each represents a hydrogen atom or an alkyl group.
  • s is the same or different and represents 0 or an integer of 1 or more.
  • R g is the same or different and represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
  • R h and R i are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and t represents 0 or an integer of 1 or more.
  • the curable resin composition characterized by including the glycoluril derivative (C) represented by these.
  • the polyorganosiloxane (A1) has the following average unit formula: (R 1 SiO 3/2) a1 ( R 1 2 SiO 2/2) a2 (R 1 3 SiO 1/2) a3 (SiO 4/2) a4 (XO 1/2) a5
  • R 1 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, provided that a part of R 1 is an alkenyl group (particularly a vinyl group), , Controlled within the range of two or more in the molecule
  • X is a hydrogen atom or an alkyl group
  • a1 is 0 or a positive number
  • a2 is 0 or a positive number
  • a3 is 0 or a positive number
  • a4 is 0 or a positive number
  • a5 is 0 or a positive number
  • (a1 + a2 + a3) is a positive number.
  • the said curable resin composition which is polyorganos
  • the present invention also provides the curable resin composition, wherein the polyorganosiloxane (A1) is a linear polyorganosiloxane represented by the following formula (I-1).
  • the polyorganosiloxane (A1) is a linear polyorganosiloxane represented by the following formula (I-1).
  • R 11 are the same or different and each represents a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R 11 are alkenyl groups.
  • m1 is an integer of 5 to 1000.
  • this invention provides the said curable resin composition whose polyorganosiloxane (A1) is the following ladder type polyorgano silsesquioxane (a) or (b).
  • R 19 represents an alkenyl group
  • R 20 are the same or different and each represents a monovalent substituted or unsubstituted hydrocarbon group.
  • the ladder-type polyorganosilsesquioxane (a) is represented by the following formula (I-2) and has two or more alkenyl groups in the molecule, and is determined by gel permeation chromatography.
  • the above curable resin composition which is a ladder type polyorganosilsesquioxane having a standard polystyrene equivalent number average molecular weight (Mn) of 500 to 1500 and a molecular weight dispersity (Mw / Mn) of 1.00 to 1.40. I will provide a.
  • R 12 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group
  • R 13 is the same or different and represents a hydrogen atom, an alkyl
  • R 14 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group
  • R 15 is the same or different and is a monovalent It is a substituted or unsubstituted hydrocarbon group
  • n1 represents an integer of 0 or more
  • R 14 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group
  • R 15 is the same or different and is a monovalent It is a substituted or unsubstituted hydrocarbon group
  • n2 represents an integer of 0 or more.
  • R 14 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group
  • R 17 is the same or different and is a monovalent It is a saturated aliphatic hydrocarbon group
  • n3 represents an integer of 0 or more.
  • the present invention also provides the curable resin composition, wherein the polyorganosilsesquioxane having a ladder structure in the ladder-type polyorganosilsesquioxane (b) is represented by the following formula (I-3): To do.
  • p represents an integer of 1 or more
  • R 18 is the same or different and represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group
  • T represents a terminal group. Indicates.
  • the present invention also provides the curable resin composition, wherein the ladder-type polyorganosilsesquioxane (b) is a ladder-type polyorganosilsesquioxane represented by the following formula (I-3 ′): To do.
  • p represents an integer of 1 or more
  • R 18 is the same or different and represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group
  • A represents A polyorganosilsesquioxane residue (a), or a hydroxy group, a halogen atom, an alkoxy group, or an acyloxy group, provided that a part or all of A is a polyorganosilsesquioxane residue (a) is there.
  • p represents an integer of 1 or more
  • R 18 is the same or different and represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group
  • A represents A polyorganosilsesquioxane residue (a), or a
  • the polyorganosiloxane (A1) has the following average unit formula: (R 1a 2 R 1b SiO 1/2 ) a6 (R 1a 3 SiO 1/2 ) a7 (SiO 4/2 ) a8 (HO 1/2 ) a9
  • R 1a is the same or different and represents an alkyl group having 1 to 10 carbon atoms
  • R 1b is the same or different and represents an alkenyl group
  • the said curable resin composition which is polyorganosiloxane represented by these is provided.
  • the polyorganosiloxysilalkylene (A2) has the following average unit formula: (R 2 2 SiO 2/2) b1 (R 2 3 SiO 1/2) b2 (R 2 SiO 3/2) b3 (SiO 4/2) b4 (R A) b5
  • R 2 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, provided that a part of R 2 is an alkenyl group (particularly a vinyl group), , Controlled within the range of two or more in the molecule
  • R A is an alkylene group; b1 is a positive number, b2 is a positive number, b3 is 0 or a positive number, b4 is 0 or a positive number, and b5 is a positive number.
  • the curable resin composition is a polyorganosiloxysilalkylene represented.
  • the present invention also provides the curable resin composition, wherein the polyorganosiloxysilalkylene (A2) is a polyorganosiloxysilalkylene having a structure represented by the following formula (II-1).
  • R 21 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, provided that at least two of R 21 are alkenyl groups;
  • R A represents an alkylene group, r1 represents an integer of 1 or more, and when r1 is an integer of 2 or more, the structures in parentheses to which r1 is attached may be the same or different, r2 represents an integer of 1 or more, and when r2 is an integer of 2 or more, the structures in parentheses to which r2 is attached may be the same or different, r3 represents 0 or an integer of 1 or more, and when r3 is an integer of 2 or more, the structures in parentheses to which r3 is attached may be the same or
  • the content (blending amount) (total amount) of the polysiloxane (A) is 50% by weight or more and less than 100% by weight with respect to the total amount (100% by weight) of the curable resin composition.
  • a curable resin composition is provided.
  • the present invention also provides the curable resin composition, wherein the ratio of the polyorganosiloxane (A1) to the total amount (100% by weight) of the polysiloxane (A) contained in the curable resin composition is 50 to 100% by weight. Offer things.
  • the present invention also relates to the curable resin composition, wherein the ratio of the polyorganosiloxysilalkylene (A2) to the total amount (100% by weight) of the polysiloxane (A) contained in the curable resin composition is 0 to 60% by weight.
  • a resin composition is provided.
  • the polyorganosiloxane (B1) has the following average unit formula: (R 3 SiO 3/2 ) c 1 (R 3 2 SiO 2/2 ) c 2 (R 3 3 SiO 1/2 ) c 3 (SiO 4/2 ) c 4 (XO 1/2 ) c 5 [In the above average unit formula, R 3 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, provided that a part of R 3 is a hydrogen atom (constituting a hydrosilyl group).
  • the hydrogen atom), and the ratio thereof is controlled in a range where two or more hydrosilyl groups are present in the molecule,
  • X is a hydrogen atom or an alkyl group, c1 is 0 or a positive number, c2 is 0 or a positive number, c3 is 0 or a positive number, c4 is 0 or a positive number, c5 is 0 or a positive number, and (c1 + c2 + c3) is a positive number.
  • the said curable resin composition which is polyorganosiloxane represented by these is provided.
  • the present invention also provides the curable resin composition, wherein the polyorganosiloxane (B1) is a linear polyorganosiloxane represented by the following formula (III-1).
  • the polyorganosiloxane (B1) is a linear polyorganosiloxane represented by the following formula (III-1).
  • R 31 are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R 31 are hydrogen atoms.
  • m2 is an integer of 5 to 1000.
  • the polyorganosiloxysilalkylene (B2) has the following average unit formula: (R 4 2 SiO 2/2 ) d1 (R 4 3 SiO 1/2 ) d2 (R 4 SiO 3/2 ) d3 (SiO 4/2 ) d4 (R A ) d5
  • R 4 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, provided that a part of R 4 is a hydrogen atom, Controlled within the range of 2 or more in the molecule
  • R A is an alkylene group
  • d1 is a positive number
  • d2 is a positive number
  • d3 is 0 or a positive number
  • d4 is 0 or a positive number
  • d5 is a positive number.
  • the curable resin composition is a polyorganosiloxysilalkylene represented by the formula:
  • the present invention also provides the curable resin composition, wherein the polyorganosiloxysilalkylene (B2) is a polyorganosiloxysilalkylene having a structure represented by the following formula (IV-1).
  • R 41 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, provided that at least two of R 41 are hydrogen atoms;
  • R A represents an alkylene group, q1 represents an integer of 1 or more, and when q1 is an integer of 2 or more, the structures in parentheses to which q1 is attached may be the same or different, q2 represents an integer of 1 or more.
  • q2 is an integer of 2 or more
  • the structures in parentheses to which q2 is attached may be the same or different
  • q3 represents 0 or an integer of 1 or more
  • q4 represents 0 or an integer of 1 or more
  • q5 represents 0 or an integer of 1 or more.
  • q5 is an integer of 2 or more
  • the structures in parentheses to which q5 is attached may be the same or different.
  • the present invention also provides the curable resin composition, wherein the content (blending amount) of the polysiloxane (B) is 1 to 200 parts by weight with respect to 100 parts by weight of the total amount of the polysiloxane (A). To do.
  • this invention is the said sclerosis
  • a resin composition is provided.
  • the present invention relates to the ratio of polyorganosiloxysilalkylene (A2) and polyorganosiloxysilalkylene (B2) to the total content (100% by weight) of polysiloxane (A) and polysiloxane (B) (total ratio). ) Is 3% by weight or more.
  • the curable resin composition is provided.
  • the content (blending amount) of the compound (C) in the curable resin composition exceeds 0 part by weight with respect to 100 parts by weight of the total amount of the polysiloxane (A) and the polysiloxane (B).
  • the curable resin composition is 20 parts by weight or less.
  • the curable resin composition containing a hydrosilylation catalyst is provided.
  • the present invention also provides a cured product obtained by curing the curable resin composition.
  • the curable resin composition as a sealing agent is provided.
  • the present invention also provides a semiconductor device obtained by sealing a semiconductor element using the curable resin composition.
  • the semiconductor device which is an optical semiconductor device is provided.
  • R a to R d are the same or different and are represented by the group represented by the following formula (1a), the group represented by the following formula (1b), or the following formula (1c).
  • at least one of R a to R d is a group selected from the group consisting of a group represented by the formula (1b) and a group represented by the formula (1c).
  • R e and R f are the same or different and each represents a hydrogen atom or an alkyl group.
  • s is the same or different and represents 0 or an integer of 1 or more.
  • R g is the same or different and represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
  • R h and R i are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and t represents 0 or an integer of 1 or more.
  • R a to R d are the same or different and are represented by the group represented by the following formula (1a), the group represented by the following formula (1b), or the following formula (1c).
  • at least one of R a to R d is a group selected from the group consisting of a group represented by the formula (1b) and a group represented by the formula (1c).
  • R e and R f are the same or different and each represents a hydrogen atom or an alkyl group.
  • s is the same or different and represents 0 or an integer of 1 or more.
  • R g is the same or different and represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
  • R h and R i are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and t represents 0 or an integer of 1 or more.
  • the cured product is excellent in all properties of thermal shock resistance, reflow resistance, and barrier property against corrosive gas (for example, SOx gas) by curing. Can be formed.
  • thermal shock such as a thermal cycle or high-temperature heat in a reflow process is applied to such an optical semiconductor device.
  • the sealing material is unlikely to crack or peel off, and it is difficult to cause problems such as non-lighting of the optical semiconductor device.
  • the cured product is particularly excellent in barrier properties against corrosive gas (especially SOx gas), when used as a sealing material for an optical semiconductor device, corrosion of the electrode of the device can be highly suppressed.
  • the durability of the optical semiconductor device can be significantly increased.
  • the curable resin composition of the present invention can be particularly preferably used as a sealant for an optical semiconductor element (LED element).
  • the curable resin composition (encapsulant) of the present invention can be used as an optical semiconductor element.
  • the optical semiconductor device obtained by encapsulating has excellent quality and durability.
  • FIG. 1 It is the schematic which shows one Embodiment of the optical semiconductor device by which the optical semiconductor element was sealed with the hardened
  • the left figure (a) is a perspective view
  • the right figure (b) is a sectional view.
  • the curable resin composition of the present invention comprises a group consisting of a polyorganosiloxane (A1) having two or more alkenyl groups in the molecule and a polyorganosiloxysilalkylene (A2) having two or more alkenyl groups in the molecule.
  • Polysiloxane (A) which is at least one selected from polysiloxane, polyorganosiloxane (B1) having two or more hydrosilyl groups in the molecule, and polyorganosiloxysilalkylene having two or more hydrosilyl groups in the molecule
  • a polysiloxane (B) which is at least one selected from the group consisting of (B2) and a glycoluril derivative (C) represented by the following formula (1) (simply “glycoluril derivative (C)" or “component (C) "may be included) as an essential component.
  • the curable resin composition of the present invention may contain other components such as a hydrosilylation catalyst described later in addition to the above-described essential components.
  • the polysiloxane (A) which is an essential component of the curable resin composition of the present invention, is a polyorganosiloxane (A1) having two or more alkenyl groups in the molecule (simply referred to as “polyorganosiloxane (A1). ) ”And polyorganosiloxysilalkylene (A2) having two or more alkenyl groups in the molecule (sometimes simply referred to as“ polyorganosiloxysilalkylene (A2) ”). At least one selected.
  • the polysiloxane (A) is a polysiloxane having an alkenyl group, and a component that causes a hydrosilylation reaction with a component having a hydrosilyl group (for example, polysiloxane (B) described later).
  • the polyorganosiloxysilalkylene (A2) in this specification has two or more alkenyl groups in the molecule, and in addition to —Si—O—Si— (siloxane bond) as a main chain, —Si—R A polyorganosiloxane containing A 2 —Si— (silalkylene bond: R A represents an alkylene group).
  • polyorganosiloxane (A1) in this specification is a polyorganosiloxane which has two or more alkenyl groups in a molecule
  • polyorganosiloxane (A1) examples include those having a linear, partially branched linear, branched, or network molecular structure.
  • polyorganosiloxane (A1) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • two or more polyorganosiloxanes (A1) having different molecular structures can be used in combination, for example, a linear polyorganosiloxane (A1) and a branched polyorganosiloxane (A1) are used in combination. You can also.
  • alkenyl group that the polyorganosiloxane (A1) has in the molecule examples include substituted or unsubstituted alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, and hexenyl group.
  • substituent examples include a halogen atom, a hydroxy group, and a carboxy group. Among these, a vinyl group is preferable.
  • the polyorganosiloxane (A1) may have only one alkenyl group or may have two or more alkenyl groups. Although the alkenyl group which polyorganosiloxane (A1) has is not specifically limited, It is preferable that it is a thing couple
  • bonded with silicon atoms other than the alkenyl group which polyorganosiloxane (A1) has is not specifically limited,
  • a hydrogen atom, an organic group, etc. are mentioned.
  • the organic group include alkyl groups [eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.], cycloalkyl groups [eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.
  • Cyclododecyl group, etc. aryl group [eg, phenyl group, tolyl group, xylyl group, naphthyl group, etc.], cycloalkyl-alkyl group [eg, cyclohexylmethyl group, methylcyclohexyl group, etc.], aralkyl group [eg, Benzyl group, phenethyl group, etc.], halogenated hydrocarbon groups in which one or more hydrogen atoms in the hydrocarbon group are replaced by halogen atoms [eg, chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoro Monovalent substituted or unsubstituted hydrocarbon groups such as halogenated alkyl groups such as propyl groups] And the like.
  • the “group bonded to a silicon atom” usually means a group not containing a silicon atom.
  • the group bonded to the silicon atom may have a hydroxy group or an alkoxy group.
  • the properties of the polyorganosiloxane (A1) are not particularly limited, and may be liquid or solid.
  • R 1 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and the above specific examples (for example, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated carbonization) Hydrogen group, etc.).
  • R 1 is an alkenyl group (especially vinyl), the ratio is controlled to the range of 2 or more in the molecule.
  • the ratio of the alkenyl group to the total amount of R 1 (100 mol%) is preferably 0.1 to 40 mol%.
  • R 1 other than the alkenyl group an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.
  • X is a hydrogen atom or an alkyl group.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.
  • a1 is 0 or positive number
  • a2 is 0 or positive number
  • a3 is 0 or positive number
  • a4 is 0 or positive number
  • a5 is 0 or positive number
  • (a1 + a2 + a3) is positive Is a number.
  • polyorganosiloxane (A1) is a linear polyorganosiloxane having two or more alkenyl groups in the molecule.
  • alkenyl group of the linear polyorganosiloxane include the above-described specific examples. Among them, a vinyl group is preferable.
  • examples of the group bonded to the silicon atom other than the alkenyl group in the linear polyorganosiloxane include the monovalent substituted or unsubstituted hydrocarbon group described above, among which an alkyl group (particularly a methyl group). ) Or an aryl group (particularly a phenyl group).
  • the ratio of the alkenyl group to the total amount (100 mol%) of groups bonded to silicon atoms in the linear polyorganosiloxane is not particularly limited, but is preferably 0.1 to 40 mol%. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 1 to 20 mol%. Further, the ratio of aryl groups (particularly phenyl groups) to the total amount of groups bonded to silicon atoms (100 mol%) is not particularly limited, but is preferably 30 to 90 mol%.
  • the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 80 mol%).
  • cured material to improve more.
  • the ratio of alkyl groups (particularly methyl groups) to 90 mol% or more (for example, 95 to 99 mol%) relative to the total amount (100 mol%) of groups bonded to silicon atoms is used, There is a tendency that the thermal shock resistance of is improved.
  • the linear polyorganosiloxane is represented, for example, by the following formula (I-1).
  • R 11 are the same or different and each represents a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R 11 are alkenyl groups.
  • m1 is an integer of 5 to 1000.
  • polyorganosiloxane (A1) is a branched polyorganosiloxane having two or more alkenyl groups in the molecule and having a siloxane unit (T unit) represented by RSiO 3/2. It is done.
  • R is a monovalent substituted or unsubstituted hydrocarbon group.
  • alkenyl group of the branched polyorganosiloxane include the specific examples described above, and among them, a vinyl group is preferable. In addition, you may have only 1 type of alkenyl group, and you may have 2 or more types of alkenyl groups.
  • Examples of the group bonded to the silicon atom other than the alkenyl group in the branched polyorganosiloxane include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, and among them, an alkyl group (particularly a methyl group). ) Or an aryl group (particularly a phenyl group). Furthermore, as R in the T unit, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.
  • the ratio of the alkenyl group to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but from the viewpoint of curability of the curable resin composition, 0.1 to 40 mol% is preferred. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of groups bonded to the silicon atom is not particularly limited, but is preferably 10 to 40 mol%. Further, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is not particularly limited, but is preferably 5 to 70 mol%.
  • the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 60 mol%).
  • cured material to improve more.
  • a cured product can be obtained by using a compound in which the ratio of alkyl groups (particularly methyl groups) is 50 mol% or more (for example, 60 to 99 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms.
  • the thermal shock resistance of is improved.
  • the branched polyorganosiloxane can be represented by the above average unit formula in which a1 is a positive number.
  • a2 / a1 is a number from 0 to 10
  • a3 / a1 is a number from 0 to 0.5
  • a4 / (a1 + a2 + a3 + a4) is a number from 0 to 0.3
  • a5 / (a1 + a2 + a3 + a4) is A number of 0 to 0.4 is preferred.
  • the molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 500 to 10,000, more preferably 700 to 3000.
  • the following ladder type polyorganosilsesquioxane (a) or (b) is used, particularly in that the barrier property against the corrosive gas of the cured product can be remarkably improved. It is preferable.
  • ladder-type polyorganosilsesquioxane While ladder-type polyorganosilsesquioxane (a) has a ladder structure, this near 1050 cm -1 in the FT-IR spectrum (e.g., 1000 ⁇ 1100 cm -1) and 1150cm around -1 (e.g., 1100 cm - 1 to 1200 cm ⁇ 1 or less), each having an intrinsic absorption peak (that is, having at least two absorption peaks at 1000 to 1200 cm ⁇ 1 ) [reference: R.R. H. Raney, M.M. Itoh, A.D. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)].
  • the FT-IR spectrum can be measured by, for example, the following apparatus and conditions.
  • Measuring device Trade name “FT-720” (manufactured by Horiba, Ltd.) Measurement method: Transmission method Resolution: 4 cm -1 Measurement wavenumber range: 400-4000cm -1 Integration count: 16 times
  • the ladder-type polyorganosilsesquioxane (a) may have other silsesquioxane structures such as a cage structure and a random structure in addition to the ladder structure.
  • the ladder-type polyorganosilsesquioxane (a) has a number average molecular weight (Mn) in terms of standard polystyrene by gel permeation chromatography of 500 to 1500, preferably 550 to 1450, more preferably 600 to 1400. .
  • Mn number average molecular weight
  • the physical properties (heat resistance, gas barrier properties, etc.) of the cured product tend to be lowered.
  • Mn exceeds 1500, it tends to be a solid at room temperature, and the handleability tends to decrease.
  • compatibility with other components may deteriorate.
  • the ladder type polyorganosilsesquioxane (a) has a molecular weight dispersity (Mw / Mn) in terms of standard polystyrene by gel permeation chromatography of 1.00 to 1.40, preferably 1.35 or less (for example, 1.05 to 1.35), more preferably 1.30 or less (for example, 1.10 to 1.30).
  • Mw / Mn molecular weight dispersity
  • the molecular weight dispersity exceeds 1.40 for example, low-molecular siloxane increases, and the adhesiveness and gas barrier properties of the cured product tend to decrease.
  • the molecular weight dispersity for example, by setting the molecular weight dispersity to 1.05 or more, it tends to be liquid at room temperature, and the handleability may be improved.
  • the number average molecular weight and molecular weight dispersion degree of ladder type polyorgano silsesquioxane (a) can be measured with the following apparatus and conditions.
  • Measuring device Product name “LC-20AD” (manufactured by Shimadzu Corporation)
  • Eluent THF, sample concentration 0.1-0.2% by weight
  • Flow rate 1 mL / min
  • Detector UV-VIS detector (trade name “SPD-20A”, manufactured by Shimadzu Corporation)
  • Molecular weight Standard polystyrene conversion
  • the 5% weight loss temperature (T d5 ) of the ladder-type polyorganosilsesquioxane (a) in a nitrogen atmosphere is not particularly limited, but is preferably 150 ° C. or higher, more preferably 240 ° C. or higher, and still more preferably 260 to 500 ° C., particularly preferably 262 ° C. or higher, most preferably 265 ° C. or higher. If the 5% weight loss temperature is less than 150 ° C. (particularly less than 240 ° C.), the required heat resistance may not be satisfied depending on the application.
  • the 5% weight reduction temperature is a temperature at the time when 5% of the weight before heating is reduced when heated at a constant rate of temperature increase, and serves as an index of heat resistance.
  • the 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under a nitrogen atmosphere under a temperature increase rate of 20 ° C./min.
  • the ladder-type polyorganosilsesquioxane (a) is not particularly limited, but is preferably liquid at room temperature (25 ° C.).
  • the viscosity at 25 ° C. is not particularly limited, but is preferably 30000 Pa ⁇ s or less (eg, 1 to 30000 Pa ⁇ s), more preferably 25000 Pa ⁇ s or less, and further preferably 10000 Pa ⁇ s or less.
  • the viscosity can be measured using a viscometer (trade name “MCR301”, manufactured by Anton Paar) under the conditions of a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25 ° C. it can.
  • the ladder-type polyorganosilsesquioxane (a) is, for example, represented by the following formula (I-2), having two or more alkenyl groups in the molecule, and converted to standard polystyrene by gel permeation chromatography And ladder type polyorganosilsesquioxane having a number average molecular weight (Mn) of 500 to 1500 and a molecular weight dispersity (Mw / Mn) of 1.00 to 1.40.
  • Mn number average molecular weight
  • Mw / Mn molecular weight dispersity
  • R 12 are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
  • R 12 include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (including alkenyl groups).
  • the ladder type polyorganosilsesquioxane (a) may or may not have an alkenyl group as R 12 .
  • the ladder type polyorganosilsesquioxane (a) has at least one group selected from the group consisting of an alkyl group and an aryl group as R 12 other than the alkenyl group in the formula (I-2). It is more preferable to have at least one group selected from the group consisting of a phenyl group and a methyl group.
  • the ratio (total content) of phenyl groups, vinyl groups, and methyl groups in the total amount (100% by weight) of R 12 in the above formula (I-2) of the ladder type polyorganosilsesquioxane (a) is as follows: Although not particularly limited, it is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and still more preferably 80 to 100% by weight.
  • the ratio (content) of the phenyl group in the total amount (100% by weight) of R 12 in the above formula (I-2) of the ladder-type polyorganosilsesquioxane (a) is not particularly limited, but is 0 to 100 % By weight is preferable, more preferably 1 to 100% by weight, still more preferably 5 to 100% by weight.
  • the ratio (content) of the vinyl group in the total amount (100 wt%) of R 12 in the above formula (I-2) of the ladder type polyorganosilsesquioxane (a) is not particularly limited, but is 0 to 100 % By weight is preferable, more preferably 1 to 100% by weight, still more preferably 5 to 90% by weight, and particularly preferably 10 to 80% by weight.
  • the ratio (content) of the methyl group in the total amount (100 wt%) of R 12 in the above formula (I-2) of the ladder type polyorganosilsesquioxane (a) is not particularly limited, but is 0 to 100 % By weight is preferable, more preferably 1 to 100% by weight, still more preferably 5 to 100% by weight.
  • composition of R 12 in the above formula (I-2) of the ladder-type polyorganosilsesquioxane (a) is, for example, an NMR spectrum (for example, 1 H-NMR spectrum) and the like.
  • R 13 is the same or different and is a hydrogen atom, an alkyl group, a monovalent group represented by the following formula (I-2-1), the following formula (I-2-2) ) Or a monovalent group represented by the following formula (I-2-3).
  • R 14 s are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
  • R 14 include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (including alkenyl groups), and among them, alkyl groups are preferable.
  • R 15 are the same or different and each represents a monovalent substituted or unsubstituted hydrocarbon group.
  • R 15 are the aforementioned monovalent substituted or unsubstituted hydrocarbon group (alkenyl group include). Among them, alkyl groups are preferred.
  • n1 represents an integer of 0 or more. n1 is preferably 0 to 5, more preferably 0 to 3, and still more preferably 0.
  • R 14 is, like the R 14 in the formula (I-2-1), the same or different and each represents a hydrogen atom, or, a monovalent substituted or unsubstituted hydrocarbon group is there.
  • R 14 is particularly preferably an alkyl group.
  • R 15 is, like the R 15 in the formula (I-2-1), the same or different, is a monovalent substituted or unsubstituted hydrocarbon group.
  • R 15 is particularly preferably an alkyl group.
  • R 16 is an alkenyl group, and among them, a vinyl group is preferable.
  • n2 represents an integer of 0 or more. n2 is preferably 0 to 5, more preferably 0 to 3, and still more preferably 0.
  • R 14 is, like the R 14 in the formula (I-2-1), the same or different and each represents a hydrogen atom, or, a monovalent substituted or unsubstituted hydrocarbon group is there.
  • R 14 is particularly preferably an alkyl group.
  • R 17 is the same or different and is a monovalent saturated aliphatic hydrocarbon group, and examples thereof include an alkyl group and a cycloalkyl group. Groups (especially methyl groups) are preferred.
  • n3 represents an integer of 0 or more. n3 is preferably 0 to 5, more preferably 0 to 3, and still more preferably 0.
  • n represents an integer of 0 or more.
  • the n is usually an even number of 0 or more (for example, an even number of 2 or more).
  • the n is not particularly limited as long as the number average molecular weight of the ladder type polyorganosilsesquioxane (a) is controlled to 500 to 1500 and the molecular weight dispersity is controlled to 1.00 to 1.40.
  • the ladder-type polyorganosilsesquioxane (a) is generally represented by the formula (I-2)
  • the ladder-type polyorganosilsesquioxane (a) preferably contains a component having n of 1 or more (particularly 2 or more) as an essential component.
  • the ladder type polyorganosilsesquioxane (a) has two or more alkenyl groups in the molecule.
  • a vinyl group is particularly preferable.
  • the ladder type polyorganosilsesquioxane (a) is represented by the formula (I-2), for example, one in which any one of R 12 in the formula (I-2) is an alkenyl group, R 14 and R 15 Having a monovalent group represented by the formula (I-2-1) in which any one of them is an alkenyl group, having a monovalent group represented by the formula (I-2-2), R 14 And those having a monovalent group represented by the formula (I-2-3) in which any one of them is an alkenyl group.
  • the ladder-type polyorganosilsesquioxane (a) can be produced by a known and commonly used method, and is not particularly limited.
  • Ladder type polyorganosilsesquioxane (b)
  • the polyorganosilsesquioxane having a ladder structure in the ladder-type polyorganosilsesquioxane (b) is represented, for example, by the following formula (I-3).
  • p represents an integer of 1 or more (for example, 1 to 5000), preferably an integer of 1 to 2000, and more preferably an integer of 1 to 1000.
  • T represents a terminal group.
  • the group directly bonded to the silicon atom in the polyorganosilsesquioxane (for example, R 18 in formula (I-3)) in the ladder-type polyorganosilsesquioxane (b) is not particularly limited, but the group The ratio of monovalent substituted or unsubstituted hydrocarbon groups to the total amount (100 mol%) is preferably 50 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more.
  • a substituted or unsubstituted C 1-10 alkyl group (especially a C 1-4 alkyl group such as a methyl group or an ethyl group), a substituted or unsubstituted C 6-
  • the total amount of 10 aryl groups (particularly phenyl groups) and substituted or unsubstituted C 7-10 aralkyl groups (particularly benzyl groups) is preferably 50 mol% or more, more preferably 80 mol% or more, More preferably, it is 90 mol% or more.
  • the ladder-type polyorganosilsesquioxane (b) has a polyorganosilsesquioxane residue (a) at part or all of the molecular chain terminals of the polyorganosilsesquioxane having the ladder structure.
  • the ladder-type polyorganosilsesquioxane (b) has a part or all of T in the formula (I-3) It is substituted with a polyorganosilsesquioxane residue (a).
  • the polyorganosilsesquioxane residue (a) includes at least a structural unit represented by the formula (I-3-1) and a structural unit represented by the formula (I-3-2). It is a residue to contain.
  • R 19 in the above formula (I-3-1) represents an alkenyl group.
  • the alkenyl group include the specific examples described above. Among them, a C 2-10 alkenyl group is preferable, a C 2-4 alkenyl group is more preferable, and a vinyl group is more preferable.
  • R 20 in the above formula (I-3-2) is the same or different and represents a monovalent substituted or unsubstituted hydrocarbon group.
  • substituted or unsubstituted hydrocarbon group the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (an alkenyl group is also included) etc. are mentioned.
  • the R 20, among them an alkyl group, more preferably C 1-20 alkyl group, more preferably a C 1-10 alkyl group, particularly preferably a C 1-4 alkyl group, and most preferably a methyl group.
  • it is preferable that all of R 20 in the formula (I-3-2) are a methyl group.
  • the polyorganosilsesquioxane residue (a) is, for example, And a structural unit represented by the following formula (I-3-1 ′).
  • 'R 19 in the formula (I-3-1)' represents a monovalent group excluding alkenyl groups.
  • a monovalent organic group excluding a hydrogen atom, a halogen atom, and an alkenyl group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, or a monovalent sulfur atom-containing group can be mentioned. It is done.
  • the amount of silicon atoms bonded to the three oxygen atoms represented by the formula (I-3-1) in the polyorganosilsesquioxane residue (a) is not particularly limited, but the polyorganosilsesquioxane residue is not limited.
  • the amount is preferably 20 to 80 mol%, more preferably 25 to 60 mol%, based on the total amount (100 mol%) of the silicon atoms constituting the group (a). If the content is less than 20 mol%, the amount of alkenyl groups contained in the ladder-type polyorganosilsesquioxane (b) becomes insufficient, and the hardness of the cured product may not be sufficiently obtained.
  • the ladder type polyorganosilsesquioxane (b) since many silanol groups and hydrolyzable silyl groups remain in the ladder type polyorganosilsesquioxane (b), the ladder type polyorganosilsesquioxane (b). May not be obtained in liquid form. Furthermore, since the condensation reaction proceeds in the product and the molecular weight changes, the storage stability may deteriorate.
  • the amount of silicon atoms bonded to one oxygen atom represented by formula (I-3-2) in the polyorganosilsesquioxane residue (a) is not particularly limited, but the polyorganosilsesquioxane residue is not limited.
  • the amount is preferably 20 to 85 mol%, more preferably 30 to 75 mol%, based on the total amount (100 mol%) of the silicon atoms constituting the group (a).
  • silanol groups and hydrolyzable silyl groups tend to remain in the ladder-type polyorganosilsesquioxane (b), and the ladder-type polyorganosilsesquioxane (b) is liquid. May not be available.
  • the condensation reaction proceeds in the product and the molecular weight changes, the storage stability may deteriorate.
  • the content exceeds 85 mol%, the amount of alkenyl groups contained in the ladder type polyorganosilsesquioxane (b) becomes insufficient, and the hardness of the cured product may not be sufficiently obtained.
  • the Si—O—Si structure (skeleton) of the polyorganosilsesquioxane residue (a) is not particularly limited, and examples thereof include a ladder structure, a cage structure, and a random structure.
  • the ladder type polyorganosilsesquioxane (b) can be represented by, for example, the following formula (I-3 ′).
  • Examples of p and R 18 in the formula (I-3 ′) are the same as those in the above formula (I-3).
  • a in the formula (I-3 ′) represents a polyorganosilsesquioxane residue (a), or a hydroxy group, a halogen atom, an alkoxy group, or an acyloxy group, and a part or all of A is a polyorgano It is a silsesquioxane residue (a).
  • the four A's may be the same or different.
  • each A is one or more Si—O—Si bonds. It may be connected via.
  • the number of alkenyl groups in the molecule may be two or more, and is not particularly limited, but is preferably 2 to 50, more preferably 2 to 30. .
  • an alkenyl group within the above-mentioned range, there is a tendency that a cured product excellent in various physical properties such as heat resistance, crack resistance, and barrier properties against corrosive gas tends to be obtained.
  • the number of alkenyl groups can be calculated by, for example, 1 H-NMR spectrum measurement.
  • the content of the alkenyl group in the ladder-type polyorganosilsesquioxane (b) is not particularly limited, but is preferably 0.7 to 5.5 mmol / g, more preferably 1.1 to 4.4 mmol / g. is there. Further, the ratio (weight basis) of the alkenyl group contained in the ladder type polyorganosilsesquioxane (b) is not particularly limited, but is preferably 2.0 to 15.0% by weight in terms of vinyl group, more preferably. Is 3.0 to 12.0% by weight.
  • the weight average molecular weight (Mw) of the ladder type polyorganosilsesquioxane (b) is not particularly limited, but is preferably from 100 to 800,000, more preferably from 200 to 100,000, still more preferably from 300 to 10,000, particularly preferably. Is from 500 to 8000, most preferably from 1700 to 7000. If the Mw is less than 100, the heat resistance of the cured product may decrease. On the other hand, if Mw exceeds 800,000, the compatibility with other components may decrease.
  • the Mw can be calculated from the molecular weight in terms of standard polystyrene by gel permeation chromatography, for example.
  • the number average molecular weight (Mn) of the ladder type polyorganosilsesquioxane (b) is not particularly limited, but is preferably from 800 to 800,000, more preferably from 150 to 100,000, still more preferably from 250 to 10,000, particularly preferably. Is from 400 to 8000, most preferably from 1500 to 7000. When Mn is less than 80, the heat resistance of the cured product may be lowered. On the other hand, if Mn exceeds 800,000, the compatibility with other components may decrease.
  • the Mn can be calculated from, for example, a molecular weight in terms of standard polystyrene by gel permeation chromatography.
  • the ladder type polyorganosilsesquioxane (b) is preferably liquid at normal temperature (about 25 ° C.). More specifically, the viscosity at 23 ° C. is preferably 100 to 100,000 mPa ⁇ s, more preferably 500 to 10,000 mPa ⁇ s, and still more preferably 1000 to 8000 mPa ⁇ s. If the viscosity is less than 100 mPa ⁇ s, the heat resistance of the cured product may decrease. On the other hand, when the viscosity exceeds 100,000 mPa ⁇ s, it may be difficult to prepare and handle the curable resin composition. The viscosity at 23 ° C.
  • the number of rotations can be measured under the condition of 20 rpm.
  • the method for producing the ladder-type polyorganosilsesquioxane (b) is not particularly limited.
  • the ladder-type polyorganosilsesquioxane (b) has a ladder structure and has a silanol group and / or a hydrolyzable silyl group (silanol group and hydrolyzable at the molecular chain terminal).
  • the method of forming the said silsesquioxane residue (a) with respect to the molecular chain terminal of the polyorgano silsesquioxane which has a silyl group (one or both) is mentioned. Specifically, it can be produced by a method disclosed in a document such as International Publication No. 2013/176238.
  • a1 and a2 are 0, and X is a hydrogen atom.
  • R 1a 2 R 1b SiO 1/2 a6
  • R 1a 3 SiO 1/2 a7
  • SiO 4/2 a8
  • HO 1/2 a9
  • R 1a is the same or different and represents an alkyl group having 1 to 10 carbon atoms.
  • R 1b is the same or different and represents an alkenyl group, and among them, a vinyl group is preferable.
  • A7 may be 0.
  • a6 / (a6 + a7) is preferably 0.2 to 0.3.
  • a8 / (a6 + a7 + a8) is preferably 0.55 to 0.60.
  • a9 / (a6 + a7 + a8) is preferably 0.01 to 0.025 from the viewpoint of the adhesiveness and mechanical strength of the cured product.
  • polyorganosiloxanes examples include polyorganosiloxanes composed of SiO 4/2 units and (CH 3 ) 2 (CH 2 ⁇ CH) SiO 1/2 units, SiO 4/2 units and (CH 3 ) Polyorganosiloxane composed of 2 (CH 2 ⁇ CH) SiO 1/2 units and (CH 3 ) 3 SiO 1/2 units.
  • the polyorganosiloxane (A1) may have two or more alkenyl groups in the molecule, and may further have a hydrosilyl group.
  • the polyorganosiloxane (A1) may be a polyorganosiloxane (B1) described later.
  • polyorganosiloxysil alkylene (A2) As described above, the polyorganosiloxysilalkylene (A2) is a polyorganosiloxane having two or more alkenyl groups in the molecule and containing a silalkylene bond as a main chain in addition to the siloxane bond.
  • the alkylene group in the silalkylene bond is preferably a C 2-4 alkylene group (particularly an ethylene group).
  • the polyorganosiloxysilalkylene (A2) is less likely to produce a low molecular weight ring in the production process than the polyorganosiloxane (A1), and is not easily decomposed by heating or the like to produce a silanol group (—SiOH).
  • the surface tackiness (tackiness) of the cured product of the curable resin composition tends to be low, and it tends to be more difficult to yellow.
  • polyorganosiloxysilalkylene (A2) examples include those having a linear, partially branched linear, branched, or network molecular structure.
  • polyorganosiloxysil alkylene (A2) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • two or more kinds of polyorganosiloxysilalkylene (A2) having different molecular structures can be used in combination, for example, linear polyorganosiloxysilalkylene (A2) and branched polyorganosiloxysilalkylene (A2).
  • A2) can also be used in combination.
  • alkenyl group that the polyorganosiloxysilalkylene (A2) has in the molecule include the specific examples described above, and among them, a vinyl group is preferable.
  • the polyorganosiloxysilalkylene (A2) may have only one alkenyl group or may have two or more alkenyl groups.
  • the alkenyl group of the polyorganosiloxysilalkylene (A2) is not particularly limited, but is preferably bonded to a silicon atom.
  • bonded with silicon atoms other than the alkenyl group which polyorganosiloxysil alkylene (A2) has is not specifically limited, For example, a hydrogen atom, an organic group, etc. are mentioned.
  • the organic group include the monovalent substituted or unsubstituted hydrocarbon group described above. Of these, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.
  • the group bonded to the silicon atom may have a hydroxy group or an alkoxy group.
  • the properties of the polyorganosiloxysilalkylene (A2) are not particularly limited, and may be liquid or solid.
  • polyorganosiloxysilalkylene (A2) As polyorganosiloxysilalkylene (A2), the following average unit formula: (R 2 2 SiO 2/2) b1 (R 2 3 SiO 1/2) b2 (R 2 SiO 3/2) b3 (SiO 4/2) b4 (R A) b5
  • R 2 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and the specific examples described above (for example, alkyl group, alkenyl group, aryl group, aralkyl group, alkyl halide) Group).
  • a part of R 2 is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of 2 or more in the molecule.
  • the ratio of the alkenyl group to the total amount of R 2 (100 mol%) is preferably 0.1 to 40 mol%.
  • R 2 other than the alkenyl group is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).
  • R A is an alkylene group as described above.
  • An ethylene group is particularly preferable.
  • b1 is a positive number
  • b2 is a positive number
  • b3 is 0 or a positive number
  • b4 is 0 or a positive number
  • b5 is a positive number.
  • b1 is preferably 1 to 200
  • b2 is preferably 1 to 200
  • b3 is preferably 0 to 10
  • b4 is preferably 0 to 5
  • b5 is preferably 1 to 100.
  • (b3 + b4) is a positive number, the mechanical strength of the cured product tends to be further improved.
  • examples of the polyorganosiloxysilalkylene (A2) include polyorganosiloxysilalkylene having a structure represented by the following formula (II-1).
  • R 21 are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
  • the R 21, specific examples of the above e.g., an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a halogenated hydrocarbon group).
  • at least two of R 21 are alkenyl groups (particularly vinyl groups).
  • R 21 other than the alkenyl group is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).
  • R A represents an alkylene group as described above, and among them, a C 2-4 alkylene group (particularly an ethylene group) is preferable.
  • RA alkylene group
  • these may be the same and may differ.
  • r1 represents an integer of 1 or more (for example, 1 to 100).
  • r1 is an integer greater than or equal to 2
  • subjected to r1 may be the same respectively, and may differ.
  • r2 represents an integer of 1 or more (for example, 1 to 400).
  • r2 is an integer greater than or equal to 2
  • subjected r2 may be respectively the same, and may differ.
  • r3 represents 0 or an integer of 1 or more (for example, 0 to 50).
  • r3 is an integer of 2 or more, the structures in parentheses to which r3 is attached may be the same or different.
  • r4 represents 0 or an integer of 1 or more (for example, 0 to 50).
  • r4 is an integer of 2 or more, the structures in parentheses to which r4 is attached may be the same or different.
  • r5 represents 0 or an integer of 1 or more (for example, 0 to 50).
  • r5 is an integer of 2 or more, the structures in parentheses to which r5 is attached may be the same or different.
  • each structural unit in the formula (II-1) is not particularly limited, and may be a random type or a block type.
  • the terminal structure of the polyorganosiloxysilalkylene having the structure represented by the formula (II-1) is not particularly limited.
  • a silanol group for example, a silanol group, an alkoxysilyl group, a trialkylsilyl group (for example, a structure to which r5 is attached) , Trimethylsilyl group, etc.).
  • Various groups such as an alkenyl group and a hydrosilyl group may be introduced at the terminal of the polyorganosiloxysilalkylene.
  • Polyorganosiloxysilalkylene (A2) can be produced by a known or commonly used method, and the production method is not particularly limited, but can be produced by, for example, the method described in JP2012-140617A. Moreover, as a product containing polyorganosiloxysilalkylene (A2), for example, trade names “ETERLED GD1130”, “ETERLED GD1125” (both manufactured by Changxing Chemical Industry) and the like are available.
  • the curable resin composition of the present invention preferably contains at least the above-mentioned branched polyorganosiloxane as the polyorganosiloxane (A1), more preferably from the viewpoint of the barrier property and strength (resin strength) of the cured product.
  • the ladder-type polyorganosilsesquioxane (a) or (b) is included, and it is particularly preferable that a polyorganosiloxysilalkylene (A2) is further included in addition to these.
  • the content (blending amount) (total amount) of the polysiloxane (A) in the curable resin composition of the present invention is not particularly limited, but is 50% by weight with respect to the total amount (100% by weight) of the curable resin composition.
  • the amount is preferably less than 100% by weight, more preferably 60 to 99% by weight, still more preferably 70 to 95% by weight.
  • the ratio of the polyorganosiloxane (A1) to the total amount (100% by weight) of the polysiloxane (A) contained in the curable resin composition of the present invention is not particularly limited, but is preferably 50 to 100% by weight, more preferably 60 to 87% by weight, more preferably 50 to 85% by weight. If the ratio is less than 50% by weight, the resin strength and the barrier property against SOx gas may be lowered.
  • the ratio of the polyorganosiloxysilalkylene (A2) to the total amount (100% by weight) of the polysiloxane (A) contained in the curable resin composition of the present invention is not particularly limited, but is preferably 0 to 60% by weight.
  • the amount is preferably 10 to 40% by weight, more preferably 15 to 30% by weight. When the ratio exceeds 60% by weight, the barrier property against the SOx gas of the cured product may be lowered.
  • the polysiloxane (B) which is an essential component of the curable resin composition of the present invention, has a polyorganosiloxane (B1) having two or more hydrosilyl groups (Si—H) in the molecule (simply “ Polyorganosiloxane (B1) ”and polyorganosiloxysilalkylene (B2) having two or more hydrosilyl groups in the molecule (sometimes simply referred to as“ polyorganosiloxysilalkylene (B2) ”) At least one selected from the group consisting of: That is, the polysiloxane (B) is a polysiloxane having a hydrosilyl group, and is a component that causes a hydrosilylation reaction with a component having an alkenyl group (for example, polysiloxane (A)).
  • the polyorganosiloxysilalkylene (B2) in the present specification has two or more hydrosilyl groups in the molecule, and in addition to —Si—O—Si— (siloxane bond) as a main chain, —Si—R A polyorganosiloxane containing A 2 —Si— (silalkylene bond: R A represents an alkylene group).
  • polyorganosiloxane (B1) in this specification is a polyorganosiloxane which has two or more hydrosilyl groups in a molecule
  • R A (alkylene group) as described above, for example, a linear or branched C 1-12 alkylene group may be mentioned, and preferably a linear or branched C 2-4 alkylene group ( In particular, ethylene group).
  • polyorganosiloxane (B1) examples include those having a linear, partially branched linear, branched, and network molecular structure.
  • polyorganosiloxane (B1) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • two or more polyorganosiloxanes (B1) having different molecular structures can be used in combination, for example, a linear polyorganosiloxane (B1) and a branched polyorganosiloxane (B1) are used in combination. You can also
  • a group other than a hydrogen atom is not particularly limited.
  • the monovalent substituted or unsubstituted hydrocarbon group described above more specifically, an alkyl group, An aryl group, an aralkyl group, a halogenated hydrocarbon group, etc. are mentioned.
  • an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.
  • the polyorganosiloxane (B1) may have an alkenyl group (for example, a vinyl group) as a group bonded to a silicon atom other than a hydrogen atom.
  • the properties of the polyorganosiloxane (B1) are not particularly limited, and may be liquid or solid. In particular, it is preferably a liquid, and more preferably a liquid having a viscosity at 25 ° C. of 0.1 to 1,000,000 mPa ⁇ s.
  • R 3 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and a hydrogen atom, the above-mentioned specific examples (for example, alkyl group, alkenyl group, aryl Group, aralkyl group, halogenated alkyl group and the like).
  • a part of R 3 is a hydrogen atom (hydrogen atom constituting a hydrosilyl group), and the ratio thereof is controlled in a range where two or more hydrosilyl groups are present in the molecule.
  • the ratio of hydrogen atoms to the total amount of R 3 (100 mol%) is preferably 0.1 to 40 mol%.
  • R 3 other than a hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).
  • X is a hydrogen atom or an alkyl group as described above.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.
  • c1 is 0 or positive number
  • c2 is 0 or positive number
  • c3 is 0 or positive number
  • c4 is 0 or positive number
  • c5 is 0 or positive number
  • (c1 + c2 + c3) is positive Is a number.
  • polyorganosiloxane (B1) includes a linear polyorganosiloxane having two or more hydrosilyl groups in the molecule.
  • group bonded to a silicon atom other than a hydrogen atom in the linear polyorganosiloxane include the monovalent substituted or unsubstituted hydrocarbon group described above, among which an alkyl group (particularly a methyl group), Aryl groups (particularly phenyl groups) are preferred.
  • the ratio of hydrogen atoms (hydrogen atoms bonded to silicon atoms) to the total amount of groups bonded to silicon atoms (100 mol%) in the linear polyorganosiloxane is not particularly limited, but is 0.1 to 40 mol%. Is preferred. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 20 to 99 mol%. Furthermore, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is not particularly limited, but is preferably 40 to 80 mol%.
  • the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 70 mol%).
  • cured material to improve more.
  • the ratio of alkyl groups (particularly methyl groups) to 90 mol% or more (for example, 95 to 99 mol%) relative to the total amount (100 mol%) of groups bonded to silicon atoms is used, There is a tendency that the thermal shock resistance of is improved.
  • the linear polyorganosiloxane is represented, for example, by the following formula (III-1).
  • R 31 are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R 31 are hydrogen atoms.
  • m2 is an integer of 5 to 1000.
  • polyorganosiloxane (B1) is a branched polyorganosiloxane having two or more hydrosilyl groups in the molecule and having a siloxane unit (T unit) represented by RSiO 3/2. It is done.
  • R is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
  • Examples of the group bonded to a silicon atom other than a hydrogen atom in the branched polyorganosiloxane include the monovalent substituted or unsubstituted hydrocarbon group described above, among which an alkyl group (particularly a methyl group), Aryl groups (particularly phenyl groups) are preferred.
  • examples of R in the T unit include a hydrogen atom and the above-mentioned monovalent substituted or unsubstituted hydrocarbon group.
  • an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.
  • the ratio of the aryl group (particularly phenyl group) to the total amount of R in the T unit (100 mol%) is not particularly limited, but is preferably 30 mol% or more from the viewpoint of the barrier property against the corrosive gas of the cured product.
  • the ratio of alkyl groups (particularly methyl groups) to the total amount of groups bonded to silicon atoms (100 mol%) in the branched polyorganosiloxane is not particularly limited, but is preferably 70 to 95 mol%. Further, the ratio of aryl groups (particularly phenyl groups) to the total amount of groups bonded to silicon atoms (100 mol%) is not particularly limited, but is preferably 10 to 70 mol%. In particular, in the branched polyorganosiloxane, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 10 mol% or more (for example, 10 to 70 mol%).
  • a cured product can be obtained by using a compound in which the ratio of alkyl groups (particularly methyl groups) is 50 mol% or more (for example, 50 to 90 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. There is a tendency that the thermal shock resistance of is improved.
  • the branched polyorganosiloxane can be represented, for example, by the above average unit formula in which c1 is a positive number.
  • c2 / c1 is a number from 0 to 10
  • c3 / c1 is a number from 0 to 0.5
  • c4 / (c1 + c2 + c3 + c4) is a number from 0 to 0.3
  • c5 / (c1 + c2 + c3 + c4) is A number of 0 to 0.4 is preferred.
  • the molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 300 to 10,000, and more preferably 500 to 3000.
  • polyorganosiloxysilalkylene (B2) As described above, the polyorganosiloxysilalkylene (B2) is a polyorganosiloxane having two or more hydrosilyl groups in the molecule and containing a silalkylene bond as a main chain in addition to a siloxane bond.
  • a silalkylene bond As an alkylene group in the said silalkylene bond, a C2-4 alkylene group (especially ethylene group) is preferable, for example.
  • the polyorganosiloxysilalkylene (B2) is less likely to form a low molecular weight ring in the production process than the polyorganosiloxane (B1), and is not easily decomposed by heating or the like to produce a silanol group (—SiOH).
  • silanol group —SiOH.
  • polyorganosiloxysilalkylene (B2) examples include those having a linear, partially branched linear, branched, or network molecular structure.
  • polyorgano siloxysil alkylene (B2) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • two or more kinds of polyorganosiloxysilalkylene (B2) having different molecular structures can be used in combination, for example, linear polyorganosiloxysilalkylene (B2) and branched polyorganosiloxysilalkylene (B2). B2) can also be used in combination.
  • bonded with silicon atoms other than the hydrogen atom which polyorganosiloxysil alkylene (B2) has is not specifically limited,
  • an organic group etc. are mentioned.
  • the organic group include the monovalent substituted or unsubstituted hydrocarbon group described above. Of these, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.
  • the properties of the polyorganosiloxysilalkylene (B2) are not particularly limited, and may be liquid or solid.
  • R 4 2 SiO 2/2 As polyorganosiloxysilalkylene (B2), the following average unit formula: (R 4 2 SiO 2/2 ) d1 (R 4 3 SiO 1/2 ) d2 (R 4 SiO 3/2 ) d3 (SiO 4/2 ) d4 (R A ) d5
  • R 4 s are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Aralkyl group, halogenated alkyl group, etc.). However, a part of R 4 is a hydrogen atom, and the ratio thereof is controlled within a range of 2 or more in the molecule.
  • the ratio of hydrogen atoms to the total amount of R 4 (100 mol%) is preferably 0.1 to 50 mol%, more preferably 5 to 35 mol%.
  • R 4 other than a hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).
  • the ratio of aryl groups (particularly phenyl groups) to the total amount of R 4 (100 mol%) is preferably 5 mol% or more (eg, 5 to 80 mol%), more preferably 10 mol% or more.
  • R A is an alkylene group as described above.
  • An ethylene group is particularly preferable.
  • d1 is a positive number
  • d2 is a positive number
  • d3 is 0 or a positive number
  • d4 is 0 or a positive number
  • d5 is a positive number.
  • d1 is preferably 1 to 50
  • d2 is preferably 1 to 50
  • d3 is preferably 0 to 10
  • d4 is preferably 0 to 5
  • d5 is preferably 1 to 30.
  • examples of the polyorganosiloxysilalkylene (B2) include polyorganosiloxysilalkylene having a structure represented by the following formula (IV-1).
  • R 41 are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
  • R 41 include the above-described specific examples (eg, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated hydrocarbon group, etc.).
  • at least two of R 41 are hydrogen atoms.
  • R 41 other than a hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).
  • R A like R A in formula (II-1), an alkylene group, among them, C 2-4 alkylene group (in particular, an ethylene group) is preferable.
  • C 2-4 alkylene group in particular, an ethylene group
  • RA when several RA exists, these may be the same and may differ.
  • q1 represents an integer of 1 or more (for example, 1 to 100).
  • q1 is an integer greater than or equal to 2
  • subjected q1 may each be the same, and may differ.
  • q2 represents an integer of 1 or more (for example, 1 to 400).
  • q2 is an integer greater than or equal to 2
  • subjected q2 may each be the same, and may differ.
  • q3 represents 0 or an integer of 1 or more (for example, 0 to 50).
  • q3 is an integer greater than or equal to 2
  • subjected q3 may be respectively the same, and may differ.
  • q4 represents 0 or an integer of 1 or more (for example, 0 to 50).
  • q4 is an integer greater than or equal to 2
  • subjected q4 may be the same respectively, and may differ.
  • q5 represents 0 or an integer of 1 or more (for example, 0 to 50).
  • q5 is an integer greater than or equal to 2
  • subjected q5 may each be the same, and may differ.
  • each structural unit in the above formula (IV-1) is not particularly limited, and may be a random type or a block type.
  • the terminal structure of the polyorganosiloxysilalkylene having the structure represented by the formula (IV-1) is not particularly limited.
  • a silanol group for example, a silanol group, an alkoxysilyl group, a trialkylsilyl group (for example, a structure to which q5 is attached) , Trimethylsilyl group, etc.).
  • Various groups such as an alkenyl group and a hydrosilyl group may be introduced at the terminal of the polyorganosiloxysilalkylene.
  • Polyorganosiloxysilalkylene (B2) can be produced by a known or commonly used method, and the production method is not particularly limited, but can be produced, for example, by the method described in JP2012-140617A.
  • the content (blending amount) of the polysiloxane (B) in the curable resin composition of the present invention is not particularly limited, but is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the total amount of the polysiloxane (A).
  • the content of polysiloxane (B) is not particularly limited, but is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the total amount of the polysiloxane (A).
  • polysiloxane (B) in the curable resin composition of the present invention only polyorganosiloxane (B1) can be used, or only polyorganosiloxysilalkylene (B2) can be used.
  • Polyorganosiloxane (B1) and polyorganosiloxysilalkylene (B2) can also be used in combination.
  • these ratios are not particularly limited and can be appropriately set.
  • the total content (total content) of the polysiloxane (A) and the polysiloxane (B) in the curable resin composition (100% by weight) of the present invention is not particularly limited, but is 70% by weight or more (for example, 70%). % By weight or more and less than 100% by weight), more preferably 80% by weight or more, and still more preferably 90% by weight or more. When the total content is 70% by weight or more, the heat resistance and transparency of the cured product tend to be further improved.
  • the ratio (total ratio) is not particularly limited, but is preferably 3% by weight or more (for example, 60 to 100% by weight), more preferably 10% by weight or more, and further preferably 15 to 50% by weight. When the ratio is 3% by weight or more, the surface tackiness of the cured product tends to be lower and the thermal shock resistance tends to be good.
  • glycoluril derivative (C) which is an essential component of the curable resin composition of the present invention, is a compound (glycoluril derivative) represented by the above formula (1).
  • R a to R d are the same or different and are represented by the group represented by the following formula (1a), the group represented by the following formula (1b), or the following formula (1c). It is a group.
  • s is the same or different and represents 0 or an integer of 1 or more.
  • s is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and still more preferably an integer of 1 to 3, from the viewpoint of the barrier property against the corrosive gas of the cured product. Note that the total of four s present in the above formula (1) may be the same or different.
  • Examples of the group represented by the above formula (1a) include a vinyl group and an allyl group.
  • examples of the group represented by the above formula (1a) include a vinyl group and an allyl group.
  • two or more groups represented by the formula (1a) are present in the formula (1), these may be the same or different.
  • R g is the same or different and represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
  • the monovalent substituted or unsubstituted hydrocarbon group include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (including alkenyl groups).
  • monovalent aliphatic carbonization Hydrogen group eg, alkyl group, alkenyl group, etc.
  • monovalent alicyclic hydrocarbon group eg, cycloalkyl group, etc.
  • monovalent aromatic hydrocarbon group eg, aryl group, etc.
  • monovalent A heterocyclic group a monovalent group formed by combining two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group (for example, an alkyl and / or alkenyl-substituted cycloalkyl group) Cycloalkyl-alkyl group, alkyl and / or alkenyl-substituted aryl group, aryl-alkyl group); groups in which one or more hydrogen atoms in these groups are substituted with a substituent (for example, a halogen atom), and the like
  • R g is preferably a monovalent aliphatic hydrocarbon group, more preferably
  • R h and R i are the same or different and each represents a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
  • the monovalent substituted or unsubstituted hydrocarbon group include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (including alkenyl groups).
  • monovalent aliphatic hydrocarbons Group for example, alkyl group, alkenyl group, etc.
  • monovalent alicyclic hydrocarbon group for example, cycloalkyl group, etc.
  • monovalent aromatic hydrocarbon group for example, aryl group, etc.
  • monovalent complex A cyclic group a monovalent group formed by combining two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group (for example, an alkyl and / or alkenyl-substituted cycloalkyl group, A cycloalkyl-alkyl group, an alkyl and / or alkenyl-substituted aryl group, an aryl-alkyl group); a group in which one or more hydrogen atoms in these groups are substituted with a substituent (for example, a halogen atom), and the like.
  • a substituent for example, a halogen atom
  • R h and R i are preferably a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group, more preferably an alkyl group (particularly a methyl group), an alkenyl group (particularly a vinyl group), an aryl group. A group (particularly a phenyl group).
  • the plurality of R h and the plurality of R i may be the same or different.
  • t represents 0 or an integer of 1 or more.
  • t is preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and still more preferably an integer of 1 to 30 from the viewpoint of the barrier property against the corrosive gas of the cured product.
  • two or more groups represented by the formula (1c) are present in the formula (1), these may be the same or different.
  • At least one of R a to R d is a group selected from the group consisting of a group represented by formula (1b) and a group represented by formula (1c). That is, the glycoluril derivative (C) contains, in the molecule, a Si—OR g group (particularly an alkoxysilyl group) and a group represented by the formula (1c) present in the group represented by the formula (1b).
  • the barrier property against the corrosive gas of the cured product can be remarkably improved.
  • the component having an alkoxysilyl group or silanol group in the composition for example, polysiloxane (A), ( B) and the like, and a component having an alkenyl group (for example, polysiloxane (A)
  • the barrier property against the corrosive gas of the cured product can be remarkably improved.
  • it also reacts with a component having a hydrosilyl group (for example, polysiloxane (B)) in the curable resin composition Therefore, the barrier property against the corrosive gas of the cured product can be remarkably improved.
  • the ratio of the groups represented by the formulas (1a) to (1c) in the glycoluril derivative (C) is not particularly limited.
  • R e and R f are the same or different and each represents a hydrogen atom or an alkyl group.
  • the alkyl group include C 1-20 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, and dodecyl group.
  • R e and R f a hydrogen atom or a C 1-4 alkyl group is preferable, and a hydrogen atom or a methyl group is more preferable.
  • cured material of the said curable resin composition can exhibit the outstanding barrier property with respect to corrosive gas because the curable resin composition of this invention contains a glycoluril derivative (C). It is presumed that the glycoluril skeleton in the glycoluril derivative (C) traps corrosive gases such as SOx gas.
  • the glycoluril derivative (C) can be produced by, for example, a known or conventional method using glycoluril or a derivative thereof as a starting material, and the production method is not particularly limited.
  • the glycoluril derivative (C) is represented by the following formula (i):
  • the method of including is illustrated as an efficient manufacturing method of a glycoluril derivative (C).
  • [In the formula (i), s, R e and R f are the same as above. ]
  • [In formula (ii), R g is the same as defined above. ]
  • [In the formula (iii), R h , R i and t are the same as above. ]
  • the hydrosilylation reaction can be carried out by known or commonly used methods, conditions, etc., and is not particularly limited. Moreover, hydrosilylation reaction can be advanced in presence of a hydrosilylation catalyst, for example, the hydrosilylation catalyst mentioned later etc. can be used. In the case where two or more compounds (compound represented by formula (ii) and compound represented by formula (iii)) are reacted with the compound represented by formula (i), the above hydrosilylation reaction Can be performed simultaneously or sequentially. In addition, when the compound represented by the formula (iii) is reacted with the compound represented by the formula (i), the compound represented by the formula (i) is used in order to prevent gelation due to a crosslinking reaction.
  • the glycoluril derivative (C) obtained by the hydrosilylation reaction can be used as it is without being purified (for example, used as a constituent of the curable resin composition of the present invention). It can also be used after being purified by conventional purification means.
  • the glycoluril derivative (C) can be used alone or in combination of two or more.
  • the content (blending amount) of the glycoluril derivative (C) in the curable resin composition of the present invention is not particularly limited, but is 0 with respect to 100 parts by weight of the total amount of the polysiloxane (A) and the polysiloxane (B).
  • the amount is preferably more than 20 parts by weight and less than 20 parts by weight, more preferably 0.01 to 18 parts by weight, still more preferably 0.1 to 15 parts by weight, and particularly preferably 0.1 to 10 parts by weight.
  • the barrier property and durability thermal shock resistance, reflow resistance, etc.
  • the transparency and durability (thermal shock resistance, reflow resistance, etc.) of the cured product tend to be further improved.
  • the curable resin composition of the present invention may further contain a hydrosilylation catalyst.
  • a hydrosilylation catalyst When the curable resin composition of the present invention contains a hydrosilylation catalyst, the hydrosilylation reaction between the alkenyl group and the hydrosilyl group in the curable resin composition can proceed more efficiently by heating. Tend.
  • hydrosilylation catalyst examples include known hydrosilylation reaction catalysts such as platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Specifically, platinum fine powder, platinum black, platinum-supported silica fine powder, platinum Supported activated carbon, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, platinum olefin complexes, platinum carbonyl complexes such as platinum-carbonylvinylmethyl complexes, platinum-divinyltetramethyldisiloxane complexes and platinum- Platinum-based catalysts such as platinum-vinylmethylsiloxane complexes such as cyclovinylmethylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, etc., and palladium-based catalysts containing palladium atoms or rhodium atoms in place of platinum atoms in the above-ment
  • a platinum vinylmethylsiloxane complex a platinum-carbonylvinylmethyl complex, or a complex of chloroplatinic acid and an alcohol or aldehyde is preferable because the reaction rate is good.
  • the hydrosilylation catalyst can be used alone or in combination of two or more.
  • the content (blending amount) of the hydrosilylation catalyst in the curable resin composition of the present invention is not particularly limited, but is 1 ⁇ 10 ⁇ 8 to 1 mol of the total amount of alkenyl groups contained in the curable resin composition.
  • 1 ⁇ 10 ⁇ 2 mol is preferable, and 1.0 ⁇ 10 ⁇ 6 to 1.0 ⁇ 10 ⁇ 3 mol is more preferable.
  • the content is 1 ⁇ 10 ⁇ 8 mol or more, there is a tendency that a cured product can be formed more efficiently.
  • the content is 1 ⁇ 10 ⁇ 2 mol or less, there is a tendency that a cured product having a more excellent hue (less coloring) can be obtained.
  • the content (blending amount) of the hydrosilylation catalyst in the curable resin composition of the present invention is not particularly limited.
  • platinum, palladium, or rhodium in the hydrosilylation catalyst is 0.01 to An amount that falls within the range of 1000 ppm is preferred, and an amount that falls within the range of 0.1 to 500 ppm is more preferred.
  • the content of the hydrosilylation catalyst is in such a range, a cured product can be formed more efficiently, and a cured product having a more excellent hue tends to be obtained.
  • the curable resin composition of the present invention may contain components other than the above-described components (sometimes referred to as “other components”).
  • other components include, but are not limited to, siloxane compounds other than polysiloxanes (A) and (B) (for example, cyclic siloxane compounds, low molecular weight linear or branched siloxane compounds, etc.), silane coupling agents. , Hydrosilylation reaction inhibitors, solvents, various additives, and the like.
  • the additive examples include precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, Inorganic fillers such as boron nitride, inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, organosilazanes; organic resins such as silicone resins, epoxy resins, and fluororesins other than those described above Fine powder: Filler such as conductive metal powder such as silver and copper, solvent, stabilizer (antioxidant, ultraviolet absorber, light stabilizer, heat stabilizer, etc.), flame retardant (phosphorous flame retardant, Halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents, lub
  • the curable resin composition of the present invention is not particularly limited, but is a composition (composition composition) in which the alkenyl group is 0.2 to 4 mol per 1 mol of hydrosilyl group present in the curable resin composition.
  • the amount is preferably 0.5 to 1.5 mol, more preferably 0.8 to 1.2 mol.
  • the curable resin composition of the present invention is not particularly limited, but can be prepared by stirring and mixing each of the above components at room temperature.
  • the curable resin composition of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, two or more stored separately. It can also be used as a multi-component (for example, two-component) composition in which the components are mixed at a predetermined ratio before use.
  • the curable resin composition of the present invention is not particularly limited, but is preferably liquid at room temperature (about 25 ° C.). More specifically, the curable resin composition of the present invention has a viscosity at 23 ° C. of preferably 300 to 20000 mPa ⁇ s, more preferably 500 to 10000 mPa ⁇ s, and still more preferably 1000 to 8000 mPa ⁇ s. There exists a tendency for the heat resistance of hardened
  • the viscosity of curable resin composition can be measured by the method similar to the viscosity of the above-mentioned ladder type polyorgano silsesquioxane (a), for example.
  • a cured product (sometimes referred to as “cured product of the present invention”) is obtained.
  • Conditions for curing are not particularly limited and can be appropriately selected from conventionally known conditions.
  • the temperature (curing temperature) is 25 to 25%. 180 ° C. (more preferably 60 to 150 ° C.) is preferable, and the time (curing time) is preferably 5 to 720 minutes.
  • the cured product of the present invention has not only high heat resistance and transparency specific to polysiloxane materials, but also excellent thermal shock resistance and reflow resistance, and particularly barrier properties against corrosive gases (for example, SOx gas). Excellent.
  • the curable resin composition of the present invention can be preferably used as a resin composition (encapsulant) for encapsulating semiconductor elements in a semiconductor device (sometimes referred to as “encapsulant of the present invention”). . Specifically, the encapsulant of the present invention can be particularly preferably used for a resin composition (encapsulant) for encapsulating an optical semiconductor element (LED element) in an optical semiconductor device.
  • the sealing material (cured product) obtained by curing the sealing agent of the present invention has not only high heat resistance and transparency specific to polysiloxane materials, but also excellent thermal shock resistance and reflow resistance. In particular, it has excellent barrier properties against corrosive gas (for example, SOx gas).
  • the sealing agent of this invention can be preferably used especially as a sealing agent etc. of a high-intensity, short wavelength optical semiconductor element.
  • An optical semiconductor device can be obtained by sealing an optical semiconductor element using the sealing agent of the present invention.
  • the sealing of the optical semiconductor element can be performed by a known or conventional method, and is not particularly limited.
  • the sealing agent of the present invention can be injected into a predetermined mold and cured by heating under predetermined conditions. .
  • the curing temperature and the curing time are not particularly limited, but can be set in the same range as in the preparation of the cured product.
  • An example of the optical semiconductor device of the present invention is shown in FIG. In FIG. 1, 100 is a reflector (light reflecting resin composition), 101 is a metal wiring (electrode), 102 is an optical semiconductor element, 103 is a bonding wire, and 104 is a cured product (sealing material).
  • the curable resin composition of the present invention is a sealing material that covers an optical semiconductor element in a high-brightness, short-wavelength optical semiconductor device, which has been difficult to handle with conventional resin materials, and has high heat resistance and high resistance.
  • a withstand voltage semiconductor device such as a power semiconductor
  • it can be preferably used for applications such as a sealing material covering a semiconductor element.
  • the curable resin composition of the present invention is not limited to the above-described encapsulant application (particularly, an encapsulant application for optical semiconductor elements).
  • a functional coating agent for example, a functional coating agent, a heat-resistant plastic lens, a transparent device, an adhesive ( Heat-resistant transparent adhesives, etc.), electrical insulating materials (insulating films, etc.), laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, optical members , Optical modeling, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, and other optical and semiconductor applications.
  • Production Example 1 [Production of ladder-type polyorganosilsesquioxane] A 100 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 65 mmol (9.64 g) vinyltrimethoxysilane and 195 mmol phenyltrimethoxysilane (38 mmol) under a nitrogen stream. .67 g) and 8.31 g of methyl isobutyl ketone (MIBK) were charged and the mixture was cooled to 10 ° C.
  • MIBK methyl isobutyl ketone
  • reaction solution 360 mmol (6.48 g) of water and 0.24 g of 5N hydrochloric acid (1.2 mmol as hydrogen chloride) were simultaneously added dropwise over 1 hour. After the dropwise addition, the mixture (reaction solution) was kept at 10 ° C. for 1 hour to allow hydrolysis condensation reaction to proceed. Thereafter, 40 g of MIBK was added to dilute the reaction solution. Next, the temperature of the reaction vessel was adjusted with a water bath, and the temperature of the reaction solution was raised to 70 ° C. in 30 minutes. When the temperature reached 70 ° C., 520 mmol (9.36 g) of water was added, and the polycondensation reaction was performed at the same temperature under a nitrogen stream for 6 hours.
  • ladder-type polyorganosilsesquioxane obtained in Production Example 1 corresponds to the ladder-type polyorganosilsesquioxane (a) described above.
  • the product (the product after the silylation reaction) had a number average molecular weight of 1280 and a molecular weight dispersity of 1.13.
  • the ladder type polyorganosilsesquioxane having a vinyl group and a TMS group at the terminal has a weight average molecular weight (Mw) of 3000, and a vinyl group content (average content) per molecule of 4.00% by weight. Yes, and the phenyl group / methyl group / vinyl group (molar ratio) was 5/80/15.
  • the ladder-type polyorganosilsesquioxane obtained in Production Example 2 corresponds to the ladder-type polyorganosilsesquioxane (b) described above.
  • polysiloxane (A) and (B) the following products were used in addition to the ladder-type polyorganosilsesquioxane obtained in Production Example 1 and Production Example 2.
  • ETERLED GD1130A manufactured by Changxing Chemical Industry, vinyl group content 4.32% by weight, phenyl group content 44.18% by weight, number average molecular weight 1107, weight average molecular weight 6099, and hydrosilylation catalyst.
  • ETERLED GD1130B manufactured by Changxing Chemical Industry, vinyl group content 3.45% by weight, phenyl group content 50.96% by weight, hydrosilyl group (Si—H) content (hydride conversion) 0.17% by weight, number average molecular weight 631, weight average molecular weight 1305 OE6630A: manufactured by Toray Dow Corning Co., Ltd., vinyl group content 2.17 wt%, phenyl group content 51.94 wt%, hydrosilyl group content (hydride conversion) 0 wt%, number average molecular weight 2532, weight average Molecular weight 4490, including hydrosilylation catalyst.
  • OE6630B manufactured by Toray Dow Corning Co., Ltd., vinyl group content 3.87% by weight, phenyl group content 50.11% by weight, hydrosilyl group content (in terms of hydride) 0.17% by weight, number average molecular weight 783, Weight average molecular weight 1330 KER-2500A: manufactured by Shin-Etsu Chemical Co., Ltd., vinyl group content 1.53% by weight, phenyl group content 0% by weight, hydrosilyl group content (hydride conversion) 0.03% by weight, number average molecular weight 4453, weight Average molecular weight 19355, including hydrosilylation catalyst.
  • KER-2500B manufactured by Shin-Etsu Chemical Co., Ltd., vinyl group content 1.08% by weight, phenyl group content 0% by weight, hydrosilyl group content (hydride conversion) 0.13% by weight, number average molecular weight 4636, weight Average molecular weight 18814
  • ETERLED GD1012A manufactured by Changxing Chemical Industry Co., Ltd., vinyl group content 1.33% by weight, phenyl group content 0% by weight, hydrosilyl group content (hydride conversion) 0% by weight, number average molecular weight 5108, weight average molecular weight 23385, hydrosilylation Contains catalyst.
  • ETERLED GD1012B manufactured by Changxing Chemical Industry, vinyl group content 1.65% by weight, phenyl group content 0% by weight, hydrosilyl group content (hydride conversion) 0.19% by weight, number average molecular weight 4563, weight average molecular weight 21873
  • glycoluril derivative (C) As the glycoluril derivative (C), the compounds obtained in Synthesis Examples 1 to 3 below were used.
  • Synthesis example 1 [Synthesis of glycoluril compound (glycoluril derivative) having two allyl groups and two trimethoxysilyl groups on average in one molecule] Glycoluril tetraallyl compound TA-G (40.00 g, manufactured by Shikoku Kasei Kogyo Co., Ltd.) in a 200 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen introduction tube , S is 1, and R e and R f are hydrogen atoms, a compound represented by formula (i)), methyl isobutyl ketone (40.00 g, manufactured by Kanto Chemical Co., Inc.), and platinum-1,4 -1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution of divinyl-1,1,4,4-tetramethyldisiloxane complex (0.244 mg, manufactured by Sigma-Aldrich, platinum content 3.
  • Synthesis example 2 [Synthesis of glycoluril compound (glycoluril derivative) having two hydrosilyl groups and two trimethoxysilyl groups on average in one molecule]
  • a 1,1,3,3-tetramethyldisiloxane 14.70 g, Tokyo Chemical Industry Co., Ltd.
  • Toluene (20.00 g, manufactured by Kanto Chemical Co., Inc.)
  • 1,3-divinyl-1 of platinum-1,4-divinyl-1,1,4,4-tetramethyldisiloxane complex 1,3,3-tetramethyldisiloxane solution (0.074 mg, Sigma-Aldrich, platinum content 3.0 wt%) was charged and heated to 80 ° C.
  • Synthesis example 3 [Synthesis of a glycoluril compound (glycoluril derivative) having four hydrosilyl groups in one molecule]
  • a 1,1,3,3-tetramethyldisiloxane 22.21 g, Tokyo Chemical Industry Co., Ltd.
  • Toluene (20.00 g, manufactured by Kanto Chemical Co., Inc.)
  • 1,3-divinyl-1 of platinum-1,4-divinyl-1,1,4,4-tetramethyldisiloxane complex 1,3,3-tetramethyldisiloxane solution (0.12 mg, Sigma-Aldrich, platinum content 0.3 wt%) was charged and heated to 70 ° C.
  • Example 1 [Production of curable resin composition] First, as shown in Table 1, ETERLED GD1130A (20 parts by weight) and the compound obtained in Synthesis Example 1 (0.2 parts by weight) were mixed and stirred at room temperature for 1 hour to prepare agent A. . Next, ETERLED GD1130B (80 parts by weight) as a B agent was mixed with the A agent (20.2 parts by weight) obtained above and stirred at room temperature for 1 hour. The compatibility of each component was good. There was obtained a curable resin composition which was a transparent and uniform liquid.
  • the LED package (InGaN element, 3.5 mm ⁇ 2.8 mm) of the embodiment shown in FIG. 1 is injected with the curable resin composition obtained above, at 60 ° C. for 1 hour, and then at 80 ° C. for 1 hour. Furthermore, the optical semiconductor device by which the optical semiconductor element was sealed with the hardened
  • the total luminous flux was measured in the same manner as described above, and this was designated as “total luminous flux after test”. From the value of the total luminous flux measured above, the luminous intensity maintenance factor was calculated according to the following formula.
  • Luminance maintenance rate (%) (total luminous flux after test / total luminous flux before test) ⁇ 100 It shows that hardened
  • Thermal shock test The optical semiconductor device manufactured above was used as a sample. Ten samples were used for each curable resin composition. The sample was used after confirming that it was turned on when a current of 20 mA was applied before the test. One cycle of the above sample was exposed to ⁇ 40 ° C. for 5 minutes and then at 100 ° C. for 5 minutes using a thermal shock tester (manufactured by Espec Corp., model number “TSB-21”). Application of thermal shock was performed in 1000 cycles for Examples 1 to 9 and Comparative Examples 1 to 3 (phenyl silicone type), and 3000 cycles for Examples 10 to 12 and Comparative Examples 4 and 5 (methyl silicone type).
  • thermal shock resistance The durability against thermal shock (thermal shock resistance) was evaluated according to the following criteria. ⁇ (Excellent durability): 0 samples that did not light X (Inferior in durability): The number of samples that did not light up was 1 or more
  • the curable resin composition of the present invention is useful for applications such as adhesives, coating agents and sealants that require heat resistance, transparency, thermal shock resistance, reflow resistance, and barrier properties against corrosive gases.
  • the curable resin composition of the present invention can be preferably used as a sealant for an optical semiconductor element (LED element).
  • Reflector resin composition for light reflection
  • Metal wiring electrode
  • Optical semiconductor element 103
  • Bonding wire 104: Cured material (sealing material)

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Abstract

La présente invention se rapporte à une composition de résine durcissable caractérisée en ce qu'elle contient un polysiloxane (A) ayant au moins deux groupes alcényle par molécule qui est au moins l'un choisi dans le groupe constitué par le polyorganosiloxanes (A1) et le polyorganosiloxysilalkylènes (A2), un polysiloxane (B) ayant au moins deux groupes hydrosilyle par molécule qui est au moins l'un choisi dans le groupe constitué par le polyorganosiloxanes (B1) et le polyorganosiloxysilalkylènes (B2), et un composé (C) représenté par la formule (1). La présente invention concerne une composition de résine durcissable qui permet de former un produit durci (matériau d'étanchéité) qui est exceptionnel en termes de toutes les caractéristiques suivantes : résistance au choc thermique, résistance à la refusion et des propriétés barrière par rapport à des gaz corrosifs (par exemple, les gaz SOx). (Dans la formule (1), au moins l'un parmi Ra-Rd est un groupe choisi dans le groupe constitué des groupes représentés par la formule (1b) et des groupes représentés par la formule (1c).)
PCT/JP2015/062210 2014-04-23 2015-04-22 Composition de résine durcissable, produit durci correspondant, dérivé du glycoluril et procédé de production correspondant WO2015163355A1 (fr)

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WO2018235811A1 (fr) * 2017-06-20 2018-12-27 株式会社ダイセル Composition de résine silicone durcissable, et article durci associé
EP3553066A1 (fr) * 2018-04-12 2019-10-16 Shin-Etsu Chemical Co., Ltd. Composé d'organosilicone contenant un anneau de glycolurile et son procédé de fabrication
CN114008140A (zh) * 2019-05-31 2022-02-01 陶氏东丽株式会社 固化性聚有机硅氧烷组合物以及由该固化性聚有机硅氧烷组合物的固化物形成的光学构件
WO2022080316A1 (fr) * 2020-10-15 2022-04-21 キヤノン株式会社 Composition de résine photodurcissable pour mise en forme tridimensionnelle par enlèvement de matière et procédé pour fabriquer un objet tridimensionnel

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CN114008140A (zh) * 2019-05-31 2022-02-01 陶氏东丽株式会社 固化性聚有机硅氧烷组合物以及由该固化性聚有机硅氧烷组合物的固化物形成的光学构件
CN114008140B (zh) * 2019-05-31 2023-11-07 陶氏东丽株式会社 固化性聚有机硅氧烷组合物以及由该固化性聚有机硅氧烷组合物的固化物形成的光学构件
WO2022080316A1 (fr) * 2020-10-15 2022-04-21 キヤノン株式会社 Composition de résine photodurcissable pour mise en forme tridimensionnelle par enlèvement de matière et procédé pour fabriquer un objet tridimensionnel

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