WO2015118992A1 - Composition de silicone traitée par addition - Google Patents

Composition de silicone traitée par addition Download PDF

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Publication number
WO2015118992A1
WO2015118992A1 PCT/JP2015/052142 JP2015052142W WO2015118992A1 WO 2015118992 A1 WO2015118992 A1 WO 2015118992A1 JP 2015052142 W JP2015052142 W JP 2015052142W WO 2015118992 A1 WO2015118992 A1 WO 2015118992A1
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group
component
addition
mass
polyorganosiloxane
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PCT/JP2015/052142
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English (en)
Japanese (ja)
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パラカシュ クマラ
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モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社
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Priority to JP2015504799A priority Critical patent/JP5805348B1/ja
Publication of WO2015118992A1 publication Critical patent/WO2015118992A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin

Definitions

  • the present invention relates to an addition-curable silicone composition, and more particularly to an addition-curable silicone composition in which the resulting cured product has excellent adhesion and appearance, and is less susceptible to heat shrinkage and change in hardness.
  • Silicone (polyorganosiloxane) compositions such as silicone rubber and silicone gel are used in various applications because they form cured products with excellent properties such as weather resistance, heat resistance, hardness, and elongation. .
  • a silicone composition having excellent heat resistance and ultraviolet resistance is used as a material for sealing the light emitting element.
  • addition-curable silicone compositions that are cured using hydrosilylation are widely used because they are cured in a short time by heating and do not generate by-products during curing.
  • the addition-curable silicone composition has lower adhesiveness than the epoxy resin, an alkoxysilyl group and / or an epoxy group, a crosslinkable vinyl group and / or a hydrosilyl group are used for the purpose of improving the adhesiveness. It has been proposed to blend an isocyanuric derivative having the above-mentioned composition (for example, see Patent Document 1).
  • the resulting cured product may crack when heated due to the component, or may be peeled off from the adherend. Sometimes happened. This was considered to occur synergistically by simultaneous progress of shrinkage and hardness change of the cured product due to heat. Therefore, an addition-curable silicone composition that provides a cured product in which the improvement in adhesiveness is sufficiently ensured by containing an adhesive-improving component, but the shrinkage and hardness change of the cured product due to the component are suppressed by heat. Development of things was desired.
  • JP 2010-0665161 A International Publication No. 2013/084699
  • the present invention has been made to solve such problems, and the obtained silicone cured product has excellent adhesiveness and appearance, and is an addition-curing type with less shrinkage and hardness change due to heat.
  • An object is to provide a silicone composition.
  • the addition-curable silicone composition of the present invention is (A) 100 parts by mass of a polyorganosiloxane having at least one alkenyl group bonded to a silicon atom in one molecule; (B) Hydrogen bonded to a silicon atom with respect to 1 mol of the total amount of alkenyl groups of the component (A) in a polyorganohydrogensiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule An amount of 0.9 to 3.0 moles of atoms, (C) catalyst amount of hydrosilylation reaction catalyst, (D) An isocyanuric acid derivative having (D1) at least one selected from an epoxy group and an alkoxysilyl group and at least one selected from a hydrosilyl group and a crosslinkable vinyl group, and (D2) ) At least one selected from silane or siloxane compounds having at least one selected from an epoxy group and an alkoxy group and having no isocyanuric ring, and (E) the following general
  • R 5 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms
  • R 6 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, a carboxy group, or As hydroxy group or two R 6 bonded to the same carbon atom, ⁇ O is shown, provided that at least one of R 6 is carboxy group or hydroxy group, or formula (3) is the same carbon atom And at least one ⁇ O as two R 6 bonded to It is characterized by containing.
  • the addition hardening type silicone composition which can suppress the change of the hardness by heat shrink and a heat
  • the addition-curable silicone composition of the present invention contains the following components (A) to (E).
  • the amount of hydrogen atoms bonded to silicon atoms is 0.9 to 3.0 moles with respect to 1 mole of the total amount of alkenyl groups in component (A).
  • the amount of hydrosilylation reaction catalyst (D ) An isocyanuric acid derivative having (D1) at least one selected from an epoxy group and an alkoxysilyl group and at least one selected from a hydrosilyl group and a crosslinkable vinyl group, and (D2) an epoxy A silane having at least one selected from a group and an alkoxy group and having no isocyanuric ring, or 0.01 to 10 parts by mass of at least one selected from rooxane compounds (E) 0.001 to 0.05 parts by mass of the organic free radical represented by the general formula (3) .
  • the component (A) is an alkenyl group-containing polyorganosiloxane that becomes the base polymer of the composition of the present invention together with the component (B) described below.
  • the component (A) is not particularly limited as long as it is a polyorganosiloxane having at least one alkenyl group bonded to a silicon atom in one molecule.
  • the structure of the polyorganosiloxane molecule of component (A) is not particularly limited, and may be any of linear, branched, cyclic and network structures, or a combination of these structures. Also good. Each of the branched structure and the network structure may be a two-dimensional structure or a three-dimensional structure.
  • branched / It is called a “network structure” molecule.
  • the polyorganosiloxane of the component (A) may be composed of one kind of polyorganosiloxane having one molecular structure or a mixture of two or more kinds, and one or more kinds of polyorganosiloxane having two or more kinds of molecular structures. It may consist of a mixture of When the component (A) is a mixture, the number of alkenyl groups bonded to silicon atoms in one molecule may be one or more as an average of the entire component (A).
  • a combination of a linear polyorganosiloxane having at least one alkenyl group bonded to a silicon atom in one molecule and a branched / network-structured polyorganosiloxane is preferable.
  • the term “linear polyorganosiloxane” includes polyorganosiloxane having some branching in the siloxane skeleton.
  • the hardness may not be sufficient.
  • the (F) silica powder may be used when the component (A) mainly contains a linear polyorganosiloxane.
  • the (A) component mainly contains a linear polyorganosiloxane refers to a case where the content of the linear polyorganosiloxane exceeds 50% by mass with respect to the total amount of the component (A).
  • linear polyorganosiloxane examples include polyorganosiloxane (A1) represented by the following general formula (1).
  • R 1 3 SiO 1/2 (R 1 2 SiO 2/2 ) n (R 1 3 SiO 1/2 ) (1)
  • R 1 each independently represents an alkenyl group or a monovalent unsubstituted or substituted hydrocarbon group not containing an aliphatic unsaturated group, and at least two of R 1 are alkenyl groups.
  • the average degree of polymerization represented by n + 2 is 50 to 2,500.
  • Examples of the polyorganosiloxane having a branched / network structure include polyorganosiloxane (A2) represented by the following average unit formula (2).
  • A2 polyorganosiloxane (A2) represented by the following average unit formula (2).
  • R 2 3 SiO 1/2 a (R 2 2 SiO 2/2 ) b (R 2 SiO 3/2 ) c (SiO 4/2 ) d
  • R 2 each independently represents an alkenyl group or a monovalent unsubstituted or substituted hydrocarbon group not containing an aliphatic unsaturated group, and at least one of R 2 is an alkenyl group.
  • a and d are positive numbers
  • b and c are 0 or positive numbers.
  • the siloxane skeleton of the polyorganosiloxane (A1) represented by the general formula (1) is linear because a polymer having a high polymerization degree as shown below can be synthesized with good control. However, there may be some branches, for example, a plurality of branches in the molecule.
  • the average degree of polymerization of the polyorganosiloxane (A1) that is, the number of siloxane units is represented by n + 2 obtained by adding 2 to the number of terminal groups in the general formula (1), and is in the range of 50 to 2,500.
  • the average degree of polymerization is preferably from 100 to 1,500.
  • the viscosity (25 ° C.) of the polyorganosiloxane (A1) is preferably 100 to 150,000 mPa ⁇ s, particularly preferably 200 to 20,000 mPa ⁇ s.
  • the viscosity of the polyorganosiloxane (A1) is within this range, the workability of the resulting composition is good, and the physical properties of the silicone cured product obtained from this composition are good.
  • a viscosity means the viscosity measured at 25 degreeC with the rotational viscometer unless there is particular notice.
  • conditions such as the number of rotations at the time of measurement are appropriately adjusted according to the viscosity of the specimen and the measuring apparatus used.
  • Polyorganosiloxane (A1) has two or more alkenyl groups bonded to silicon atoms in one molecule.
  • the number of alkenyl groups is preferably 250 or less, and more preferably 50 or less. If the number of alkenyl groups exceeds 250 per molecule, the cured product may be fragile and may not have sufficient strength.
  • the number of alkenyl groups here is an average number per molecule in the polyorganosiloxane (A1).
  • R 1 in the general formula (1) is each independently an alkenyl group or a monovalent unsubstituted or substituted hydrocarbon group not containing an aliphatic unsaturated group.
  • the number (ratio) in which R 1 in the formula (1) is an alkenyl group is appropriately adjusted so that the number of alkenyl groups per molecule falls within the above range.
  • R 1 is a monovalent unsubstituted or substituted hydrocarbon group containing no aliphatic unsaturated group
  • specific examples of R 1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • Alkyl groups such as phenyl groups; aryl groups such as phenyl groups, tolyl groups and xylyl groups; aralkyl groups such as benzyl groups and phenethyl groups; chloromethyl groups, 3-chloropropyl groups, 3,3,3-trifluoropropyl groups, Examples thereof include substituted hydrocarbon groups such as a 3-cyanopropyl group and a 3-methoxypropyl group.
  • R 1 is an alkenyl group
  • specific examples of R 1 include a vinyl group, an allyl group, a 3-butenyl group, a 4-pentenyl group, and a 5-hexenyl group.
  • the alkenyl group is preferably a vinyl group because the synthesis and handling of the polyorganosiloxane (A1) is easy and the addition reaction is easily performed.
  • the alkenyl group may be bonded to any silicon atom in the molecule, but it is preferable that a part of the alkenyl group is bonded to a silicon atom at the molecular end because it exhibits excellent reactivity.
  • the plurality of alkenyl groups may be the same or different, but are preferably the same in terms of easy synthesis.
  • R 1 other than an alkenyl group represents a plurality of R 1 representing a monovalent unsubstituted or substituted hydrocarbon group (hereinafter, R 1 other than an alkenyl group is represented by “R 11 ”). (Number of all R 1 minus the number of the alkenyl group).
  • the plurality of R 11 may be the same or different. In terms of easy synthesis, these R 11 are preferably the same. However, different groups may be introduced into a part thereof depending on the physical properties required for the obtained silicone cured product.
  • Synthesis and handling of the polyorganosiloxane (A1) is easy, since the excellent heat resistance can be obtained, it is preferable that 50% or more of R 11 to the polyorganosiloxane (A1) has is a methyl group, the R 11 It is particularly preferred that all are methyl groups.
  • a combination in which a part of R 11 of the polyorganosiloxane (A1) is a phenyl group and the remaining R 11 is all a methyl group is used. be able to.
  • a combination in which R 1 of the unit surrounded by n in the formula (1) is partially a phenyl group and R 1 other than the alkenyl group among the remaining R 1 is all a methyl group is preferable.
  • R 11 of the polyorganosiloxane (A1) is converted to a 3,3,3-trifluoropropyl group, and the rest A combination in which all R 11's are methyl groups can be used.
  • R 1 of the unit surrounded by n in the formula (1) is partially a 3,3,3-trifluoropropyl group, and R 1 other than the alkenyl group in the remaining R 1 is all a methyl group.
  • a linear polyorganosiloxane when used as the component (A), one type may be used or two or more types may be used in combination. Moreover, about polyorganosiloxane (A1), 1 type may be used or 2 or more types may be used together.
  • the polyorganosiloxane (A1) may be prepared by mixing two or more types of polyorganosiloxane (A1) having different average polymerization degrees and adjusting the viscosity of the mixture. .
  • the adjustment to the desired viscosity is facilitated and the range of usable polyorganosiloxanes is widened.
  • the polyorganosiloxane (A2) represented by the above average unit formula (2) is a (R 2 3 SiO 1/2 ) unit (hereinafter also referred to as “M unit”), (R 2 2 SiO 2/2 ) unit. (Hereinafter also referred to as “D unit”), (R 2 SiO 3/2 ) unit (hereinafter also referred to as “T unit”), and (SiO 4/2 ) unit (hereinafter also referred to as “Q unit”). .) In a ratio of a: b: c: d.
  • a and d are positive numbers
  • b and c are 0 or positive numbers. That is, the M unit and the Q unit are essential structural units, and the D unit and the T unit are arbitrary structural units.
  • the relationship of a, b, c, d in the average unit formula (2) satisfies 0 ⁇ a / (c + d) ⁇ 3 and 0 ⁇ b / (c + d) ⁇ 2.
  • the mass average molecular weight of the polyorganosiloxane (A2) measured by gel permeation chromatography is preferably in the range of 1,000 to 100,000, more preferably 3,000 to 30,000.
  • mass average molecular weight of the polyorganosiloxane (2) is within the above range, there is no problem in operation due to remarkably high viscosity of the composition, and the mechanical strength after curing is good.
  • the polyorganosiloxane (A2) has a relatively high viscosity even if it is solid at room temperature (25 ° C.), for example, 200 Pa ⁇ s or more, as long as the composition of the siloxane unit is within the above range. It may be liquid.
  • R 2 is independently in each unit, and when there are a plurality of R 2 in the same unit, independently in the unit, a substituted or unsubstituted monovalent A hydrocarbon group or an alkenyl group is shown.
  • R 2 include the same groups as the substituted or unsubstituted monovalent hydrocarbon group or alkenyl group shown for R 1 in the polyorganosiloxane (A1). Also, it includes the same groups as the regard to preferred embodiments of R 2 indicated for R 1.
  • the polyorganosiloxane (A2) has at least one alkenyl group bonded to a silicon atom in one molecule.
  • the polyorganosiloxane (A2) preferably has two or more alkenyl groups bonded to silicon atoms in one molecule. Further, the content of the alkenyl group in the polyorganosiloxane (A2) is preferably 50 or less.
  • the alkenyl group that the polyorganosiloxane (2) has at least one in a molecule may be in any of the above M to T units.
  • the component (A) when a polyorganosiloxane having a branched / network structure is used as the component (A), one type may be used or two or more types may be used in combination. Moreover, about polyorganosiloxane (A2), 1 type may be used or 2 or more types may be used together.
  • the component (A) is an alkenyl group-containing polyorganosiloxane that serves as a base polymer.
  • the component (A) when a linear polyorganosiloxane and a branched / network-structured polyorganosiloxane are used in combination, the ratio can be arbitrarily set according to the application.
  • polyorganosiloxane (A1) and polyorganosiloxane (A2) are used as a member for an optical semiconductor element, polyorganosiloxane (A1) and polyorganosiloxane (A2)
  • the ratio of the polyorganosiloxane (A2) to 100 parts by mass of the total is preferably 5 to 60 parts by mass, and more preferably 10 to 30 parts by mass.
  • the content ratio of the polyorganosiloxane (A1) and the polyorganosiloxane (A2) is within the above range, it is possible to give the cured product an optimum hardness and sufficient mechanical strength in the above application.
  • Component (B) The polyorganohydrogensiloxane having a hydrogen atom bonded to at least two silicon atoms in one molecule as the component (B) acts as a crosslinking component that reacts with the component (A).
  • component (B) There is no restriction
  • Component polyorganohydrogensiloxane has 2 or more, preferably 3 or more, hydrogen atoms bonded to silicon atoms, that is, hydrosilyl groups (Si—H groups) in one molecule.
  • Si—H groups hydrosilyl groups
  • the polyorganohydrogensiloxane as the component (B) is linear, these Si—H groups are located in either one of the molecular chain terminal or the middle part, but not both. It may be.
  • the number of Si—H groups referred to here is the average number per molecule in polyorganohydrogensiloxane.
  • the average number (average polymerization degree) of silicon atoms in one molecule of component (B) is preferably 2 to 1,000, and more preferably 3 to 100.
  • the viscosity (25 ° C.) of the component (B) is preferably 500 mPa ⁇ s or less, particularly preferably in the range of 10 to 100 mPa ⁇ s. When the viscosity of the component (B) is within this range, the workability of the resulting composition is good, and the physical properties of the silicone cured product obtained from this composition are good.
  • the amount of Si—H groups in the molecule is preferably 0.3 to 15 mmol / g, more preferably 1 to 10 mmol / g.
  • component (B) for example, polyorganohydrogensiloxane represented by the following average composition formula (4) is used.
  • P and q are 0.7 ⁇ p ⁇ 2.1, 0.8.
  • It is a positive number satisfying 001 ⁇ q ⁇ 1.0 and (p + q) ⁇ 3.0.
  • R 4 examples include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, and decyl group.
  • Alkyl groups such as phenyl groups, aryl groups such as tolyl groups, xylyl groups and naphthyl groups; aralkyl groups such as benzyl groups, phenylethyl groups and phenylpropyl groups; some or all of hydrogen atoms in these hydrocarbon groups Groups substituted with a halogen atom, for example, a chloromethyl group, a 3-chloropropyl group, a bromoethyl group, a 3,3,3-trifluoropropyl group, and the like.
  • R 4 is preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group, and particularly preferably a methyl group.
  • component (B) examples include molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends trimethylsiloxy group.
  • component (B) among the polyorganohydrogensiloxanes, in particular, polymethylhydrogensiloxane having only a methyl group as an organic group bonded to a silicon atom, specifically, the average composition formula (4) Polymethylhydrogensiloxane in which R 4 is all methyl groups is preferred.
  • the content of the polyorganohydrogensiloxane that is the component (B) in the addition-curable silicone composition according to the embodiment of the present invention is such that the Si—H group that the component (B) has is the alkenyl group that the component (A) has ( For example, the amount is 0.9 to 3.0 mol with respect to 1 mol of the total amount of vinyl groups).
  • the content of the component (B) is an effective curing amount of the component (B) relative to the component (A), and the Si—H group of the component (B) with respect to 1 mol of the total amount of alkenyl groups of the component (A).
  • the amount of is preferably 1.0 to 2.8 mol, more preferably 1.1 to 2.5 mol.
  • the addition-curable silicone composition according to the embodiment of the present invention sufficiently proceeds with the curing reaction and contains unreacted Si—H groups in the cured silicone product. Since a large amount does not remain, the physical properties of the obtained silicone cured product hardly change over time.
  • the hydrosilylation reaction catalyst as component (C) is a catalyst that accelerates the addition reaction (hydrosilylation reaction) between the alkenyl group contained in component (A) and the Si—H group in component (B).
  • the component (C) include platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, and the like, but platinum-based catalysts are preferable from the viewpoint of economy.
  • platinum-based catalyst for example, chloroplatinic acid, alcohol-modified chloroplatinic acid, a coordination compound of chloroplatinic acid and olefins, vinylsiloxane or acetylene compound can be used. These can be used singly or in combination of two or more.
  • the content of the component (C) is not particularly limited as long as it is an amount effective as a catalyst for the hydrosilylation reaction.
  • the content of the component (C) is a platinum atom relative to the total amount (mass) of the component (A) and the component (B). In terms of conversion, it can be in the range of 0.1 to 100 ppm, more preferably 1 to 20 ppm, and still more preferably 1 to 10 ppm. When the content is within this range, the addition reaction is sufficiently accelerated, so that sufficient curing can be obtained and it is economically advantageous.
  • the addition curable silicone composition of the embodiment of the present invention is selected from (D) at least one selected from an epoxy group and an alkoxysilyl group, and a hydrosilyl group and a crosslinkable vinyl group as (D) an adhesion-imparting agent. And (D2) at least one selected from silane or siloxane compounds having at least one selected from an epoxy group and an alkoxy group and having no isocyanuric ring.
  • the content of the (D) adhesion-imparting agent in the addition-curable silicone composition is 0.01 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the component (A).
  • the (D) adhesion-imparting agent having the above-described structure has a function of contributing to improvement in adhesion to a plastic of a silicone cured product, specifically, PPA (polyphthalamide resin).
  • ((D1) component) The isocyanuric acid derivative having at least one selected from an epoxy group and an alkoxysilyl group as component (D1) and at least one selected from a hydrosilyl group and a crosslinkable vinyl group is represented by the following formula (D11). Are preferred.
  • the compound represented by the formula (D11) is also referred to as a compound (D11). The same applies to compounds represented by other formulas.
  • Y 1 to Y 3 each independently represent a vinyl group, a methacryloxy group, an acryloxy group, a group represented by the following formula (T1), an alkoxysilyl group, or an epoxy group
  • Y 1 to Y 3 1 or 2 is a vinyl group, a methacryloxy group, an acryloxy group or a group represented by the following formula (T1), and the remainder is an alkoxysilyl group or an epoxy group.
  • the alkoxysilyl group is an alkoxydialkylsilyl group in which one alkoxy group and two monovalent hydrocarbon groups are bonded to a silicon atom, and a dialkoxy in which two alkoxy groups and one monovalent hydrocarbon group are bonded to a silicon atom. Either an alkylsilyl group or a trialkoxysilyl group in which three alkoxy groups are bonded to a silicon atom may be used. A dialkoxyalkylsilyl group and a trialkoxysilyl group are preferred.
  • Examples of the alkoxy group that the alkoxysilyl group has include an alkoxy group that may have a branched structure having 1 to 4 carbon atoms.
  • a methoxy group, an ethoxy group, and a propoxy group are preferable, and a methoxy group and an ethoxy group are particularly preferable.
  • Examples of the hydrocarbon group include hydrocarbon groups that may have a branched structure having 1 to 4 carbon atoms, preferably a methyl group, an ethyl group, and a propyl group, and particularly preferably a methyl group and an ethyl group.
  • alkoxysilyl group examples include a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a trimethoxysilyl group, and a triethoxysilyl group.
  • Q 1 to Q 3 are each independently a divalent hydrocarbon group having 1 to 7 carbon atoms which may have a linking group represented by the following formula (L1) and an etheric oxygen atom between carbon-carbon atoms. .
  • the carbon number is a number that does not include the carbon number of the linking group.
  • s is 1 to 10, and preferably 1 to 4.
  • t is 1 to 10, and preferably 1 to 4.
  • -Q 1 -Y 1 , -Q 2 -Y 2 , and -Q 3 -Y 3 in (D11) are each preferably any one of the groups shown below.
  • examples of the compound represented by (D11) include compounds represented by the following formulas (D11-1) to (D11-7).
  • a component may be used individually by 1 type, and 2 or more types may be used together.
  • Compound (D11), Compound (D11-1) and Compound (D11-2), Compound (D11-4) and Compound (D11-5), Compound (D11-6) and Compound (D11-7) Combinations are preferred, and mixtures of 1: 1 in each molar ratio are particularly preferred.
  • the component (D2) which is a silane or siloxane compound having at least one selected from an epoxy group and an alkoxy group and having no isocyanuric ring, is a compound represented by the following formula (D21), represented by the formula (D22) It is preferably at least one selected from a compound and a compound represented by formula (D23).
  • Y 4 , Y 5 and Y 6 are each independently an epoxy group, a cyclic alkyl group containing an epoxy group, or an alkoxysilyl group
  • Q 4 , Q 5 and Q 6 are Each independently represents an etheric oxygen atom between carbon-carbon atoms and a divalent hydrocarbon group having 1 to 10 carbon atoms which may have an ester bond
  • u is 3 to 5
  • x1 and x2 are each independently 1 to 10
  • each R 10 independently represents an alkyl group having 1 to 5 carbon atoms which may be substituted with a hydrogen atom or a chlorine atom.
  • R 10 when a Si—H group is present, R 10 is a group other than an alkenyl group.
  • Y 7 is an epoxy group or a cyclic alkyl group containing an epoxy group
  • Q 7 is a divalent carbon atom having 1 to 10 carbon atoms which may have an etheric oxygen atom between carbon-carbon atoms. Represents a hydrogen group, v is 1 or 2, and w is 0 or 1.
  • X is a hydrolyzable group selected from alkoxy groups and chlorine atoms
  • R 11 represents each an alkyl group having 1 to carbon atoms which may be substituted by a chlorine atom 4,
  • X and (Y 7 -Q 7 -) When a plurality of are present, they may be the same or different.
  • cyclic alkyl group containing an epoxy group represented by Y 4 to Y 7 include a 3,4-epoxycyclohexyl group.
  • -SiR 11 w X (4- vw) when Y 4 to Y 6 in formulas (D21) and (D22) and X is an alkoxy group in (D23) are the above (D11) Examples thereof include the same groups as the alkoxysilyl groups exemplified when Y 1 to Y 3 are an alkoxysilyl group.
  • -Q 4 -Y 4 , -Q 5 -Y 5 , and -Q 6 -Y 6 in (D21) and (D22) are each independently any of the groups shown in the following (i) to (iv) It is preferable that (I) — (CH 2 CHCH 3 —C ( ⁇ O) —O—) n11 — (CH 2 ) n12 -alkoxysilyl group (where n11 is 1 or 0, n12 is an integer of 1 to 5, preferably 2 Or 3.) (Ii) — (CH 2 ) n13 -epoxy group (where n13 is an integer of 1 to 5, preferably 3.) (Iii) — (CH 2 ) n14 -glycidoxy group (where n14 is an integer of 1 to 5, preferably 3) (Iv) — (CH 2 ) n15 — (3,4-epoxycyclohexyl group) (where n15 is an integer of 1 to 5, preferably 2.)
  • a component may be used individually by 1 type, and 2 or more types may be used together. From the viewpoint of maintaining high adhesion and excellent appearance, it is preferable to combine at least one compound (D21) and at least one compound (D23).
  • the adhesion-imparting agent may be used alone or in combination of two or more.
  • a preferred combination is a combination of at least one of the above (D1) isocyanuric acid derivatives and at least one of the above (D2) silane or siloxane compound.
  • the content ratio of at least one of the above (D1) isocyanuric acid derivative and at least one of the above (D2) silane or siloxane compound is 0.1 to 3 as a mass ratio represented by (D1) / (D2). 0.0 is preferable, and 0.25 to 1.5 is more preferable.
  • the addition-curable silicone composition contains the component (D1) and the component (D2) in such a ratio
  • the obtained silicone cured product has a particularly high adhesiveness, for example, an improvement in adhesive strength and various coatings.
  • An excellent appearance can be imparted, for example, when the adhesive can be used.
  • the ratio of the hydrosilyl group to the alkenyl group in the entire addition-curable silicone composition obtained that is, (A ) Component, (B) component, and (D) component
  • the ratio of the total amount of hydrosilyl groups and the total amount of alkenyl groups is, for example, 0.9 to 3.0 mol of hydrosilyl group per mol of alkenyl group It is preferable to adjust the amount.
  • the ratio is preferably 1.0 to 2.8 mol, more preferably 1.1 to 2.5 mol.
  • the component (E) is an organic free radical represented by the following general formula (3).
  • Compound (3) is an organic free radical having a 5- or 6-membered nitrogen-containing heterocyclic skeleton having 1 nitrogen atom and a structure in which the nitrogen is bonded to an oxy radical, and is opposed to the nitrogen atom of the heterocyclic ring. It has at least one electron-withdrawing atom or group as an atom or group bonded to a carbon atom.
  • each R 5 independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms
  • each R 6 independently represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, a carboxy group or a hydroxy group
  • the group or two R 6 bonded to the same carbon atom represent ⁇ O.
  • at least one of R 6 is a carboxy group or a hydroxy group, or the formula (3) has at least one ⁇ O as two R 6 bonded to the same carbon atom.
  • the compound (3) which is an organic free radical of the component (E) is obtained due to the adhesiveness imparting agent of the component (D). It becomes possible to suppress shrinkage and change in hardness due to heat in the silicone cured product.
  • the compound (3) is an organic free radical having a 5-membered nitrogen-containing heterocyclic skeleton represented by the following formula (31), and an organic free radical having a 6-membered nitrogen-containing heterocyclic skeleton represented by the following formula (32). Radicals. R 5 and R 6 in formula (31) and formula (32) have the same meaning as R 5 and R 6 in formula (3).
  • R 5 in Formula (31) and Formula (32) is an atom or group bonded to the carbon atom adjacent to both sides of the nitrogen atom of the heterocyclic ring, each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
  • R 5 is each independently preferably a linear hydrocarbon group having 1 to 3 carbon atoms, that is, a methyl group, an ethyl group, or a propyl group, and a linear alkyl group having 1 or 2 carbon atoms, that is, a methyl group or an ethyl group, More preferred.
  • Four R 5 may be the same or different.
  • R 6 in Formula (31) and Formula (32) is an atom or group bonded to a carbon atom facing the nitrogen atom of the heterocyclic ring, specifically, a carbon atom other than the carbon atoms adjacent to the nitrogen atom.
  • R 6 independently represents ⁇ O as a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, a carboxy group or a hydroxy group, or two R 6 bonded to the same carbon atom.
  • At least one of R 6 in the formula (3) is a carboxy group or a hydroxy group, or in the formula (3), at least one ⁇ O is present as two R 6 bonded to the same carbon atom.
  • a carboxy group, a hydroxy group, and ⁇ O are collectively referred to as a substituent (I).
  • the number of substituents (I) is preferably 1 to 3, more preferably 1 or 2, and most preferably 1.
  • the 4-position carbon atom has a substituent (I) with respect to the 1-position nitrogen atom.
  • Substituent (I) is an electron-withdrawing group or atom.
  • R 6 other than the substituent (I) is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
  • R 6 other than the substituent (I) is preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • Specific examples of the compound (3) include compounds represented by the following formula (31-1) classified as the compound (31), and formulas (32-1) and (32-2) classified as the compound (32). ) Or a compound represented by (32-3). In the formulas (31-1) and (32-1) to (32-3), the description of “H” when R 6 is a hydrogen atom is omitted.
  • Compound (3) can be produced by a known method. Moreover, in this invention, you may use a commercial item as a compound (3).
  • the compound (3) as the component (E) may be used alone or in combination of two or more.
  • the content of the compound (3) as the component (E) is 0.001 to 0.05 parts by mass with respect to 100 parts by mass of the component (A). Yes, preferably 0.002 to 0.03 parts by mass.
  • the addition-curable silicone composition of the embodiment of the present invention may contain (F) component silica powder as an optional component.
  • component silica powder of a component may be a well-known thing generally mix
  • Component (F) imparts appropriate fluidity and thixotropy to the composition before crosslinking, and imparts high mechanical strength required for the application to the crosslinked polyorganosiloxane obtained by crosslinking. Has an effect.
  • the component (A) is composed only of a linear polyorganosiloxane, for example, polyorganosiloxane (A1), it is preferable to contain the silica powder of the component (F).
  • the silica powder of component (F) preferably has a BET specific surface area (hereinafter referred to as BET specific surface area) of 50 m 2 / g or more, more preferably 50 to 600 m 2 / g. 100 to 400 m 2 / g is particularly preferable.
  • BET specific surface area The type of silica is not particularly limited, but precipitated silica, fumed silica (fumed silica), calcined silica, and the like are preferably used. From the viewpoint of reinforcing and thixotropic properties, fumed silica is preferred.
  • the surface treatment amount is preferably such that the amount of carbon on the silica surface is 2.0% by mass or more, more preferably 3.0% by mass or more. If it is less than 2.0 mass%, there is little effect in the thickening of a composition and the improvement of a pot life.
  • the upper limit of the carbon amount is not particularly limited, but is usually 20% by mass or less, preferably 12% by mass or less, and particularly 8% by mass or less.
  • organosilicon compound used as the surface treatment agent include organosilazanes, silane coupling agents, dimethylpolysiloxane (including a cyclic structure), organohydrogenpolysiloxane, and the like. There may be.
  • organosilazanes examples include hexaorganodisilazanes such as 1,3-divinyltetramethyldisilazane, 1,3-dimethyltetravinyldisilazane, hexamethyldisilazane; octamethyltrisilazane, 1,5-divinyl.
  • organosilazanes include hexaorganodisilazanes such as 1,3-divinyltetramethyldisilazane, 1,3-dimethyltetravinyldisilazane, hexamethyldisilazane; octamethyltrisilazane, 1,5-divinyl.
  • organosilazanes examples include octaorganotrisilazane such as hexamethyltrisilazane.
  • silane coupling agent examples include alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, and butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, and diethyl Dialkyl dialkoxysilanes such as diethoxysilane; alkenyltrialkoxysilanes such as vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (methoxyethoxy) silane; dialkenyldialkoxysilanes such as divinyldimethoxysilane and divinyldiethoxysilane; trimethyl Trialkylalkoxysilanes such as methoxysilane and triethylmethoxysilane, trivinylmethoxysilane, trivinylethoxys
  • Tri alkenyl alkoxysilanes trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, vinyltrichlorosilane, divinyldichlorosilane, organochlorosilanes such as trivinyl chlorosilane; and chloropropyl trimethoxy silane, and the like.
  • silane coupling agents cyclic dimethylpolysiloxanes and organosilazanes in which the substituent bonded to the silicon atom other than the hydrolyzable group is a methyl group are preferred.
  • a commercially available product may be used as the silica powder of component (F).
  • Examples of commercially available products as fumed silica surface-untreated, Aerosil 200 (trade name, EVONIC made, BET specific surface area: 200m 2 / g), Aerosil 300 (trade name, EVONIC made, BET specific surface area: 300m 2 / g ) And the like.
  • the component (F) one type may be used, or two or more types may be used in combination.
  • the content of the component (F) in the composition of the present invention is preferably 10 parts by mass or less with respect to 100 parts by mass of the component (A) from the viewpoint that the viscosity of the composition can be appropriately controlled.
  • the component (A) is composed only of the polyorganosiloxane (A1)
  • the component (F) is preferably contained, and the content thereof is 0 with respect to 100 parts by mass of the component (A). 1 to 10 parts by mass is preferable, and 1 to 4 parts by mass is more preferable.
  • the content of the silica powder as the component (F) is in the above range, the viscosity of the composition will be moderate and the workability during molding will be kept good, and the mechanical strength and hardness of the resulting cured silicone will be further improved. Etc. are sufficiently maintained.
  • the addition-curable silicone composition of the embodiment of the present invention may further contain an addition reaction inhibitor as an optional component (G).
  • the addition reaction inhibitor of component (G) does not reduce the catalytic activity during storage of the hydrosilylation reaction catalyst of component (C), and includes the alkenyl group of component (A) and the Si—H group of component (B). It suppresses the addition reaction with and increases the storage stability of the addition-curable silicone composition.
  • (G) As the addition reaction inhibitor, a known one can be used. For example, 1-ethynylcyclohexane-1-ol, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, Acetylenic alcohols such as phenylbutynol; acetylenic compounds such as 3-methyl-3-penten-1-in and 3,5-dimethyl-1-hexyne-3-in; these acetylenic compounds and alkoxysilanes; Reaction products with alkoxy siloxane, hydrogen silane or hydrogen siloxane; vinyl siloxanes such as tetramethylvinylsiloxane cyclics; organic nitrogen compounds such as benzotriazole and other organic phosphorus compounds; oxime compounds, organic chromium compounds, diallyl maleate Etc.
  • the content of the addition reaction inhibitor of component (G) is not particularly limited as long as the stability of the addition-curable silicone composition is obtained, but is 0.001 to 0 with respect to 100 parts by mass of component (A). 1 part by mass is preferable, and 0.01 to 0.05 part by mass is more preferable.
  • the addition-curable silicone composition of the present embodiment is added to the component (E) for the purpose of maintaining excellent adhesiveness by suppressing shrinkage and change in hardness due to heat while maintaining good appearance in the obtained silicone cured product.
  • the carboxylic acid metal salt represented by the following general formula (5) as component (H) (hereinafter also referred to as carboxylic acid metal salt (5)) is contained in an amount of 0.001 to 0.015 parts by mass in terms of metal atoms. May be.
  • a more preferable content of the component (H) is 0.002 to 0.010 parts by mass in terms of metal atoms with respect to 100 parts by mass of the component (A).
  • the addition-curable silicone composition contains the carboxylic acid metal salt (5) as the component (H)
  • the resulting silicone cured product covers or seals a metal member such as a silver electrode. In addition, these can be protected from corrosion.
  • R 3 COO (R 3 COO) k M (5)
  • M is a metal atom selected from Ce, Fe, Cr, La, Nd, Pr, and Sm
  • k is a positive number of 2 to 4
  • R 3 is a substituted or unsubstituted hydrocarbon of 4 to 17 carbon atoms. Group.
  • M represents a metal atom selected from Ce, Fe, Cr, La, Nd, Pr, and Sm.
  • M may be composed of one kind selected from Ce, Fe, Cr, La, Nd, Pr, and Sm, or may be composed of a mixture of two or more kinds.
  • Specific examples of the mixture include a rare earth element mixture of Ce, La, Nd, Pr, and Sm, and a mixture containing cerium (Ce) as a main component is preferable.
  • the mixture which has cerium as a main component means the mixture whose content of cerium is more than 50 mass% with respect to the mixture whole quantity.
  • the carboxylic acid metal salt (5) used as the component (H) is preferably a carboxylic acid metal salt in which M is cerium (Ce) alone, iron (Fe) alone, or chromium (Cr) alone in the formula (5), A carboxylic acid metal salt of cerium alone is particularly preferred.
  • k is given by 2 to 4 depending on the valence of the metal used.
  • R 3 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 4 to 17 carbon atoms.
  • carboxylic acids that give such carboxylic acid metal salts include 2-ethylhexanoic acid, octanoic acid, decanoic acid. Oleic acid, lauric acid, stearic acid and the like.
  • carboxylic acid mixtures such as a naphthenic acid, may be sufficient.
  • carboxylic acid metal salt (5) examples include cerium (III) octoate, cerium (III) 2-ethylhexanoate, iron (II) 2-ethylhexanoate, and iron (III) 2-ethylhexanoate.
  • Chromium (III) 2-ethylhexanoate, cerium (IV) decanoate, cerium (III) decanoate and the like, and cerium (III) octoate and cerium (III) 2-ethylhexanoate are particularly preferred.
  • octanoate and 2-ethylhexanoate of a rare earth element mixture containing cerium as a main component can be preferably used. Use of a rare earth element mixture containing cerium as a main component is advantageous in terms of economy. The higher the cerium content in the mixture, that is, the higher the cerium purity, the better in terms of effect.
  • a commercially available product may be used as the component.
  • Examples of commercially available products include rare earth-OCTOATE 6% (trade name, manufactured by DIC, 2-ethylhexanoic acid rare earth element salt (rare earth element content 6 mass%: Ce 3.1 mass%, Nd 0.95 mass%, Pr0.31% by mass, Sm0.01% by mass, La1.59% by mass), Nikka Octix iron (trade name, manufactured by Nippon Chemical Industry Co., Ltd., iron (III) 2-ethylhexanoate (metal content: Fe6% by mass) )), 8% chromium Hex-Cem (trade name, OMG manufactured by Americas Inc., chromium (III) 2-ethylhexanoate (metal content: Cr 8 mass%)), and the like.
  • Carboxylic acid metal salts (5) such as cerium (III) octanoate, cerium (2-ethylhexanoate), rare earth element 2-ethylhexanoate, iron (II) 2-ethylhexanoate, (III ), 2-ethylhexanoic acid chromium (III) and the like are preferably used as an organic solvent solution from the viewpoint of easy handling and compatibility with other components in the composition.
  • organic solvents include petroleum solvents such as standard solvent, mineral spirit, ligroin and petroleum ether, and aromatic solvents such as toluene and xylene.
  • the addition-curable silicone composition according to the embodiment of the present invention contains the components (A) to (E) as essential components in the above-described content, and optionally contains the components (F) as optional components. ) Component, (G) component, and (H) component are contained in the above content.
  • the addition curable silicone composition of the present embodiment further includes the above (F) such as polyorganosiloxane, pulverized silica (quartz fine powder), aluminum oxide other than the above as optional components other than the components (F) to (H).
  • Inorganic fillers other than silica powder conductive fillers such as silver powder, for example, phosphors for obtaining a desired emission color when used in optical semiconductor devices, toluene, xylene, hexane, heptane, ethanol
  • organic solvents such as isopropyl alcohol, acetone, methyl ethyl ketone, dyes, pigments, flame retardants, heat resistance improvers, oxidation degradation agents, wavelength adjusting agents, etc. within the range not impairing the effects of the present invention Also good.
  • each component is not particularly limited, and the essential components (A) to (E) and optional components that are preferably added. And (F) component, (G) component, (H) component and other optional components described above are kneaded with a known kneader.
  • the mixture is prepared by previously mixing the component (A) and the organic solvent solution of the carboxylic acid metal salt (5). You may perform operation which removes an organic solvent from. In that case, the remaining components are added to the mixture after removal of the organic solvent and kneading is performed. Even when the carboxylic acid metal salt (5) of the component (H) is used as the organic solvent solution, depending on the amount of the organic solvent, all components constituting the addition-curable silicone composition containing the component (H) May be simultaneously kneaded with a kneader.
  • Examples of the kneader include a planetary mixer, a three-roller, a kneader, and a Shinagawa mixer, which are provided with a heating unit and a cooling unit, if necessary, and these can be used alone or in combination.
  • Curing in the addition-curable silicone composition of the embodiment of the present invention is performed mainly by subjecting the (A) component and the (B) component to a hydrosilylation reaction in the presence of the (C) component.
  • hardening reaction can be suitably adjusted according to the kind and addition amount of the said addition reaction inhibitor.
  • Preferred curing conditions include heating at 50 to 200 ° C. for 60 to 300 minutes.
  • the silicone cured product thus obtained is a hard rubber or flexible resin, has excellent adhesion and appearance, and has suppressed thermal shrinkage and changes in hardness due to heat. It is.
  • the addition-curable silicone composition of the present invention is excellent when used as a sealant or die attach agent for COB (chip-on-board), for example, when an optical semiconductor chip such as an LED is mounted on a substrate and sealed. Yes. Further, it can be widely used for general-purpose optical semiconductor packages such as photodiodes, CCDs, and CMOSs.
  • the support structure on which the optical semiconductor chip is mounted is particularly limited.
  • a package-less support substrate such as a ceramic substrate, a silicon substrate, a glass epoxy substrate, a bakelite (epoxy resin) substrate, a metal substrate, a plastic, specifically, a PPA (polyphthalamide resin) substrate, etc. Good.
  • a silicone cured product having high adhesion to a PPA substrate can be obtained.
  • an addition-curable silicone composition in which a silicone cured product obtained according to specifications has excellent adhesion to metal. Furthermore, it is also possible for the cured silicone obtained according to the specifications to be an addition-curable silicone composition having excellent adhesion to a metal such as silver.
  • the viscosity is a measured value at 25 ° C.
  • Adhesiveness imparting agent (D1) Adhesiveness imparting agent (D2)
  • D1 Adhesiveness imparting agent
  • D2 Adhesiveness imparting agent
  • D11-1) and D11-2) were used as the adhesion-imparting agent (D1).
  • a 1: 1 (molar ratio) mixture of (D11-1) and (D11-2) was used.
  • the compounds (D21-1) and (D23-1) were used as the adhesion-imparting agent (D2).
  • Component (F) Silica powder
  • Silica powder (F1) Homosilica having a specific surface area of about 200 m 2 / g, the surface of which was treated with hexamethyldisilazane. 2.5% by mass of carbon on the silica surface.
  • Component Carboxylic acid metal salt (5) Cerium (III) 2-ethylhexanoate (12% cerium Hex-Cem (trade name, manufactured by OMG Americas Inc., metal content: Ce 12% by mass, composition: 49% by mass of cerium (III) 2-ethylhexanoate, 2-ethylhexanoic acid 48% by mass, dipropylene glycol monomethyl ether 3% by mass)).
  • Examples 1 to 15, Comparative Examples 1 to 5 All components shown in Tables 1 to 3 were kneaded and deaerated to produce addition-curable silicone compositions of Examples 1 to 15 and Comparative Examples 1 to 5, respectively.
  • the content of the component (C) is the content (ppm) in terms of platinum atoms with respect to the total mass of the components (A) and (B). Moreover, about the mass part of carboxylic acid metal salt (5) of (H) component, it is a mass part in conversion of the metal atom of carboxylic acid metal salt (5).
  • Tables 1 to 3 show the total Vi group (molar ratio) of the Si—H group of the (B) component / (A) component and the entire composition, that is, the (A) component, the (B) component, (D ) Component Si-H group / Vi group (molar ratio).
  • the mass of the obtained test piece of the cured product was measured using an electronic analytical balance (product name: AEU-210, manufactured by Shimadzu Corporation).
  • the mass error range obtained is ⁇ 0.001 g, and the mass change rate (%) error range is ⁇ 0.01%.
  • ⁇ The cured product cannot be peeled off from the interface (surface) of the substrate, and the cured product is destroyed.
  • X Hardened
  • the cured silicone products obtained by curing the addition-curable silicone compositions of the examples have excellent adhesion and appearance, and are less susceptible to shrinkage and hardness due to heat.
  • the cured silicone obtained by curing the addition-curable silicone composition of the comparative example shown in Table 3 is insufficient in at least one of adhesiveness, appearance, hardness change, and heat shrinkage.

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Abstract

L'invention concerne une composition de silicone traitée par addition de telle sorte que le produit de silicone durci obtenu est supérieur en ce qui concerne l'adhérence et l'aspect, et se contracte ou change peu en dureté en raison de la chaleur. La composition de silicone traitée par addition contient : (A) 100 parties en masse d'un polyorganosiloxane ayant un groupe alcényle ; (B) un polyorganohydrogénosiloxane en quantité telle que 0,9 à 3,0 moles d'atomes d'hydrogène sont liés à des atomes de silicium pour chaque total de 1 mole de groupes alcényle que le composant (A) comprend ; (C) une quantité catalytique de catalyseur d'hydrosilylation ; (D) 0,01 à 10 parties en masse d'un agent conférant une adhésivité ; et (E) 0,001 à 0,05 parties en masse d'un radical organique libre (composé ayant un squelette hétérocyclique à 5 ou 6-chaînons d'azote et dont les atomes d'azote sont liés aux atomes d'oxygène des radicaux libres).
PCT/JP2015/052142 2014-02-07 2015-01-27 Composition de silicone traitée par addition WO2015118992A1 (fr)

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CN111548729A (zh) * 2019-02-12 2020-08-18 信越化学工业株式会社 管芯键合用有机改性硅酮树脂组合物、其固化物及光学半导体元件
WO2020203597A1 (fr) * 2019-04-01 2020-10-08 信越化学工業株式会社 Composition de gel de silicone auto-adhésive et produit durci à base de gel de silicone
CN114174454A (zh) * 2019-07-17 2022-03-11 信越化学工业株式会社 紫外线固化型有机聚硅氧烷组合物
CN114381202A (zh) * 2022-01-20 2022-04-22 广东鼎立森新材料有限公司 一种有机硅组合物及pu-有机硅合成革

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KR102257952B1 (ko) * 2016-06-15 2021-06-01 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 경화성 폴리오가노실록산 조성물 및 그 사용
CN112876858B (zh) * 2021-01-15 2023-08-08 杭州之江新材料有限公司 一种有机聚硅氟组合物及其制备方法

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