WO2014129347A1 - Composition de résine durcissable - Google Patents

Composition de résine durcissable Download PDF

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Publication number
WO2014129347A1
WO2014129347A1 PCT/JP2014/053045 JP2014053045W WO2014129347A1 WO 2014129347 A1 WO2014129347 A1 WO 2014129347A1 JP 2014053045 W JP2014053045 W JP 2014053045W WO 2014129347 A1 WO2014129347 A1 WO 2014129347A1
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group
groups
organopolysiloxane
curable resin
resin composition
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PCT/JP2014/053045
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English (en)
Japanese (ja)
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奈央 佐藤
石川　和憲
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横浜ゴム株式会社
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Priority to JP2014526297A priority Critical patent/JPWO2014129347A1/ja
Priority to KR1020157023881A priority patent/KR20150119882A/ko
Publication of WO2014129347A1 publication Critical patent/WO2014129347A1/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
    • C08K5/56—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
    • 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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • 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 a curable resin composition.
  • a curable resin composition containing a silicone resin is known, and is used as, for example, a composition for optical semiconductor sealing.
  • a curable resin composition containing a silicone resin is known, and is used as, for example, a composition for optical semiconductor sealing.
  • (A) a branched chain having at least 3 alkenyl groups in one molecule and at least 30 mol% of all silicon-bonded organic groups is an aryl group”.
  • Organopolysiloxane (B) linear organopolysiloxane having both ends of the molecular chain blocked with diorganohydrogensiloxy groups and having an aryl group, (C) at least 3 diorganohydrogens in one molecule
  • a curable organopolysiloxane composition comprising a branched organopolysiloxane having a siloxy group and at least 15 mol% of all silicon-bonded organic groups being an aryl group, and (D) a catalyst for hydrosilylation reaction. Is described.
  • the present invention has been made in view of the above points, and an object of the present invention is to provide a curable resin composition having excellent adhesion, particularly adhesion after a moisture-resistant reflow test.
  • the present inventors have found that the adhesion after the moisture-resistant reflow test is improved by adding a specific block copolymer to the curable resin composition. Completed the invention.
  • the present invention provides the following (I) to (V).
  • the mass ratio (c1 / c2) between the polysiloxane block (c1) and the hydrocarbon polymer block (c2) is 20/80 to 80/20.
  • each R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group. However, in one molecule, at least one of R 1 is an alkenyl group, and at least one of R 1 is Each is an aryl group.
  • X 1 is a hydrogen atom or an alkyl group.
  • a is a positive number
  • b is 0 or a positive number
  • c is 0 or a positive number
  • d is 0 or a positive number
  • e is 0 or a positive number
  • B / a is a number in the range 0-10
  • c / a is a number in the range 0-5
  • d / (a + b + c + d) is a number in the range 0-0.3
  • e / (a + b + c + d) is a number in the range of 0 to 0.4.
  • V The curable resin composition according to any one of (I) to (IV) above, which is a composition for optical semiconductor element sealing.
  • the curable resin composition of the present invention includes a branched organopolysiloxane (A) having an alkenyl group and at least two silicon-bonded hydrogen atoms in one molecule.
  • the branched organopolysiloxane (A) is a branched organopolysiloxane having an alkenyl group.
  • the alkenyl group include alkenyl groups having 2 to 18 carbon atoms such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and an octenyl group, and a vinyl group (hereinafter referred to as “Vi”). Is preferred).
  • the alkenyl group in one molecule is preferably 2 to 12% by mass, and more preferably 3 to 10% by mass.
  • the branched organopolysiloxane (A) preferably has at least one aryl group, more preferably at least 30 mol% of all silicon-bonded organic groups are aryl groups, and at least 40 mol% is aryl. More preferably, it is a group.
  • the aryl group include aryl groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group, and a phenyl group is preferable.
  • the resulting cured product is less attenuated by light refraction, reflection, scattering and the like, and when the linear organopolysiloxane (B) described later has an aryl group, Excellent compatibility with siloxane (B), turbidity and the like are suppressed, and the transparency of the cured product is excellent.
  • Examples of the group bonded to the other silicon atom in the branched organopolysiloxane (A) include substituted or unsubstituted monovalent hydrocarbon groups excluding alkenyl groups and aryl groups. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, An alkyl group having 1 to 18 carbon atoms such as cyclopentyl group and cyclohexyl group; an aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group; a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, etc.
  • a halogenated alkyl group having 1 to 18 carbon atoms; and other small groups include silicon-bonded hydroxy groups and silicon atoms. It may have a slip alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • Such a branched organopolysiloxane (A) is preferably an organopolysiloxane represented by the following average unit formula (1).
  • each R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group.
  • the monovalent hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, and various hexyl groups.
  • Alkyl groups having 1 to 18 carbon atoms such as various octyl groups, various decyl groups, cyclopentyl groups, and cyclohexyl groups; and those having 2 to 18 carbon atoms such as vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, and octenyl groups.
  • At least one of R 1 is an alkenyl group, and the amount of R 1 that is an alkenyl group is preferably 2 to 12% by mass, and more preferably 3 to 10% by mass.
  • at least one R 1 is preferably an aryl group, more preferably at least 30 mol% of all R 1 is an aryl group, and at least 40 mol% is an aryl group. Further preferred.
  • X 1 is a hydrogen atom or an alkyl group.
  • alkyl group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, and various octyl groups.
  • Groups, various decyl groups, cyclopentyl groups, cyclohexyl groups and the like, and alkyl groups having 1 to 18 carbon atoms, and a methyl group is preferable.
  • a is a positive number
  • b is 0 or a positive number
  • c is 0 or a positive number
  • d is 0 or a positive number
  • e is 0 or a positive number
  • B / a is a number in the range 0-10
  • c / a is a number in the range 0-5
  • d / (a + b + c + d) is a number in the range 0-0.3
  • e / (a + b + c + d) is a number in the range of 0 to 0.4.
  • the weight average molecular weight (Mw) of the branched organopolysiloxane (A) is preferably 1,000 to 300,000, more preferably 2,000 to 100,000.
  • a weight average molecular weight shall be the weight average molecular weight of polystyrene conversion by the gel permeation chromatography (GPC) which uses chloroform as a solvent.
  • GPC gel permeation chromatography
  • the branched organopolysiloxane (A) is a very viscous semi-solid or solid material, and it is difficult to measure the viscosity.
  • linear organopolysiloxane (B) is an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule. If linear organopolysiloxane (B) is mainly linear, it may have a small amount (for example, less than 2 mol% of all siloxane units) of a branch.
  • the linear organopolysiloxane (B) undergoes an addition reaction (hydrosilylation reaction) with the alkenyl group of the branched organopolysiloxane (A) described above. At this time, since the linear organopolysiloxane (B) has at least two silicon-bonded hydrogen atoms (Si—H), it functions as a cross-linking agent between the branched organopolysiloxanes (A). Can do.
  • the degree of polymerization of the linear organopolysiloxane (B) is preferably more than 10, more preferably more than 30, more preferably more than 30 and not more than 1,000, and particularly preferably more than 30 and not more than 500.
  • the composition of this invention is more excellent in adhesiveness. This is presumably because toughness occurs in the cured product by containing a polymer component. Also, workability is improved.
  • the linear organopolysiloxane (B) preferably has at least one aryl group because the resulting cured product is less attenuated by light refraction, reflection, scattering, etc. More preferably, at least 30 mol% is an aryl group, and at least 40 mol% is more preferably an aryl group.
  • the aryl group include aryl groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group, and a phenyl group is preferable.
  • Examples of the group bonded to the silicon atom in the linear organopolysiloxane (B) include a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated group. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, An alkyl group having 1 to 18 carbon atoms such as cyclopentyl group and cyclohexyl group; an aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group and xylyl group; an aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group; A halogenated alkyl group having 1
  • Such a linear organopolysiloxane (B) is preferably a linear organopolysiloxane having both ends of the molecular chain blocked with diorganohydrogensiloxy groups.
  • the organopolysiloxane represented is mentioned. HR 2 2 SiO (R 2 2 SiO) n SiR 2 2 H (2)
  • each R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond.
  • the monovalent hydrocarbon group for R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, and various types.
  • Alkyl groups having 1 to 18 carbon atoms such as hexyl group, various octyl groups, various decyl groups, cyclopentyl groups, and cyclohexyl groups; aryl groups having 6 to 18 carbon atoms such as phenyl groups, tolyl groups, and xylyl groups; benzyl groups and phenethyl groups Aralkyl groups having 7 to 18 carbon atoms such as a group; halogenated alkyl groups having 1 to 18 carbon atoms such as a 3-chloropropyl group and 3,3,3-trifluoropropyl group; It is preferably an alkyl group of 1 to 18, more preferably a methyl group (hereinafter sometimes referred to as “Me”).
  • R 2 is preferably an aryl group, more preferably at least 30 mol% is an aryl group, and even more preferably at least 40 mol% is an aryl group.
  • the aryl group is an aryl group having 6 to 18 carbon atoms, and is preferably a phenyl group (hereinafter sometimes referred to as “Ph”).
  • n is an integer of 1 or more, preferably an integer of more than 10, more preferably an integer of more than 30, more preferably an integer of more than 30 and less than 1,000, particularly preferably an integer of more than 30 and less than 500 preferable. If n is the said range, adhesiveness will be more excellent.
  • the weight average molecular weight (Mw) of the linear organopolysiloxane (B) is preferably from 500 to 1,000,000, more preferably from 1,000 to 30,000, because toughness occurs in the cured product. Further, the viscosity of the linear organopolysiloxane (B) at 25 ° C. is preferably 20 to 1,000,000 mPa ⁇ s, and more preferably 200 to 100,000 mPa ⁇ s. In the present invention, the viscosity is measured at 25 ° C. in accordance with 4.1 (Brookfield rotary viscometer) of JIS K7117-1.
  • the production method of the linear organopolysiloxane (B) is not particularly limited.
  • the above-mentioned polysiloxane (B) main product is produced by reacting with disiloxane (b2) having water (H 2 O) as a by-product and optionally dehydrating and condensing silanol groups remaining by the reaction. The method obtained as a thing is mentioned.
  • the reaction is traced by 1 H-NMR to confirm the disappearance of the peak derived from the silanol group of the organopolysiloxane (b1) or the appearance of the peak derived from a component other than the component used in the reaction.
  • the reaction can be completed as a reaction product containing the linear organopolysiloxane (B), which is the main product, and by-products.
  • organopolysiloxane (b1) used in the above reaction examples include organopolysiloxanes represented by the following formula (3).
  • examples of the disiloxane (b2) include those represented by the following formula (4).
  • the disiloxane represented is mentioned. HO (R 2 2 SiO) m H (3) HR 2 2 SiOSiR 2 2 H (4)
  • R 2 has the same meaning as R 2 described above.
  • m is an integer below n mentioned above.
  • the blending ratio of each component in the above reaction is preferably such that the disiloxane (b2) is 0.001 to 0.2 mol per 10 mol of silanol groups in the organopolysiloxane (b1).
  • the above reaction is preferably carried out by stirring. In stirring, for example, heating is preferably performed in a temperature range of 50 to 65 ° C., and the stirring time (reaction time) is preferably 1 to 5 hours, for example.
  • the content of the linear organopolysiloxane (B) is preferably 20 to 60 parts by mass and more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the above-mentioned branched organopolysiloxane (A). If content of linear organopolysiloxane (B) is this range, the sclerosis
  • the block copolymer (C) contained in the composition of the present invention is a block copolymer (block copolymer) containing a polysiloxane block (c1) and a hydrocarbon polymer block (c2).
  • Such a block copolymer (C) includes, for example, a polysiloxane (c1 ′) having a terminal reactive group and a hydrocarbon polymer (c2 ′) having a terminal group capable of reacting with the terminal reactive group. It is obtained by forming a copolymer chain containing a polysiloxane block (c1) and a hydrocarbon-based polymer block (c2) by reacting under conditions where the reaction between the terminal reactive group and the terminal group proceeds. .
  • a polysiloxane (c1 ′) in which the terminal reactive group is a silicon atom-bonded hydrogen atom (Si—H) and a hydrocarbon heavy polymer in which the terminal group is an alkenyl group for example, a polysiloxane (c1 ′) in which the terminal reactive group is a silicon atom-bonded hydrogen atom (Si—H) and a hydrocarbon heavy polymer in which the terminal group is an alkenyl group.
  • a method in which the compound (c2 ′) is hydrosilylated using a hydrosilylation reaction catalyst; the polysiloxane (c1 ′) in which the terminal reactive group is an alkenyl group; and the terminal group is a silicon-bonded hydrogen atom ( And a method of hydrosilylating the hydrocarbon polymer (c2 ′) which is Si—H) in the same manner.
  • the hydrosilylation reaction catalyst (D) described later can be used as the hydrosilylation reaction catalyst.
  • the composition of the present invention contains such a block copolymer (C) in combination with the above-mentioned branched organopolysiloxane (A) and linear organopolysiloxane (B).
  • the adhesiveness after the moisture-resistant reflow test is excellent.
  • the reason is considered as follows. First, since the block copolymer (C) contains the polysiloxane block (c1), it has high compatibility with the above-mentioned branched organopolysiloxane (A) and linear organopolysiloxane (B), It is considered to be incorporated.
  • the block copolymer (C) includes a hydrocarbon polymer block (c2) such as an isobutylene polymer block or a (meth) acrylic polymer block.
  • hydrocarbon polymer blocks (c2) Since the main chain consists of hydrocarbon chains and the side chains may have many hydrocarbon groups, the moisture resistance is relatively high (low water vapor permeability) compared to polysiloxane. It is considered that the cured product of the composition of the invention suppresses the intrusion of moisture even in a high humidity environment and improves the adhesion after the moisture reflow test.
  • composition of the present invention contains, for example, mere polyisobutylene that is not block copolymerized
  • this polymer is a branched organopolysiloxane (A )
  • the linear organopolysiloxane (B) are not incorporated and become an isolated state, so that the effect of suppressing the intrusion of moisture into the cured product is reduced.
  • this polymer is not compatible with the branched organopolysiloxane (A) and the linear organopolysiloxane (B), which are silicones, the cured product becomes turbid and inferior in transparency.
  • the polysiloxane block (c1) contained in the block copolymer (C) has a polysiloxane structure composed of a plurality of siloxane units.
  • the polysiloxane block (c1) is mainly linear, it may have a small amount (for example, less than 2 mol% of all siloxane units) of branches.
  • the polysiloxane block (c1) is derived from, for example, the polysiloxane (c1 ′) having a terminal reactive group.
  • the terminal reactive group possessed by the polysiloxane (c1 ′) include a silicon atom-bonded hydrogen atom (Si—H): 2 carbon atoms such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, and octenyl group. -18 alkenyl groups; and the like.
  • a polysiloxane (c1 ′) for example, a polysiloxane represented by the following formula (5) is preferably exemplified.
  • R 31 is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group.
  • the monovalent hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, and various hexyl groups.
  • Alkyl groups having 1 to 18 carbon atoms such as various octyl groups, various decyl groups, cyclopentyl groups, and cyclohexyl groups; and those having 2 to 18 carbon atoms such as vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, and octenyl groups.
  • R 31 may be hydrogen atoms or an alkenyl group, in which case, in one molecule, 2 to 4 R 31 is is preferably a hydrogen atom or an alkenyl group, is two to three R 31 A hydrogen atom or an alkenyl group is more preferable.
  • R 32 is independently the above-mentioned terminal reactive group, specifically, for example, hydrogen atom; carbon number such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, etc. 2-18 alkenyl groups; and the like.
  • k is an integer of 1 or more, preferably 1 to 1,000, and can be a numerical value corresponding to the weight average molecular weight of the polysiloxane (c1 ′).
  • the weight average molecular weight of the polysiloxane (c1 ′) is preferably from 100 to 100,000, more preferably from 500 to 50,000, from the viewpoints of elongation characteristics and transparency.
  • the hydrocarbon polymer block (c2) contained in the block copolymer (C) has a structure composed of a hydrocarbon polymer, and contributes to improvement of moisture resistance.
  • a hydrocarbon polymer block (c2) include an isobutylene polymer block, a (meth) acrylic polymer block, and a hydrogenated polybutadiene block.
  • the isobutylene polymer block and / or the (meth) acrylic polymer block are preferred because they have better moisture resistance and better adhesion after the moisture reflow test in the composition of the present invention.
  • An isobutylene polymer block is more preferable.
  • Such a hydrocarbon-based polymer block (c2) is derived from, for example, the hydrocarbon-based polymer (c2 ′) having the above end groups as described above.
  • Examples of the terminal group of the hydrocarbon polymer (c2 ′) include silicon-bonded hydrogen atoms (Si—H); carbon such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, and octenyl group.
  • Examples of the alkenyl group having 2 to 18 are vinyl group and allyl group.
  • Examples of such a hydrocarbon polymer (c2 ′) include a (meth) acrylic polymer having the terminal group, an isobutylene polymer having the terminal group, and the like.
  • the weight average molecular weight of the hydrocarbon polymer (c2 ′) is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000, from the viewpoint of better moisture resistance.
  • the (meth) acrylic polymer having the terminal group those in which the main chain is mainly polymerized from a (meth) acrylic monomer are preferable.
  • “mainly” means that 50 mol% or more of the monomer units constituting the main chain is the above monomer, and preferably 70 mol% or more.
  • a (meth) acrylic-type monomer a (meth) acrylic acid monomer, a (meth) acrylic acid ester monomer, etc. are mentioned, for example, A (meth) acrylic acid ester monomer is preferable.
  • the (meth) acrylate monomer examples include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
  • the (meth) acrylic acid ester monomer may be copolymerized with other monomers, and further block copolymerized. In this case, the (meth) acrylic acid ester monomer is 40% by mass. It is preferable that it is contained above.
  • the bonding mode between the terminal group and the main chain of the (meth) acrylic polymer is not particularly limited, and examples thereof include a carbon-carbon bond, an ester bond, an ether bond, a carbonate bond, an amide bond, and a urethane bond. A combined form is mentioned.
  • the “isobutylene polymer” is not limited to those in which all of the monomer units are formed from isobutylene units, and is a monomer having a copolymerizability with isobutylene.
  • examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes.
  • the monomer copolymerizable with isobutylene is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and all of the monomer units are formed from isobutylene units.
  • isobutylene polymer having such a terminal group for example, diallyl-terminated polyisobutylene represented by the following formula (6) is preferably exemplified.
  • PIB represents polyisobutylene.
  • polysiloxane (c1 ′) represented by the above formula (5) and R 32 represents a hydrogen atom or an alkenyl group
  • the block copolymer (C) containing the polysiloxane block (c1) and the hydrocarbon polymer block (c2) composed of polyisobutylene can be obtained by proceeding the polymerization with the polymer (c2 ′).
  • the mass ratio (c1 / c2) between the polysiloxane block (c1) and the hydrocarbon polymer block (c2) is such that the polysiloxane block (c1) and the hydrocarbon polymer block (c2).
  • 20/80 to 80/20 are preferable, and 35/65 to 65/35 are more preferable, because the balance with the above is excellent and the adhesion after the moisture-resistant reflow test becomes better.
  • the content of the block copolymer (C) is 100 parts by mass in total of the above-mentioned branched organopolysiloxane (A) and linear organopolysiloxane (B) because the adhesion after the moisture reflow test is more excellent.
  • the amount is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and still more preferably 10 to 25 parts by mass.
  • the hydrosilylation reaction catalyst (D) contained in the composition of the present invention is used in combination with a linear organopolysiloxane (B) having a silicon atom-bonded hydrogen atom to form a branched organopolysiloxane (A). It functions as a catalyst for promoting an addition reaction (hydrosilylation reaction) to an alkenyl group.
  • a linear organopolysiloxane (B) having a silicon atom-bonded hydrogen atom to form a branched organopolysiloxane (A). It functions as a catalyst for promoting an addition reaction (hydrosilylation reaction) to an alkenyl group.
  • the block copolymer (C) has a silicon atom-bonded hydrogen atom or an alkenyl group, the reaction also proceeds for these groups by the hydrosilylation reaction catalyst (D).
  • hydrosilylation catalyst (D) a conventionally known catalyst can be used, and examples thereof include a platinum-based catalyst, a rhodium-based catalyst, a palladium-based catalyst, and the like, and a platinum-based catalyst is preferable.
  • platinum-based catalysts include chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-divinyltetramethyldisiloxane complexes, chloroplatinic acid-alcohol coordination compounds, platinum diketone complexes, and the like. May be used alone or in combination of two or more.
  • the content of the hydrosilylation reaction catalyst (D) is a catalytic amount, but because of the excellent curability of the composition of the present invention, the aforementioned branched organopolysiloxane (A) and linear organopolysiloxane described above are used.
  • the amount is preferably 0.00001 to 0.1 parts by weight, more preferably 0.0001 to 0.01 parts by weight, based on 100 parts by weight of the total amount of siloxane (B).
  • the composition of the present invention may further contain a curing retarder (E).
  • the curing retarder (E) is a component for adjusting the curing rate and working life of the composition of the present invention.
  • Specific examples of the curing retarder (E) include 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, phenylbutynol, 1-ethynyl- Alcohol derivatives having a carbon-carbon triple bond such as 1-cyclohexanol; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; tetramethyltetravinyl Low molecular weight siloxanes containing alkenyl groups such as cyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; methyl-tris (3-methyl-1-butyne-3-oxy)
  • the content of the curing retarder (E) is appropriately selected according to the method of using the composition of the present invention, and for example, the above-described branched organopolysiloxane (A) and linear organopolysiloxane (The total amount is 100 parts by mass of B), preferably 0.00001 to 0.1 parts by mass, and more preferably 0.0001 to 0.01 parts by mass.
  • the composition of the present invention may further contain an adhesion promoter (F).
  • adhesion-imparting agent (F) include a silane coupling agent.
  • Specific examples of the silane coupling agent include amino silane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, imino silane, reaction products thereof, compounds obtained by reaction of these with polyisocyanate, and the like, which are epoxy silanes. Is preferred.
  • the epoxy silane is not particularly limited as long as it is a compound having an epoxy group and an alkoxysilyl group.
  • Specific examples thereof include ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropylethyldiethoxysilane, Dialkoxyepoxysilanes such as ⁇ -glycidoxypropylmethyldiethoxysilane and ⁇ - (3,4 epoxycyclohexyl) ethylmethyldimethoxysilane; ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4 epoxycyclohexyl) Trialkoxy epoxy silanes such as ethyltrimethoxysilane; and the like.
  • the adhesion-imparting agent (F) may be, for example, a dehydration condensate of the above epoxy silane. Specifically, for example, ⁇ -glycidoxypropyltrimethoxysilane, phenyltrimethoxysilane, 1 , 3-divinyl-1,1,3,3-tetramethyldisiloxane and the dehydrated condensation product of epoxysilane.
  • the content of the adhesion-imparting agent (F) is not particularly limited, but is 0.5 to 0.5 parts per 100 parts by mass in total of the branched organopolysiloxane (A) and the linear organopolysiloxane (B). 10 parts by mass is preferable, and 1 to 5 parts by mass is more preferable.
  • the manufacturing method of the composition of this invention is not specifically limited, For example, the method of manufacturing by mixing the essential component mentioned above and an arbitrary component is mentioned. Further, the method for obtaining a cured product by curing the composition of the present invention is not particularly limited, and examples thereof include a method of heating the composition of the present invention at 80 to 200 ° C. for 10 to 720 minutes.
  • composition of the present invention is, for example, in the field of display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, semiconductor integrated circuit peripheral materials, etc. It can be used as a primer, a sealing material, etc.
  • the composition of the present invention can be suitably used as a composition for encapsulating an optical semiconductor because it has excellent adhesion and its cured product exhibits good transparency and high refractive index.
  • the optical semiconductor to which the composition of the present invention can be applied is not particularly limited, and examples thereof include a light emitting diode (LED), an organic electroluminescent element (organic EL), a laser diode, and an LED array.
  • LED light emitting diode
  • organic EL organic electroluminescent element
  • laser diode a laser diode
  • LED array As a method for using the composition of the present invention as an optical semiconductor sealing composition, for example, the composition of the present invention is applied to an optical semiconductor, and the optical semiconductor to which the composition of the present invention is applied is heated. The method of hardening the composition of invention is mentioned.
  • the method for applying and curing the composition of the present invention is not particularly limited, and examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection
  • block copolymer 1 100 parts by mass of dimethylsiloxane / diphenylsiloxane copolymer having a dimethylhydrogensiloxy group blocked at both molecular chains (weight average molecular weight: 12,000) and 50 parts by mass of diallyl-terminated polyisobutylene (weight average molecular weight: 12,000)
  • a block copolymer 1 containing a polysiloxane block and a polyisobutylene block is obtained by using 0.001 part by mass of the hydrosilylation reaction catalyst 1 described later at 70 ° C. for 4 hours to proceed with the hydrosilylation reaction. Obtained.
  • the mass ratio (c1 / c2) of the obtained block copolymer 1 was 50/50.
  • the obtained cured product was measured for transmittance (unit:%) at a wavelength of 400 nm using an ultraviolet / visible (UV-Vis) absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation) in accordance with JIS K 0115: 2004.
  • the measurement results are shown in Table 1 below. If the transmittance value is 80% or more, it can be evaluated as having excellent “transparency”.
  • ⁇ CF> The prepared composition was bonded to an adherend (aluminum alloy plate, A1050P, manufactured by Partec Co., Ltd.) with an adhesion area of 12.5 mm ⁇ 25 mm, and then cured by heating at 150 ° C. for 2 hours, and tested. Got the body. Using the obtained test body, a tensile test was performed in accordance with JIS K6850: 1999, and the ratio (unit:%) of the cohesive failure (CF) area to the adhesion area was measured. The results are shown in Table 1 below. The closer the value of CF is to 100, the better the adhesion.
  • ⁇ Peeling evaluation> The manufactured composition was applied to an LED package (manufactured by Enomoto) and cured by heating at 150 ° C. for 2 hours to prepare a plurality of test bodies for each example. Next, for each of the following three types of tests, eight test bodies were provided for each example, and the number of the test bodies in which peeling of the cured product was not confirmed was counted. The larger the number, the better the adhesion. (Reflow test) After leaving the test body on a hot plate heated to 280 ° C. for 40 seconds, the presence or absence of peeling of the cured product was visually confirmed. (Moist heat test) The specimen was left for 1000 hours in an environment at a temperature of 85 ° C.
  • Polyisobutylene 1 Polymer of isobutylene (weight average molecular weight: 12,000) -Hydrosilylation reaction catalyst 1: Chloroplatinic acid-divinyltetramethyldisiloxane complex (manufactured by Gelest) Curing retarder 1: 3-methyl-1-butyn-3-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) Adhesion imparting agent 1: ⁇ -glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), phenyltrimethoxysilane (KBM-103 manufactured by Shin-Etsu Chemical Co., Ltd.), and 1,3-divinyl-1 Epoxysilane dehydration condensate obtained by dehydration condensation with 1,1,3,3-tetramethyldisiloxane
  • Examples 1 to 4 using the block copolymer 1 had good peeling evaluation and excellent adhesion, and in particular, the results of the moisture reflow resistance test were good.
  • the standard example 1 which did not contain the block copolymer 1 was inferior in the results of the moisture reflow test.
  • the comparative example 1 using the simple polyisobutylene 1 which is not made into a block copolymer is inferior in transparency because of poor compatibility and inferior in transparency, and has insufficient results in the moisture reflow test.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
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Abstract

L'invention concerne une composition de résine durcissable ayant une excellente adhérence, notamment une adhérence après un essai de refusion de résistance à l'humidité. Cette composition de résine durcissable contient : (A) un organopolysiloxane ramifié ayant un groupe alcényle; (B) un organopolysiloxane linéaire ayant au moins deux atomes d'hydrogène liés à un atome de silicium par molécule; (C) un copolymère à blocs contenant (c1) un bloc polysiloxane et (c2) un bloc polymère hydrocarboné; et (D) un catalyseur pour une réaction d'hydrosilylation.
PCT/JP2014/053045 2013-02-20 2014-02-10 Composition de résine durcissable WO2014129347A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016136244A1 (fr) * 2015-02-26 2016-09-01 東レ・ダウコーニング株式会社 Composition d'amorce, procédé de liaison, et composant électrique/électronique
WO2018193392A1 (fr) * 2017-04-21 2018-10-25 3M Innovative Properties Company Articles et compositions adhésives barrières
CN113166626A (zh) * 2018-12-04 2021-07-23 信越化学工业株式会社 紫外线固化型有机硅压敏粘合剂组合物及其固化物

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01217040A (ja) * 1988-02-26 1989-08-30 Nippon Yunikaa Kk オルガノポリシロキサン―ポリメチレンブロック交互共重合体及びその製造法
JPH0275644A (ja) * 1988-09-12 1990-03-15 Kanegafuchi Chem Ind Co Ltd 硬化性樹脂組成物
JPH08291254A (ja) * 1995-04-21 1996-11-05 Shin Etsu Chem Co Ltd シリコーン接着性組成物
JPH09183903A (ja) * 1995-12-28 1997-07-15 Toray Dow Corning Silicone Co Ltd 硬化性シリコーン組成物
JPH09278896A (ja) * 1996-04-15 1997-10-28 Dow Corning Asia Ltd ポリプロピレン−オルガノポリシロキサン共重合体の製造方法
JPH09278895A (ja) * 1996-04-15 1997-10-28 Dow Corning Asia Ltd ポリプロピレン−オルガノポリシロキサン共重合体
JPH10259251A (ja) * 1997-02-03 1998-09-29 Dow Corning Corp ポリイソブチレンシロキサンブロックコポリマーの調製方法
JP2000327920A (ja) * 1999-05-18 2000-11-28 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JP2003522265A (ja) * 2000-02-11 2003-07-22 ダウ・コーニング・ソシエテ・アノニム シリコーンポリマーエマルジョン
JP2006083299A (ja) * 2004-09-16 2006-03-30 Nippon Shokubai Co Ltd 光電子部品用組成物
JP2010242043A (ja) * 2009-04-10 2010-10-28 Kaneka Corp シリコーン系重合体粒子を含有するシリコーン系硬化性組成物
JP2011042732A (ja) * 2009-08-20 2011-03-03 Kaneka Corp Ｌｅｄ封止剤

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01217040A (ja) * 1988-02-26 1989-08-30 Nippon Yunikaa Kk オルガノポリシロキサン―ポリメチレンブロック交互共重合体及びその製造法
JPH0275644A (ja) * 1988-09-12 1990-03-15 Kanegafuchi Chem Ind Co Ltd 硬化性樹脂組成物
JPH08291254A (ja) * 1995-04-21 1996-11-05 Shin Etsu Chem Co Ltd シリコーン接着性組成物
JPH09183903A (ja) * 1995-12-28 1997-07-15 Toray Dow Corning Silicone Co Ltd 硬化性シリコーン組成物
JPH09278896A (ja) * 1996-04-15 1997-10-28 Dow Corning Asia Ltd ポリプロピレン−オルガノポリシロキサン共重合体の製造方法
JPH09278895A (ja) * 1996-04-15 1997-10-28 Dow Corning Asia Ltd ポリプロピレン−オルガノポリシロキサン共重合体
JPH10259251A (ja) * 1997-02-03 1998-09-29 Dow Corning Corp ポリイソブチレンシロキサンブロックコポリマーの調製方法
JP2000327920A (ja) * 1999-05-18 2000-11-28 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JP2003522265A (ja) * 2000-02-11 2003-07-22 ダウ・コーニング・ソシエテ・アノニム シリコーンポリマーエマルジョン
JP2006083299A (ja) * 2004-09-16 2006-03-30 Nippon Shokubai Co Ltd 光電子部品用組成物
JP2010242043A (ja) * 2009-04-10 2010-10-28 Kaneka Corp シリコーン系重合体粒子を含有するシリコーン系硬化性組成物
JP2011042732A (ja) * 2009-08-20 2011-03-03 Kaneka Corp Ｌｅｄ封止剤

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016136244A1 (fr) * 2015-02-26 2016-09-01 東レ・ダウコーニング株式会社 Composition d'amorce, procédé de liaison, et composant électrique/électronique
JPWO2016136244A1 (ja) * 2015-02-26 2017-12-07 東レ・ダウコーニング株式会社 プライマー組成物、接着方法、および電気・電子部品
US10479910B2 (en) 2015-02-26 2019-11-19 Dow Toray Co., Ltd. Primer composition, adhering method, and electric/electronic part
WO2018193392A1 (fr) * 2017-04-21 2018-10-25 3M Innovative Properties Company Articles et compositions adhésives barrières
CN113166626A (zh) * 2018-12-04 2021-07-23 信越化学工业株式会社 紫外线固化型有机硅压敏粘合剂组合物及其固化物
CN113166626B (zh) * 2018-12-04 2023-09-05 信越化学工业株式会社 紫外线固化型有机硅压敏粘合剂组合物及其固化物

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