WO2015012141A1 - Curable resin composition - Google Patents

Curable resin composition Download PDF

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Publication number
WO2015012141A1
WO2015012141A1 PCT/JP2014/068684 JP2014068684W WO2015012141A1 WO 2015012141 A1 WO2015012141 A1 WO 2015012141A1 JP 2014068684 W JP2014068684 W JP 2014068684W WO 2015012141 A1 WO2015012141 A1 WO 2015012141A1
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WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
general formula
component
resin composition
Prior art date
Application number
PCT/JP2014/068684
Other languages
French (fr)
Japanese (ja)
Inventor
雅子 斎藤
孝明 神林
Original Assignee
株式会社Adeka
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Filing date
Publication date
Application filed by 株式会社Adeka filed Critical 株式会社Adeka
Priority to JP2015528235A priority Critical patent/JP6484172B2/en
Priority to KR1020157022131A priority patent/KR102215439B1/en
Priority to CN201480009108.5A priority patent/CN104995260B/en
Publication of WO2015012141A1 publication Critical patent/WO2015012141A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

Definitions

  • the present invention relates to a polysiloxane-based curable resin composition, and relates to a curable resin composition having a high heat and light resistance and a cured product having good grindability.
  • Reflective coating materials for light-emitting diode substrates reflective coating materials used for backlight units of liquid crystal display devices, reflective coating materials for concentrating panels of solar cells, reflective coating materials used for roofs, rooftops, or outer walls of buildings, and lighting fixtures
  • a reflective coating material that has heat resistance and light resistance such as a reflective coating material used for the above-mentioned, that is, that maintains a high light reflectance even in an environment exposed to high temperature or high energy light.
  • Examples of the curable resin composition for the reflective coating material include those in which an epoxy resin is filled with a white pigment (for example, see Patent Documents 1 and 2) and those in which a silicone resin is filled with a white pigment (for example, Patent Document 3).
  • a silicone resin filled with a white pigment for example, see Patent Documents 1 and 2
  • a silicone resin filled with a white pigment for example, Patent Document 3
  • heat resistance and light resistance are not sufficient, and they gradually color in environments exposed to high temperatures and high energy light for long periods of time.
  • a silicone resin filled with a white pigment has been studied.
  • a method of forming a reflective coating portion on a substrate there are a method of applying and curing a curable resin composition only on the reflective coating portion, a method of applying a curable resin composition capable of photolithography, exposing and developing, and the like. has been done.
  • a method for forming a reflective coating portion a method of applying a curable resin composition on a substrate and grinding and removing unnecessary portions after curing (see, for example, Patent Document 7) has been proposed. Silicone resin-based cured products do not have sufficient grindability, and there is a need for a curable resin composition that provides a cured product with good grindability.
  • An object of the present invention is to provide a curable resin composition that gives a white cured product having good grindability and high heat and light resistance.
  • a group represented by the following general formula (1) and / or a group represented by the following general formula (2) is any one of the following general formulas (3) to (7):
  • a siloxane compound linked by a residue obtained by removing a vinyl group from the represented compound, a chain siloxane compound represented by the following general formula (8) as the component (B), a thermal radical generator as the component (C), and (D) It is a curable resin composition containing an inorganic filler as a component.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a represents a number of 2 to 5. However, R 1 may all be the same group, Different groups may be used.
  • b represents a number from 2 to 6 in which ab + 1 is a number from 0 to 4, and R 1 and a have the same meaning as in the general formula (1).
  • c represents a number of 1 or 2
  • d represents a number of 1 or 2.
  • R 2 represents an alkyl group having 1 to 4 carbon atoms, a glycidyl group or an allyl group.
  • R 3 to R 5 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, e represents a number of 1 or 2, and f and g are each independently And represents a number from 0 to 6.
  • R 6 and R 7 represents a number from 2 to 6 in which ab + 1 is a number from
  • the effect of the present invention is to provide a curable resin composition that gives a white cured product having good grindability and high heat and light resistance.
  • the group represented by the following general formula (1) and / or the group represented by the following general formula (2), which is the component (A) of the present invention is any one of the above general formulas (3) to (7).
  • excluded the vinyl group from the compound represented by is demonstrated.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. However, R 1 may all be the same group or different groups. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, t-butyl group and the like.
  • aryl group having 6 to 10 carbon atoms examples include phenyl group, ethylphenyl group, tolyl group, cumenyl group, xylyl group, pseudocumenyl group, mesityl group, t-butylphenyl group, and phenethyl group.
  • R 1 is preferably a methyl group or a phenyl group, and most preferably a methyl group, because heat resistance is improved.
  • a represents a number of 2 to 5, and a is preferably a number of 2 to 4, more preferably a number of 2 to 3, since it is easy to obtain industrial raw materials. A number of 3 is most preferred.
  • b represents a number from 2 to 6 in which ab + 1 is a number from 0 to 4, and R 1 and a have the same meaning as in the above general formula (1).
  • the group represented by the general formula (1) and / or the group represented by the general formula (2) is represented by any one of the general formulas (3) to (7). It is a siloxane compound linked by a residue obtained by removing a vinyl group from a compound.
  • the compounds represented by the general formulas (3) to (7) are all compounds having two or three vinyl groups in one molecule.
  • the compound represented by the general formula (3) is a compound having two or three vinyl groups in one molecule.
  • c represents a number of 1 or 2.
  • Examples of the compound represented by the general formula (3) in which c is the number 1 include 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene.
  • Examples of the compound represented by the general formula (3) in which c is a number of 2 include 1,2,4-trivinylbenzene and 1,3,5-trivinylbenzene.
  • the compound represented by the general formula (4) is a compound having two or three vinyl groups in one molecule.
  • d represents 1 or 2.
  • Examples of the compound represented by the general formula (4) in which d is the number 1 include 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, and 1,4-divinylcyclohexane.
  • Examples of the compound represented by the general formula (4) in which d is a number of 2 include 1,2,4-trivinylcyclohexane and 1,3,5-trivinylcyclohexane.
  • the compound represented by the general formula (5) is a compound having two or three vinyl groups in one molecule.
  • R 2 represents an alkyl group having 1 to 4 carbon atoms, a glycidyl group or an allyl group.
  • R 2 is preferably a methyl group, an ethyl group, a glycidyl group, or an allyl group.
  • preferred compounds are 1,3-diallyl-5-methylisocyanurate, 1,3-diallyl-5-ethylisocyanurate, 1,3-diallyl-5.
  • the compound represented by the general formula (6) is a compound having two or three vinyl groups in one molecule.
  • R 6 and R 7 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R 1 in the general formula (1), and the like.
  • a methyl group, an ethyl group, a propyl group, and a phenyl group are preferable, a methyl group, an ethyl group, and a phenyl group are more preferable, and a methyl group is most preferable.
  • e represents a number of 1 or 2
  • f and g each independently represents a number of 0 to 6.
  • preferred compounds include dimethyldivinylsilane, diethyldivinylsilane, diphenyldivinylsilane, 1,1,3,3-tetramethyl-1 , 3-divinyldisiloxane, 1,1,3,3-tetraethyl-1,3-divinyldisiloxane, 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane, 1,1,5, 5-tetramethyl-3,3-diphenyl-1,5-divinyltrisiloxane, 1,1,7,7-tetramethyl-3,3,5,5-tetraphenyl-1,7-divinyltrisiloxane, etc.
  • dimethyldivinylsilane, diethyldivinylsilane, and diphenyldivinylsilane are preferred, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane is preferred. Emissions is more preferable.
  • preferred compounds include methyltrivinylsilane, ethyltrivinylsilane, phenyltrivinylsilane, 1,1,3,5,5-pentamethyl- 1,3,5-trivinyltrisiloxane, 1,1,5,5-tetramethyl-3-phenyl-1,3,5-trivinyltrisiloxane, tris (dimethylvinylsiloxy) methylsilane, tris (dimethylvinylsiloxy) ) Phenylsilane and the like.
  • the compound represented by the general formula (7) is a compound having two vinyl groups in one molecule.
  • R 6 and R 7 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include groups exemplified by R 1 in the above general formula (1), and the like.
  • An ethyl group, a propyl group, and a phenyl group are preferable, a methyl group, an ethyl group, and a phenyl group are more preferable, and methyl is most preferable.
  • preferred compounds are 1,2-bis (dimethylvinylsilyl) benzene, 1,3-bis (dimethylvinylsilyl) benzene, 1,4-bis ( And dimethylvinylsilyl) benzene, 1,2-bis (diethylvinylsilyl) benzene, 1,3-bis (diethylvinylsilyl) benzene, 1,4-bis (diethylvinylsilyl) benzene, and the like.
  • Bis (dimethylvinylsilyl) benzene and 1,4-bis (dimethylvinylsilyl) benzene are preferred, and 1,4-bis (dimethylvinylsilyl) benzene is more preferred.
  • residues obtained by removing the vinyl group from the compounds represented by the general formulas (3) to (7) from the viewpoint of handling properties, the residue of a compound having two vinyl groups in one molecule is preferable.
  • the residue of the compound represented by the general formula (3) or the general formula (4) is preferable from the viewpoint of easy availability of raw materials and reactivity.
  • the molecular weight of the component (A) is preferably 5000 to 200,000, more preferably 5000 to 150,000, and more preferably 10,000 to 100,000 in terms of mass average molecular weight from the viewpoint of heat resistance and handling properties. Most preferred.
  • the mass average molecular weight refers to a polystyrene-reduced mass average molecular weight when GPC (Gel Permeation Chromatography) analysis is performed using tetrahydrofuran as a solvent.
  • the component (A) can be obtained by hydrosilylating the SiH group of the cyclic siloxane compound represented by the following general formula (1a) with the vinyl group of the compounds represented by the general formulas (3) to (7). . (In the formula, R 1 and a have the same meaning as in general formula (1).)
  • This hydrosilylation reaction is preferably performed using a catalyst.
  • the hydrosilylation catalyst include a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst.
  • platinum catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, etc., platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetramethyldisiloxane complexes.
  • platinum-cyclovinylmethylsiloxane complex platinum-octylaldehyde complex
  • platinum-phosphine complex for example, Pt [P (C 6 H 5 ) 3 ] 4 , PtCl [P (C 6 H 5 ) 3 ]) 3 , Pt [P (C 4 H 9 ) 3 ) 4
  • platinum-phosphite complexes eg Pt [P (OC 6 H 5 ) 3 ] 4
  • Pt [P (OC 4 H 9 ) 3 ] 4 Dicarbonyldichloroplatinum and the like.
  • the palladium catalyst or rhodium catalyst include compounds containing a palladium atom or a rhodium atom instead of the platinum atom of the platinum catalyst. These may be used alone or in combination of two or more.
  • the hydrosilylation catalyst is preferably a platinum-based catalyst from the viewpoint of reactivity, more preferably a platinum-divinyltetramethyldisiloxane complex and a platinum-carbonylvinylmethyl complex, and most preferably a platinum-carbonylvinylmethyl complex.
  • the amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, most preferably 0.001 to 0.1% by mass of the total amount of each raw material from the viewpoint of reactivity.
  • the reaction conditions for the hydrosilylation are not particularly limited, and may be carried out under the conditions known in the art using the above catalyst. From the viewpoint of the reaction rate, it is preferably carried out at room temperature (25 ° C.) to 130 ° C.
  • a conventionally known solvent such as hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used.
  • a compound having a group represented by the general formula (1) and a group represented by the general formula (2) as a main component is usually obtained.
  • the cyclic siloxane compound represented by the general formula (1a) is compared with the general formulas (3) to (7).
  • the compound represented by the reaction is used in a large excess, and after completion of the reaction, the excess compound represented by the above general formulas (3) to (7) may be removed.
  • R 8 and R 9 each independently represents an alkyl group having 1 to 4 carbon atoms
  • R 10 represents an aryl group having 6 to 10 carbon atoms
  • R 11 represents 1 to carbon atoms
  • 4 represents an alkyl group or an aryl group having 6 to 10 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R 1 in the general formula (1).
  • R 8 and R 9 are preferably a methyl group or an ethyl group, and more preferably a methyl group, because of good heat resistance.
  • R 10 is preferably a phenyl group because of good heat resistance.
  • R 11 is preferably an aryl group having 6 to 10 carbon atoms from the viewpoint of heat resistance, and more preferably a phenyl group, but an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of flexibility, and methyl group More preferably an ethyl group, and most preferably a methyl group.
  • h and j are numbers that make the mass average molecular weight of the chain siloxane compound represented by the general formula (8) 3000 to 1,000,000.
  • the weight average molecular weight of the chain siloxane compound represented by the general formula (8) is preferably 5,000 to 50,000, and more preferably 8,000 to 20,000.
  • the ratio of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms is preferably larger from the aryl group having 6 to 10 carbon atoms from the viewpoint of heat resistance. Therefore, when R 11 is an alkyl group having 1 to 4 carbon atoms, h: j is preferably 95: 5 to 0: 100, more preferably 90:10 to 0: 100, and 50:50 to 0 : 100 is most preferable. On the other hand, when R 11 is an aryl group having 6 to 10 carbon atoms, if the ratio of j in h: j is too large, flexibility may decrease. : 0 to 50:50 is preferable, 98: 2 to 65:35 is more preferable, and 95: 5 to 70:30 is most preferable.
  • the ratio of SiH groups to vinyl groups is preferably 0.5 to 10, more preferably 0.9 to 5, more preferably 1 to 5 in terms of curability and grindability. 3 is most preferred. What is necessary is just to determine the compounding quantity of (A) component and (B) component based on ratio of this vinyl group and SiH group.
  • the thermal radical generator refers to a compound that generates radicals by heating.
  • the radical generated from the component (C) functions to activate a methyl group (Si—CH 3 group) bonded to a SiH group or a silicon atom to react with a vinyl group or a methyl group bonded to a silicon atom.
  • thermal radical generator examples include diisobutyryl peroxide, cumylperoxyneodecanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, dipropylperoxydicarbonate, diisopropylperoxydicarbonate, -Sec-butylperoxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, t -Hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-heptylperoxypivalate, t-butylperoxypivalate, t-pentylperoxypi Bis (3,5,5-trimethylhexanoy
  • 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexyl-1-carbonitrile), 2,2′-azobis (N- (2-propenyl) -2-methylpropionamide), 1-((1-cyano-1-methylethyl) azo) formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropion) Amide) and azo compound-based thermal radical generators such as 2,2′-azobisisobutyronitrile.
  • a compound having a high half-life temperature is preferable from the viewpoint of prevention of abnormal reaction during production of the curable resin composition of the present invention and storage stability. In such a case, the curing temperature of the curable resin composition of the present invention is increased and workability is deteriorated. For this reason, as the component (C), a compound having a one-minute half-life temperature of 130 to 250 ° C., particularly 150 to 200 ° C. is preferable.
  • organic peroxide thermal radical generators having a 1-minute half-life temperature of 150 to 200 ° C.
  • examples of organic peroxide thermal radical generators having a 1-minute half-life temperature of 150 to 200 ° C. include 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-pentylperoxy) cyclohexane, , 2-bis (4,4-di (t-butylperoxy) cyclohexylpropane, t-hexylperoxyisopropyl monocarbonate, t-pentylperoxyisopropyl carbonate, t-pentylperoxynormal octoate, t-butylperoxymaleic acid, 1 , 1-di (t-butylperoxy) cyclohexane, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-buty
  • Examples of the azo compound-based thermal radical generator having a 1-minute half-life temperature of 150 to 200 ° C. include 2,2′-azobis (N- (2-propenyl) -2-methylpropionamide), 1-((1-cyano -1-methylethyl) azo) formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide).
  • the amount of component (C) varies depending on the type of component (C) and the curing temperature, but if it is too small, curing of the curable resin composition of the present invention will be insufficient, and if too large, In addition to not being able to obtain a suitable increase effect, the physical properties of the cured product may be adversely affected, so 0.001 to 5 masses per 100 mass parts of the total amount of component (A) and component (B) Part, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and most preferably 0.1 to 1.5 parts by weight.
  • the inorganic filler as component (D) will be described.
  • the inorganic filler is divided into a white inorganic pigment and an inorganic filler
  • the white inorganic pigment is an inorganic filler that has no specific absorption in the visible region and has a large refractive index.
  • white inorganic pigments include titanium oxide, potassium titanate, calcium titanate, barium titanate, zirconium oxide, zinc oxide, magnesium oxide, antimony oxide, strontium oxide, niobium oxide, beryllium oxide, boron nitride, zinc sulfide, and barium sulfate. Etc.
  • inorganic fillers include fused silica, fused spherical silica, crystalline silica, colloidal silica, fumed silica, silica gel, and the like; aluminum oxide, iron oxide, antimony trioxide, silicon nitride, aluminum nitride, boron nitride , Silicon carbide, calcium carbonate, calcium silicate, magnesium carbonate, barium carbonate, mica, montmorillonite, kaolin, talc, graphite, carbon black and the like.
  • titanium oxide is preferable from the viewpoint of light reflectance.
  • Titanium oxide is classified into a rutile type, anatase type, and brookite type from the crystal structure, but the rutile type is preferred from the viewpoint of the thermal stability and light stability of the cured product.
  • the inorganic filler silica is preferable from the viewpoint of fluidity of the resin composition of the present invention and grindability of the cured product. Only one type of inorganic filler may be used, or two or more types may be used in combination.
  • a white inorganic pigment as the component (D) to obtain a white curable resin composition.
  • the particle diameter of the inorganic filler as component (D) is preferably 0.01 to 5 ⁇ m, more preferably 0.05 to 3 ⁇ m, more preferably 0.1 to 5 ⁇ m in terms of grindability. Most preferably, it is 1 ⁇ m.
  • the average particle size can be determined as a mass average value D 50 in the particle size distribution measurement by laser diffraction method (or median diameter).
  • the blending amount of the component (D) is preferably 40 to 500 parts by mass with respect to 100 parts by mass of the composition of the present invention (excluding the component (D)) from the viewpoint of grindability. 60 to 300 parts by mass is more preferable.
  • the curable resin composition of the present invention contains a siloxane compound represented by the following general formula (9) as the component (E) because the crosslink density is increased and the grindability of the cured product is improved. Is preferred. (Wherein R 12 and R 13 each independently represents an aryl group having 6 to 10 carbon atoms, and k represents a number of 1 to 5)
  • R 12 and R 13 each independently represents an aryl group having 6 to 10 carbon atoms.
  • the aryl group having 6 to 10 carbon atoms include aryl groups having 6 to 10 carbon atoms exemplified as R 1 in the general formula (1).
  • R 12 and R 13 a phenyl group is preferable because the effect of improving grindability is high.
  • k represents a number of 1 to 5, and is preferably a number of 1 or 2 and more preferably a number of 1 because the effect of improving grindability is high.
  • preferred compounds include 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyltrisiloxane, 1,1,5, Examples include 7,7-tetramethyl-3,3,5,5-tetraphenyl-1,7-divinyltrisiloxane.
  • the blending amount of the component (E) is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is ⁇ 70 parts by mass.
  • the amount of the component (B) may be determined based on the ratio of the vinyl group and the SiH group.
  • the curable resin composition of the present invention preferably further contains a compound having an isocyanuric acid structure because the adhesion between the cured product and the substrate is improved.
  • the compound having an isocyanuric acid structure include, in addition to the compound represented by the general formula (5), isocyanuric acid, 1,3,5-triglycidyl isocyanuric acid, 1-allyl-3,5-diglycidyl isocyanuric. And acid, tris (2-hydroxyethyl) isocyanuric acid, tris (2,3-dihydroxypropyl) isocyanuric acid and the like.
  • the curable resin composition of the present invention includes an antioxidant, an ultraviolet absorber, a release agent, an antistatic agent, a platinum-based hydrosilylation catalyst, a curing retarder, a coupling agent, a flame retardant, an organic solvent, and the like. Can be added within a range not impairing the object and effects of the present invention.
  • the curable resin composition of the present invention is excellent in fluidity and can be cured by heating after being applied to an object such as a substrate.
  • Examples of the method for applying the curable resin composition of the present invention to a target material include spin coating, dip coating, knife coating, roll coating, spray coating, slit coating, and screen printing. It is done.
  • the curable resin composition of the present invention can be cured by heating and can be a cured product.
  • This curing reaction varies depending on the type of component (C), but is preferably from 80 to 350 ° C, more preferably from 100 to 250 ° C, from the viewpoint of workability.
  • the curing time is preferably 2 to 120 minutes, more preferably 20 to 60 minutes.
  • the cured product of the curable resin composition of the present invention is excellent in various physical properties such as heat resistance, light resistance, crack resistance, and colorability.
  • a sealing material, a molding material, a coating material, an insulating material, a reflective material, and the like can be used as a material, and can be suitably used as a reflective material for light emitting elements such as LEDs.
  • the cured product of the curable resin composition of the present invention is excellent in grindability, a method of using a grinding apparatus having a hard rotating blade in which a plurality of hard blades made of diamond or the like are arranged in the radial direction of the rotating plate is used.
  • the cured product of the curable resin composition of the present invention flattens the upper surface by moving the hard rotary blade along the upper surface of the fixedly supported wiring board. Can do.
  • polishing method the method of lightly grind
  • Examples 1 to 8 and Comparative Examples 1 to 5 were formed using a bar coater on a glass epoxy substrate on which five copper wire patterns were formed with a width of 1 mm, a length of 20 mm, and an interval of 1 mm, using a bar coater. The curable composition was applied. A test piece was prepared by heating the substrate in a thermostatic bath at 150 ° C. for 1 hour. [Grindability evaluation method] The surface of the test piece was polished with a P220 polishing paper until a copper wire pattern appeared, and the grindability was evaluated according to the following criteria according to the state of the resin part in the vicinity of the copper wire pattern. The results are shown in [Table 2].
  • the test piece was pressed against a hard polyvinyl chloride tube having an outer diameter of 140 mm to warp the crosscut portion, and the adhesion was evaluated according to the following criteria depending on whether or not the crosscut portion was peeled off. The results are shown in [Table 2].
  • -Evaluation standard (circle): Peeling is not seen but it is excellent in adhesiveness.
  • ⁇ Peeling was observed at 1 to 10 locations, and the adhesion was slightly inferior.
  • X Peeling is observed at 11 or more places, and the adhesion is poor.

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Abstract

The present invention provides a curable resin composition which can provide a white cured article having good grindability and high heat resistance and light resistance. Specifically, the present invention provides a curable resin composition comprising: a component (A) which is a siloxane compound in which a group represented by general formula (1) and/or a group represented by general formula (2) is linked through a residue produced by removing a vinyl group from a compound represented by any one of formulae (3) to (7); a component (B) which is a linear siloxane compound represented by general formula (8); a component (C) which is a thermal radical generator; and a component (D) which is an inorganic filler. The specific definitions for the general formulae are as mentioned in the description.

Description

硬化性樹脂組成物Curable resin composition
　本発明は、ポリシロキサン系の硬化性樹脂組成物に関するものであり、高い耐熱耐光性を有し、良好な被研削性を有する硬化物が得られる硬化性樹脂組成物に関するものである。 The present invention relates to a polysiloxane-based curable resin composition, and relates to a curable resin composition having a high heat and light resistance and a cured product having good grindability.
　発光ダイオード基板用の反射コーティング材、液晶表示装置のバックライトユニットに用いる反射コーティング材、太陽電池の集光パネル用の反射コーティング材、或いは建物の屋根や屋上或いは外壁に用いる反射コーティング材、照明器具に用いる反射コーティング材等、耐熱耐光性を有する、すなわち高温や高いエネルギーの光にさらされる環境下においても、高い光反射率を保つ反射コーティング材が求められている。 Reflective coating materials for light-emitting diode substrates, reflective coating materials used for backlight units of liquid crystal display devices, reflective coating materials for concentrating panels of solar cells, reflective coating materials used for roofs, rooftops, or outer walls of buildings, and lighting fixtures There is a need for a reflective coating material that has heat resistance and light resistance, such as a reflective coating material used for the above-mentioned, that is, that maintains a high light reflectance even in an environment exposed to high temperature or high energy light.
　反射コーティング材用の硬化性樹脂組成物としては、エポキシ樹脂に白色顔料を充填したもの（例えば、特許文献１及び２を参照）や、シリコーン樹脂に白色顔料を充填したもの（例えば、特許文献３～６を参照）が知られているが、エポキシ樹脂に白色顔料を充填したものは、耐熱耐光性が十分ではなく、高温や高いエネルギーの光に長時間さらされる環境下では徐々に着色して光反射率が低下するという問題があることから、高い耐熱耐光性が要求される分野では、シリコーン樹脂に白色顔料を充填したものが検討されている。 Examples of the curable resin composition for the reflective coating material include those in which an epoxy resin is filled with a white pigment (for example, see Patent Documents 1 and 2) and those in which a silicone resin is filled with a white pigment (for example, Patent Document 3). However, heat resistance and light resistance are not sufficient, and they gradually color in environments exposed to high temperatures and high energy light for long periods of time. In the field where high heat and light resistance is required due to the problem that the light reflectance is lowered, a silicone resin filled with a white pigment has been studied.
　基板上に反射コーティング部分を形成する方法としては、反射コーティング部分のみに硬化性樹脂組成物を塗布し硬化させる方法、フォトリソグラフィーが可能な硬化性樹脂組成物を塗布し露光・現像する方法等が行われている。近年、反射コーティング部分の形成方法として、基板上に硬化性樹脂組成物を塗布し硬化後に不要部分を研削除去する方法（例えば、特許文献７を参照）が提案されているが、従来知られたシリコーン樹脂系の硬化物は被研削性が十分ではなく、被研削性の良好な硬化物が得られる硬化性樹脂組成物が求められている。 As a method of forming a reflective coating portion on a substrate, there are a method of applying and curing a curable resin composition only on the reflective coating portion, a method of applying a curable resin composition capable of photolithography, exposing and developing, and the like. Has been done. In recent years, as a method for forming a reflective coating portion, a method of applying a curable resin composition on a substrate and grinding and removing unnecessary portions after curing (see, for example, Patent Document 7) has been proposed. Silicone resin-based cured products do not have sufficient grindability, and there is a need for a curable resin composition that provides a cured product with good grindability.
特開２００７－１２９１７３号公報JP 2007-129173 A 特開２００９－１９４２２２号公報JP 2009-194222 A 特開２０１０－２２９３８２号公報JP 2010-229382 A 特開２０１１－１０５８６９号公報JP 2011-105869 A 特開２０１２－２３３０３５号公報JP 2012-233303 A 米国特許公開第２０１３／００７５１５４号明細書US Patent Publication No. 2013/0075154 特開２０１２－２５３３２２号公報JP 2012-253322 A
　本発明の目的は、被研削性が良好で高い耐熱耐光性を有する白色硬化物を与える硬化性樹脂組成物を提供することにある。 An object of the present invention is to provide a curable resin composition that gives a white cured product having good grindability and high heat and light resistance.
　本発明者らは、上記に鑑み鋭意研究の結果、本発明に到達した。即ち本発明は、（Ａ）成分として、下記一般式（１）で表わされる基及び／又は下記一般式（２）で表わされる基が、下記一般式（３）～（７）の何れかで表わされる化合物からビニル基を除いた残基で連結されたシロキサン化合物、（Ｂ）成分として、下記一般式（８）で表わされる鎖状シロキサン化合物、（Ｃ）成分として、熱ラジカル発生剤、及び（Ｄ）成分として、無機フィラーを含有する硬化性樹脂組成物である。
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ1は炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わし、ａは２～５の数を表わす。但し、Ｒ1は全て同一の基でもよいし、異なる基でもよい。）
Figure JPOXMLDOC01-appb-C000011
 （式中、ｂはａ－ｂ＋１が０～４の数となる２～６の数を表わし、Ｒ1及びａは上記一般式（１）と同義である。）
Figure JPOXMLDOC01-appb-C000012
 （式中、ｃは１又は２の数を表わす。）
Figure JPOXMLDOC01-appb-C000013
 （式中、ｄは１又は２の数を表わす。）
Figure JPOXMLDOC01-appb-C000014
 （式中、Ｒ2は炭素数１～４のアルキル基、グリシジル基又はアリル基を表わす。）
Figure JPOXMLDOC01-appb-C000015
 （式中、Ｒ3～Ｒ5は各々独立して炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わし、ｅは１又は２の数を表わし、ｆ及びｇは各々独立して０～６の数を表わす。）
Figure JPOXMLDOC01-appb-C000016
 （式中、Ｒ6及びＲ7は各々独立して炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わす。）
Figure JPOXMLDOC01-appb-C000017
 （式中、Ｒ8及びＲ9は各々独立して炭素数１～４のアルキル基を表わし、Ｒ10は炭素数６～１０のアリール基を表わし、Ｒ11は炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わし、ｈ及びｊは一般式（８）で表される鎖状シロキサン化合物の質量平均分子量を１０００～１００万とする数である。） The present inventors have reached the present invention as a result of intensive studies in view of the above. That is, in the present invention, as the component (A), a group represented by the following general formula (1) and / or a group represented by the following general formula (2) is any one of the following general formulas (3) to (7): A siloxane compound linked by a residue obtained by removing a vinyl group from the represented compound, a chain siloxane compound represented by the following general formula (8) as the component (B), a thermal radical generator as the component (C), and (D) It is a curable resin composition containing an inorganic filler as a component.
Figure JPOXMLDOC01-appb-C000010
 (In the formula, R 1 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a represents a number of 2 to 5. However, R 1 may all be the same group, Different groups may be used.)
Figure JPOXMLDOC01-appb-C000011
 (In the formula, b represents a number from 2 to 6 in which ab + 1 is a number from 0 to 4, and R 1 and a have the same meaning as in the general formula (1).)
Figure JPOXMLDOC01-appb-C000012
 (Wherein c represents a number of 1 or 2)
Figure JPOXMLDOC01-appb-C000013
 (In the formula, d represents a number of 1 or 2.)
Figure JPOXMLDOC01-appb-C000014
 (Wherein R 2 represents an alkyl group having 1 to 4 carbon atoms, a glycidyl group or an allyl group.)
Figure JPOXMLDOC01-appb-C000015
 (Wherein R 3 to R 5 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, e represents a number of 1 or 2, and f and g are each independently And represents a number from 0 to 6.)
Figure JPOXMLDOC01-appb-C000016
 (Wherein R 6 and R 7 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.)
Figure JPOXMLDOC01-appb-C000017
 (Wherein R 8 and R 9 each independently represents an alkyl group having 1 to 4 carbon atoms, R 10 represents an aryl group having 6 to 10 carbon atoms, and R 11 represents an alkyl group having 1 to 4 carbon atoms) Or an aryl group having 6 to 10 carbon atoms, and h and j are numbers that make the mass average molecular weight of the chain siloxane compound represented by the general formula (8) 1,000 to 1,000,000.)
　本発明の効果は、被研削性が良好で高い耐熱耐光性を有する白色硬化物を与える硬化性樹脂組成物を提供したことにある。 The effect of the present invention is to provide a curable resin composition that gives a white cured product having good grindability and high heat and light resistance.
＜（Ａ）成分＞
　先ず、本発明の（Ａ）成分である、下記一般式（１）で表わされる基及び／又は下記一般式（２）で表わされる基が、上記一般式（３）～（７）の何れかで表わされる化合物からビニル基を除いた残基で連結されたシロキサン化合物について説明する。 <(A) component>
First, the group represented by the following general formula (1) and / or the group represented by the following general formula (2), which is the component (A) of the present invention, is any one of the above general formulas (3) to (7). The siloxane compound connected by the residue which remove | excluded the vinyl group from the compound represented by is demonstrated.
　上記一般式（１）において、Ｒ1は、炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わす。但し、Ｒ1は全て同一の基でもよいし、異なる基でもよい。炭素原子数１～４のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔ－ブチル基等が挙げられる。炭素数６～１０のアリール基としては、例えば、フェニル基、エチルフェニル基、トリル基、クメニル基、キシリル基、プソイドクメニル基、メシチル基、ｔ－ブチルフェニル基、フェネチル基等が挙げられる。Ｒ1としては、耐熱性が向上することから、メチル基、フェニル基が好ましく、メチル基が最も好ましい。 In the general formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. However, R 1 may all be the same group or different groups. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, t-butyl group and the like. Examples of the aryl group having 6 to 10 carbon atoms include phenyl group, ethylphenyl group, tolyl group, cumenyl group, xylyl group, pseudocumenyl group, mesityl group, t-butylphenyl group, and phenethyl group. R 1 is preferably a methyl group or a phenyl group, and most preferably a methyl group, because heat resistance is improved.
　上記一般式（１）において、ａは２～５の数を表わし、工業的な原料の入手が容易であることから、ａは２～４の数が好ましく、２～３の数が更に好ましく、３の数が最も好ましい。 In the general formula (1), a represents a number of 2 to 5, and a is preferably a number of 2 to 4, more preferably a number of 2 to 3, since it is easy to obtain industrial raw materials. A number of 3 is most preferred.
　上記一般式（２）において、ｂはａ－ｂ＋１が０～４の数となる２～６の数を表わし、Ｒ1及びａは上記一般式（１）と同義である。 In the above general formula (2), b represents a number from 2 to 6 in which ab + 1 is a number from 0 to 4, and R 1 and a have the same meaning as in the above general formula (1).
　本発明の（Ａ）成分は、上記一般式（１）で表わされる基及び／又は上記一般式（２）で表わされる基が、上記一般式（３）～（７）の何れかで表わされる化合物からビニル基を除いた残基で連結されたシロキサン化合物である。上記一般式（３）～（７）で表わされる化合物は、いずれも、１分子中に２つ又は３つのビニル基を有する化合物である。 In the component (A) of the present invention, the group represented by the general formula (1) and / or the group represented by the general formula (2) is represented by any one of the general formulas (3) to (7). It is a siloxane compound linked by a residue obtained by removing a vinyl group from a compound. The compounds represented by the general formulas (3) to (7) are all compounds having two or three vinyl groups in one molecule.
　上記一般式（３）で表わされる化合物は、１分子中に２つ又は３つのビニル基を有する化合物である。上記一般式（３）において、ｃは１又は２の数を表わす。ｃが１の数である一般式（３）で表わされる化合物としては、１，２－ジビニルベンゼン、１，３－ジビニルベンゼン、１，４－ジビニルベンゼンが挙げられる。ｃが２の数である一般式（３）で表わされる化合物としては、１，２，４－トリビニルベンゼン、１，３，５－トリビニルベンゼンが挙げられる。 The compound represented by the general formula (3) is a compound having two or three vinyl groups in one molecule. In the general formula (3), c represents a number of 1 or 2. Examples of the compound represented by the general formula (3) in which c is the number 1 include 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene. Examples of the compound represented by the general formula (3) in which c is a number of 2 include 1,2,4-trivinylbenzene and 1,3,5-trivinylbenzene.
　上記一般式（４）で表わされる化合物は、１分子中に２つ又は３つのビニル基を有する化合物である。上記一般式（４）において、ｄは１又は２を表わす。ｄが１の数である上記一般式（４）で表わされる化合物としては、１，２－ジビニルシクロヘキサン、１，３－ジビニルシクロヘキサン、１，４－ジビニルシクロヘキサンが挙げられる。ｄが２の数である上記一般式（４）で表わされる化合物としては、１，２，４－トリビニルシクロヘキサン、１，３，５－トリビニルシクロヘキサンが挙げられる。 The compound represented by the general formula (4) is a compound having two or three vinyl groups in one molecule. In the general formula (4), d represents 1 or 2. Examples of the compound represented by the general formula (4) in which d is the number 1 include 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, and 1,4-divinylcyclohexane. Examples of the compound represented by the general formula (4) in which d is a number of 2, include 1,2,4-trivinylcyclohexane and 1,3,5-trivinylcyclohexane.
　上記一般式（５）で表わされる化合物は、１分子中に２つ又は３つのビニル基を有する化合物である。上記一般式（５）において、Ｒ2は炭素数１～４のアルキル基、グリシジル基又はアリル基を表わす。Ｒ2としては、メチル基、エチル基、グリシジル基、アリル基が好ましい。上記一般式（５）で表わされる化合物の中で、好ましい化合物としては、１，３－ジアリル－５－メチルイソシアヌレート、１，３－ジアリル－５－エチルイソシアヌレート、１，３－ジアリル－５－グリシジルイソシアヌレート、１，３，５－トリアリルイソシアヌレート等挙げられる。 The compound represented by the general formula (5) is a compound having two or three vinyl groups in one molecule. In the general formula (5), R 2 represents an alkyl group having 1 to 4 carbon atoms, a glycidyl group or an allyl group. R 2 is preferably a methyl group, an ethyl group, a glycidyl group, or an allyl group. Among the compounds represented by the general formula (5), preferred compounds are 1,3-diallyl-5-methylisocyanurate, 1,3-diallyl-5-ethylisocyanurate, 1,3-diallyl-5. -Glycidyl isocyanurate, 1,3,5-triallyl isocyanurate, etc.
　上記一般式（６）で表わされる化合物は、１分子中に２つ又は３つのビニル基を有する化合物である。上記一般式（６）において、Ｒ6及びＲ7は各々独立して炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わす。炭素数１～４のアルキル基及び炭素数６～１０のアリール基としては、上記一般式（１）のＲ1で例示した基等が挙げられ、
耐熱性が良好であることから、メチル基、エチル基、プロピル基、フェニル基が好ましく、メチル基、エチル基、フェニル基が更に好ましく、メチル基が最も好ましい。ｅは１又は２の数を表わし、ｆ及びｇは各々独立して０～６の数を表わす。 The compound represented by the general formula (6) is a compound having two or three vinyl groups in one molecule. In the general formula (6), R 6 and R 7 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R 1 in the general formula (1), and the like.
From the viewpoint of good heat resistance, a methyl group, an ethyl group, a propyl group, and a phenyl group are preferable, a methyl group, an ethyl group, and a phenyl group are more preferable, and a methyl group is most preferable. e represents a number of 1 or 2, and f and g each independently represents a number of 0 to 6.
　ｅが１の数である上記一般式（６）で表わされる化合物の中で、好ましい化合物としては、ジメチルジビニルシラン、ジエチルジビニルシラン、ジフェニルジビニルシラン、１，１，３，３－テトラメチル－１，３－ジビニルジシロキサン、１，１，３，３－テトラエチル－１，３－ジビニルジシロキサン、１，１，３，３－テトラフェニル－１，３－ジビニルジシロキサン、１，１，５，５－テトラメチル－３，３－ジフェニル－１，５－ジビニルトリシロキサン、１，１，７，７－テトラメチル－３，３，５，５－テトラフェニル－１，７－ジビニルトリシロキサン等が挙げられ、ジメチルジビニルシラン、ジエチルジビニルシラン、ジフェニルジビニルシランが好ましく、１，１，３，３－テトラメチル－１，３－ジビニルジシロキサンが更に好ましい。ｅが２の数である上記一般式（６）で表わされる化合物の中で、好ましい化合物としては、メチルトリビニルシラン、エチルトリビニルシラン、フェニルトリビニルシラン、１，１，３，５，５－ペンタメチル－１，３，５－トリビニルトリシロキサン、１，１，５，５－テトラメチル－３－フェニル－１，３，５－トリビニルトリシロキサン、トリス（ジメチルビニルシロキシ）メチルシラン、トリス（ジメチルビニルシロキシ）フェニルシラン等が挙げられる。 Among the compounds represented by the general formula (6) wherein e is the number 1, preferred compounds include dimethyldivinylsilane, diethyldivinylsilane, diphenyldivinylsilane, 1,1,3,3-tetramethyl-1 , 3-divinyldisiloxane, 1,1,3,3-tetraethyl-1,3-divinyldisiloxane, 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane, 1,1,5, 5-tetramethyl-3,3-diphenyl-1,5-divinyltrisiloxane, 1,1,7,7-tetramethyl-3,3,5,5-tetraphenyl-1,7-divinyltrisiloxane, etc. And dimethyldivinylsilane, diethyldivinylsilane, and diphenyldivinylsilane are preferred, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane is preferred. Emissions is more preferable. Among the compounds represented by the general formula (6) in which e is a number of 2, preferred compounds include methyltrivinylsilane, ethyltrivinylsilane, phenyltrivinylsilane, 1,1,3,5,5-pentamethyl- 1,3,5-trivinyltrisiloxane, 1,1,5,5-tetramethyl-3-phenyl-1,3,5-trivinyltrisiloxane, tris (dimethylvinylsiloxy) methylsilane, tris (dimethylvinylsiloxy) ) Phenylsilane and the like.
　上記一般式（７）で表わされる化合物は、１分子中に２つのビニル基を有する化合物である。上記一般式（７）において、Ｒ6及びＲ7は各々独立して炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わす。炭素数１～４のアルキル基及び炭素数６～１０のアリール基としては、上記一般式（１）のＲ1で例示した基等が挙げられ、耐熱性が良好であることから、メチル基、エチル基、プロピル基、フェニル基が好ましく、メチル基、エチル基、フェニル基が更に好ましく、メチルが最も好ましい。上記一般式（７）で表される化合物の中で、好ましい化合物としては、１，２－ビス（ジメチルビニルシリル）ベンゼン、１，３－ビス（ジメチルビニルシリル）ベンゼン、１，４－ビス（ジメチルビニルシリル）ベンゼン、１，２－ビス（ジエチルビニルシリル）ベンゼン、１，３－ビス（ジエチルビニルシリル）ベンゼン、１，４－ビス（ジエチルビニルシリル）ベンゼン等が挙げられ、１，２－ビス（ジメチルビニルシリル）ベンゼン、１，４－ビス（ジメチルビニルシリル）ベンゼンが好ましく、１，４－ビス（ジメチルビニルシリル）ベンゼンが更に好ましい。 The compound represented by the general formula (7) is a compound having two vinyl groups in one molecule. In the general formula (7), R 6 and R 7 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include groups exemplified by R 1 in the above general formula (1), and the like. An ethyl group, a propyl group, and a phenyl group are preferable, a methyl group, an ethyl group, and a phenyl group are more preferable, and methyl is most preferable. Among the compounds represented by the general formula (7), preferred compounds are 1,2-bis (dimethylvinylsilyl) benzene, 1,3-bis (dimethylvinylsilyl) benzene, 1,4-bis ( And dimethylvinylsilyl) benzene, 1,2-bis (diethylvinylsilyl) benzene, 1,3-bis (diethylvinylsilyl) benzene, 1,4-bis (diethylvinylsilyl) benzene, and the like. Bis (dimethylvinylsilyl) benzene and 1,4-bis (dimethylvinylsilyl) benzene are preferred, and 1,4-bis (dimethylvinylsilyl) benzene is more preferred.
　上記一般式（３）～（７）で表わされる化合物からビニル基を除いた残基のうち、ハンドリング性の点からは、１分子中に２つのビニル基を有する化合物の残基が好ましいが、原料の入手の容易さと、反応性から、上記一般式（３）又は上記一般式（４）で表わされる化合物の残基が好ましい。 Of the residues obtained by removing the vinyl group from the compounds represented by the general formulas (3) to (7), from the viewpoint of handling properties, the residue of a compound having two vinyl groups in one molecule is preferable. The residue of the compound represented by the general formula (3) or the general formula (4) is preferable from the viewpoint of easy availability of raw materials and reactivity.
　（Ａ）成分の分子量は、耐熱性及びハンドリング性の点から、質量平均分子量で、５０００～２０万であることが好ましく、５０００～１５万であることが更に好ましく、１万～１０万であることが最も好ましい。なお、本発明において、質量平均分子量とは、テトラヒドロフランを溶媒としてＧＰＣ（Gel Permeation Chromatography）分析を行った場合のポリスチレン換算の質量平均分子量をいう。 The molecular weight of the component (A) is preferably 5000 to 200,000, more preferably 5000 to 150,000, and more preferably 10,000 to 100,000 in terms of mass average molecular weight from the viewpoint of heat resistance and handling properties. Most preferred. In the present invention, the mass average molecular weight refers to a polystyrene-reduced mass average molecular weight when GPC (Gel Permeation Chromatography) analysis is performed using tetrahydrofuran as a solvent.
　（Ａ）成分は、上記一般式（３）～（７）で表わされる化合物のビニル基に下記一般式（１ａ）で表わされる環状シロキサン化合物のＳｉＨ基をヒドロシリル化反応させることにより得ることができる。
Figure JPOXMLDOC01-appb-C000018
 （式中、Ｒ1及びａは一般式（１）と同義である。） The component (A) can be obtained by hydrosilylating the SiH group of the cyclic siloxane compound represented by the following general formula (1a) with the vinyl group of the compounds represented by the general formulas (3) to (7). .
Figure JPOXMLDOC01-appb-C000018
 (In the formula, R 1 and a have the same meaning as in general formula (1).)
　このヒドロシリル化反応は、触媒を用いて行うことが好ましく、ヒドロシリル化触媒としては、例えば、白金系触媒、パラジウム系触媒、ロジウム系触媒等が挙げられる。白金系触媒としては、例えば、塩化白金酸、塩化白金酸とアルコール、アルデヒド、ケトン等との錯体、白金－オレフィン錯体、白金－カルボニルビニルメチル錯体（Ｏｓｓｋｏ触媒）、白金－ジビニルテトラメチルジシロキサン錯体（Ｋａｒｓｔｅｄｔ触媒）、白金－シクロビニルメチルシロキサン錯体、白金－オクチルアルデヒド錯体、白金－ホスフィン錯体（例えば、Ｐｔ［Ｐ（Ｃ6Ｈ5）3］4、ＰｔＣｌ［Ｐ（Ｃ6Ｈ5）3］3、Ｐｔ［Ｐ（Ｃ4Ｈ9）3）4］、白金－ホスファイト錯体（例えば、Ｐｔ［Ｐ（ＯＣ6Ｈ5）3］4）、Ｐｔ［Ｐ（ＯＣ4Ｈ9）3］4）、ジカルボニルジクロロ白金等が挙げられる。パラジウム系触媒又はロジウム系触媒としては、例えば、上記白金系触媒の白金原子の代わりにパラジウム原子又はロジウム原子を含有する化合物が挙げられる。これらは１種で用いてもよく、２種以上を併用してもよい。ヒドロシリル化触媒としては、反応性の点から、白金系触媒が好ましく、白金－ジビニルテトラメチルジシロキサン錯体及び白金－カルボニルビニルメチル錯体が更に好ましく、白金－カルボニルビニルメチル錯体が最も好ましい。また、触媒の使用量は反応性の点から、各原料の合計量の５質量％以下が好ましく、０．０００１～１．０質量％が更に好ましく、０．００１～０．１質量％が最も好ましい。ヒドロシリル化の反応条件は特に限定されず、上記触媒を使用して従来公知の条件で行なえばよいが、反応速度の点から、室温（２５℃）～１３０℃で行なうのが好ましく、反応時にトルエン、ヘキサン、メチルイソブチルケトン、シクロペンタノン、プロピレングリコールモノメチルエーテルアセテート等の従来公知の溶媒を使用してもよい。 This hydrosilylation reaction is preferably performed using a catalyst. Examples of the hydrosilylation catalyst include a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst. Examples of platinum catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, etc., platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetramethyldisiloxane complexes. (Karstedt catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (for example, Pt [P (C 6 H 5 ) 3 ] 4 , PtCl [P (C 6 H 5 ) 3 ]) 3 , Pt [P (C 4 H 9 ) 3 ) 4 ], platinum-phosphite complexes (eg Pt [P (OC 6 H 5 ) 3 ] 4 ), Pt [P (OC 4 H 9 ) 3 ] 4 ), Dicarbonyldichloroplatinum and the like. Examples of the palladium catalyst or rhodium catalyst include compounds containing a palladium atom or a rhodium atom instead of the platinum atom of the platinum catalyst. These may be used alone or in combination of two or more. The hydrosilylation catalyst is preferably a platinum-based catalyst from the viewpoint of reactivity, more preferably a platinum-divinyltetramethyldisiloxane complex and a platinum-carbonylvinylmethyl complex, and most preferably a platinum-carbonylvinylmethyl complex. The amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, most preferably 0.001 to 0.1% by mass of the total amount of each raw material from the viewpoint of reactivity. preferable. The reaction conditions for the hydrosilylation are not particularly limited, and may be carried out under the conditions known in the art using the above catalyst. From the viewpoint of the reaction rate, it is preferably carried out at room temperature (25 ° C.) to 130 ° C. A conventionally known solvent such as hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used.
　本反応では、通常、主成分として、上記一般式（１）で表わされる基と上記一般式（２）で表わされる基とを有する化合物が得られる。上記一般式（１）で表わされる基のみを有する化合物を選択的に得る場合には、上記一般式（１ａ）で表わされる環状シロキサン化合物に対して、上記一般式（３）～（７）で表わされる化合物を大過剰に使用して反応させ、反応終了後、過剰の上記一般式（３）～（７）で表わされる化合物を除去すればよい。 In this reaction, a compound having a group represented by the general formula (1) and a group represented by the general formula (2) as a main component is usually obtained. When a compound having only the group represented by the general formula (1) is selectively obtained, the cyclic siloxane compound represented by the general formula (1a) is compared with the general formulas (3) to (7). The compound represented by the reaction is used in a large excess, and after completion of the reaction, the excess compound represented by the above general formulas (3) to (7) may be removed.
　次に、（Ｂ）成分である上記一般式（８）で表わされる鎖状シロキサン化合物について説明する。上記一般式（８）において、Ｒ8及びＲ9は各々独立して炭素数１～４のアルキル基を表わし、Ｒ10は炭素数６～１０のアリール基を表わし、Ｒ11は炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わす。炭素数１～４のアルキル基及び炭素数６～１０のアリール基としては、上記一般式（１）のＲ1で例示した基等が挙げられる。
Ｒ8及びＲ9としては、耐熱性が良好であることから、メチル基、エチル基が好ましく、メチル基が更に好ましい。Ｒ10としては、耐熱性が良好であることから、フェニル基が好ましい。Ｒ11としては、耐熱性の点からは、炭素数６～１０のアリール基が好ましく、フェニル基が更に好ましいが、可撓性の点からは、炭素数１～４のアルキル基が好ましく、メチル基、エチル基が更に好ましく、メチル基が最も好ましい。 Next, the chain siloxane compound represented by the general formula (8) as the component (B) will be described. In the general formula (8), R 8 and R 9 each independently represents an alkyl group having 1 to 4 carbon atoms, R 10 represents an aryl group having 6 to 10 carbon atoms, and R 11 represents 1 to carbon atoms. 4 represents an alkyl group or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R 1 in the general formula (1).
R 8 and R 9 are preferably a methyl group or an ethyl group, and more preferably a methyl group, because of good heat resistance. R 10 is preferably a phenyl group because of good heat resistance. R 11 is preferably an aryl group having 6 to 10 carbon atoms from the viewpoint of heat resistance, and more preferably a phenyl group, but an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of flexibility, and methyl group More preferably an ethyl group, and most preferably a methyl group.
　上記一般式（８）において、ｈ及びｊは上記一般式（８）で表される鎖状シロキサン化合物の質量平均分子量を３０００～１００万とする数である。上記一般式（８）で表される鎖状シロキサン化合物の質量平均分子量が３０００よりも小さい場合には耐熱性が低く、１００万よりも大きい場合には、高粘度となりハンドリング性が低下する。上記一般式（８）で表される鎖状シロキサン化合物の質量平均分子量は５０００～５万が好ましく、８０００～２万が更に好ましい。 In the general formula (8), h and j are numbers that make the mass average molecular weight of the chain siloxane compound represented by the general formula (8) 3000 to 1,000,000. When the weight average molecular weight of the chain siloxane compound represented by the general formula (8) is smaller than 3000, the heat resistance is low, and when it is larger than 1 million, the viscosity becomes high and the handling property is lowered. The weight average molecular weight of the chain siloxane compound represented by the general formula (8) is preferably 5,000 to 50,000, and more preferably 8,000 to 20,000.
　上記一般式（８）において、炭素数１～４のアルキル基と炭素数６～１０のアリール基との割合は、耐熱性の点からは炭素数６～１０のアリール基が多いほうが好ましい。このため、Ｒ11が炭素数１～４のアルキル基である場合には、ｈ：ｊは９５：５～０：１００が好ましく、９０：１０～０：１００が更に好ましく、５０：５０～０：１００が最も好ましい。一方、Ｒ11が炭素数６～１０のアリール基である場合には、ｈ：ｊのｊの割合があまりに多い場合には、可撓性が低下する場合があることから、ｈ：ｊは１００：０～５０：５０が好ましく、９８：２～６５：３５が更に好ましく、９５：５～７０：３０が最も好ましい。 In the general formula (8), the ratio of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms is preferably larger from the aryl group having 6 to 10 carbon atoms from the viewpoint of heat resistance. Therefore, when R 11 is an alkyl group having 1 to 4 carbon atoms, h: j is preferably 95: 5 to 0: 100, more preferably 90:10 to 0: 100, and 50:50 to 0 : 100 is most preferable. On the other hand, when R 11 is an aryl group having 6 to 10 carbon atoms, if the ratio of j in h: j is too large, flexibility may decrease. : 0 to 50:50 is preferable, 98: 2 to 65:35 is more preferable, and 95: 5 to 70:30 is most preferable.
　本発明の硬化性樹脂組成物において、ビニル基に対するＳｉＨ基の比は、硬化性及び被研削性の点からモル比で０．５～１０が好ましく、０．９～５が更に好ましく、１～３が最も好ましい。（Ａ）成分と（Ｂ）成分の配合量は、このビニル基とＳｉＨ基との比に基づいて決めればよい。 In the curable resin composition of the present invention, the ratio of SiH groups to vinyl groups is preferably 0.5 to 10, more preferably 0.9 to 5, more preferably 1 to 5 in terms of curability and grindability. 3 is most preferred. What is necessary is just to determine the compounding quantity of (A) component and (B) component based on ratio of this vinyl group and SiH group.
　次に、（Ｃ）成分の熱ラジカル発生剤について説明する。本発明において熱ラジカル発生剤とは、加熱によりラジカルを発生する化合物をいう。（Ｃ）成分から発生するラジカルは、ＳｉＨ基やケイ素原子に結合したメチル基（Ｓｉ－ＣＨ3基）を活性化させて、ビニル基やケイ素原子に結合したメチル基と反応させる働きをする。熱ラジカル発生剤としては、例えば、ジイソブチリルペルオキシド、クミルペルオキシネオデカノエート、３－ヒドロキシ－１，１－ジメチルブチルペルオキシネオデカノエート、ジプロピルペルオキシジカーボネート、ジイソプロピルペルオキシジカーボネート、ジ－ｓｅｃ－ブチルペルオキシジカーボネート、１，１，３，３，－テトラメチルブチルペルオキシネオデカノエート、ビス（４－ｔ－ブチルシクロヘキシル）ペルオキシジカーボネート、ビス(２－エチルヘキシル)ペルオキシジカーボネート、ｔ－ヘキシルペルオキシネオデカノエート、ｔ－ブチルペルオキシネオデカノエート、ｔ－ブチルペルオキシネオヘプタノエート、ｔ－ヘプチルペルオキシピバラート、ｔ－ブチルペルオキシピバラート、ｔ－ペンチルペルオキシピバレート、ビス（３，５，５－トリメチルヘキサノイル）ペルオキシド、ジラウロリルペルオキシド、１，１，３，３，－テトラメチルブチルペルオキシ－２－エチルヘキサノエート、ジコハク酸ペルオキシド、１，１，３，３－テトラメチルブチルペルオキシ－２－エチルヘキサノエート、ｔ－ペンチルペルオキシ－２－エチルヘキサノエート、ｔ－ブチルペルオキシ－２－エチルヘキサノエート、１，１－ジ（ｔ－ヘキシルペルオキシ）シクロヘキサン、１，１－ジ（ｔ－ブチルペルオキシ）シクロヘキサン、１，１－ジ（ｔ－ペンチルペルオキシ）シクロヘキサン、２，２－ビス（４，４－ジ（ｔ－ブチルペルオキシ）シクロヘキシルプロパン、ｔ－ヘキシルペルオキシイソプロピルモノカーボネート、ｔ－ペンチルペルオキシイソプロピルカーボネート、ｔ－ペンチルペルオキシノルマルオクトエート、ｔ－ブチルペルオキシマレイン酸、１，１－ジ（ｔ－ブチルペルオキシ）シクロヘキサン、ｔ－ブチルペルオキシ－３，５，５－トリメチルヘキサノエート、ｔ－ブチルペルオキシラウレート、ｔ－ブチルペルオキシイソプロピルモノヘキサノエート、ｔ－ペンチルペルオキシ－２－エチルヘキシルカーボネート、ｔ－ブチルペルオキシ－２－エチルヘキシルモノヘキサノエート、ｔ－ヘキシルペルオキシベンゾエート、ｔ－ペンチルペルオキシアセテート、２，５、－ジメチル－２，５－ジ（ベンゾイルペルオキシ）ヘキサン、ｔ－ブチルペルオキシアセテート、２，２－ジ（ｔ－ブチルペルオキシ）ブタン、ｔ－ブチルペルオキシベンゾエート、ブチル－４，４－ジ（ｔ－ブチルペルオキシ）バレレート、エチル３，３－ジ（ｔ－ブチルパーオキシ）ブチレート、ビス（２－ｔ－ブチルペルオキシイソプロピル）ベンゼン、ジクミルペルオキシド、ジ－ｔ－ヘキシルペルオキシド、２，５ジメチル２，５ジ（ｔ－ブチルパーオキシ）ヘキサン、ジーｔ－ブチルパーオキサイド、ｔ－ブチルペルオキシイソフブチレート、２，５－ジメチル－２，５－ジ（ｔ－ブチルペルオキシ）ヘキサン等の有機過酸化物系熱ラジカル発生剤； Next, the thermal radical generator of component (C) will be described. In the present invention, the thermal radical generator refers to a compound that generates radicals by heating. The radical generated from the component (C) functions to activate a methyl group (Si—CH 3 group) bonded to a SiH group or a silicon atom to react with a vinyl group or a methyl group bonded to a silicon atom. Examples of the thermal radical generator include diisobutyryl peroxide, cumylperoxyneodecanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, dipropylperoxydicarbonate, diisopropylperoxydicarbonate, -Sec-butylperoxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, t -Hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-heptylperoxypivalate, t-butylperoxypivalate, t-pentylperoxypi Bis (3,5,5-trimethylhexanoyl) peroxide, dilaurol peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-pentylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, 1,1-di (t-hexylperoxy) ) Cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-pentylperoxy) cyclohexane, 2,2-bis (4,4-di (t-butylperoxy) cyclohexylpropane, t -Hexylperoxyisopropyl monocarbonate, t-pentylperoxyisopropyl Pyrcarbonate, t-pentylperoxynormal octoate, t-butylperoxymaleic acid, 1,1-di (t-butylperoxy) cyclohexane, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl Peroxylaurate, t-butylperoxyisopropylmonohexanoate, t-pentylperoxy-2-ethylhexyl carbonate, t-butylperoxy-2-ethylhexylmonohexanoate, t-hexylperoxybenzoate, t-pentylperoxyacetate, 2 , 5, -dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di (t-butylperoxy) butane, t-butylperoxybenzoate, butyl-4,4-di ( -Butylperoxy) valerate, ethyl 3,3-di (t-butylperoxy) butyrate, bis (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5 dimethyl 2, Organic peroxides such as 5-di (t-butylperoxy) hexane, di-t-butyl peroxide, t-butylperoxyisobutyrate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane Thermal radical generators;
　２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２－メチルブチロニトリル）、１，１’－アゾビス（シクロヘキシル－１－カルボニトリル）、２，２’－アゾビス（Ｎ－（２－プロペニル）－２－メチルプロピオンアミド）、１－（（１－シアノ－１－メチルエチル）アゾ）ホルムアミド、２，２’－アゾビス（Ｎ－ブチル－２－メチルプロピオンアミド）、２，２’－アゾビス（Ｎ－シクロヘキシル－２－メチルプロピオンアミド）、２，２’－アゾビスイソブチロニトリル等のアゾ化合物系熱ラジカル発生剤等が挙げられる。 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexyl-1-carbonitrile), 2,2′-azobis (N- (2-propenyl) -2-methylpropionamide), 1-((1-cyano-1-methylethyl) azo) formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropion) Amide) and azo compound-based thermal radical generators such as 2,2′-azobisisobutyronitrile.
（Ｃ）成分としては、本発明の硬化性樹脂組成物の製造時の異常反応の防止や、保存安定性の点からは半減期温度の高い化合物が好ましいが、あまりに半減期温度の高い化合物の場合には本発明の硬化性樹脂組成物の硬化温度が高くなり、作業性が悪化する。このため、（Ｃ）成分としては、１分間半減期温度が、１３０～２５０℃、特に１５０～２００℃である化合物が好ましい。 As the component (C), a compound having a high half-life temperature is preferable from the viewpoint of prevention of abnormal reaction during production of the curable resin composition of the present invention and storage stability. In such a case, the curing temperature of the curable resin composition of the present invention is increased and workability is deteriorated. For this reason, as the component (C), a compound having a one-minute half-life temperature of 130 to 250 ° C., particularly 150 to 200 ° C. is preferable.
　１分間半減期温度が１５０～２００℃の有機過酸化物系熱ラジカル発生剤としては、１，１－ジ（ｔ－ブチルペルオキシ）シクロヘキサン、１，１－ジ（ｔ－ペンチルペルオキシ）シクロヘキサン、２，２－ビス（４，４－ジ（ｔ－ブチルペルオキシ）シクロヘキシルプロパン、ｔ－ヘキシルペルオキシイソプロピルモノカーボネート、ｔ－ペンチルペルオキシイソプロピルカーボネート、ｔ－ペンチルペルオキシノルマルオクトエート、ｔ－ブチルペルオキシマレイン酸、１，１－ジ（ｔ－ブチルペルオキシ）シクロヘキサン、ｔ－ブチルペルオキシ－３，５，５－トリメチルヘキサノエート、ｔ－ブチルペルオキシラウレート、ｔ－ブチルペルオキシイソプロピルモノヘキサノエート、ｔ－ペンチルペルオキシ－２－エチルヘキシルカーボネート、ｔ－ブチルペルオキシ－２－エチルヘキシルモノヘキサノエート、ｔ－ヘキシルペルオキシベンゾエート、ｔ－ペンチルペルオキシアセテート、２，５、－ジメチル－２，５－ジ（ベンゾイルペルオキシ）ヘキサン、ｔ－ブチルペルオキシアセテート、２，２－ジ（ｔ－ブチルペルオキシ）ブタン、ｔ－ブチルペルオキシベンゾエート、ブチル－４，４－ジ（ｔ－ブチルペルオキシ）バレレート、エチル３，３－ジ（ｔ－ブチルパーオキシ）ブチレート、ビス（２－ｔ－ブチルペルオキシイソプロピル）ベンゼン、ジクミルペルオキシド、ジ－ｔ－ヘキシルペルオキシド、２，５ジメチル２，５ジ（ｔ－ブチルパーオキシ）ヘキサン、ジーｔ－ブチルパーオキサイド、ｔ－ブチルペルオキシイソフブチレート、２，５－ジメチル－２，５－ジ（ｔ－ブチルペルオキシ）ヘキサンが挙げられる。
　１分間半減期温度が１５０～２００℃のアゾ化合物系熱ラジカル発生剤としては、２，２’－アゾビス（Ｎ－（２－プロペニル）－２－メチルプロピオンアミド）、１－（（１－シアノ－１－メチルエチル）アゾ）ホルムアミド、２，２’－アゾビス（Ｎ－ブチル－２－メチルプロピオンアミド）、２，２’－アゾビス（Ｎ－シクロヘキシル－２－メチルプロピオンアミド）が挙げられる。 Examples of organic peroxide thermal radical generators having a 1-minute half-life temperature of 150 to 200 ° C. include 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-pentylperoxy) cyclohexane, , 2-bis (4,4-di (t-butylperoxy) cyclohexylpropane, t-hexylperoxyisopropyl monocarbonate, t-pentylperoxyisopropyl carbonate, t-pentylperoxynormal octoate, t-butylperoxymaleic acid, 1 , 1-di (t-butylperoxy) cyclohexane, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropylmonohexanoate, t-pentylperoxy- 2-ethylhexyl car Nate, t-butylperoxy-2-ethylhexyl monohexanoate, t-hexylperoxybenzoate, t-pentylperoxyacetate, 2,5, -dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate 2,2-di (t-butylperoxy) butane, t-butylperoxybenzoate, butyl-4,4-di (t-butylperoxy) valerate, ethyl 3,3-di (t-butylperoxy) butyrate, Bis (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5 dimethyl 2,5 di (t-butylperoxy) hexane, di-t-butyl peroxide, t-butyl Peroxyisobutyrate, 2,5-dimethyl- , 5-di (t-butylperoxy) hexane and the like.
Examples of the azo compound-based thermal radical generator having a 1-minute half-life temperature of 150 to 200 ° C. include 2,2′-azobis (N- (2-propenyl) -2-methylpropionamide), 1-((1-cyano -1-methylethyl) azo) formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide).
（Ｃ）成分の配合量は、（Ｃ）成分の種類や硬化温度により異なるが、あまりに少ないと、本発明の硬化性樹脂組成物の硬化が不十分となり、また、あまりに多いと、配合量に見合う増量効果が得られないばかりか、却って硬化物の物性に悪影響を及ぼすことがあることから、（Ａ）成分と（Ｂ）成分の合計量１００質量部に対して、０．００１～５質量部が好ましく、０．０５～３質量部がより好ましく、０．１～２質量部がさらに好ましく、０．１～１．５質量部が最も好ましい。 The amount of component (C) varies depending on the type of component (C) and the curing temperature, but if it is too small, curing of the curable resin composition of the present invention will be insufficient, and if too large, In addition to not being able to obtain a suitable increase effect, the physical properties of the cured product may be adversely affected, so 0.001 to 5 masses per 100 mass parts of the total amount of component (A) and component (B) Part, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and most preferably 0.1 to 1.5 parts by weight.
　次に、（Ｄ）成分である上記無機フィラーについて説明する。本発明において、無機フィラーは、白色無機顔料と無機充填材に分けられ、白色無機顔料とは、可視領域に特定の吸収を有せず、屈折率が大きい無機フィラーであり、無機充填材とは白色無機顔料以外の無機フィラーをいう。白色無機顔料としては、酸化チタン、チタン酸カリウム、チタン酸カルシウム、チタン酸バリウム、酸化ジルコニウム、酸化亜鉛、酸化マグネシウム、酸化アンチモン、酸化ストロンチウム、酸化ニオブ、酸化ベリリウム、窒化ホウ素、硫化亜鉛、硫酸バリウム等が挙げられる。また、無機充填材としては、溶融シリカ、溶融球状シリカ、結晶性シリカ、コロイダルシリカ、ヒュームドシリカ、シリカゲル等のシリカ類；酸化アルミニウム、酸化鉄、三酸化アンチモン、窒化ケイ素、窒化アルミニウム、窒化ホウ素、炭化ケイ素、炭酸カルシウム、ケイ酸カルシウム、炭酸マグネシウム、炭酸バリウム、マイカ、モンモリロナイト、カオリン、タルク、グラファイト、カーボンブラック等が挙げられる。白色無機顔料としては、光反射率の点から、酸化チタンが好ましい。酸化チタンには結晶構造からルチル型、アナタース型、ブルカイト型に分類されるが、硬化物の熱安定性や光安定性の点から、ルチル型が好ましい。無機充填材としては、本発明の樹脂組成物の流動性と、硬化物の被研削性の点からシリカが好ましい。無機フィラーは１種のみを用いてもよいし、２種以上を組み合わせて用いてもよい。本発明の樹脂組成物を反射コーティング材用途で使用する場合には、（Ｄ）成分として白色無機顔料を用いて白色硬化性樹脂組成物とすることが好ましい。 Next, the inorganic filler as component (D) will be described. In the present invention, the inorganic filler is divided into a white inorganic pigment and an inorganic filler, and the white inorganic pigment is an inorganic filler that has no specific absorption in the visible region and has a large refractive index. An inorganic filler other than a white inorganic pigment. Examples of white inorganic pigments include titanium oxide, potassium titanate, calcium titanate, barium titanate, zirconium oxide, zinc oxide, magnesium oxide, antimony oxide, strontium oxide, niobium oxide, beryllium oxide, boron nitride, zinc sulfide, and barium sulfate. Etc. Examples of inorganic fillers include fused silica, fused spherical silica, crystalline silica, colloidal silica, fumed silica, silica gel, and the like; aluminum oxide, iron oxide, antimony trioxide, silicon nitride, aluminum nitride, boron nitride , Silicon carbide, calcium carbonate, calcium silicate, magnesium carbonate, barium carbonate, mica, montmorillonite, kaolin, talc, graphite, carbon black and the like. As the white inorganic pigment, titanium oxide is preferable from the viewpoint of light reflectance. Titanium oxide is classified into a rutile type, anatase type, and brookite type from the crystal structure, but the rutile type is preferred from the viewpoint of the thermal stability and light stability of the cured product. As the inorganic filler, silica is preferable from the viewpoint of fluidity of the resin composition of the present invention and grindability of the cured product. Only one type of inorganic filler may be used, or two or more types may be used in combination. When the resin composition of the present invention is used for a reflective coating material, it is preferable to use a white inorganic pigment as the component (D) to obtain a white curable resin composition.
　（Ｄ）成分の無機フィラーの粒径は、被研削性の点から、平均粒径で０．０１～５μｍであることが好ましく、０．０５～３μｍであることが更に好ましく、０．１～１μｍであることが最も好ましくい。なお、平均粒径は、レーザー光回折法による粒度分布測定における質量平均値Ｄ50（又はメジアン径）として求めることができる。 The particle diameter of the inorganic filler as component (D) is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm, more preferably 0.1 to 5 μm in terms of grindability. Most preferably, it is 1 μm. The average particle size can be determined as a mass average value D 50 in the particle size distribution measurement by laser diffraction method (or median diameter).
　また、（Ｄ）成分の配合量は、被研削性の点から、本発明の組成物（但し、（Ｄ）成分を除く）１００質量部に対して、４０～５００質量部であることが好ましく、６０～３００質量部であることが更に好ましい。 In addition, the blending amount of the component (D) is preferably 40 to 500 parts by mass with respect to 100 parts by mass of the composition of the present invention (excluding the component (D)) from the viewpoint of grindability. 60 to 300 parts by mass is more preferable.
　本発明の硬化性樹脂組成物は、架橋密度が上がり、硬化物の被研削性が向上することから、更に、（Ｅ）成分として、下記一般式（９）で表わされるシロキサン化合物を含有することが好ましい。
Figure JPOXMLDOC01-appb-C000019
 （式中、Ｒ12及びＲ13は各々独立して炭素数６～１０のアリール基を表わし、ｋは１～５の数を表わす。） The curable resin composition of the present invention contains a siloxane compound represented by the following general formula (9) as the component (E) because the crosslink density is increased and the grindability of the cured product is improved. Is preferred.
Figure JPOXMLDOC01-appb-C000019
 (Wherein R 12 and R 13 each independently represents an aryl group having 6 to 10 carbon atoms, and k represents a number of 1 to 5)
　上記一般式（９）において、Ｒ12及びＲ13は各々独立して炭素数６～１０のアリール基を表わす。炭素数６～１０のアリール基としては、一般式（１）のＲ1で例示した炭素数６～１０のアリール基が挙げられる。Ｒ12及びＲ13としては、被研削性の向上効果が高いことからフェニル基が好ましい。ｋは１～５の数を表わし、被研削性の向上効果が高いことから１～２の数が好ましく、１の数が更に好ましい。一般式（９）で表わされる鎖状シロキサン化合物の中で、好ましい化合物としては、１，１，５，５－テトラメチル－３，３－ジフェニル－１，５－ジビニルトリシロキサン、１，１，７，７－テトラメチル－３，３，５，５－テトラフェニル－１，７－ジビニルトリシロキサン等が挙げられる。 In the general formula (9), R 12 and R 13 each independently represents an aryl group having 6 to 10 carbon atoms. Examples of the aryl group having 6 to 10 carbon atoms include aryl groups having 6 to 10 carbon atoms exemplified as R 1 in the general formula (1). As R 12 and R 13 , a phenyl group is preferable because the effect of improving grindability is high. k represents a number of 1 to 5, and is preferably a number of 1 or 2 and more preferably a number of 1 because the effect of improving grindability is high. Among the chain siloxane compounds represented by the general formula (9), preferred compounds include 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyltrisiloxane, 1,1,5, Examples include 7,7-tetramethyl-3,3,5,5-tetraphenyl-1,7-divinyltrisiloxane.
　本発明の（Ｅ）成分である上記一般式（９）で表わされるシロキサン化合物の配合量があまりに少ない場合には、被研削性の向上効果が十分ではなく、またあまりに多い場合には、架橋密度が上がり過ぎて逆に被研削性が低下する場合があることから、（Ｅ）成分の配合量は、（Ａ）成分１００質量部に対して、２０～８０質量部であることが好ましく、３０～７０質量部であることが更に好ましい。（Ｅ）成分を配合する場合には、上記のビニル基とＳｉＨ基との比に基づいて（Ｂ）成分の量を決めればよい。 When the amount of the siloxane compound represented by the general formula (9), which is the component (E) of the present invention, is too small, the effect of improving the grindability is not sufficient, and when it is too large, the crosslinking density In other words, the grindability may be lowered due to excessive increase in the amount of the component (E). Therefore, the blending amount of the component (E) is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is ˜70 parts by mass. When the component (E) is blended, the amount of the component (B) may be determined based on the ratio of the vinyl group and the SiH group.
　本発明の硬化性樹脂組成物は、硬化物と基材との密着性が向上することから、更にイソシアヌル酸構造を有する化合物を含有することが好ましい。イソシアヌル酸構造を有する化合物としては、例えば、上記一般式（５）で表わされる化合物に加えて、イソシアヌル酸、１，３，５－トリグリシジルイソシアヌル酸、１－アリル－３，５－ジグリシジルイソシアヌル酸、トリス（２－ヒドロキシエチル）イソシアヌル酸、トリス（２，３－ジヒドロキシプロピル）イソシアヌル酸等が挙げられる。 The curable resin composition of the present invention preferably further contains a compound having an isocyanuric acid structure because the adhesion between the cured product and the substrate is improved. Examples of the compound having an isocyanuric acid structure include, in addition to the compound represented by the general formula (5), isocyanuric acid, 1,3,5-triglycidyl isocyanuric acid, 1-allyl-3,5-diglycidyl isocyanuric. And acid, tris (2-hydroxyethyl) isocyanuric acid, tris (2,3-dihydroxypropyl) isocyanuric acid and the like.
　本発明の硬化性樹脂組成物は、この他に、酸化防止剤、紫外線吸収剤、離型剤、帯電防止剤、白金系ヒドロシリル化触媒、硬化遅延剤、カップリング剤、難燃剤、有機溶剤等を本発明の目的及び効果を損なわない範囲において添加することができる。 In addition to this, the curable resin composition of the present invention includes an antioxidant, an ultraviolet absorber, a release agent, an antistatic agent, a platinum-based hydrosilylation catalyst, a curing retarder, a coupling agent, a flame retardant, an organic solvent, and the like. Can be added within a range not impairing the object and effects of the present invention.
　本発明の硬化性樹脂組成物は、流動性に優れており、基板等の対象物に塗布した後、加熱して硬化させることができる。本発明の硬化性樹脂組成物を対象材料に塗布する方法としては、例えば、スピンコート法、ディップコート法、ナイフコート法、ロールコート法、スプレーコート法、スリットコート法、スクリーン印刷法等が挙げられる。 The curable resin composition of the present invention is excellent in fluidity and can be cured by heating after being applied to an object such as a substrate. Examples of the method for applying the curable resin composition of the present invention to a target material include spin coating, dip coating, knife coating, roll coating, spray coating, slit coating, and screen printing. It is done.
　本発明の硬化性樹脂組成物は、加熱することにより硬化させることができ、硬化物とすることができる。この硬化反応は、（Ｃ）成分の種類によっても異なるが、作業性の点から、８０～３５０℃が好ましく、１００～２５０℃がより好ましい。硬化時間は２～１２０分が好ましく、２０～６０分がより好ましい。 The curable resin composition of the present invention can be cured by heating and can be a cured product. This curing reaction varies depending on the type of component (C), but is preferably from 80 to 350 ° C, more preferably from 100 to 250 ° C, from the viewpoint of workability. The curing time is preferably 2 to 120 minutes, more preferably 20 to 60 minutes.
　本発明の硬化性樹脂組成物の硬化物は、耐熱性、耐光性、耐クラック性、着色性等の諸物性に優れており、例えば、封止材、モールド材、コーティング材、絶縁材、反射材として使用でき、特にＬＥＤ等の発光素子の反射材として好適に使用できる。
　また、本発明の硬化性樹脂組成物の硬化物は被研削性に優れているため、ダイヤモンド製等の硬質刃を回転板の半径方向に複数配置した硬質回転刃を有する研削装置を使用する方法や、サンダ、ベルトサンダ、グラインダ、平面研削盤、硬質砥粒成形品等を用いる方法等により研削できる。本発明の硬化性樹脂組成物の硬化物は、研削装置を使用すると、当該硬質回転刃を回転させながら、固定支持された配線基板の上面に沿って移動させることによって、上面を平坦化することができる。また、研磨の方法としては、ベルトサンダ、バフ研磨等により軽く研磨する方法が挙げられる。 The cured product of the curable resin composition of the present invention is excellent in various physical properties such as heat resistance, light resistance, crack resistance, and colorability. For example, a sealing material, a molding material, a coating material, an insulating material, a reflective material, and the like. It can be used as a material, and can be suitably used as a reflective material for light emitting elements such as LEDs.
Further, since the cured product of the curable resin composition of the present invention is excellent in grindability, a method of using a grinding apparatus having a hard rotating blade in which a plurality of hard blades made of diamond or the like are arranged in the radial direction of the rotating plate is used. Further, it can be ground by a method using a sander, a belt sander, a grinder, a surface grinder, a hard abrasive molded product, or the like. When using a grinding apparatus, the cured product of the curable resin composition of the present invention flattens the upper surface by moving the hard rotary blade along the upper surface of the fixedly supported wiring board. Can do. Moreover, as a grinding | polishing method, the method of lightly grind | polishing by a belt sander, buff grinding | polishing, etc. is mentioned.
　以下、実施例により本発明を更に説明するが、本発明はこれらの実施例によって限定されるものではない。尚、特に限定のない限り、実施例中の「部」や「％」は質量基準によるものである。 Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts” and “%” in the examples are based on mass.
［合成例１］（Ａ）成分：化合物Ａ１の合成
　窒素ガス導入管、温度計、冷却管及び攪拌装置を備えた反応容器に２，４，６，８－テトラメチルシクロテトラシロキサン４８．０ｇ（０．２０ｍｏｌ）、ジビニルベンゼン２６．０ｇ（０．２０ｍｏｌ）、触媒として白金-ジビニルテトラメチルジシロキサン錯体０．００２ｇ及び溶媒としてトルエン１５０ｇを仕込み、１０５℃で２時間反応させた。その後、７０℃で溶媒を減圧留去し化合物Ａ１を得た。化合物Ａ１のＧＰＣ分析により求めた重量平均分子量は１０，０００であり、Ｈ－ＮＭＲ分析により求めた１ｇあたりのＳｉＨ基の含有量は５．４０ｍｍｏｌである。 [Synthesis Example 1] Component (A): Synthesis of Compound A1 48.0 g of 2,4,6,8-tetramethylcyclotetrasiloxane was added to a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, a cooling tube and a stirring device. 0.20 mol), 26.0 g (0.20 mol) of divinylbenzene, 0.002 g of platinum-divinyltetramethyldisiloxane complex as a catalyst, and 150 g of toluene as a solvent were reacted at 105 ° C. for 2 hours. Thereafter, the solvent was distilled off under reduced pressure at 70 ° C. to obtain Compound A1. The weight average molecular weight determined by GPC analysis of Compound A1 is 10,000, and the content of SiH groups per gram determined by H-NMR analysis is 5.40 mmol.
［合成例２］（Ａ）成分：化合物Ａ２の合成
　１，４－ジビニルベンゼンの配合量を２６．０ｇ（０．２０ｍｏｌ）から１８．２ｇ（０．１４ｍｏｌ）に変更した以外は、合成例１と同様の操作を行い、化合物Ａ２を得た。化合物Ａ２のＧＰＣ分析により求めた重量平均分子量は１４０００であり、Ｈ－ＮＭＲ分析により求めた１ｇあたりのＳｉＨ基の含有量は７．８５ｍｍｏｌである。 [Synthesis Example 2] Component (A): Synthesis of Compound A2 Synthesis Example 1 except that the amount of 1,4-divinylbenzene was changed from 26.0 g (0.20 mol) to 18.2 g (0.14 mol). The same operation was carried out to obtain compound A2. The weight average molecular weight determined by GPC analysis of Compound A2 is 14000, and the content of SiH groups per gram determined by H-NMR analysis is 7.85 mmol.
［合成例３］（Ａ）成分：化合物Ａ３の合成
　１，４－ジビニルベンゼン２６．０ｇ（０．２０ｍｏｌ）の代わりに１，４－ビス（ジメチルビニルシリル）ベンゼン４９．３ｇ（０．２０ｍｏｌ）を使用した以外は合成例１と同様の操作を行い、化合物Ａ３を得た。化合物Ａ３のＧＰＣ分析により求めた重量平均分子量は１０，０００であり、Ｈ－ＮＭＲ分析により求めた１ｇあたりのＳｉＨ基の含有量は２．２７ｍｍｏｌである。 [Synthesis Example 3] Component (A): Synthesis of Compound A3 49.3 g (0.20 mol) of 1,4-bis (dimethylvinylsilyl) benzene instead of 26.0 g (0.20 mol) of 1,4-divinylbenzene The same procedure as in Synthesis Example 1 was carried out except that was used to obtain compound A3. The weight average molecular weight determined by GPC analysis of Compound A3 is 10,000, and the content of SiH groups per gram determined by H-NMR analysis is 2.27 mmol.
［合成例４］（Ａ）成分：化合物Ａ４の合成
　１，４－ジビニルベンゼン２６．０ｇ（０．２０ｍｏｌ）の代わりに１，３，５－トリアリルイソシアヌレート２９．９ｇ（０．１２ｍｏｌ）を使用した以外は合成例１と同様の操作を行い、化合物Ａ３を得た。化合物Ａ３のＧＰＣ分析により求めた重量平均分子量は８，０００であり、Ｈ－ＮＭＲ分析により求めた１ｇあたりのＳｉＨ基の含有量は５．６５ｍｍｏｌである。 [Synthesis Example 4] Component (A): Synthesis of Compound A4 In place of 26.0 g (0.20 mol) of 1,4-divinylbenzene, 29.9 g (0.12 mol) of 1,3,5-triallyl isocyanurate was used. The same operation as in Synthesis Example 1 was carried out except that the compound A3 was used. The weight average molecular weight determined by GPC analysis of Compound A3 is 8,000, and the content of SiH groups per gram determined by H-NMR analysis is 5.65 mmol.
［合成例５］（Ｆ）成分：化合物Ｆ２の合成
　ＷＯ２０１１／１５５４５９号公報の合成例１の方法に準じて（１／１０のスケール）、フェニルトリメトキシシラン１９．８ｇ（０．１ｍｏｌ）、ビニルトリメトキシシラン７．４ｇ（０．０５ｍｏｌ）、メチルトリメトキシシラン６．８ｇ（０．０５ｍｏｌ）及びジメチルジメトキシシラン３．０ｇ（０．０２５ｍｏｌ）を用いてケイ素含有重合体である化合物Ｆ２を得た（ビニル基含量：１．０５ｍｍｏｌ／ｇ）。 [Synthesis Example 5] Component (F): Synthesis of Compound F2 According to the method of Synthesis Example 1 of WO2011 / 155559 (scale of 1/10), 19.8 g (0.1 mol) of phenyltrimethoxysilane, vinyl Compound F2 which is a silicon-containing polymer was obtained using 7.4 g (0.05 mol) of trimethoxysilane, 6.8 g (0.05 mol) of methyltrimethoxysilane and 3.0 g (0.025 mol) of dimethyldimethoxysilane. (Vinyl group content: 1.05 mmol / g).
［実施例１～８及び比較例１～６］硬化性樹脂組成物の調製及び評価
　以上の合成例で得られた各化合物、及び下記化合物を用い、［表１］に示す組成で、（Ａ）成分～（Ｆ）成分等を配合して、本発明及び比較用の硬化性樹脂組成物を得た。得られた硬化性樹脂組成物について、シェア硬度、全反射率、被研削性及び密着性の評価を、それぞれ以下に示す方法で行った。 [Examples 1 to 8 and Comparative Examples 1 to 6] Preparation and Evaluation of Curable Resin Composition Using the respective compounds obtained in the above synthesis examples and the following compounds, the compositions shown in [Table 1] were used as (A Components) to (F) were blended to obtain curable resin compositions for the present invention and for comparison. About the obtained curable resin composition, shear hardness, total reflectance, grindability, and evaluation of adhesion were performed by the methods shown below.
＜硬化性樹脂組成物のその他の原料＞
（Ｂ）成分
　化合物Ｂ１：
Figure JPOXMLDOC01-appb-C000020
 　（ビニル基含量：０．１７３ｍｍｏｌ／ｇ）
　化合物Ｂ２：
Figure JPOXMLDOC01-appb-C000021
 　（ビニル基含量：０．１７７ｍｍｏｌ／ｇ）
　（Ｃ）成分
　Ｃ１：２，５－ジメチル－２，５－ジ（ｔ－ブチルパ－オキシ）ヘキサン
　（Ｄ）成分
　Ｄ１：ルチル型酸化チタン（平均粒径０．２５μｍ）
　Ｄ２：球状シリカ（平均粒径５μｍ）
　Ｄ３：酸化亜鉛（平均粒径１０μｍ）
　（Ｅ）成分
　化合物Ｅ１：１，１，５，５－テトラメチル－３，３－ジフェニル－１，５－ジビニルトリシロキサン
（ビニル基含量：５．２０ｍｍｏｌ／ｇ）
　混合物Ｅ２：１，１，５，５－テトラメチル－３，３－ジフェニル－１，５－ジビニルトリシロキサンと１，１，７，７－テトラメチル－３，３，５，５－テトラフェニル－１，７－ジビニルトリシロキサンの質量比２：１混合物（ビニル基含量：５．００ｍｍｏｌ／ｇ）
（Ｆ）その他
　Ｆ１：白金-ジビニルテトラメチルジシロキサン錯体
　Ｆ３：２，４，６，８－テトラメチル－２，４，６，８－テトラビニルシクロテトラシロキサン（ビニル基含量：２．０９ｍｍｏｌ／ｇ）
　Ｆ４：プロピレングリコールモノメチルエーテルアセテート（溶剤として使用） <Other raw materials of curable resin composition>
(B) Component Compound B1:
Figure JPOXMLDOC01-appb-C000020
 (Vinyl group content: 0.173 mmol / g)
Compound B2:
Figure JPOXMLDOC01-appb-C000021
 (Vinyl group content: 0.177 mmol / g)
(C) Component C1: 2,5-Dimethyl-2,5-di (t-butylperoxy) hexane (D) Component D1: Rutile type titanium oxide (average particle size 0.25 μm)
D2: Spherical silica (average particle size 5 μm)
D3: Zinc oxide (average particle size 10 μm)
Component (E) Compound E1: 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyltrisiloxane (vinyl group content: 5.20 mmol / g)
Mixture E2: 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyltrisiloxane and 1,1,7,7-tetramethyl-3,3,5,5-tetraphenyl- 1,7-divinyltrisiloxane mass ratio 2: 1 mixture (vinyl group content: 5.00 mmol / g)
(F) Others F1: Platinum-divinyltetramethyldisiloxane complex F3: 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (vinyl group content: 2.09 mmol / g) )
F4: Propylene glycol monomethyl ether acetate (used as solvent)
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
＜シェア硬度＞
〔試験片の作成〕
　直径１０ｃｍのガラスシャーレに硬化後の厚さが１０ｍｍとなるように実施例１～８又は比較例１～５の硬化性樹脂組成物を流し込み、１５０℃の恒温槽で１時間硬化して、硬化物を、容器から取り出し試験片を調製した。
〔硬度測定方法〕
　ＪＩＳ　Ｚ２２４６（ショア硬さ試験－試験方法）に準拠し、ショア硬度を測定した。結果を［表２］に示す。
＜全反射率＞
　シェア硬度の測定に用いた試験片について、紫外可視分光光度計により３００～８００ｎｍにおける全反射率を測定した。なお測定には積分球を用いた。結果を［表２］に示す。 <Share hardness>
[Preparation of specimen]
The curable resin compositions of Examples 1 to 8 or Comparative Examples 1 to 5 were poured into a glass petri dish with a diameter of 10 cm so that the thickness after curing was 10 mm, and cured for 1 hour in a constant temperature bath at 150 ° C. to be cured. The thing was taken out from the container and the test piece was prepared.
[Hardness measurement method]
Shore hardness was measured according to JIS Z2246 (Shore hardness test-test method). The results are shown in [Table 2].
<Total reflectance>
About the test piece used for the measurement of shear hardness, the total reflectance in 300-800 nm was measured with the ultraviolet visible spectrophotometer. An integrating sphere was used for the measurement. The results are shown in [Table 2].
＜被研削性＞
〔試験片の作成〕
　幅１ｍｍ、長さ２０ｍｍ、間隔１ｍｍで５本の銅線パターンが形成されたガラスエポキシ基板上に、バーコーターを用いて膜厚が１００μｍとなるように実施例１～８及び比較例１～５の硬化性組成物を塗布した。この基板を１５０℃の恒温槽で１時間加熱することにより、試験片を調製した。
〔被研削性評価方法〕
　試験片の表面を、Ｐ２２０の研磨紙で、銅線パターンが現れるまで研磨し、銅線パターンの近傍の樹脂部の状態により下記の基準により被研削性を評価した。結果を［表２］に示す。
・評価基準
○：凹部が見られず、被研削性に優れる。
△：凹部がやや見られ、被研削性にやや劣る。
×：凹部が多く、被研削性に劣る。 <Grindability>
[Preparation of specimen]
Examples 1 to 8 and Comparative Examples 1 to 5 were formed using a bar coater on a glass epoxy substrate on which five copper wire patterns were formed with a width of 1 mm, a length of 20 mm, and an interval of 1 mm, using a bar coater. The curable composition was applied. A test piece was prepared by heating the substrate in a thermostatic bath at 150 ° C. for 1 hour.
[Grindability evaluation method]
The surface of the test piece was polished with a P220 polishing paper until a copper wire pattern appeared, and the grindability was evaluated according to the following criteria according to the state of the resin part in the vicinity of the copper wire pattern. The results are shown in [Table 2].
-Evaluation standard (circle): A recessed part is not seen but it is excellent in grindability.
(Triangle | delta): A recessed part is seen a little and it is a little inferior to grindability.
X: There are many concave parts, and the grindability is poor.
＜密着性＞
〔試験片の作成〕
　幅５０ｍｍ、長さ１００ｍｍ及び厚さ０．３ｍｍの銅板上に、バーコーターを用いて膜厚が１００μｍとなるように実施例１～８及び比較例１～５の硬化性組成物を塗布後、１５０℃の恒温槽で１時間加熱することにより、試験片を調製した。結果を［表２］に示す。〔密着性評価方法〕
試験片の硬化膜の中央部分に１ｍｍ間隔で縦６本、横６本の格子状のクロスカットを入れる。この試験片を外径１４０ｍｍの硬質塩化ビニル管に押し付けてクロスカット部分を反らせ、クロスカット部分の剥離等の有無により、下記の基準により密着性を評価した。結果を［表２］に示す。
・評価基準
○：剥離が見られず、密着性に優れる。
△：１～１０箇所で剥離が見られ、密着性にやや劣る。
×：１１箇所以上で剥離が見られ、密着性に劣る。 <Adhesion>
[Preparation of specimen]
After applying the curable compositions of Examples 1 to 8 and Comparative Examples 1 to 5 on a copper plate having a width of 50 mm, a length of 100 mm, and a thickness of 0.3 mm, using a bar coater, the film thickness was 100 μm. A test piece was prepared by heating in a thermostatic bath at 150 ° C. for 1 hour. The results are shown in [Table 2]. [Adhesion evaluation method]
A grid-like crosscut of 6 vertical and 6 horizontal grids is made at 1 mm intervals in the center of the cured film of the test piece. The test piece was pressed against a hard polyvinyl chloride tube having an outer diameter of 140 mm to warp the crosscut portion, and the adhesion was evaluated according to the following criteria depending on whether or not the crosscut portion was peeled off. The results are shown in [Table 2].
-Evaluation standard (circle): Peeling is not seen but it is excellent in adhesiveness.
Δ: Peeling was observed at 1 to 10 locations, and the adhesion was slightly inferior.
X: Peeling is observed at 11 or more places, and the adhesion is poor.
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023

Claims (4)

  1. 　（Ａ）成分として、下記一般式（１）で表わされる基及び／又は下記一般式（２）で表わされる基が、下記一般式（３）～（７）の何れかで表わされる化合物からビニル基を除いた残基で連結されたシロキサン化合物、（Ｂ）成分として、下記一般式（８）で表わされる鎖状シロキサン化合物、（Ｃ）成分として、熱ラジカル発生剤、及び（Ｄ）成分として、無機フィラーを含有する硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1は炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わし、ａは２～５の数を表わす。但し、Ｒ1は全て同一の基でもよいし、異なる基でもよい。）
    Figure JPOXMLDOC01-appb-C000002
     （式中、ｂはａ－ｂ＋１が０～４の数となる２～６の数を表わし、Ｒ1及びａは上記一般式（１）と同義である。）
    Figure JPOXMLDOC01-appb-C000003
     （式中、ｃは１又は２の数を表わす。）
    Figure JPOXMLDOC01-appb-C000004
     （式中、ｄは１又は２の数を表わす。）
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｒ2は炭素数１～４のアルキル基、グリシジル基又はアリル基を表わす。）
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｒ3～Ｒ5は各々独立して炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わし、ｅは１又は２の数を表わし、ｆ及びｇは各々独立して０～６の数を表わす。）
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｒ6及びＲ7は各々独立して炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わす。）
    Figure JPOXMLDOC01-appb-C000008
     （式中、Ｒ8及びＲ9は各々独立して炭素数１～４のアルキル基を表わし、Ｒ10は炭素数６～１０のアリール基を表わし、Ｒ11は炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わし、ｈ及びｊは一般式（８）で表される鎖状シロキサン化合物の質量平均分子量を１０００～１００万とする数である。）     As the component (A), a group represented by the following general formula (1) and / or a group represented by the following general formula (2) is converted from a compound represented by any one of the following general formulas (3) to (7) to vinyl As a siloxane compound linked by a residue excluding a group, as a component (B), a chain siloxane compound represented by the following general formula (8), as a component (C), as a thermal radical generator, and as a component (D) A curable resin composition containing an inorganic filler.
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a represents a number of 2 to 5. However, R 1 may all be the same group, Different groups may be used.)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, b represents a number from 2 to 6 in which ab + 1 is a number from 0 to 4, and R 1 and a have the same meaning as in the general formula (1).)
    Figure JPOXMLDOC01-appb-C000003
     (Wherein c represents a number of 1 or 2)
    Figure JPOXMLDOC01-appb-C000004
     (In the formula, d represents a number of 1 or 2.)
    Figure JPOXMLDOC01-appb-C000005
     (Wherein R 2 represents an alkyl group having 1 to 4 carbon atoms, a glycidyl group or an allyl group.)
    Figure JPOXMLDOC01-appb-C000006
     (Wherein R 3 to R 5 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, e represents a number of 1 or 2, and f and g are each independently And represents a number from 0 to 6.)
    Figure JPOXMLDOC01-appb-C000007
     (Wherein R 6 and R 7 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.)
    Figure JPOXMLDOC01-appb-C000008
     (Wherein R 8 and R 9 each independently represents an alkyl group having 1 to 4 carbon atoms, R 10 represents an aryl group having 6 to 10 carbon atoms, and R 11 represents an alkyl group having 1 to 4 carbon atoms) Or an aryl group having 6 to 10 carbon atoms, and h and j are numbers that make the mass average molecular weight of the chain siloxane compound represented by the general formula (8) 1,000 to 1,000,000.)
  2. 　更に、（Ｅ）成分として、下記一般式（９）で表わされるシロキサン化合物を含有する請求項１に記載の硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000009
     （式中、Ｒ12及びＲ13は各々独立して炭素数６～１０のアリール基を表わし、ｋは１～５の数を表わす。）     Furthermore, the curable resin composition of Claim 1 containing the siloxane compound represented by following General formula (9) as (E) component.
    Figure JPOXMLDOC01-appb-C000009
     (Wherein R 12 and R 13 each independently represents an aryl group having 6 to 10 carbon atoms, and k represents a number of 1 to 5)
  3. 　（Ｄ）成分である無機フィラーが白色無機顔料である請求項１又は２に記載の白色硬化性樹脂組成物。 The white curable resin composition according to claim 1 or 2, wherein the inorganic filler as component (D) is a white inorganic pigment.
  4. 　請求項３に記載の白色硬化性樹脂組成物を硬化した反射コーティング材。 A reflective coating material obtained by curing the white curable resin composition according to claim 3.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016141615A (en) * 2015-01-29 2016-08-08 旭化成株式会社 Organopolysiloxane and thermosetting resin composition comprising the same

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* Cited by examiner, † Cited by third party
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KR20200117978A (en) * 2018-02-13 2020-10-14 가부시키가이샤 아데카 Coating composition, method for curing the composition, method for producing barrier film and cured product
JP6981933B2 (en) * 2018-08-15 2021-12-17 信越化学工業株式会社 A curable composition, a cured product of the composition, and a semiconductor device using the cured product.

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006090609A1 (en) * 2005-02-24 2006-08-31 Adeka Corporation Silicon-containing curable composition and its cured product
WO2008133228A1 (en) * 2007-04-23 2008-11-06 Adeka Corporation Silicon-containing compound, curable composition and cured product
WO2008133227A1 (en) * 2007-04-23 2008-11-06 Adeka Corporation Silicon-containing compound, curable composition and cured product
WO2008133229A1 (en) * 2007-04-23 2008-11-06 Adeka Corporation Silicon-containing compound, curable composition and cured product
JP2010018719A (en) * 2008-07-11 2010-01-28 Adeka Corp Silicon-containing curable composition
WO2011048894A1 (en) * 2009-10-21 2011-04-28 株式会社Adeka Silicon-containing curable composition and cured product thereof
WO2011155459A1 (en) * 2010-06-11 2011-12-15 株式会社Adeka Silicon-containing curable composition, cured product of the silicon-containing curable composition and lead frame substrate formed of the silicon-containing curable composition
WO2013021717A1 (en) * 2011-08-10 2013-02-14 株式会社Adeka Silicon-containing curable composition and cured product of same
JP2013159776A (en) * 2012-02-09 2013-08-19 Adeka Corp Silicon-containing curable white resin composition, cured product thereof, and optical semiconductor package and reflecting material using the cured product
WO2013157551A1 (en) * 2012-04-18 2013-10-24 株式会社Adeka Silicon-containing curable composition and cured product thereof
JP2013256587A (en) * 2012-06-12 2013-12-26 Adeka Corp Curable composition

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5303097B2 (en) 2005-10-07 2013-10-02 日立化成株式会社 Thermosetting light reflecting resin composition, optical semiconductor mounting substrate using the same, manufacturing method thereof, and optical semiconductor device.
JP2009194222A (en) 2008-02-15 2009-08-27 Denki Kagaku Kogyo Kk White alkali-developable photocurable and thermosetting solder resist composition, and metal-base circuit substrate using the same
JP5532384B2 (en) 2009-02-19 2014-06-25 山栄化学株式会社 Si-based resin-containing curable resin composition
JP2011105869A (en) 2009-11-18 2011-06-02 Kaneka Corp White curable composition and reflective coating material
JP5522116B2 (en) 2011-04-28 2014-06-18 信越化学工業株式会社 Addition-curing silicone composition and optical semiconductor device using the same
JP6121099B2 (en) 2011-05-11 2017-04-26 株式会社ダイワ工業 Light-emitting element mounting substrate and manufacturing method thereof
CN103125380A (en) * 2011-11-30 2013-06-05 江苏美尚生态景观股份有限公司 Method for restraining butterfly orchid tissue from browning
KR20130075154A (en) 2011-12-27 2013-07-05 대우조선해양 주식회사 Chilling module and method using carbon dioxide

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006090609A1 (en) * 2005-02-24 2006-08-31 Adeka Corporation Silicon-containing curable composition and its cured product
WO2008133228A1 (en) * 2007-04-23 2008-11-06 Adeka Corporation Silicon-containing compound, curable composition and cured product
WO2008133227A1 (en) * 2007-04-23 2008-11-06 Adeka Corporation Silicon-containing compound, curable composition and cured product
WO2008133229A1 (en) * 2007-04-23 2008-11-06 Adeka Corporation Silicon-containing compound, curable composition and cured product
JP2010018719A (en) * 2008-07-11 2010-01-28 Adeka Corp Silicon-containing curable composition
WO2011048894A1 (en) * 2009-10-21 2011-04-28 株式会社Adeka Silicon-containing curable composition and cured product thereof
WO2011155459A1 (en) * 2010-06-11 2011-12-15 株式会社Adeka Silicon-containing curable composition, cured product of the silicon-containing curable composition and lead frame substrate formed of the silicon-containing curable composition
WO2013021717A1 (en) * 2011-08-10 2013-02-14 株式会社Adeka Silicon-containing curable composition and cured product of same
JP2013159776A (en) * 2012-02-09 2013-08-19 Adeka Corp Silicon-containing curable white resin composition, cured product thereof, and optical semiconductor package and reflecting material using the cured product
WO2013157551A1 (en) * 2012-04-18 2013-10-24 株式会社Adeka Silicon-containing curable composition and cured product thereof
JP2013256587A (en) * 2012-06-12 2013-12-26 Adeka Corp Curable composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016141615A (en) * 2015-01-29 2016-08-08 旭化成株式会社 Organopolysiloxane and thermosetting resin composition comprising the same

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