JP6227884B2 - Curable resin composition, curable resin composition tablet, molded product, semiconductor package, semiconductor component, and light emitting diode - Google Patents

Description

The present invention relates to a curable resin composition, a curable resin composition tablet, a molded body, a semiconductor package, a semiconductor component, and a light emitting diode.

  Conventionally, packages using curable resins of various shapes are applied to semiconductors. These packages use various metal materials for electrical connection between the semiconductor and the outside of the package, to maintain the strength of the package, or to transfer the heat generated from the semiconductor to the outside of the package. Often done.

  However, since the resin generally has a large linear expansion coefficient, and the coefficient of linear expansion is generally difficult to match that of a metal material having a small linear expansion coefficient, various types of heating during heat molding, post-curing, or in use as a semiconductor component- Problems such as warpage, peeling, cracking, and damage to the semiconductor may occur in the process involving cooling.

  In particular, there is a method for reducing warpage by forming a curable resin so as to be uniform on both surfaces of a metal with respect to warpage due to mismatch of linear expansion.

  However, in recent years, a design with high heat dissipation has been required due to an increase in the amount of heat generated from a semiconductor. In order to effectively conduct heat to the outside of the package, the metal bonding the semiconductor element forms the bottom surface of the package. Such package design has been made (Patent Documents 1 and 2). In that case, it is not possible to reduce the warp as described above, and the problem of warp becomes important.

In the past, measures have been taken to reduce the warpage caused by the resin by reducing the linear expansion of the resin to approach the linear expansion of the metal that is integrally formed, or by reducing the elastic modulus of the resin.
However, if a large amount of inorganic filler is filled in order to reduce the linear expansion, there is a limit because the fluidity at the time of molding of the resin is lowered and the moldability is impaired, and if the elasticity is lowered, the strength of the resin is lowered and the semiconductor is lowered. This also impairs the main function of the package for protecting the element.
In view of the above, there is a demand for a curable resin that can reduce warpage in a semiconductor package.

JP 2010-62272 A JP 2009-302241 A

  Accordingly, an object of the present invention is to provide a curable resin composition that provides a cured product having a low coefficient of linear expansion, and a semiconductor package with reduced warpage integrally formed with a metal using the same, and It is providing the semiconductor manufactured using this.

  In order to solve such problems, the present inventors have conducted intensive studies, and as a result, (A) a thermosetting resin, (B) a curing catalyst, (C) a fluorine-based resin, and (D) an inorganic filler are essential components. The present inventors have found that the above-mentioned problems can be achieved by using a curable resin composition, and have reached the present invention.

  That is, the present invention has the following configuration.

  1). A curable resin composition comprising (A) a thermosetting resin, (B) a curing catalyst, (C) a fluororesin, and (D) an inorganic filler as essential components.

  2). (C) The curable resin according to 1), wherein the fluororesin is any one of polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-ethylene copolymer. Composition.

  3). The curable resin composition according to 1) or 2), wherein the thermosetting resin is a silicone-based thermosetting resin.

  4). (A) A silicone-based thermosetting resin (A-1) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule; and (A-2) in one molecule The curable resin composition according to 1) to 3), wherein the curable resin composition comprises a compound containing at least two SiH groups.

  5). (B) The curable resin composition according to any one of 1) to 4), wherein the curing catalyst is a hydrosilylation catalyst.

  6). (C) The curable resin composition of any one of 1) -5) whose average particle diameter of a component is 0.5 micrometer or more and 500 micrometers or less.

  7). (D) The curable resin composition according to any one of 1) to 6), wherein the component is spherical silica.

  8). The curable resin composition according to any one of 1) to 7), further comprising (E) a white pigment.

  9). (E) The curable resin composition as described in 8) whose average particle diameter of a component is 1.0 micrometer or less.

  10). (E) The curable resin composition according to 8) or 9), wherein the component is at least one selected from titanium oxide, zinc oxide, zirconia oxide, strontium oxide, niobium oxide, boron nitride, barium titanate and barium sulfate.

  11). (E) The curable resin composition according to 10), wherein the component is zinc oxide.

  12). (E) The curable resin composition according to 10), wherein the component is surface-treated with an organosiloxane.

  13). (E) The curable resin composition according to 10), wherein the component is surface-treated with an inorganic compound.

  14). The curable resin composition according to 10), wherein the component (E) is surface-treated with an aluminum compound.

  15). Furthermore, the curable resin composition of any one of 1) -14) containing (F) metal soap.

  16). (F) The curable resin composition according to 15), wherein the component is a metal stearate.

  17). (F) The curable resin composition according to 16), wherein the component is one or more selected from the group consisting of calcium stearate, magnesium stearate, zinc stearate, and aluminum stearate.

  18). 18. The curable resin composition according to any one of 1) to 17), wherein the total amount of component (C) in the entire curable resin composition is 1% by weight to 20% by weight. .

  19). The curable resin composition according to any one of 1) to 18), wherein the total amount of the component (D) in the entire curable resin composition is 20% by weight or more and 95% by weight or less.

  20). 21. The curable resin composition according to any one of 7) to 19), wherein the content of the component (E) in the entire curable resin composition is 10% by weight to 60% by weight.

  21). The total content of the component (D) and the component (E) in the entire curable resin composition is 40% by weight to 95% by weight, and any one of 7) to 20) Curable resin composition.

  22). The content of the component (F) in the entire curable resin composition is 0.01 to 5% by weight, and the curable resin composition according to any one of 15) to 21).

  23). The curable resin composition according to any one of 1) to 22), which is used for a semiconductor package.

  24). A tablet comprising the curable resin composition according to any one of 1) to 23).

  25). 1. A molded product obtained by curing the curable resin composition according to any one of 1) to 24), wherein the light reflectance at a surface wavelength of 470 nm is 90% or more.

  26). 23) A semiconductor package formed by using the curable resin composition described in 23).

  27). 23. A semiconductor package, which is integrally formed with a metal using the curable resin composition according to 23).

  28). The semiconductor package according to 26) or 27), wherein the curable resin composition and the lead frame are integrally formed by transfer molding.

  29). 29. The semiconductor package according to any one of 26) to 28), wherein the semiconductor package is a package formed by substantially molding a resin on one side of a metal.

  30). A semiconductor package, which is transfer molded using the curable resin composition described in 23).

  31). A semiconductor component manufactured using the semiconductor package according to any one of 26) to 30).

  32). A light emitting diode manufactured using the semiconductor package according to any one of 26) to 30).

  By using the curable resin composition of the present invention, it is possible to obtain a curable resin composition that gives a cured product having a low linear expansion coefficient. Therefore, a semiconductor that is integrally molded with a metal and that has a reduced warpage. Package and a semiconductor manufactured using the same package.

Hereinafter, the present invention will be described in detail.
The curable resin composition of the present invention is a curable resin composition containing (A) a thermosetting resin, (B) a curing catalyst, (C) a fluororesin, and (D) an inorganic filler as essential components. .
Hereinafter, each component will be described.

((A) component)
As the thermosetting resin of component (A), those used in the field of surface mount light emitting devices can be used without any particular limitation. For example, epoxy-based thermosetting resins such as epoxy resins and modified epoxy resins, silicone resins And silicone-based thermosetting resins such as modified silicone resins, acrylate resins, and polyurethanes. These thermosetting resins can be used alone or in combination of two or more. Among these thermosetting resins, epoxy-based thermosetting resins and silicone-based thermosetting resins are widely used and are preferable.
Here, the modified epoxy resin is a resin obtained by reacting an epoxy resin with a special modifier, and the modified silicone resin is an organopolysiloxane containing an organic group other than a hydrocarbon group.

  The epoxy-based thermosetting resin described above represents a group of compounds having an epoxy group as a reactive group. For example, bisphenol A type epoxy resin: bisphenol F type epoxy resin: brominated epoxy resin such as glycidyl ether of tetrabromobisphenol A: novolac type epoxy resin: glycidyl ether type epoxy resin such as glycidyl ether of bisphenol A propylene oxide adduct: Glycidyl ester type epoxy resins such as reaction product of aromatic carboxylic acid and epichlorohydrin, reaction product of hydrogenated aromatic carboxylic acid and epichlorohydrin: N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine Glycidylamine type epoxy resin such as: Urethane-modified epoxy resin: Aliphatic epoxy resin such as hydrogenated bisphenol A type epoxy resin: Triglycidyl isocyanurate: Polyalkylene glycol diglycid Examples include glycidyl ethers of polyhydric alcohols such as ethers and glycerin triglycidyl ethers: hydantoin type epoxy resins: epoxidized products of unsaturated polymers such as petroleum resins, but are not limited thereto, and are generally known Any epoxy resin can be used.

Examples of the silicone-based thermosetting resin include a condensation-type silicone-based thermosetting resin that is cured by a condensation reaction of an alkoxy group or a silanol group, or an addition-type silicone that is cured by an addition reaction with a SiH group for a double bond. System thermosetting resin and the like. Among these, it is preferable to use an addition-type silicone-based thermosetting resin from the viewpoint that the generation amount of volatile components of water and alcohol is small at the time of curing.
Among the above thermosetting resins, as the component (A), a silicone-based thermosetting resin is more preferable from the viewpoint of the heat resistance of the resin. From the balance between heat resistance and toughness, the silicone-based thermosetting resin comprises (A-1) an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups and (A- 2) More preferably, it is composed of a compound containing at least two SiH groups in one molecule.

((A-1) component)
The component (A-1) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule.

  The organic compound (A-1) can be classified into an organic polymer compound and an organic monomer compound.

  Examples of the (A-1) component of the organic polymer system include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol -What has formaldehyde type | system | group (phenol resin type | system | group) and a polyimide-type frame | skeleton can be mentioned.

  Examples of the organic monomer (A-1) component include, for example, aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as linear and alicyclics: heterocyclics And a mixture thereof.

(Specific examples of component (A-1))
Specific examples of the component (A) of the organic polymer system include 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), novolak phenol Allyl ether, allylated polyphenylene oxide,

(In the formula, R ¹ is H or CH ₃ , R ² , R ³ is a C 1 -C 6 divalent organic group containing no elements other than C, H, N, O, S and halogen as constituent elements, X and Y are divalent substituents having 0 to 10 carbon atoms, and n, m, and l are numbers 1 to 300.)

(Wherein R ¹ is H or CH ₃ , R ⁴ , R ⁵ is a divalent organic group having 1 to 6 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n, m, l represents a number from 1 to 300.)

(Wherein R ¹ is H or CH ₃ , R ⁶ , R ⁷ is a divalent organic group having 1 to 20 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n, m, l represents a number from 1 to 300.)

(Wherein R ¹ is H or CH ₃ , R ⁸ , R ⁹ is a divalent organic group having 1 to 6 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n, m, l represents a number from 1 to 300.)

Wherein R ¹ is H or CH ₃ , R ¹⁰ , R ¹¹ , R ¹² is a divalent organic group having 1 to 6 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n , M, l, and p each represent a number of 1 to 300).

  Specific examples of the organic monomer type (A-1) component include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2 , 2-tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably purity 80-100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof,

In addition, there may be mentioned those in which part or all of the glycidyl group of a conventionally known epoxy resin is replaced with an allyl group.

As the component (A-1), it is also possible to use low molecular weight compounds that are difficult to express by dividing into a skeleton portion and an alkenyl group as described above. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.
(A-1) A component can be used individually or in mixture of 2 or more types.

((A-2) component)
The component (A-2) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule. For example, it is a compound described in International Publication WO96 / 15194, and at least two in one molecule. Those having a SiH group can be used.

  Among these, from the viewpoint of availability, a chain and / or cyclic organopolysiloxane having at least two SiH groups in one molecule is preferable, and from the viewpoint of good compatibility with the component (A-1). Is the following general formula (VI)

(Wherein R ¹ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic organopolysiloxane having at least two SiH groups in one molecule. Is preferred.

The substituent R ¹ in the compound represented by the general formula (VI) is preferably composed of C, H and O, more preferably a hydrocarbon group, and a methyl group. Further preferred.

  From the viewpoint of availability, the compound represented by the general formula (VI) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane.

(Preferred structure of component (A-2))
From the viewpoint of having good compatibility with the component (A-1), and from the viewpoint that the problem of outgas from the curable resin composition that can reduce the volatility of the component (A-2) is difficult to occur (A -2) The component includes an organic compound (α) containing one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule and a compound having at least two SiH groups in one molecule ( β) is preferably a compound obtainable by a hydrosilylation reaction.

((Α) component)
Here, the component (α) is the same component (A1) as described above (α1), which is the same as the organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group. Can be used. When the component (α1) is used, the resulting cured product has a high crosslink density and tends to be a cured product having high mechanical strength.

  In addition, an organic compound (α2) containing one carbon-carbon double bond having reactivity with the SiH group in one molecule can also be used. When the (α2) component is used, the obtained cured product tends to have low elasticity.

((Α2) component)
The component (α2) is not particularly limited as long as it is an organic compound containing one carbon-carbon double bond having reactivity with the SiH group in one molecule.

  The bonding position of the carbon-carbon double bond having reactivity with the SiH group of the (α2) component is not particularly limited and may be present anywhere in the molecule.

  Specific examples of the component (α2) include propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-undecene, Idemitsu Petrochemical's linearene, 4,4-dimethyl-1-pentene, 2-methyl-1-hexene, 2,3,3-trimethyl-1-butene, 2,4,4-trimethyl-1-pentene, etc. Chain aliphatic hydrocarbon compounds such as cyclohexene, methylcyclohexene, methylenecyclohexane, norbornylene, ethylidenecyclohexane, vinylcyclohexane, camphene, carene, α-pinene, β-pinene and the like, Styrene, α-methylstyrene, indene, phenylacetylene, 4-ethynyltoluene, allylbenzene, 4- Aromatic hydrocarbon compounds such as phenyl-1-butene, allyl ethers such as alkyl allyl ether and allyl phenyl ether, glycerin monoallyl ether, ethylene glycol monoallyl ether, 4-vinyl-1,3-dioxolane- Substitution of aliphatic compounds such as 2-one, aromatic compounds such as 1,2-dimethoxy-4-allylbenzene, o-allylphenol, monoallyl dibenzyl isocyanurate, monoallyl diglycidyl isocyanurate, etc. Examples include isocyanurates, silicon compounds such as vinyltrimethylsilane, vinyltrimethoxysilane, and vinyltriphenylsilane. Furthermore, polyether resins such as one-end allylated polyethylene oxide and one-end allylated polypropylene oxide, hydrocarbon resins such as one-end allylated polyisobutylene, one-end allylated polybutyl acrylate, one-end allylated polymethyl methacrylate Examples thereof also include polymers or oligomers having a vinyl group at one end, such as acrylic resins.

  As the above (α1) component and / or (α2) component, a single component may be used, or a plurality of components may be used in combination.

((Β) component)
The component (β) is a compound having at least two SiH groups in one molecule, and chain and / or cyclic polyorganosiloxanes are also examples.
Specifically, for example

Is mentioned.
Here, from the viewpoint of easy compatibility with the component (α), the following general formula (VI)

(Wherein R ¹ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic polyorganosiloxane having at least three SiH groups in one molecule. Is preferred.

The substituent R ¹ in the compound represented by the general formula (VI) is preferably composed of C, H, and O, more preferably a hydrocarbon group, and a methyl group. Is more preferable.

  In view of availability, 1,3,5,7-tetramethylcyclotetrasiloxane is preferable.

  Other examples of the (β) component include compounds having a SiH group such as bisdimethylsilylbenzene.

  Various (β) components as described above can be used alone or in admixture of two or more.

  As an example of the (A-2) component which is a reaction product of the (α) component and the (β) component as described above, the reaction of bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane Product, reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, dicyclopentadiene and 1,3,3 Reaction product of 5,7-tetramethylcyclotetrasiloxane, reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5,7-tetra Reaction product of methylcyclotetrasiloxane, allyl glycidyl ether and 1,3,5,7-tetramethylcyclotetra A reaction product of siloxane, a reaction product of α-methylstyrene and 1,3,5,7-tetramethylcyclotetrasiloxane, a reaction product of monoallyldiglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, Examples include a reaction product of vinyl norbornene and bisdimethylsilylbenzene.

((B) component)
The component (B) is not particularly limited as long as the component (A) can be cured. A condensation catalyst can be used as a curing catalyst for the condensation-type silicone-based thermosetting resin, and a hydrosilylation catalyst can be used as a curing catalyst for the addition-type silicone-based thermosetting resin. Examples of the curing agent for the epoxy thermosetting resin include an acid anhydride curing agent, an isocyanuric acid derivative, and a phenol curing agent.

  Although it does not specifically limit as a condensation catalyst, A boron type compound or / and an aluminum type compound or / and a titanium type compound are preferable. Examples of the aluminum compound used as the silanol condensation catalyst include aluminum alkoxides such as aluminum triisopropoxide, sec-butoxyaluminum diisoflopoxide, aluminum trisec-butoxide, ethyl acetoacetate aluminum diisopropoxide, aluminum tris ( Ethyl acetoacetate), aluminum chelate M (manufactured by Kawaken Fine Chemicals, alkyl acetoacetate aluminum diisopropoxide), aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), etc. Aluminum chelates are more preferable from the viewpoint of handleability. Titanium compounds used as silanol condensation catalysts include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium: titanium chelates such as titanium tetraacetylacetonate: general residues having residues such as oxyacetic acid and ethylene glycol And titanate coupling agents.

The hydrosilylation catalyst is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. For example, a platinum simple substance, a support made of alumina, silica, carbon black or the like on which solid platinum is supported, chloroplatinic acid, platinum chloride Complexes of acids with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (eg Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ), platinum-vinyl Siloxane complexes (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complexes (for example, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phos Fight complexes _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me represents a methyl group, Bu a butyl group, Vi represents a vinyl group Ph represents a phenyl group, and n and m represent integers.), Dicarbonyldichloroplatinum, Karstedt catalyst, and also described in Ashby US Pat. Nos. 3,159,601 and 3,159,662. Platinum-hydrocarbon complexes, as well as platinum alcoholate catalysts described in Lamoreaux US Pat. No. 3,220,972. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. , Etc.

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

The addition amount of the hydrosilylation catalyst is not particularly limited. However, the lower limit of the addition amount is preferably a SiH group of the component (A-2) in order to have sufficient curability and keep the cost of the curable resin composition relatively low. ^{10 -8} mol relative to 1 mol, more preferably ^{10 -6} mole, preferable amount of the upper limit is ^{10 -1} moles per mole of the SiH group (beta) component, more preferably ^{10 -2} mol It is.

In addition, a cocatalyst can be used in combination with the hydrosilylation catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl, and the like. Examples include acetylene alcohol compounds such as -1-butyne, sulfur compounds such as simple sulfur, and amine compounds such as triethylamine. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

  The acid anhydride curing agent that is a curing agent for the epoxy thermosetting resin is not particularly limited, but for example, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, Examples include tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, and methyl tetrahydrophthalic anhydride.

  Examples of the isocyanuric acid derivatives include 1,3,5-tris (1-carboxymethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3- Carboxypropyl) isocyanurate, 1,3-bis (2-carboxyethyl) isocyanurate and the like.

  Examples of phenolic curing agents include phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenols and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene, and formaldehyde , Novolak-type phenol resins obtained by condensation or co-condensation with a compound having an aldehyde group such as benzaldehyde and salicylaldehyde under an acidic catalyst; phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl; Phenol-aralkyl resins synthesized from aralkyl-type phenol resins such as biphenylene-type phenol-aralkyl resins and naphthol-aralkyl resins; phenols and / or naphth Dicyclopentadiene-type phenolic resins such as dicyclopentadiene-type phenol novolak resins and dicyclopentadiene-type naphthol novolak resins synthesized by copolymerization of tolls and dicyclopentadiene; triphenylmethane-type phenol resins; terpene-modified phenols Examples include resins; paraxylylene and / or metaxylylene-modified phenol resins; melamine-modified phenol resins; cyclopentadiene-modified phenol resins; and phenol resins obtained by copolymerizing two or more of these.

((C) component)
The component (C) of the present invention is a fluororesin. By using the component (C), a curable resin composition that gives a cured product having a smaller linear expansion coefficient when mixed with the inorganic filler of the component (D) can be obtained.

  Further, the component (C) also has a function as a white pigment that reflects light from the light emitting element. For this reason, the effect of raising the reflection characteristics by adding this is also expected.

  Moreover, the compound of (C) component is a compound which does not contain a volatile component. Therefore, for example, when molding a compound on the lead frame, the volatile component bleeds on the surface of the lead frame, and the concern that the solder wettability of the portion deteriorates is eliminated.

  The component (C) is not particularly limited as long as it is a polymer having a fluorine atom in its molecule. For example, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer and the like can be mentioned. Among these, polytetrafluoroethylene is preferable in terms of availability and cost.

  The average particle size of the component (C) is preferably 0.5 μm or more and 500 μm or less, more preferably 0.5 μm or more and 300 μm or less, and further preferably 0.5 μm or more and 100 μm or less. When the particle size is in this range, the fluidity at the time of molding becomes better. The average particle diameter here means the median of the particle size distribution of the particles. The average particle diameter can be measured using a laser diffraction / scattering particle size distribution analyzer.

  As the amount of the component (C), the weight of the component (C) in the entire curable resin composition is preferably 1% by weight or more and 20% by weight, and more preferably 1% by weight or more and 10% by weight. . When the weight of the component (C) is 1% by weight or less, the effect of reducing the linear expansion coefficient by the component (C) may not be obtained. When the amount of the component (C) is 20% by weight or more, Liquidity may deteriorate.

((D) component)
Component (D) is an inorganic filler. (D) component has the effect of making the intensity | strength and hardness of the hardened | cured material obtained high, or reducing a linear expansion coefficient.

  As the inorganic filler of the component (D), various types are used. For example, silica-based materials such as quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine powder amorphous silica. Inorganic filler, alumina, zircon, silicon nitride, aluminum nitride, silicon carbide, glass fiber, alumina fiber, carbon fiber, mica, graphite, carbon black, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate Inorganic fillers such as calcium silicate, inorganic balloons, silver powder, etc., and inorganic fillers that are generally used and / or proposed as fillers for conventional sealing materials such as epoxy-based materials can be used. The inorganic filler is preferably low radiation from the viewpoint of hardly damaging the semiconductor element.

  The inorganic filler may be appropriately surface treated. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a coupling agent, and the like.

  Examples of the coupling agent in this case include a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes which can be exemplified.

  In addition, the method of adding an inorganic filler is mentioned. For example, a hydrolyzable silane monomer or oligomer such as alkoxysilane, acyloxysilane or halogenated silane, or an alkoxide, acyloxide or halide of a metal such as titanium or aluminum is added to the curable resin composition of the present invention. A method of reacting in a curable resin composition or a partial reaction product of the curable resin composition to produce an inorganic filler in the curable resin composition can also be mentioned.

  Of the inorganic fillers as described above, a silica-based inorganic filler is preferable from the viewpoint that it is difficult to inhibit the curing reaction, has a large effect of reducing the linear expansion coefficient, and tends to have high adhesion to the lead frame. Furthermore, fused silica is preferable in terms of a good balance of physical properties such as moldability and electrical characteristics, and crystalline silica is preferable in terms of easy package thermal conductivity and high heat dissipation. Alumina is preferable in that heat dissipation tends to be higher.

  As the average particle size and particle size distribution of the inorganic filler, various types are used without particular limitation, including those used or / and proposed as fillers for conventional sealing materials such as epoxy type, The lower limit of the average particle size usually used is 0.1 μm, preferably 0.5 μm from the viewpoint that the fluidity tends to be good, and the upper limit of the average particle size usually used is 120 μm, the fluidity tends to be good. From the viewpoint, it is preferably 60 μm, more preferably 15 μm.

  The specific surface area of the inorganic filler can also be set in various ways including those used and / or proposed as fillers for conventional sealing materials such as epoxy.

  As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape are used. Various aspect ratios are used. The aspect ratio of 10 or more is preferable in that the strength of the obtained cured product tends to increase. From the viewpoint of isotropic shrinkage of the resin, a powder form is preferable to a fiber form. Or the spherical thing is preferable at the point that the fluidity | liquidity at the time of shaping | molding becomes easy also at the time of high filling.

  These inorganic fillers may be used alone or in combination of two or more.

  The amount of the component (D) is not particularly limited, but the total amount of the component (D) in the entire curable resin composition is preferably 20% by weight to 95% by weight, and preferably 30% by weight to 95% by weight. More preferably, it is more preferably 40 wt% or more and 93 wt% or less. If the amount of the component (D) is less than 20% by weight, the effect of increasing the strength and hardness or reducing the linear expansion coefficient may be difficult to obtain. The liquidity of the time may deteriorate.

  As the order of mixing the inorganic filler of the component (D), various methods can be used. In the point that the storage stability of the intermediate raw material of the curable resin composition tends to be good, (A-1 The method of mixing the component (B) and the inorganic filler with the component (A) and the component (A-2) is preferred. When the method of mixing the component (A-1) with the component (B-2) and / or the inorganic filler mixed with the component (A-2) is used, in the presence and / or absence of the component (B) Since component (A-2) has reactivity with moisture and / or inorganic fillers in the environment, it may be altered during storage. In addition, (A-1) component, (A-1) component, (A-1) component, (A-2) component, (A-2) component, and (B) component are well mixed and stable molded product is easily obtained. -2) It is preferable to mix what mixed the component and (B) component, and an inorganic filler.

  As means for mixing the inorganic filler of component (D), various means conventionally used and / or proposed for epoxy resins and the like can be used. For example, a two-roll or three-roll, a planetary stirring and defoaming device, a stirrer such as a homogenizer, a dissolver and a planetary mixer, a melt kneader such as a plast mill, and the like can be mentioned. Of these, a triple roll and a melt kneader are preferred in that sufficient dispersibility of the inorganic filler is easily obtained even with high filling. The mixing of the inorganic filler may be performed at normal temperature or may be performed by heating. Moreover, you may carry out under a normal pressure and may carry out in a pressure-reduced state. In view of the fact that sufficient dispersibility of the inorganic filler can be easily obtained even at high filling, it is preferable to mix in a heated state, and it is easy to obtain sufficient dispersibility by improving the wettability of the inorganic filler surface. Therefore, it is preferable to mix in a reduced pressure state.

((E) component)
The curable resin composition of the present invention desirably contains a white pigment (component (E)).
(E) component of this invention is a white pigment, and has the effect of improving the light reflectivity of the hardened | cured material obtained.

  Various components can be used as the component (E), for example, titanium oxide, zinc oxide, magnesium oxide, antimony oxide, zirconia oxide, strontium oxide, niobium oxide, boron nitride, barium titanate, zinc sulfide, barium sulfate. , Magnesium carbonate, hollow glass particles, potassium titanate and the like. Among these, titanium oxide or zinc oxide is preferable from the viewpoint of ease of handling, availability, and cost.

  Various types of titanium oxide can be used as the component (E), and it may be anatase type or rutile type, but it has no photocatalytic action and the curable resin composition is likely to be stable. A rutile type is preferred.

  Although various things are used also as an average particle diameter of (E) component, it is 1.0 micrometer or less from a viewpoint that the light reflectivity of the hardened | cured material obtained becomes high easily, and a curable resin composition tablet becomes harder. Are preferred, those with 0.30 μm or less are more preferred, and those with 0.25 μm or less are most preferred.

  On the other hand, in terms of high fluidity of the curable resin composition, it is preferably 0.05 μm or more, and more preferably 0.1 μm or more.

  As the method for producing the component (E) titanium oxide, those produced by any method such as sulfuric acid method and chlorine method can be used.

  (E) component may be surface-treated. In the surface treatment of the component (E), the surface of the component (E) is coated with at least one selected from an inorganic compound and an organic compound. Examples of inorganic compounds include aluminum compounds, silicon compounds, zirconium compounds, tin compounds, titanium compounds, antimony compounds, and the like, and examples of organic compounds include polyhydric alcohols, alkanolamines or derivatives thereof, and organic siloxanes. Examples thereof include organosilicon compounds, higher fatty acids or metal salts thereof, and organometallic compounds.

  When the surface of the component (E) is coated with an inorganic compound or an organic compound, a known method such as a wet method or a dry method is used. It can be carried out. In addition, there are various methods such as a liquid phase method and a gas phase method.

Among these, the cured product obtained is preferably treated with an organic siloxane treatment because the light reflectance is high and the heat and light resistance is improved. In addition, the inclusion of an organosiloxane-treated titanium oxide is suitable for producing an excellent light-emitting diode that has high light extraction efficiency and does not decrease light extraction efficiency even when used for a long period of time.
In this case, various organic siloxane treating agents are used. For example, polysiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, or copolymers thereof, hexamethylcyclotrisiloxane, heptamethylcyclotetrasiloxane, 1,3,5,7-tetra Cyclosiloxanes such as methylcyclotetrasiloxane, chlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and other silanes having an epoxy functional group, 3-methacryloxypropyltrimethyl Xysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, Silanes having a methacrylic group or an acrylic group such as acryloxymethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, etc. Silanes, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane and other mercaptosilanes, γ-aminopropyltriethoxy Γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, Silanes having amino groups, such as N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, isocyanate Silanes having an isocyanate group such as propyltrimethoxysilane and isocyanatepropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxy Silane coupling agents exemplified by various silanes such as silanes having alkyl groups such as silane and octyltriethoxysilane, and other silanes such as γ-chloropropyltrimethoxysilane and γ-anilinopropyltrimethoxysilane And hexamethyldisiloxane and hexamethyldisilazane. These surface treatment agents preferably contain no carbon-carbon double bonds, and if they contain carbon-carbon double bonds, the heat resistance tends to decrease. Further, a surface treatment other than the organic siloxane can be used in combination, and treatment with Al, Zr, Zn, or the like can also be performed.

Moreover, it may be surface-treated with an inorganic compound.
The surface treatment with an inorganic compound is not particularly limited, and various surface treatments such as an aluminum compound, a silicon compound, and a zirconium compound are used. Titanium oxide may be surface-treated with an inorganic compound or an organic compound for the purpose of improving durability, improving affinity with the medium, or preventing the collapse of the particle shape. It is considered that the surface treatment with the compound improves the affinity with the component contained in the curable resin composition, improves the dispersibility of the component (E) with respect to the curable resin composition, and improves the strength of the cured product. .

  Various methods can be applied as the surface treatment method, and various methods such as a wet method, a dry method, a liquid phase method, and a gas phase method can be exemplified.

  The amount of the component (E) is not particularly limited, but the amount of the component (F) in the entire curable resin composition is preferably 10% by weight to 60% by weight, and more preferably 15% by weight to 55%. It is more preferable that it is 20 wt% or more and 50 wt% or less. If it is less than 10% by weight, the light reflectance of the resulting cured product may be lowered, and if it is more than 60% by weight, the fluidity during molding may be insufficient.

((D) component and (E) component)
The total amount of component (D) and component (E) is not particularly limited, but the total amount of component (D) and component (E) in the entire curable resin composition is 40% by weight or more and 95% by weight or less. It is preferably 60% by weight or more and 95% by weight or less, and more preferably 80% by weight or more and 93% by weight or less.

  When the total amount of the component (D) and the component (E) is small, it is difficult to obtain the effect of increasing the strength and hardness or reducing the linear expansion coefficient, and when the total amount is large, Liquidity may deteriorate.

  (E) Although various methods can be taken as the order of mixing the components, the preferred embodiment is the same as (D) already described. Moreover, you may add (E) component and (D) component simultaneously.

  As the means for mixing the component (E), the same means as the means for mixing the component (D) can be used.

((F) component)
The curable resin composition of the present invention preferably contains a metal soap (component (F)).
(F) A component is added in order to improve the moldability including the mold release property of curable resin composition.

  Examples of the component (F) include various metal soaps conventionally used. The metal soap here is generally a combination of long-chain fatty acids and metal ions. The nonpolar or low polarity part based on fatty acids and the polar part based on the metal binding part are combined in one molecule. Can be used. Examples of the long chain fatty acid include saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, and aliphatic dicarboxylic acids. Among these, saturated fatty acids having 1 to 18 carbon atoms are preferable from the viewpoint of easy availability and high industrial feasibility, and 6 to 18 carbon atoms from the viewpoint of high effect of releasability. The saturated fatty acid is more preferable. Examples of metal ions include zinc, cobalt, aluminum, strontium, and the like in addition to alkali metals and alkaline earth metals. Specific examples of metal soaps include lithium stearate, lithium 12-hydroxystearate, lithium laurate, lithium oleate, lithium 2-ethylhexanoate, sodium stearate, sodium 12-hydroxystearate, lauric acid Sodium, sodium oleate, sodium 2-ethylhexanoate, potassium stearate, potassium 12-hydroxystearate, potassium laurate, potassium oleate, potassium 2-ethylhexanoate, magnesium stearate, magnesium 12-hydroxystearate, Magnesium laurate, magnesium oleate, magnesium 2-ethylhexanoate, calcium stearate, calcium 12-hydroxystearate, calcium laurate , Calcium oleate, calcium 2-ethylhexanoate, barium stearate, barium 12-hydroxystearate, barium laurate, zinc stearate, zinc 12-hydroxystearate, zinc laurate, zinc oleate, 2-ethylhexane Examples include zinc acid, lead stearate, lead 12-hydroxystearate, cobalt stearate, aluminum stearate, manganese oleate, barium ricinoleate, and the like. Among these metal soaps, metal stearates are preferred from the viewpoint of easy availability, safety and industrial feasibility, and calcium stearate, magnesium stearate, stearin are particularly preferred from the viewpoint of economy. Most preferred is one or more selected from the group consisting of zinc acid.

  Although there is no restriction | limiting in particular as addition amount of this metal soap, The minimum of a preferable amount is 0.01 weight part with respect to 100 weight part of the whole curable resin composition, More preferably, it is 0.025 weight part, More preferably, it is 0. The upper limit of the preferable amount is 5 parts by weight, more preferably 4 parts by weight with respect to 100 parts by weight of the entire curable resin composition. When the addition amount is too large, the physical properties of the cured product are deteriorated. When the addition amount is too small, mold releasability may not be obtained.

(Additive)
Various additives can be added to the curable resin composition of the present invention.

(Curing retarder)
A curing retarder can be used for the purpose of improving the storage stability of the curable resin composition of the present invention or adjusting the reactivity of the hydrosilylation reaction during the production process. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne and 1-ethynyl-1-cyclohexanol. And maleate esters such as ene-yne compounds and dimethyl malate. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Among these curing retarders, from the viewpoint of good retarding activity and good raw material availability, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1- Cyclohexanol is preferred.

The addition amount of the curing retarder can be selected at various levels, the preferred amount of the lower limit is 10 ^-1 moles with respect to hydrosilylation catalyst 1mol used, more preferably 1 mol, the upper limit of the preferable amount is 10 ³ mol, more preferably Is 50 moles.

  Moreover, these hardening retarders may be used independently and may be used together 2 or more types.

(Adhesion improver)
An adhesion improver can also be added to the curable resin composition of the present invention. In addition to commonly used adhesives as adhesion improvers, for example, various coupling agents, epoxy compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene-vinyltoluene A copolymer, polyethylmethylstyrene, aromatic polyisocyanate, etc. can be mentioned.

Examples of coupling agents include silane coupling agents and titanate coupling agents.
Examples and preferred examples of the coupling agent are the same as those described above.

  The addition amount of the coupling agent can be variously set, but the lower limit of the preferable addition amount relative to 100 parts by weight of [(A) component + (B) component] is 0.1 parts by weight, more preferably 0.5 parts by weight. The upper limit of the preferable addition amount is 50 parts by weight, more preferably 25 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  Examples of the epoxy compound include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl). Propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl cyclohexylene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl iso Cyanurate, mention may be made of diallyl monoglycidyl isocyanurate and the like.

  Although the addition amount of the epoxy compound can be variously set, the lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is preferably 1 part by weight, more preferably 3 parts by weight. The upper limit of the addition amount is 50 parts by weight, more preferably 25 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  These coupling agents, silane coupling agents, epoxy compounds, etc. may be used alone or in combination of two or more.

  In the present invention, a silanol condensation catalyst can be further used to enhance the effect of the coupling agent or the epoxy compound, and the adhesion can be improved and / or stabilized. Such a silanol condensation catalyst is not particularly limited, but is preferably a boron compound or / and an aluminum compound or / and a titanium compound. Examples of the aluminum compound used as the silanol condensation catalyst include aluminum alkoxides such as aluminum triisopropoxide, sec-butoxyaluminum diisoflopoxide, aluminum trisec-butoxide, ethyl acetoacetate aluminum diisopropoxide, aluminum tris ( Ethyl acetoacetate), aluminum chelate M (manufactured by Kawaken Fine Chemicals, alkyl acetoacetate aluminum diisopropoxide), aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), etc. Aluminum chelates are more preferable from the viewpoint of handleability. Titanium compounds used as silanol condensation catalysts include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium: titanium chelates such as titanium tetraacetylacetonate: general residues having residues such as oxyacetic acid and ethylene glycol And titanate coupling agents.

  Examples of the boron compound that serves as a silanol condensation catalyst include boric acid esters. As the borate ester, those represented by the following general formulas (VII) and (VIII) can be preferably used.

(In the formula, R ¹ represents an organic group having 1 to 48 carbon atoms.)
Specific examples of boric acid esters include tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, trinormal butyl borate, tri-sec-butyl borate, Tri-tert-butyl borate, triisopropyl borate, trinormalpropyl borate, triallyl borate, triethyl borate, trimethyl borate, and boron methoxyethoxide can be preferably used.

  These borate esters may be used alone or in combination of two or more. Mixing may be performed in advance or may be performed at the time of producing a cured product.

  Of these borate esters, trimethyl borate, triethyl borate, and trinormal butyl borate are preferable, and trimethyl borate is more preferable among them because it is easily available and has high industrial practicality.

  From the point that the volatility at the time of curing can be suppressed, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, trinormal butyl borate, tri-sec-butyl borate, boric acid Tri-tert-butyl, triisopropyl borate, tripropylpropyl borate, triallyl borate, and boron methoxyethoxide are preferred. Among these, normal trioctadecyl borate, tri-tert-butyl borate, triphenyl borate, and tributyl normal borate are more preferred. preferable.

  From the viewpoint of suppression of volatility and good workability, trinormal butyl borate, triisopropyl borate and trinormal propyl borate are preferable, and trinormal butyl borate is more preferable.

  From the viewpoint of low colorability at high temperatures, trimethyl borate and triethyl borate are preferred, and trimethyl borate is more preferred.

  The amount used in the case of using a silanol condensation catalyst can be variously set, but the lower limit of the preferred addition amount with respect to 100 parts by weight of the coupling agent and / or epoxy compound epoxy compound is 0.1 parts by weight, more preferably 1 part by weight. The upper limit of the preferable addition amount is 50 parts by weight, more preferably 30 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  These silanol condensation catalysts may be used alone or in combination of two or more.

  In the present invention, a silanol source compound can be further used in order to further enhance the effect of improving adhesiveness, and the adhesiveness can be improved and / or stabilized. Examples of such a silanol source include silanol compounds such as triphenylsilanol and diphenyldihydroxysilane, and alkoxysilanes such as diphenyldimethoxysilane, tetramethoxysilane, and methyltrimethoxysilane.

  The amount used in the case of using a silanol source compound can be variously set, but the lower limit of the preferable addition amount with respect to 100 parts by weight of the coupling agent and / or epoxy compound is 0.1 parts by weight, more preferably 1 part by weight. The upper limit of the preferable addition amount is 50 parts by weight, more preferably 30 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  Moreover, these silanol source compounds may be used independently and may be used together 2 or more types.

  In the present invention, carboxylic acids and / or acid anhydrides can be used to enhance the effect of the coupling agent or epoxy compound, and adhesion can be improved and / or stabilized. Such carboxylic acids and acid anhydrides are not particularly limited,

2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylheimic acid, norbornene dicarboxylic acid, hydrogenated methylnadic acid, maleic acid, acetylenedicarboxylic acid , Lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenecarboxylic acid, naphthalenedicarboxylic acid, and single or complex acid anhydrides thereof Can be mentioned.

Of these carboxylic acids and / or acid anhydrides, they react with SiH groups in that they have hydrosilylation reactivity and are unlikely to impair the physical properties of the resulting cured product with little possibility of seepage from the cured product. What contains the carbon-carbon double bond which has property is preferable. Preferred carboxylic acids and / or acid anhydrides include, for example,

, Tetrahydrophthalic acid, methyltetrahydrophthalic acid, and single or complex acid anhydrides thereof.

  The amount used in the case of using carboxylic acids or / and acid anhydrides can be variously set, but the lower limit of the preferred addition amount with respect to 100 parts by weight of the coupling agent or / and epoxy compound epoxy compound is 0.1 parts by weight, More preferably, it is 1 part by weight, and the upper limit of the preferable addition amount is 50 parts by weight, more preferably 10 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  Moreover, these carboxylic acids or / and acid anhydrides may be used alone or in combination of two or more.

  The silane compound described above can be used in the curable resin composition of the present invention. The silane compound contributes to improvement in adhesion to the lead and is effective in preventing moisture from entering from the interface between the package and the lead. Illustrative examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, and the like, with dimethyldimethoxysilane being particularly preferred.

(Hardened product of curable resin composition)
A curable resin composition obtained by curing a resin may be pulverized and mixed in a particle state. When the curable resin is dispersed and used, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. The particle system may be distributed, and may be monodispersed or have a plurality of peak particle diameters. However, from the viewpoint that the viscosity of the curable resin composition is low and the moldability tends to be good. The diameter variation coefficient is preferably 10% or less.

(Thermoplastic resin)
Various thermoplastic resins can be added to the curable resin composition of the present invention for the purpose of modifying the properties. Various thermoplastic resins can be used. For example, a homopolymer of methyl methacrylate or a polymethyl methacrylate resin such as a random, block or graft polymer of methyl methacrylate and other monomers (for example, Hitachi Chemical) Optretz, etc.), acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3, A polycarbonate resin such as a polycarbonate resin containing 3,5-trimethylcyclohexylidenebisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), a norbornene derivative, a vinyl monomer, or the like is copolymerized alone or copolymerized. Cycloolefin resins such as fat, norbornene derivative ring-opening metathesis polymer, or hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), ethylene and Olefin-maleimide resins such as maleimide copolymers (eg TI-PAS manufactured by Tosoh Corporation), bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene, and diols such as diethylene glycol Polyester resins such as polyester obtained by polycondensation of phthalic acids and aliphatic dicarboxylic acids such as terephthalic acid and isophthalic acid (eg O-PET manufactured by Kanebo Co., Ltd.), polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, Polyethylene resin Polypropylene resins, polystyrene resins, polyamide resins, silicone resins, other like fluorine resin, not natural rubber, but the rubber-like resin is exemplified such EPDM is not limited thereto.

  As a thermoplastic resin, you may have the carbon-carbon double bond or / and SiH group which have a reactivity with SiH group in a molecule | numerator. In the point that the obtained cured product tends to be tougher, the molecule has one or more carbon-carbon double bonds or / and SiH groups having reactivity with SiH groups in the molecule on average. It is preferable.

  The thermoplastic resin may have other crosslinkable groups. Examples of the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the obtained cured product tends to be high, it is preferable to have one or more crosslinkable groups in one molecule on average.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10,000 or less, and preferably 5,000 or less in terms of easy compatibility with the component (A). More preferred. On the contrary, the number average molecular weight is preferably 10,000 or more, and more preferably 100,000 or more in that the obtained cured product tends to be tough. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, in that the viscosity of the mixture tends to be low and the moldability tends to be good. More preferably, it is as follows.

  The blending amount of the thermoplastic resin is not particularly limited, but the lower limit of the preferable amount used is 5% by weight of the entire curable resin composition, more preferably 10% by weight, and the upper limit of the preferable amount used is the curable resin composition. 50% by weight in the product, more preferably 30% by weight. When the addition amount is small, the obtained cured product tends to be brittle, and when it is large, the heat resistance (elastic modulus at high temperature) tends to be low.

  A single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.

  The thermoplastic resin may be dissolved in the component (A) and mixed in a uniform state, pulverized and mixed in a particle state, or dissolved in a solvent and mixed to be in a dispersed state. In the point that the hardened | cured material obtained becomes easy to become more transparent, it is preferable to melt | dissolve in (A) component and mix as a uniform state. Also in this case, the thermoplastic resin may be directly dissolved in the component (A), or may be uniformly mixed using a solvent or the like, and then the solvent is removed to obtain a uniform dispersed state or / and mixed state. Also good.

  When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. The particle system may be distributed, and may be monodispersed or have a plurality of peak particle diameters. However, from the viewpoint that the viscosity of the curable resin composition is low and the moldability tends to be good. The diameter variation coefficient is preferably 10% or less.

(Anti-aging agent)
An aging inhibitor may be added to the curable resin composition of the present invention. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type.

  As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.

Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.
Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

(Radical inhibitor)
A radical inhibitor may be added to the curable resin composition of the present invention. Examples of radical inhibitors include 2,6-di-tert-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like.

Moreover, these radical inhibitors may be used alone or in combination of two or more.

(UV absorber)
An ultraviolet absorber may be added to the curable resin composition of the present invention. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned.
Moreover, these ultraviolet absorbers may be used independently and may be used together 2 or more types.

(solvent)
The curable resin composition of the present invention can be used by dissolving in a solvent. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. An ether solvent, a ketone solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and a halogen solvent such as chloroform, methylene chloride, and 1,2-dichloroethane can be preferably used.
As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable.

Although the amount of solvent to be used can be set as appropriate, the lower limit of the preferable usage amount relative to 1 g of the curable resin composition to be used is 0.1 mL, and the upper limit of the preferable usage amount is 10 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a low viscosity, and if the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also from a cost standpoint. It is disadvantageous and the industrial utility value decreases.
These solvents may be used alone or as a mixed solvent of two or more.

(Additive for light emitting diode)
Furthermore, you may add the additive for various light emitting diode characteristic improvement to the curable resin composition of this invention as needed. Examples of additives include phosphors such as yttrium, aluminum, and garnet phosphors activated with cerium that absorb light from the light emitting element to emit longer wavelength fluorescence, and blue that absorbs a specific wavelength. Coloring agents such as ing agents, diffusion materials such as titanium oxide, aluminum oxide, melamine resin, CTU guanamine resin, benzoguanamine resin for diffusing light, metal oxides such as aluminosilicate, aluminum nitride, boron nitride, etc. Examples thereof include thermally conductive fillers such as metal nitrides.
The additive for improving the characteristics of the light emitting diode may be contained uniformly, or the content may be added with a gradient.

(Release agent)
Various releasing agents may be added to the curable resin composition of the present invention in order to improve the releasing property at the time of molding. Examples of the release agent include the component (F) already described and waxes.
Examples of waxes include natural wax, synthetic wax, oxidized or non-oxidized polyolefin, and polyethylene wax. In addition, it is better not to use a release agent when sufficient release properties can be obtained without adding a release agent.

(Other additives)
In addition, the curable resin composition of the present invention includes a colorant, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, an anti-fogging agent, an ion trapping agent such as antimony-bismuth, Thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity enhancer, Antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, thermal conductivity-imparting agents, physical property modifiers, and the like that do not impair the purpose and effect of the present invention Can be added.

(B stage)
The curable resin composition of the present invention may be used as it is by blending each component and additives, or may be used after being partially reacted (B-staged) by heating or the like. Viscosity can be adjusted by using B-stage, and transfer moldability can also be adjusted. In addition, there is an effect of further suppressing curing shrinkage.

(Curable resin composition properties)
As described above, various combinations can be used as the curable resin composition of the present invention. However, the curable resin composition has a temperature of 150 ° C. or less in terms of good moldability by transfer molding or the like. And those having fluidity are preferred.

  The curability of the curable resin composition can be arbitrarily set, but the gelation time at 120 ° C. is preferably within 120 seconds, more preferably within 60 seconds in that the molding cycle can be shortened. preferable. Further, the gelation time at 150 ° C. is preferably within 60 seconds, and more preferably within 30 seconds. Further, the gelation time at 100 ° C. is preferably within 180 seconds, and more preferably within 120 seconds.

  The gelation time in this case is examined as follows. An aluminum foil having a thickness of 50 μm is placed on a hot plate adjusted to a set temperature, and 100 mg of the curable resin composition is placed thereon, and the time until gelation is measured is defined as the gelation time.

  In the manufacturing process in which the curable resin composition is used, the weight during the curing is from the viewpoint that the generation of voids in the curable resin composition and the process problems due to the outgas from the curable resin composition hardly occur. The decrease is preferably 5% by weight or less, more preferably 3% by weight or less, and further preferably 1% or less.

The weight loss during curing is examined as follows. Using a thermogravimetric analyzer, 10 mg of the sealant is heated from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, and can be determined as a ratio of the initial weight of the reduced weight.
In addition, when used as an electronic material or the like, it is preferable that the content of Si atoms in the volatile component in this case is 1% or less in that the problem of silicone contamination hardly occurs.

(Curing property)
From the viewpoint of good heat resistance, the cured product obtained by curing the curable resin composition preferably has a Tg of 100 ° C. or higher, more preferably 150 ° C. or higher.
In this case, Tg is examined as follows. Dynamic viscoelasticity measurement using a 3 mm x 5 mm x 30 mm prismatic test piece under the conditions of tensile mode, measurement frequency 10 Hz, strain 0.1%, static / power ratio 1.5, temperature rising side 5 ° C / min ( Let Tg be the peak temperature of tan δ of DVA-200 manufactured by IT Measurement & Control Co.).

  In addition, in terms of high reliability and less likely to cause problems such as ion migration in the lead frame and the like, the content of ions extracted from the cured product is preferably less than 10 ppm, more preferably less than 5 ppm, More preferably, it is less than 1 ppm.

  In this case, the extracted ion content is examined as follows. 1 g of the cut cured product is put in a Teflon (registered trademark) container together with 50 ml of ultrapure water, sealed, and treated under conditions of 121 ° C., 2 atm and 20 hours. The obtained extract was analyzed by ICP mass spectrometry (using HP-4500 manufactured by Yokogawa Analytical Systems), and the obtained Na and K content values were converted to the concentration in the cured product used. Ask. On the other hand, the same extract was analyzed by ion chromatography (using Dionex DX-500, column: AS12-SC), and the resulting Cl and Br content values were converted to the concentration in the cured product used. Ask. The contents of Na, K, Cl, and Br obtained as described above in the cured product are totaled to obtain the extracted ion content.

Moreover, as a molded body obtained by curing the curable resin composition of the present invention, the light reflectance at a surface wavelength of 470 nm is preferably 90% or more, more preferably 95% or more, 97 % Or more is more preferable, and 99% or more is particularly preferable.
The light reflectance of the surface can be measured as follows.
Using a PET film as a release film, a 0.5 mm-thick molded body without voids is prepared by press molding under a predetermined temperature condition. The obtained molded body is subjected to predetermined post-curing as necessary. It can obtain | require by measuring the total reflection of 470 nm using the spectrophotometer which installed the integrating sphere about the obtained molded object.

(Curable resin composition tablet)
When the curable resin composition of the present invention contains at least the component (E) in addition to the components (A) to (D), the curable resin composition tablet can be formed.
Specifically, the curable resin composition tablet is a powder in which at least one of the component (A) is a liquid having a viscosity of 50 Pa seconds or less at 23 ° C., and the component (B) for curing the component (A). (D) component and (E) component which are these, Furthermore, (C) component is contained, It is characterized by the above-mentioned.

  In this curable resin composition tablet, the viscosity of the component (A) decreases at a high temperature so that the entire curable resin composition can flow, and further, when the heating is continued, the curing reaction proceeds to be molded into a desired shape. Is possible.

The molding method is not particularly limited, and a molding method such as transfer molding or compression molding, which is generally used for molding a curable resin composition, can be used. When using these molding methods, if the curable resin composition as a raw material is in the form of a paste or clay, it cannot maintain a constant shape and is attached, integrated, or deformed. Supply to the molding machine becomes very difficult. On the other hand, the tablet shape makes it easy to measure, transport, and supply to a molding machine, and can be automated, greatly improving productivity. As used herein, a tablet means a solid that retains a constant shape at room temperature, has substantially no change in shape over time, and does not stick together or become integrated when brought into contact with each other. .
The shape of the tablet of the present invention is not particularly limited, and includes a columnar shape, a prismatic shape, a disk shape, a spherical shape, and the like, and a general columnar shape for transfer molding is preferable.

(Semiconductor package)
The semiconductor package referred to in the present invention is a member provided for supporting and / or protecting a semiconductor element or / and an external extraction electrode. The semiconductor element may not be directly covered but may be one that supports and fixes an external extraction electrode or the like, or that forms the periphery or bottom surface of a semiconductor element such as a light emitting diode reflector.
In this case, various types of semiconductor elements can be mentioned. For example, an integrated circuit such as an IC or LSI, an element such as a transistor, a diode, or a light emitting diode, or a light receiving element such as a CCD can be used.

  Although the shape is not specified, the effect of the present invention is particularly easily obtained when the semiconductor package has a shape in which a resin is substantially molded on one side of a metal (MAP type).

  In addition, in the case where the semiconductor package of the present invention does not directly cover the semiconductor element as described above, it can be further sealed with a sealing agent, for example, a conventionally used epoxy resin, silicone resin, A sealing resin such as an acrylic resin, a urea resin, or an imide resin can be used. Further, aliphatic organic compounds having at least two carbon-carbon double bonds having reactivity with SiH groups as proposed in JP-A Nos. 2002-80733 and 2002-88244, A sealant made of a curable resin composition containing a compound having at least two SiH groups in the molecule and a hydrosilylation catalyst may be used. Adhesion with the package resin is better when this sealant is used. It is preferable in that it is highly effective and the effect of high transparency and high light resistance of the package of the present invention is remarkable. On the other hand, it is possible to cover with glass or the like and seal with hermetic sealing without using resin sealing.

  Further, in the case of a light emitting diode or a light receiving element, a lens can be further applied, and a sealing agent can be molded into a lens shape to have a lens function.

(Molding method)
Various methods are used as a method for forming a semiconductor package in the present invention. For example, various molding methods generally used for thermosetting resins such as thermoplastic resins, epoxy resins, and silicone resins, such as injection molding, transfer molding, RIM molding, casting molding, press molding, compression molding, and the like are used. Of these, transfer molding is preferred in that the molding cycle is short and the moldability is good. The molding conditions can be arbitrarily set, for example, the molding temperature is also arbitrary. However, in terms of fast curing and a short molding cycle, the moldability tends to be good, more preferably 100 ° C. or higher, more preferably 120 ° C. or higher. A temperature of 150 ° C. or higher is preferable. After molding by the various methods as described above, post-curing (after-curing) is optional as required. Post-curing tends to increase the heat resistance.

  Molding may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. It is preferable to carry out the reaction while raising the temperature in a multistage manner or continuously, as compared with the case where the temperature is constant, in that a uniform cured product without distortion can be easily obtained. Moreover, it is preferable to perform at a constant temperature in that the molding cycle can be shortened.

  Although various curing times can be set, it is preferable to react at a relatively low temperature for a long time rather than reacting at a high temperature for a short time because a uniform cured product without distortion can be easily obtained. Conversely, the reaction at a high temperature in a short time is preferable in that the molding cycle can be shortened.

  The pressure at the time of molding can be variously set as required, and the molding can be performed at normal pressure, high pressure, or reduced pressure. It is preferable to cure under reduced pressure in terms of suppressing the generation of voids, improving the filling property, and easily removing volatile components generated in some cases. In terms of preventing cracks in the molded body, it is preferable to cure under pressure.

(Application of light emitting diode)
The semiconductor of the present invention can be used for various known applications. Specific examples include LSIs such as logic and memory, various sensors, light emitting and receiving devices, and the like. Also, when the semiconductor is a light emitting diode, it can be used for various known applications. Specifically, for example, backlights such as liquid crystal display devices, illumination, sensor light sources, vehicle instrument light sources, signal lights, display lights, display devices, planar light source, display, decoration, various lights, etc. it can.

(warp)
The curable resin composition of the present invention desirably has a package warpage of ± 1.0 mm or less when formed into a package by molding on one side of a lead frame for a light emitting diode.
The warpage in this case is measured based on the maximum warpage measuring method described in JIS C 6481. A semiconductor package is suspended vertically at the center of one side, and a straight ruler is applied parallel to that side. The straight ruler is applied to the concave surface of the semiconductor package, and the maximum distance between the straight ruler and the base surface of the semiconductor package is measured to a unit of 1.0 mm with a metal straight scale. When the resin is molded on the concave surface of the semiconductor package, measure the maximum distance between the straight ruler and the resin surface molded on the semiconductor package to a unit of 1.0 mm with a metal linear scale. The value obtained by subtracting the thickness is rounded to the nearest 1.0 mm. The other sides are also measured sequentially, and the greatest gap is warped.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

(Synthesis Example 1)
A stirrer, a dropping funnel and a condenser were set in a 5 L four-necked flask. To this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and heated and stirred in an oil bath at 120 ° C. To this, a mixed solution of 200 g of triallyl isocyanurate, 200 g of toluene and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours, and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. The obtained compound has a structure shown below in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with triallyl isocyanurate by 1H-NMR measurement. I understood.

(Synthesis Example 2)
720 g of toluene and 240 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 2 L autoclave, the gas phase was replaced with nitrogen, and then heated and stirred at a jacket temperature of 50 ° C. To this, a mixed solution of 171 g of allyl glycidyl ether, 171 g of toluene and 0.049 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped over 90 minutes. After completion of the dropping, the jacket temperature was raised to 60 ° C. and the reaction was further continued for 40 minutes, and it was confirmed by ¹ H-NMR that the allyl group reaction rate was 95% or more.

To the resulting reaction mixture, a mixture of 17 g of triallyl isocyanurate and 17 g of toluene was added dropwise, the jacket temperature was raised to 105 ° C., and 66 g of triallyl isocyanurate, 66 g of toluene and a xylene solution of platinum vinylsiloxane complex ( 0.033 g of a mixed solution was added dropwise over 30 minutes. Four hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling.

The unreacted rate of 1,3,5,7-tetramethylcyclotetrasiloxane was 0.8%. The total amount of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, toluene, and allyl glycidyl ether by-products (inner transition products of allylic glycidyl ether vinyl group (cis isomer and trans isomer)) total 5,000 ppm or less The solution was distilled off under reduced pressure until a colorless and transparent liquid was obtained. ^{According to 1} H-NMR measurement, this is a product in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with allyl glycidyl ether and triallyl isocyanurate. It was found to have the structure shown. In the following, a + b = 3, c + d = 3, e + f = 3, a + c + e = 3.5, and b + d + f = 5.5.

(Formulation example)
Each component was mix | blended according to the content of Table 1, and composition A-C was adjusted.

(Examples 1-3, Comparative Examples 1-3)
In accordance with the blending ratio shown in Table 2, each component was blended, and the mixture of the obtained white curable resin composition was stretched with a round bar-shaped jig, then repeatedly folded and stretched again, and then uniformly Turned into. In the case of flakes or powders, they were crushed with a mortar and made uniform. Or it knead | mixed using the electric cutter roller (feed rate 1.3min / mm, Oshima Kogyo Co., Ltd. make, ER-440).

(Sample creation)
The curable resin composition of Table 2 was pressed under the condition of 170/5 minutes using a rectangular frame made of stainless steel (SUS304) having an internal dimension of 80 mm × 50 mm and a thickness of 2 mm, using a PET film as a release film. Molded. The produced rectangular plate-shaped press-molded body was post-cured in an oven at 180 ° C./1 hour to obtain a sample for evaluation.

(Measuring method of linear expansion coefficient)
The sample prepared above was cut into a size of 5 mm × 5 mm and measured at 25 ° C. to 200 ° C. using a Rigaku Thermoplus-TMA8510 in compression mode, 2 gf load, and a heating rate of 10 ° C./min. . From this data, the average value of the linear expansion coefficient at 30 ° C. to 50 ° C. was taken as the linear expansion coefficient.

  As shown in Table 2, it can be seen that a smaller linear expansion coefficient can be achieved by using the curable resin composition of the present invention. Therefore, it is possible to suppress warping of the obtained molded body when it is integrally formed with the substrate by transfer molding or the like.

Claims (30)

(A) thermosetting resin (B) curing catalyst or curing agent (C) fluorine-based resin (D) inorganic filler (E) containing white pigment as an essential component,
(A) a thermosetting resin-added type silicone-based thermosetting resin, (B) a curing catalyst of the hydrosilylation catalyst combination,
Or
(A) A curable resin composition for transfer molding, wherein the thermosetting resin is an epoxy thermosetting resin and (B) the curing agent is a combination of an acid anhydride curing agent. The transfer molding according to claim 1, wherein (C) the fluororesin comprises any one of polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-ethylene copolymer. Curable resin composition. In (A) thermosetting resin-added type silicone-based thermosetting resin, (B) a transfer molding curable according to claim 1 or 2 curing catalyst is characterized by a combination of a hydrosilylation catalyst Resin composition. The addition-type silicone-based thermosetting resin comprises (A-1) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule and (A-2) in one molecule. The curable resin composition for transfer molding according to any one of claims 1 to 3, comprising a compound containing at least two SiH groups. The average particle diameter of (C) component is 0.5 micrometer or more and 500 micrometers or less, The curable resin composition for transfer molding of any one of Claims 1-4 . (D) A component is spherical silica, The curable resin composition for transfer molding of any one of Claims 1-5 . (E) The average particle diameter of a component is 1.0 micrometer or less, The curable resin composition for transfer molding of any one of Claims 1-6 . The transfer according to any one of claims 1 to 7 , wherein the component (E) is at least one selected from titanium oxide, zinc oxide, zirconia oxide, strontium oxide, niobium oxide, boron nitride, barium titanate and barium sulfate. A curable resin composition for molding. The curable resin composition for transfer molding according to claim 8 , wherein the component (E) is zinc oxide. The curable resin composition for transfer molding according to claim 8 , wherein the component (E) is surface-treated with an organosiloxane. The curable resin composition for transfer molding according to claim 8 , wherein the component (E) is surface-treated with an inorganic compound. The curable resin composition for transfer molding according to claim 8 , wherein the component (E) is surface-treated with an aluminum compound. Further, (F) transfer molding curable resin composition according to any one of claims 1 to 12 containing the metal soap. The curable resin composition for transfer molding according to claim 13 , wherein the component (F) is a metal stearate. The curable resin composition for transfer molding according to claim 14 , wherein the component (F) is one or more selected from the group consisting of calcium stearate, magnesium stearate, zinc stearate, and aluminum stearate. The total amount of the component (C) in the entire curable resin composition is 1% by weight or more and 20% by weight or less, and the curability for transfer molding according to any one of claims 1 to 15 . Resin composition. The curable resin composition for transfer molding according to any one of claims 1 to 16 , wherein the total amount of the component (D) in the entire curable resin composition is 20 wt% or more and 95 wt% or less. The curable resin composition for transfer molding according to any one of claims 1 to 17 , wherein the content of the component (E) in the entire curable resin composition is 10 wt% or more and 60 wt% or less. 19. The total content of the component (D) and the component (E) in the entire curable resin composition is 40% by weight or more and 95% by weight or less, 19. A curable resin composition for transfer molding. 20. The curable resin composition for transfer molding according to any one of claims 13 to 19 , wherein the content of the component (F) in the entire curable resin composition is 0.01 to 5% by weight. object. The curable resin composition for transfer molding according to any one of claims 1 to 20 , which is used for a semiconductor package. A tablet comprising the curable resin composition for transfer molding according to any one of claims 1 to 21 . A molded product, wherein the curable resin composition for transfer molding according to any one of claims 1 to 21 is cured, and the light reflectance at a surface wavelength of 470 nm is 90% or more. A semiconductor package formed by using the curable resin composition for transfer molding according to claim 21 . A semiconductor package, which is integrally formed with a metal using the curable resin composition for transfer molding according to claim 21 . 26. The semiconductor package according to claim 24 or 25 , wherein the curable resin composition for transfer molding and the lead frame are integrally formed by transfer molding. 27. The semiconductor package according to any one of claims 24 to 26 , wherein the semiconductor package is a package formed by substantially molding a resin on one side of a metal. A semiconductor package, which is transfer molded using the curable resin composition for transfer molding according to claim 21 . A semiconductor component manufactured using the semiconductor package according to any one of claims 24 to 28 . A light-emitting diode manufactured using the semiconductor package according to any one of claims 24 to 28 .