JP6227975B2 - Curable resin composition, curable resin composition tablet, molded product, semiconductor package - Google Patents

Description

  The present invention relates to a curable resin composition.

Conventionally, a product obtained by integrating a resin and a metal part as typified by a semiconductor package is manufactured by various molding methods typified by transfer molding. In this case, since the resin generally has a larger linear expansion than the metal part, there is a known problem that the product is warped after molding.
In order to solve such a problem, there is a method of reducing warpage by forming a curable resin so as to be even on both sides of a metal.
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.
Until now, measures have been taken to reduce the warpage caused by the resin by reducing the linear expansion of the resin by filling it with an inorganic filler and bringing it closer to the linear expansion of the integrally formed metal. However, when an inorganic filler having a small linear expansion coefficient is highly filled, there is a problem that the flexibility of the obtained molded article is impaired.

  In addition, when such a curable resin composition with a high filler content is used as an optical semiconductor package, it is known that a white content such as titanium oxide or zinc oxide is added. In addition, curable resin compositions with a high inorganic filler content generally have a high viscosity. For example, when a white content such as zinc oxide that exhibits coloration due to shear or compression stress is used, a curable resin composition is prepared. At times, there is a problem that the molded body is colored when kneaded by roll kneading or the like, or when it is flowed in a mold for molding the composition, and the optical characteristics of the optical semiconductor are impaired.

JP 2010-62272 A JP 2009-302241 A

  An object of the present invention is to provide a curable resin composition capable of reducing the linear expansion coefficient without impairing the flexibility of a molded article even when highly filled with an inorganic filler, and to light the composition. It is to provide a curable resin composition that gives good optical properties even when using a white pigment that is easily colored when used as a package for a semiconductor.

In order to solve such problems, the present inventors have intensively studied, and as a result of adding crosslinked rubber particles, it is possible to achieve both flexibility and a low linear expansion coefficient while being highly filled with an inorganic filler. It has been found that even when a filler that is easily colored by stress is used as a pigment, coloring of the cured product of the curable resin composition can be suppressed, and the present invention has been achieved.

That is, the present invention has the following configuration.
1) A curable resin composition comprising, as an essential component, (A) a silicone-based thermosetting resin, (B) a curing catalyst, (C) an inorganic filler, and (D) a low linear expansion agent composed of crosslinked rubber particles. object.

  2) The curable resin composition according to 1), wherein the component (D) is a crosslinked rubber particle having a durometer A hardness of 10 to 100.

  3) The curable composition according to 1) or 2), wherein the component (C) is in the range of 50% by weight to 95% by weight in the total composition.

  4) The curable resin composition according to any one of 1) to 3), wherein the component (C) is spherical silica.

5) The component (A) is
(A-1) a compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(A-2) a compound containing at least two SiH groups in one molecule,
The curable resin composition according to any one of 1) to 4), wherein the component (B) is a hydrosilylation catalyst.

  6) The curable resin composition according to any one of 1) to 5), further comprising (E) a white pigment.

  7) The curable resin according to 6), wherein the component (E) is at least one selected from titanium oxide, zinc oxide, zirconia, strontium oxide, niobium oxide, boron nitride, barium titanate and barium sulfate, and organic white pigment. Composition.

  8) The curable resin composition according to any one of 1) to 7), wherein the component (E) is zinc oxide or an organic white pigment.

  9) The linear expansion coefficient of hardened | cured material is 7-27 ppm, The curable resin composition as described in 1) -8) characterized by the above-mentioned.

  10) Bending fracture elongation of hardened | cured material is 0.5 mm-5.0 mm, The curable resin composition of any one of 1) -9) characterized by the above-mentioned.

  11) The curable resin composition according to any one of 1) to 10), wherein the light reflectance at a wavelength of 470 nm on the surface of the cured product is 90% or more.

  12) A tablet comprising the curable resin composition according to any one of 1) to 11).

  13) A molded article formed and cured using the curable resin composition according to 1) to 11) or the tablet of 12).

  14) A semiconductor package, which is molded and cured using the curable resin composition according to 1) to 11) or the tablet of 12).

  15) A package for an optical semiconductor, which is molded and cured using the curable resin composition according to 1) to 11) or the tablet of 12).

  When the curable resin composition of the present invention is used, a highly flexible cured product can be obtained while highly filling with an inorganic filler having a low coefficient of linear expansion, so that warpage is suppressed when integrally molded with various metal substrates. However, chipping and cracking of the molded body can be prevented. Further, by using the crosslinked rubber particles in the present invention, when the composition is used as a package for an optical semiconductor, an optical semiconductor having good optical characteristics can be obtained even when a white pigment that is easily colored is used. .

It is a conceptual diagram of the molded article which concerns on this invention.

Hereinafter, the present invention will be described in detail.
The curable resin composition of the present invention contains (A) a silicone-based thermosetting resin (B) a curing catalyst (C) an inorganic filler (D) and a low linear expansion agent composed of crosslinked rubber particles as an essential component. The curable resin composition is characterized.
Hereinafter, each component will be described.

((A) component)
The component (A) can be used without particular limitation as long as it is a silicone-based thermosetting resin, but if it is intentionally exemplified, a condensation-type silicone resin that cures by a condensation reaction of an alkoxy group or a silanol group, Examples include addition-type silicone resins that are cured by an addition reaction with SiH groups for a heavy bond. Among these, it is preferable to use an addition-type silicone resin from the viewpoint that the generation amount of volatile components of water and alcohol is small during curing.
The component (A) is preferably formed not only from a silicon skeleton but also from an organic skeleton from the viewpoint of toughness. Specific methods for introducing the organic skeleton include a method using an organic compound as a monomer and a method using an organically modified silicone obtained by modifying a part of the silicon skeleton with an organic compound. Specific examples of the organically modified silicone include norbornene modified silicone modified with a hydrocarbon compound, imide modified silicone modified with a heterocyclic compound, triazine modified silicone, or epoxy modified silicone. Of these, imide-modified silicone and triazine-modified silicone are preferably used from the viewpoint of heat resistance, and triazine-modified silicone is more preferably used from the viewpoint of cost. The above organically modified silicones may be used alone or in combination.
Moreover, (A) component is a compound containing at least two carbon-carbon double bonds having reactivity with SiH groups from the viewpoint of a balance between heat resistance and toughness,
(A-2) a compound containing at least two SiH groups in one molecule,
More preferably, it is comprised. Hereinafter, each component will be described in detail.

The component (A-1) is not limited as long as it is a compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule, and various organic compounds and inorganic compounds are used. Can do.
If the specific example of (A-1) component is dared to be illustrated, as an organic compound, diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylol propane diallyl ether, pentaerythritol triallyl ether, 1,1 , 2,2-tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzene (Purity of 50 to 100%, preferably 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, butadiene, Aliphatic chain polyene compound systems such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene, norbornadiene, vinyl cyclopentene, vinyl cyclohexene, etc. Examples thereof include substituted aliphatic cyclic olefin compound systems. Among the above, from the viewpoint of heat resistance, triallyl cyanurate, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (purity 50-100% Divinyl biphenyl), preferably triallyl cyanurate, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, 1,2,4- Trivinylcyclohexane is more preferably used, and triallyl isocyanurate, diallyl monoglycidyl isocyanurate, and diallyl monomethyl isocyanurate are more preferably used.

Examples of inorganic compounds include
CH ₂ = CHSiMe ₂ O (SiMe ₂ O) _n SiMe ₂ CH = CH ₂ (n = 0-10), CH ₂ = CHSiMe ₂ O (SiMe ₂ O) _m (SiPh ₂ O) _n SiMe ₂ CH = CH ₂ (m = 0-5, n = 1-4), CH ₂ = CHSiPh ₂ O (SiMe ₂ O) _m (SiPh ₂ O) _n SiPh ₂ CH = CH ₂ (m = 0-3, n = 1-2 ), CH ₂ = CHSiMe ₂ O (SiMe ₂ O) _m (SiPhMeO) _n SiMe ₂ CH = CH ₂ (m = 0-5, n = 1-6), Me ₃ SiO (SiMe ₂ O) _m (SiMe ( CH = CH ₂ ) O) _n SiMe ₃ (m = 0-5, n = 1-9), MeSi [O (SiMe ₂ O) _m SiMe ₂ CH = CH ₂ ] ₃ (m = 0-2), etc. Linear, branched siloxane compounds,
1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-pentamethylcyclotetrasiloxane, 1,3-divinyl-hexamethylcyclotetrasiloxane 1,5-divinyl-hexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1-phenyl-3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-tetravinyl- 1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1,5-diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetra Vinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl-1,3,5,7-tetra Tylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-diphenyl-3,7-divinyl-1,3,5,7 -Tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethyl Examples thereof include cyclic siloxane compounds such as cyclopentasiloxane and 1,3,5,7,9,11-hexavinyl-1,3,5,7,9,11-hexamethylcyclohexasiloxane.

The compounds other than siloxane include ClCH ₂ CH ₂ CH ₂ SiMe (CH = CH ₂ ) ₂ , (CH ₂ = CH) ₂ SiMe ₂ , (CH ₂ = CH) ₂ SiPhMe, (CH ₂ = CH) ₂ SiPh ₂ , (CH ₂ = CH) ₂ Si (OEt) ₂ , PhSi (CH = CH ₂ ) ₃ , (CH ₂ = CH) ₄ Si, CH ₂ = CHMe ₂ Si-C ₆ H ₄ p-SiMe ₂ CH = CH ₂ , CH ₂ ═CHMe ₂ SiO—C ₆ H ₄ p-OSiMe ₂ CH═CH _{2 and the} like.
Among the specific examples shown above, in a compound containing a phenyl (Ph) group, part or all of the phenyl group may be replaced with the following aryl group. Examples of such aryl groups include naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2 -Propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 3-isobutyl Phenyl group, 4-isobutylphenyl group, 3-tbutylphenyl group, 4-tbutylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 3-cyclohexyl Phenyl group, 4-cyclohexylphenyl group, 2,3-dimethylphenyl group, 2,4- Methylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group Group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-diethylphenyl group, biphenyl group, 2,3,4-trimethylphenyl group, 2,3 2,5-trimethylphenyl group, 2,4,5-trimethylphenyl group, 3-epoxyphenyl group, 4-epoxyphenyl group, 3-glycidylphenyl group, 4-glycidylphenyl group and the like. These may be used alone or in combination of two or more.

Among the above, it has good availability, low volatility, good compatibility with other components in the present invention, high reactivity associated with hydrosilylation curing, and the curable resin composition of the present invention. From the viewpoint of having a low linear expansion coefficient and toughness, the cured product obtained by curing, CH ₂ = CHSiMe ₂ O (SiMe ₂ O) _n SiMe ₂ CH = CH ₂ (n = 1-3) , CH ₂ = CHSiMe ₂ OSiPh ₂ OSiMe ₂ CH = CH ₂ , CH ₂ = CHSiMe ₂ O (SiPh ₂ O) ₂ SiMe ₂ CH = CH ₂ , CH ₂ = CHSiMe ₂ OSiPhMeOSiMe ₂ CH = CH ₂ , CH ₂ = CHSiMe ₂ O (SiPhMeO) ₂ SiMe ₂ CH = CH ₂ , CH ₂ = CHSiPh ₂ OSiPh ₂ CH = CH ₂ , 1,3,5-trivinyl-pentamethylcyclotetrasiloxane, 1,3-divinyl-hexamethylcyclotetrasiloxane 1,5-divinyl-hexamethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, , 5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 1,5-diphenyl-3,7-divinyl-1,3,5,7-tetramethyl _{cyclotetrasiloxane, CH 2 = CHMe 2 Si-} C _{6 H 4 p-SiMe 2 CH} = CH 2, CH 2 = CHMe 2 SiO-C 6 H 4 p-OSiMe 2 CH = CH 2 can be preferably used.

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, the compound described in International Publication WO96 / 15194 is at least two compounds in one molecule. Those having SiH groups 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 further represented by the following general formula (I)

(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 (I) 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 (I) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane.
(A-2) A component can be used individually or in mixture of 2 or more types.

(Preferred structure of component (A-2))
(A-2) From the viewpoint that the problem of outgas from the curable resin composition that can be reduced in volatility of the component is less likely to occur, and from the viewpoint of giving practical strength and toughness to the cured product obtained from the composition. It is more preferable to have a component that is substantially non-volatile and has a component in which a skeleton derived from an organic compound is introduced in addition to the siloxane skeleton. Although the production method of the compound is not limited, the component (A-2) is composed of an organic compound (α) containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule and one molecule. It is preferable that the compound (β) having at least two SiH groups is obtained by hydrosilylation reaction.

((Α) component)
Here, the component (α) is the same as the compound containing at least two carbon-carbon double bonds having reactivity with the SiH group shown in the description of the component (A-1). α1) can also 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, a 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 (α2) component is not particularly limited as long as it is a 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.

The structure of the (α2) component may be linear or branched, and the molecular weight is not particularly limited, and various types can be used. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and more preferably 1.5 or less in that the viscosity of the mixture is low and the moldability is likely to be good. More preferably it is.
In the case where the glass transition temperature of the component (α2) is present, there is no particular limitation on this, and various materials are used. However, the glass point transfer temperature is 100 ° C. or lower in that the obtained cured product tends to be tough. Preferably, it is 50 ° C. or lower, and more preferably 0 ° C. or lower. Examples of preferred resins include polybutyl acrylate resins. Conversely, the glass transition temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, in that the heat resistance of the cured product obtained is increased. Most preferably, it is 170 ° C. or higher. The glass transition temperature can be determined as a temperature at which tan δ exhibits a maximum in the dynamic viscoelasticity measurement.

  The component (α2) is preferably a hydrocarbon compound in that the heat resistance of the resulting cured product is increased. In this case, the preferable lower limit of the carbon number is 7, and the preferable upper limit of the carbon number is 10.

The component (α2) may have other reactive groups. Examples of the reactive 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. When it has these functional groups, the adhesiveness of the obtained curable resin composition tends to be high, and the strength of the obtained cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high. Specific examples include monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyloxyethyl methacrylate, allyloxyethyl acrylate, vinyltrimethoxysilane, and the like.
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 (II)

(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 (II) 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.

(Reaction of (α) component and (β) component)
Next, as the component (A-2) of the present invention, when a compound that can be obtained by hydrosilylation reaction of the component (α) and the component (β) is used, the component (α) and the component (β) The hydrosilylation reaction will be described.
In addition, when the (α) component and the (β) component are subjected to a hydrosilylation reaction, a mixture of a plurality of compounds including the component (A-2) of the present invention may be obtained. The curable resin composition of the present invention can also be produced using the mixture as it is without separation.
The mixing ratio of the (α) component and the (β) component when the (α) component and the (β) component are subjected to a hydrosilylation reaction is not particularly limited, but the obtained (A-2) component and (A-1) component When considering the strength of the cured product by hydrosilylation with (A-2), it is preferable that the component (A-2) has a larger amount of SiH groups, so that carbon-carbon having reactivity with the SiH groups in the component (α) to be generally mixed is preferable. The ratio of the total number of double bonds (X) to the total number of SiH groups (Y) in the (β) component to be mixed is preferably Y / X ≧ 2, and Y / X ≧ 3 More preferred. Moreover, it is preferable that it is 10> = Y / X from the point that compatibility with the (A-1) component of (A-2) component becomes easy, and it is more preferable that it is 5> = Y / X.

When the (α) component and the (β) component are subjected to a hydrosilylation reaction, an appropriate catalyst may be used. As the catalyst, for example, the following can be used. Platinum simple substance, alumina, silica, carbon black or the like supported on solid platinum, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone or the like, platinum-olefin complex (for example, Pt (CH ₂ = CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ), platinum-vinylsiloxane complex (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ]) _m ), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄₎ (in the formula, Me represents a methyl group, Bu a butyl group, Vi is vinyl group, Ph represents a phenyl group, n, m is an integer.), dicarbonyl dichloroplatinum, Karushuteto Karstedt catalyst, as well as the platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,622, and Lamoreaux US Pat. No. 3,220,972. And platinum alcoholate catalysts. 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.

Although the addition amount of the catalyst is not particularly limited, the lower limit of the preferable addition amount is sufficient with respect to 1 mol of SiH groups of the (β) component in order to have sufficient curability and keep the cost of the curable resin composition relatively low. 10 ^-8 mol Te, 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 moles.
In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount with respect 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.

Various methods can be used for mixing the (α) component, the (β) component, and the catalyst in the reaction, and the (α) component mixed with the catalyst is mixed with the (β) component. The method is preferred. If the catalyst is mixed with the mixture of the (α) component and the (β) component, it is difficult to control the reaction. When the method of mixing the (β) component with the mixture of the (β) component and the catalyst, the (β) component is reactive in the presence of the catalyst and may be altered due to its reactivity with water. .
The reaction temperature can be variously set. In this case, the lower limit of the preferable temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferable temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.
Various reaction times and pressures during the reaction can be set as required.

A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.
In addition, various additives may be used for the purpose of controlling reactivity.

  After reacting the (α) component and the (β) component, the solvent or / and the unreacted (α) component or / and the (β) component can be removed. By removing these volatile components, the resulting component (A-2) does not have volatile components, and in the case of curing with the component (A-1), the problem of voids and cracks due to volatilization of the volatile components occurs. Hateful. Examples of the removal method include treatment with activated carbon, aluminum silicate, silica gel and the like in addition to vacuum devolatilization. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 100 ° C, more preferably 60 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

  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.

(Component (B)) Curing Catalyst The component (B) in the present invention is not particularly limited as long as it is a catalyst used for curing the silicone-based thermosetting resin as the component (A). A condensation catalyst can be used as the curing catalyst for the condensation-type silicone-based thermosetting resin shown in the description of the components, and a hydrosilylation catalyst can be used as the curing catalyst for the addition-type silicone-based thermosetting resin. it can.

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.
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 (III) and (IV) 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 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 catalyst is not particularly limited, but the lower limit of the preferred addition amount is 1 mol of SiH group of the component (A-2) in order to have sufficient curability and keep the cost of the curable resin composition relatively low. against ^{10 -8} mole, more preferably ^{10 -6} mole, preferable amount of the upper limit (a-2) ^{10 -1} moles per mole of the SiH group in component, more preferably ^{10 -2} mol It is.
In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount with respect 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.

(Component (C)) The inorganic filler (C) is an inorganic filler.
Component (C) has the effect of increasing the strength and hardness of the resulting cured product and reducing the linear expansion coefficient.
As the inorganic filler of the component (C), 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 magnesium carbonate, potassium titanate, calcium silicate, silver powder, and other inorganic fillers that are generally used and / or proposed as fillers for conventional sealing materials such as epoxy type be able to. 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 adhesiveness 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. In addition, glass fiber, potassium titanate, and calcium silicate are preferable in that the reinforcing effect is high and the strength of the package tends to be high.

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 (C) is not particularly limited, but the total amount of the component (C) in the entire curable resin composition is preferably 50% by weight to 95% by weight, and 60% by weight to 95% by weight or more. It is more preferable that it is 70 wt% to 95 wt%. When the component (C) is less than 50% by weight, the effect of the component (D) in the present invention may not be suitably exhibited. When the component exceeds 95% by weight, for example, a curable resin composition is molded. The molded product obtained in this way lacks flexibility and may become brittle.

  As means for mixing the inorganic filler of component (C), 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.

(Component (D)) The low linear expansion agent (D) composed of crosslinked rubber particles is a low linear expansion agent composed of crosslinked rubber particles. Hereinafter, the component (D) will be described in detail.

(Crosslinked rubber particles)
The crosslinked rubber particles in the present invention are not particularly limited as long as they are rubber particles having a crosslinked structure, and various rubber particles from organic crosslinked rubber particles to inorganic crosslinked rubber particles can be used.

  The crosslinked rubber particles may be spherical or non-spherical, and the physical structure is not particularly limited. However, the crosslinked rubber particles are not limited to a structure having a uniform composition, and a core particle forming a nucleus is covered with a plurality of coating layers. Such a core-shell type structure or an inclined structure type whose composition changes from the center toward the surface can be used.

  On the other hand, if the crosslinked rubber particles are classified from the chemical structure, urethane rubber particles having urethane bonds, acrylic rubber particles obtained by polymerization of acrylic monomers, butadiene rubber particles, styrene-butadiene rubber particles, silicone type Examples thereof include rubber particles.

If these specific examples are given, organic crosslinked rubber particles such as acrylic crosslinked particle Haya beads M-11 manufactured by Hayakawa Rubber Co., Ltd. and Matsumoto Microsphere Series, which is acrylic particles manufactured by Matsumoto Yushi Seiyaku Co., Ltd., are used. Acrylic rubber particles, butadiene rubber particles represented by JP-A-2003-137907, and the like, and as inorganic crosslinked rubber particles, silicone composite powder KMP series manufactured by Shin-Etsu Silicone Co., Ltd., manufactured by Toray Dow Corning Co., Ltd. Silicone rubber powder EP-5500, silicone-based rubber particles represented by core-shell silicone fine particles described in WO2010 / 055632 are exemplified, and among these, from the viewpoint of heat resistance and light resistance, manufactured by Shin-Etsu Silicone Co., Ltd. Silicone composite powder KMP series Rui, it is preferred to use a silicone-based crosslinked rubber particles such as silicone rubber produced by Dow Corning Toray Co., Ltd. powder EP-5500.
It is preferable to use inorganic crosslinked rubber particles. These (D) components may be used individually by 1 type, and may be used combining several things.

    The particle diameter of the crosslinked rubber particles in the present invention is preferably in the range of 0.1 μm to 50 μm, and more preferably in the range of 1 μm to 20 μm. If the particle size is less than 0.1 μm, the particles are likely to aggregate and a uniform composition may not be obtained. If the particle size exceeds 50 μm, the effect of component (D) in the present invention is low linear expansion. There is a risk that the effect will not be obtained.

  Moreover, in order to express the effect of (D) component suitably in this invention, it is preferable that (D) component has the durometer A hardness in the range of 10-100, and exists in the range of 15-80. More preferably, it is further in the range of 20-70.

  By adding (D) component in this invention, the linear expansion coefficient of the molded object formed by shape | molding curable resin composition can be reduced. (D) As addition amount of a component, it is preferable that it is 1-20 weight% in 100 weight% of all compositions, It is more preferable that it is 1-15 weight%, It is further more preferable that it is 1-10 weight% preferable. When the addition amount exceeds 20% by weight, the linear expansion coefficient of the molded product obtained by molding the curable resin composition in the present invention may increase by addition of the component (D). If it is less than 1, the effect of lowering the linear expansion may not be obtained.

(Component (E)) White Pigment The curable resin composition of the present invention preferably contains a white pigment (component (E)).
The component (E) is a white pigment and has an effect of increasing the light reflectance of the obtained cured product.
Various components can be used as the component (E), and can be classified into inorganic white pigments and organic white pigments.
Examples of inorganic white pigments include titanium oxide, zinc oxide, magnesium oxide, antimony oxide, zirconia oxide, strontium oxide, niobium oxide, boron nitride, barium titanate, zinc sulfide, barium sulfate, magnesium carbonate, and hollow glass particles. It is done. Among these, titanium oxide or zinc oxide is preferable from the viewpoint of easy handling and availability, and zinc oxide is more preferable from the viewpoint of cost.

Organic white pigments include organic compound salts (groups A to D below) and alkylene bismelamine derivatives (general formula V below (where R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or an alicyclic group). R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and may form a heterocyclic group together with the nitrogen atom. X represents a lower alkylene group having 2 to 3 carbon atoms.), Specifically, NN′-bis (4,6diamino-1,3,5-triazin-2-yl) ethylenediamine and the like). . Specific examples of the white pigment include Shigenox OWP, Shigenox OWPL, Shigenox FWP, Shigenox FWG, Shigenox UL, and Shigenox U (all trade names manufactured by Hackol Chemical Co., Ltd.).

  In addition, it is desirable to use zinc oxide and organic white pigment that are easily colored during kneading of the curable resin composition in the present invention because coloring can be suppressed.

  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.

(E) Although various things are used also as an average particle diameter of a component, from a viewpoint that the light reflectivity of the hardened | cured material obtained becomes high easily, and a curable resin composition tablet becomes harder, it is 1.0 micrometer or less. 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.
The average particle diameter can be measured using a laser diffraction / scattering particle size distribution analyzer.

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. For example, when titanium oxide is dry pulverized, slurried, or wet pulverized. It can be carried out. In addition, there are various methods such as a liquid phase method and a gas phase method.
In these, since the light reflectivity of the hardened | cured material obtained is high and heat-resistant light resistance becomes favorable, it is preferable to process by the organosiloxane process. 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 (E) in the entire curable resin composition is preferably 10% by weight or more, more preferably 15% by weight or more, More preferably, it is 20% by weight or more. If it is less than 10% by weight, the light reflectance of the resulting cured product may be lowered.

The component (E) is used when a white curable resin composition is prepared, but when applied to a black matrix of a display device, the black curable resin composition can be used. .
As the black pigment that can be used in this case, either an inorganic pigment or an organic pigment may be used, or a single pigment or a mixture of two or more pigments may be used. Examples of the inorganic pigment include carbon black, graphite, iron black, titanium carbon, titanium black, manganese diacid value, and copper chromium manganese oxide. From the viewpoint of improving coloring power, carbon black or titanium black is preferable. Furthermore, titanium black is more preferable from the viewpoint of increasing the optical density and the electrical resistance value. Carbon black or titanium black whose surface is coated with a resin or the like can also be used. Aniline black, anthraquinone black pigment, perylene black pigment and the like can also be used.

  The metal composite oxide black pigment contains a copper-chromium-manganese composite oxide black pigment, copper oxide, manganese oxide, cobalt oxide and aluminum oxide. When the ratio of copper, manganese, cobalt and aluminum constituting the pigment is 100 mol%, the copper is 5 to 30 mol% and the manganese is 5 to 30 Complex oxide black pigments with mol%, cobalt 15-40 mol% and aluminum 25-50 mol% can also be used.

((C) component and (E) component)
The total amount of the component (C) and the component (E) is not particularly limited, but the total amount of the component (C) and the component (E) in the entire curable resin composition is 50% by weight to 95% by weight. Preferably, it is more preferably 60% by weight to 95% by weight or more, and further preferably 70% by weight to 95% by weight. When the total amount of the component (C) and the component (E) is less than 50% by weight, the effect of the component (D) in the present invention may not be suitably expressed. A molded product obtained by molding the curable resin composition lacks flexibility and may become brittle.
As the mixing order of the component (E), various methods can be used, but the preferred embodiment is the same as the component (C) already described. Moreover, you may add (C) component and (E) component simultaneously.
As the means for mixing the component (E), the same means as the means for mixing the component (C) can be used.

(Other additives)
In this invention, the various additives shown below can be used as needed.

(Hydrosilylation retarder)
When an addition-type silicone-based thermosetting resin is used as the component (A) in the present invention, the hydrosilylation curing delay is used for the purpose of improving the storage stability or adjusting the reactivity of the hydrosilylation reaction during the production process. Agents can be used. Examples of the hydrosilylation curing retardant include compounds containing aliphatic unsaturated bonds, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, etc., and these may be used in combination. Absent.

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

Although the addition amount of the hydrosilylation curing retarder can be variously set, the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst to be used is 10 ⁻¹ mol, more preferably 1 mol, and the upper limit of the preferable addition amount is 10 ³ mol, More preferably, it is 50 mol.
Moreover, these hydrosilylation hardening retarders may be used independently and may be used together 2 or more types.

(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.

(Tablet characterized by containing curable resin composition)
The curable resin composition in the present invention can also be used as a tablet for various moldings. 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.

(Hardened product obtained by curing curable resin composition)
The linear expansion coefficient of the cured product obtained by thermosetting the curable resin composition in the present invention is desirably close to the linear expansion coefficient of copper generally used as a lead frame of a semiconductor package such as an LED. Therefore, it is preferably in the range of 7 ppm to 27 ppm, and more preferably in the range of 12 ppm to 22 ppm.

    By using the curable resin composition in the present invention, a cured product having excellent flexibility can be obtained. As an index of flexibility, the breaking elongation in a bending test according to ISO 178 can be exemplified, and the breaking elongation of the cured product in the test is preferably in the range of 0.5 mm to 5.0 mm, 0.5 mm to More preferably within the range of 4.0 mm, and even more preferably within the range of 0.5 mm to 3.0 mm. When the bending fracture elongation is less than 0.5 mm, there is a possibility that cracking or chipping may occur when the resulting molded product is cut or processed such as dicing. It may be easily deformed by an external force or the like.

(Molded product obtained by curing curable resin composition)
As an example of a molded product obtained by curing the curable resin composition in the present invention, an optical semiconductor package is exemplified. When using the curable composition in this invention for this use, in order to give the brightness | luminance of an optical semiconductor favorable, the high light reflectivity and low coloring degree are requested | required of the molded object formed by hardening.

The molded product obtained by curing the curable resin composition in the present invention has a light reflectance at 470 nm of 80% or more, and a light reflectance retention after a heat test at 180 ° C. for 24 hours (after the heat test). The light reflectance / initial light reflectance × 100) is desirably 90% or more.
About the measuring method of the light reflectivity of hardened | cured material, it can measure using a micro surface spectral color difference meter (Nippon Denshoku Industries Co., Ltd. VSS400), for example.

  In addition, by using the component (D) in the present invention, when using a filler that exhibits coloration by applying compression or shear stress as represented by zinc oxide as the white content of the component (E), Coloring can be reduced by the stress relaxation effect of component D), and both high light reflectance and a low degree of coloring can be achieved. There are various indicators of the degree of coloring of the cured product, and a typical example is the yellow index (YI). The YI of the cured product in the present invention is preferably 7.5 or less, more preferably 5.0 or less, and even more preferably 4.5 or less. When the YI of the cured product exceeds 7.5, for example, when the curable resin composition according to the present invention is used as a package for an optical semiconductor, there is a possibility that problems such as a decrease in luminance of the optical semiconductor may occur. About the measuring method of YI of hardened | cured material, it can measure, for example using a micro surface spectral color difference meter (Nippon Denshoku Industries Co., Ltd. VSS400).

(Semiconductor package)
The curable resin composition in the present invention can be molded to make a 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.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.
(Synthesis Example 1)
A stirrer, a dropping funnel, and a condenser tube were set in a 5 L four-necked flask. Into this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, heated and stirred in an oil bath at 120 ° C. 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 added dropwise 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. ¹ H-NMR measurement revealed that this had the following structure in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane reacted with triallyl isocyanurate.

(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. 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 added dropwise over 90 minutes. After completion of dropping, the jacket temperature was raised to 60 ° C. for 40 minutes, and ¹ H-NMR confirmed that the reaction rate of allyl group was 95% or more. After dropwise addition of 17 g of triallyl isocyanurate and 17 g of toluene, the jacket temperature was raised to 105 ° C., and xylene solution of triallyl isocyanurate 66 g, toluene 66 g and a platinum vinylsiloxane complex (containing 3 wt% as platinum) 033 g of the 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- and trans-isomers)) is 5,000 ppm or less in total The solution was distilled off under reduced pressure until a colorless and transparent liquid was obtained. ^{As a result of 1} H-NMR measurement, this is one in which a part of SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane is reacted with allyl glycidyl ether and triallyl isocyanurate, and on average, the following structure It was found that

(A + b = 3, c + d = 3, e + f = 3, a + c + e = 3.5, b + d + f = 5.5)

(Preparation of curable resin composition)
As shown in Table 1, the curable resin compositions of Examples 1 to 3 and Comparative Example 1 were produced, and various evaluations shown below were performed.

  In preparation of the blend, first, the components (A) and (B), the curing retarder and the antioxidant are weighed in a cup-shaped container, mixed, and then kneaded with a plastic spatula. These components were added little by little, and after that, they were stretched with a round bar-shaped jig, then folded and re-stretched again.

(Method of creating a cured product by transfer molding)
Transfer molding was performed using a G-Line manual press manufactured by Apic Yamada Corporation. The mold clamping force was 30 ton, the injection pressure was 8 MPa, and the injection speed was 3 mm / s. 11.0 g of a white compound was weighed and loaded into a cylinder for molding. The molding temperature and molding time were 170 ° C. and 180 seconds. After molding, it was post-cured (aftercured) at 180 ° C. for 1 hour in a hot air oven. Two types of cured products, 1.0 mm thickness and 4.0 mm thickness, are prepared. The 1.0 mm thick cured product is used for measuring the linear expansion coefficient, and the 4.0 mm thick cured product is used for measuring the bending fracture elongation. did.

(Linear expansion coefficient)
The linear expansion coefficient of the molded product obtained by the above molding was measured according to JIS K 6911.

(Bending fracture elongation)
The bending fracture elongation of the molded body obtained by the above molding was measured by ISO 178.

(Tablet)
The produced curable resin composition was compressed into a tablet by a tablet production jig composed of a metal punch and mortar. Specifically, a predetermined amount of the composition was put into a 13 mm diameter mortar and compressed from the top with a spatula at a pressure of 100 kg / cm 2 for 5 seconds to obtain a tablet having a predetermined volume.

(MAP molding method by transfer molding)
An Ag-plated lead frame for a light emitting diode made of Cu having a length of 50 mm, a width of 55 mm, and a thickness of 0.25 mm is prepared. A molded MAP (Mold Array Package: a type in which a semiconductor package has a shape in which a resin is substantially formed on one side of a metal) includes a total of 180 reflectors in 15 rows and 12 rows. Each reflector has a top surface of 2.1 mm, a bottom surface of 1.8 mm (taper angle: 15 degrees), a height of 0.55 mm, a width of 0.20 mm from the right end along the transverse diameter, and a width of 0.20 mm. The electrode slit which consists of a white compound which hardened the conductive resin composition is provided vertically. The interval between the reflectors is 1.1 mm in both the vertical and horizontal diameter directions. The lead frame and the mold are not particularly limited as long as a reflector with a lead frame that satisfies the above requirements can be manufactured. This shape of the molded product is called a 3030 MAP type. A conceptual diagram of the molded product is shown in FIG.
Transfer molding was performed using a G-Line manual press manufactured by Apic Yamada Corporation. Clamping force 30 ton, injection pressure 8 MPa, injection speed 3 mm / s. A white compound (5.0 g) was weighed, shaped into a cylindrical shape (tablet as described above), loaded into a cylinder, and molded. The molding conditions were 170 ° C. and 150 seconds. After molding, it was post-cured (aftercured) at 180 ° C. for 1 hour in a hot air oven.

(warp)
When the molded part is placed on a smooth surface with the molded part facing up, the warp is defined as a forward warp when the molded part is concave when viewed from the side, and the reverse warp is defined as a convex part. As for the degree of warpage, a MAP product was placed on a smooth surface, and the value (mm) having the longest distance among the four sides away from the surface was quantified.

(Measurement of light reflectance and yellow index (YI))
About the package of the curable resin composition obtained by the said shaping | molding, and the package of Comparative Examples 2-6, the light in wavelength 400nm -700nm (20nm space | interval) using a micro surface spectral color difference meter (Nippon Denshoku Industries Co., Ltd. VSS400). The reflectance and the yellow index (YI) were measured. The yellow index was measured according to ASTM 1925. Here, as the measurement values at each wavelength, the average value of the measurement values at arbitrary four locations (measurement area 0.2 mmφ) on the upper surface of the package was adopted.

  From Table 2, it can be seen from the comparison between each Example and Comparative Example 1 that the linear expansion coefficient of the cured product is decreased and the warpage of MAP is decreased by the addition of the component (D) in the present invention. On the other hand, in Comparative Example 2 which does not have the component (D) in the present invention, high expansion of the inorganic filler spherical silica having a low linear expansion coefficient reduces the linear expansion coefficient and decreases the warpage of MAP. The cured product has a small breaking elongation. It turns out that it lacks flexibility. From the above, it can be seen that by using the curable resin composition of the present invention, it is possible to achieve both a low linear expansion coefficient and flexibility of the obtained molded product and cured product.

  Furthermore, from the comparison between Example 1 to Example 3 and Comparative Example 1, even if zinc oxide, which is a coloring filler, is used due to the addition of component (D) in the present invention, stress relaxation of component (D) It can be seen that the stress applied to zinc oxide is relaxed by the effect, and a cured product having both low YI and light reflectance can be obtained.

Claims (14)

(A) Silicone-based thermosetting resin (B) Curing catalyst (C) Inorganic filler (D) Low linear expansion agent comprising crosslinked rubber particles (E) White pigment as an essential component A curable resin composition for a package. The curable resin composition for a semiconductor package according to claim 1, wherein the component (D) is a crosslinked rubber particle having a durometer A hardness in the range of 10 to 100. 3. The curable resin composition for a semiconductor package according to claim 1, wherein the component (C) is in the range of 50 wt% to 95 wt% in the total composition. (C) A component is spherical silica, The curable resin composition for semiconductor packages of any one of Claims 1-3. The component (A) is
(A-1) a compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(A-2) a compound containing at least two SiH groups in one molecule,
The curable resin composition for a semiconductor package according to any one of claims 1 to 4, wherein the component (B) is a hydrosilylation catalyst. 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, and an organic white pigment. The curable resin composition for semiconductor packages described in 1. (E) A component is a zinc oxide and an organic white pigment, The curable resin composition for semiconductor packages of any one of Claims 1-6 characterized by the above-mentioned. The linear expansion coefficient of hardened | cured material is 7-27 ppm, The curable resin composition for semiconductor packages of any one of Claims 1-7 characterized by the above-mentioned. The curable resin composition for a semiconductor package according to any one of claims 1 to 8, wherein the bending fracture elongation of the cured product is 0.5 mm to 5.0 mm. The curable resin composition for a semiconductor package according to any one of claims 1 to 9, wherein the light reflectance at a wavelength of 470 nm on the surface of the cured product is 90% or more. The tablet for semiconductor packages characterized by including the curable resin composition for semiconductor packages of any one of Claims 1-10. A molded body, which is molded and cured using the curable resin composition for a semiconductor package according to any one of claims 1 to 10 or the tablet for a semiconductor package according to claim 11. The semiconductor package is characterized in that the molded cured using semiconductor package tablets according to the semiconductor package curable resin composition or claim 11, according to any one of claims 1 to 10. Semiconductor package curable resin composition according to any one of claims 1 to 10 or molded with the semiconductor package tablet according to claim 11, cured for an optical semiconductor package, characterized in that the,.