JP2016074835A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for increasing flow length without changing the composition of a thermosetting resin composition while guaranteeing physical properties required as a resin for a semiconductor package.SOLUTION: There are provided a method for producing a curable composition for obtaining a curable resin composition having a moisture content of 250 to 3000 ppm by adding moisture to a curable resin composition comprising (A) a curable resin, (B) a zinc oxide and (C) an inorganic filler as essential components; and a curable composition obtained by the method, in which the curable resin is a silicone resin which comprises an epoxy resin containing a triglycidyl isocyanurate and an aliphatic acid anhydride or an organic compound having at least two SiH groups and carbon double bonds in one molecule, a silicon compound having at least two SiH groups in one molecule, a hydrosilylation catalyst and a silicone compound having at least one SiH group and carbon double bond in one molecule.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition.

Conventionally, packages using curable resins of various shapes are applied to semiconductors. Various metal materials are used for these packages in order to make electrical connection between the semiconductor and the outside of the package, to maintain the strength of the package, or to transfer heat generated from the semiconductor to the outside of the package. Often molded integrally with resin.
From the standpoint of maintaining the strength of the package, the amount of curable resin molded on both sides of the metal and the structure can be made uniform, thereby eliminating the difference in linear expansion on both sides and increasing the strength. Because of the increase in the amount of heat generated from the material, a design with high heat dissipation is required, so it has become difficult to equalize the amount of curable resin formed on both surfaces of the metal and the structure (Patent Document 1, 2).

In that case, a difference in linear expansion between both surfaces of the metal occurs, and thus a problem that warpage occurs newly occurs.
In the past, measures have been taken to reduce the warpage caused by the resin by reducing the linear expansion of the resin so as 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 an inorganic filler is filled in order to reduce linear expansion, the fluidity at the time of molding of the resin is lowered and the moldability is impaired, so there is a limit, and if the elastic modulus is lowered, the strength of the resin is reduced. Therefore, the main function as a package for protecting the semiconductor element is impaired.
In view of the above, a curable resin capable of reducing warpage is demanded.

On the other hand, since heat and light generated from semiconductors are increasing, the heat resistance and light resistance of resins for semiconductor packages are further required.
Responding to these requirements, resins that cure by a hydrosilylation reaction with high heat resistance have been applied as semiconductor package resins (Patent Documents 1 and 3).

  In order to solve these problems, a curable resin described in Patent Document 4 has been developed. From the viewpoint of moldability, it has been desired to further increase the flow length of the compound. The method of increasing the flow length of the compound is not easy to change because the composition of the compound has to be changed, and there is a concern that the physical properties may be lowered as the flow length increases.

JP 2010-62272 A JP 2009-302241 A JP 2005-146191 A WO2011 / 125753

  An object of the present invention is to provide a method for increasing the flow length without changing the composition of a thermosetting resin composition while ensuring the physical properties required as a resin for a semiconductor package. .

As a result of intensive studies in view of the above problems, the present inventors have completed the present invention.
That is, the present invention has the following configuration.
1). A curable resin composition containing (A) a curable resin, (B) zinc oxide, and (C) an inorganic filler as essential components, and having a moisture content of 250 to 3000 ppm. Resin composition.

  2). The water content is 350 to 2500 ppm, and the curable resin composition according to 1).

  3). The curable resin composition according to 1) or 2), wherein the (A) curable resin is an epoxy resin containing triglycidyl isocyanurate and an aliphatic acid anhydride.

4). The curable resin composition according to claim 1 or 2, wherein the (A) curable resin is a silicone compound having the following components (a) to (d) as essential components.
(A) an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(B) a silicon compound containing at least two SiH groups in one molecule;
(C) a hydrosilylation catalyst,
(D) A silicone compound having a molecular weight of 1000 or more and containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule.

  5). 1) to 4) A tablet obtained by pressure molding the curable composition according to any one of items 1 to 4.

  6). A package for a light emitting diode, which is molded using the curable composition according to any one of 1) to 4) or the tablet according to claim 5.

  7). Water is added to a curable resin composition containing (A) a curable resin, (B) zinc oxide, and (C) an inorganic filler as essential components, and the curable resin composition having a moisture content of 350 to 2500 ppm ppm is added. The manufacturing method of the curable composition characterized by obtaining.

  8). 7. The method for producing a curable composition according to 7), wherein the spiral flow value is 35 cm or more by adding water to the curable composition having a spiral flow value of 35 cm or less.

  According to the present invention, a method for increasing the flow length without changing the composition of the thermosetting resin composition while ensuring the physical properties required as a resin for a semiconductor package and the curable resin composition are provided.

Hereinafter, the present invention will be described in detail.
<Curable resin composition>
The curable resin composition referred to in the present invention is a composition comprising (A) a curable resin, (B) zinc oxide, and (C) an inorganic filler as essential components.

<(A) component: curable resin>
The curable resin as the component (A) means a thermosetting resin. Examples of the thermosetting resin of the present invention include resins such as epoxy resins and silicon-based thermosetting resins, and modified resins thereof, but are not limited to those described herein.

  Examples of the transparent epoxy resin include bisphenol A diglycidyl ether, 2,2′-bis (4-glycidyloxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and vinylcyclohexene dioxide. 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropane Epoxy resins such as dicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trial Rutetorahidoro phthalic anhydride include those cured with aliphatic acid anhydrides such as hydrogenated methylnadic anhydride. These epoxy resins or curing agents may be used alone or in combination. In particular, from the viewpoint of heat resistance, an epoxy resin containing triglycidyl isocyanurate and an aliphatic acid anhydride is preferable.

Silicon-based thermosetting resins include silicone resins and modified products thereof.
Silicone resin is a resin having, as a skeleton, an organic group such as an alkyl group, an aryl group, an aralkyl group, an epoxy group, a hydrogen atom, or a siloxane bond in which silicon atoms directly bonded to a hydroxyl group are bonded to oxygen atoms, Examples of the curable composition described in JP-A No. 2004-186168, JP-A No. 4071639, JP-A No. 2004-292807, and JP-A No. 2005-171021 are not particularly limited thereto. .

  In the present invention, the “silicone resin” includes a resin in which the siloxane bond and an epoxy resin or an organic compound having an addition-reactive carbon-carbon double bond are connected to form a skeleton. Examples of such a silicone resin composition include curable compositions described in JP-A No. 2002-338833, JP-A No. 2005-314591 and JP-A No. 4112443, but are particularly limited thereto. It is not a thing.

Among the silicon-based thermosetting resins,
(A) an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(B) a silicon compound containing at least two SiH groups in one molecule;
(C) a hydrosilylation catalyst,
(D) It is more preferable that it is composed of a silicone compound composed of a silicone compound having a molecular weight of 1000 or more and containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule.
Hereinafter, components (a) to (d) will be described.

<(A) component>
The component (a) 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 is preferably a compound other than a compound containing a siloxane unit (Si—O—Si), such as polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, and C, H, N, O as constituent elements. , Compounds containing no elements other than S and halogen are more preferred. In the case of a compound containing a siloxane unit, there are problems such as reactivity. The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.

(A) A component may be used independently and may be used in combination of 2 or more types.
The compound (a) can be classified into an organic polymer compound and an organic monomer compound. Although it does not specifically limit as an organic polymer type compound, For example, polyether type, polyester type, polyarylate type, polycarbonate type, saturated hydrocarbon type, unsaturated hydrocarbon type, polyacrylate ester type, polyamide type, phenol-formaldehyde Examples thereof include a phenolic compound and a polyimide compound.

  Although it does not specifically limit as an organic monomer type compound, For example, aromatic hydrocarbon type, such as phenol type, bisphenol type, benzene, and naphthalene; And the like.

Although it does not specifically limit as a carbon-carbon double bond which has a reactivity with SiH group of (a) component, The following general formula (1)
CH ₂ = CR ¹ − (1)
(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
Is preferable from the viewpoint of reactivity. Among them, a group in which R ¹ is a hydrogen atom is particularly preferable because of easy availability of raw materials. Furthermore, as the carbon-carbon double bond having reactivity with the SiH group of component (a), the following general formula (2)
―R ² C = CR ² ― (2)
(In the formula, R ² represents a hydrogen atom or a methyl group. The two R ^{2 s} may be the same or different.)
An alicyclic group having a partial structure represented by the formula is preferable from the viewpoint that the cured product has high heat resistance. Among them, a group in which R ² is a hydrogen atom is particularly preferable because of easy availability of raw materials.

  The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the component (a) or may be covalently bonded via a divalent or higher valent substituent. Although the divalent or higher valent substituent is not particularly limited, a substituent having 0 to 10 carbon atoms is preferable, and a substituent that does not contain elements other than C, H, N, O, S, and halogen is more preferable as a constituent element. .

  Examples of the group covalently bonded to the skeleton of the component (a) include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis ( And allyloxymethyl) butyl group and 3-allyloxy-2,2-bis (allyloxymethyl) propyl group.

  As the organic compound of component (a), low molecular weight compounds that are difficult to express by dividing into a skeleton portion and a group having a carbon-carbon double bond can also be used. Specific examples of the low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, and aliphatic cyclic polyene compounds such as cyclopentadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. And substituted aliphatic cyclic olefin compounds such as vinylcyclopentene and vinylcyclohexene.

  The component (a) preferably contains 0.001 mol or more of a carbon-carbon double bond having reactivity with the SiH group per gram of the component (A), from the viewpoint that heat resistance can be further improved. What contains 005 mol or more is more preferable, and what contains 0.008 mol or more is further more preferable.

  As specific examples of the component (a), in addition to the above, diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2- Tetraallyloxyethane, diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane, divinylbenzene (With a purity of 50 to 100%, preferably with a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, oligomers thereof, 1,2- Polybutadiene (1, 2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), allyl ether of novolak phenol, allylated polyphenylene oxide, glycidyl group of epoxy resin was replaced with allyl group And the like.

  Among these, from the viewpoint of good optical properties such as light resistance, the component (a) is preferably an aromatic ring component weight ratio of 50% by weight or less, more preferably 40% by weight or less. 30% by weight or less is more preferable. Most preferred are those that do not contain an aromatic hydrocarbon ring.

The number of carbon-carbon double bonds reactive with the SiH group of component (a) may be at least two per molecule, but may exceed two from the viewpoint that heat resistance can be further improved. Preferably, the number is 3 or more, more preferably 4 or more. However, when the component (a) is a mixture of various compounds and the number of the carbon-carbon double bonds of each compound cannot be identified, the average of the carbon-carbon double bonds per molecule for the whole mixture The number is obtained and used as the number of carbon-carbon double bonds of component (a).
(A) When the number of carbon-carbon double bonds reactive with the SiH group of the component is 1 or less per molecule, the reaction with the component (b) only results in a graft structure and a crosslinked structure. Don't be.

  As the component (a), in order to obtain uniform mixing with other components and good workability, a component having fluidity at a temperature of 100 ° C. or lower is preferable. The component (a) may be linear or branched. Although there is no restriction | limiting in particular in the molecular weight of (a) component, Arbitrary things of 50-1000 can be used conveniently. The component (a) preferably has a molecular weight of less than 900, more preferably less than 700, and even more preferably less than 500.

  Component (a) includes bisphenol A diallyl ether, 2,2'-diallyl bisphenol A, novolak phenol allyl ether, diallyl phthalate, vinylcyclohexene, divinylbenzene, divinylbiphenyl, triallyl, in terms of availability and reactivity. Isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, and 1,2,4-trivinylcyclohexane are preferable, and triallyl isocyanurate is particularly preferable from the viewpoint of heat resistance and light resistance.

<(B) component>
The component (b) is not particularly limited as long as it is a silicon compound containing at least two SiH groups in one molecule. For example, compounds described in International Publication No. WO96 / 15194 having at least two SiH groups in one molecule can be used. From the viewpoint of availability, a linear and / or cyclic organopolysiloxane having at least two SiH groups in one molecule is preferable. Among these, from the viewpoint of good compatibility with the component (a), the following general formula (3)

(In the formula, R ³ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10).
A cyclic polyorganosiloxane having at least two SiH groups in one molecule is more preferred. Incidentally, the substituent R ³ in the compound represented by the general formula (3) is, C, substituents preferably containing no elements other than H and O, a hydrocarbon group is more preferable.

  The component (b) was selected from a linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule and an organic compound having a carbon-carbon double bond reactive with SiH groups. Also preferred are reactants with one or more compounds. In this case, in order to further enhance the compatibility of the reactant with the component (a), a product obtained by removing unreacted siloxanes from the reactant by devolatilization or the like can be used.

<(C) component>
Component (c) is a hydrosilylation catalyst.
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.

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 group of component (b) 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 in component (b), 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 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.

<(D) component>
The component (d) of the present invention is a silicone compound having a molecular weight of 1000 or more and containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule. By using a silicone compound composed of a siloxane skeleton consisting essentially of Si-O-Si bonds, a cured product having excellent heat resistance and light resistance can be obtained compared to the case of using a general organic polymer. be able to. Furthermore, by using the component (d) of the present invention, a curable resin composition that, when mixed with the inorganic filler of the component (C), gives a cured product excellent in toughness while having a smaller linear expansion coefficient. It can be. Further, it is possible to provide a molded product that hardly warps when molded on a substantially single side of a metal base material such as a lead frame including Cu.

  The silicone compound of component (d) is a compound whose skeleton is substantially formed by Si—O—Si bonds, and various compounds such as linear, cyclic, branched, and partial networks are included. Can be used.

  In this case, examples of the substituent bonded to the skeleton include alkyl groups such as methyl group, ethyl group, propyl group, and octyl group, aryl groups such as phenyl group, 2-phenylethyl group, and 2-phenylpropyl group, methoxy group, Examples thereof include alkoxy groups such as ethoxy group and isopropoxy group, and groups such as hydroxyl group. Among these, a methyl group, a phenyl group, a hydroxyl group, and a methoxy group are preferable, and a methyl group and a phenyl group are more preferable in that heat resistance tends to be high. Examples of the substituent having a carbon-carbon double bond reactive with the SiH group include a vinyl group, an allyl group, an acryloxy group, a methacryloxy group, an acryloxypropyl group, and a methacryloxypropyl group. Of these, a vinyl group is preferred in terms of good reactivity.

As an example of the component (d), it may be expressed by the following formula.
_{Rn (CH 2 = CH) m} SiO (4-nm) / 2
(Wherein R is a group selected from a hydroxyl group, a methyl group or a phenyl group, and n and m are numbers satisfying 0 ≦ n <4, 0 <m ≦ 4, and 0 <n + m ≦ 4). These are the above silicone compounds.

  Examples of component (d) include polydimethylsiloxane, polydiphenylsiloxane, polymethylphenylsiloxane, and two or three random or block copolymers having vinyl groups as terminal groups or side groups. be able to. As the component (d), a plurality of components may be mixed and used.

  Of these, linear polysiloxanes having vinyl groups at the ends are preferable, linear polysiloxanes having vinyl groups at both ends are more preferable, and both ends are more preferable in that the effects of the present invention are more easily obtained. More preferred are linear polydimethyl-polydiphenylsiloxane or linear polymethylphenylsiloxane having vinyl groups at the ends, and linear polydimethyl-polydiphenylsiloxane or linear polymethylphenylsiloxane having vinyl groups at both ends. And it is especially preferable that it is siloxane whose quantity of the phenyl group with respect to all the substituents is 10 mol% or more.

  As the molecular weight of the component (d), the weight average molecular weight (Mw) is preferably 2,000 or more, more preferably 5,000 or more, and further preferably 10,000 or more. When the molecular weight is high, the obtained cured product tends to have low stress. Further, the molecular weight of the component (d) is preferably 1,000,000 or less, and more preferably 100,000 or less. When the molecular weight is large, it becomes difficult to obtain compatibility with the component (a) and the component (b).

  The amount of the component (d) is preferably 30% by weight or more, more preferably 50% by weight or more based on the total weight of the component (a) and the component (b). 80% by weight or more is more preferable.

  The mixing ratio of the component (a), the component (b), and the component (d) is not particularly limited as long as the required strength is not lost, but the component (a) having the number of SiH groups (Y) in the component (b) And (d) the ratio of the number of carbon-carbon double bonds reactive with SiH groups in component (X) is preferably Y / X ≧ 0.3, more preferably Y / X ≧ 0. 0.5, more preferably Y / X ≧ 0.7, and the upper limit of the preferred range is 3 ≧ Y / X, more preferably 2 ≧ Y / X, and even more preferably 1.5 ≧ Y / X. When it deviates from the preferred range, sufficient strength may not be obtained or thermal deterioration may easily occur.

  About (A) component, you may add the hardening accelerator for promoting the thermosetting reaction of the said resin component, and the hardening retarder for delaying thermosetting reaction.

<(B) component>
Component (B) is zinc oxide. In general, it is known that when shear energy such as shear is applied to a zinc oxide crystal, the crystal lattice is distorted. The strained zinc oxide coloring region shifts to yellow as the strain becomes stronger, causing a problem that it can no longer serve as a white pigment. Because of this problem, when preparing a white compound containing zinc oxide, it will turn yellow if kneading is applied with high mechanical energy such as shearing force, so it will knead for a long time with a weak kneading force. There was no choice but to perform kneading with poor productivity.

The average particle diameter of zinc oxide to which the present invention can be applied is 0.1 to 100 μm. When the particle size is less than this range, the particle size is too small, so that kneading becomes difficult. When the particle size is more than this range, the flow during compound kneading changes greatly, so that kneading becomes difficult.
Preferably it is 1-50 micrometers, More preferably, it is 2-25 micrometers. If it is this range, the function as a binder of the liquid resin component at the time of kneading | mixing will not be impaired, the flow of the zinc oxide at the time of kneading | mixing will become smooth, and it will become difficult to apply a local shear.

  The shape of zinc oxide is not particularly limited. It has been found in the present invention that the fluidity of the resin is improved and the zinc oxide is prevented from shifting to yellow by using the water content described later.

<(C) component>
Component (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.
Examples of the component (C) include silica, alumina, boron nitride, aluminum nitride, etc., excluding zinc oxide, but are not limited to those exemplified here.

  The shape is not particularly limited, but 50% or more of the filler is preferably spherical. When 50% or more of the filler is spherical, the liquid resin component as a binder is less likely to be absorbed in the filler particles and the fluidity is improved, so that uniform kneading is facilitated.

The hardness is not particularly limited, but in the case of a filler harder than 4 which is the Mohs hardness of zinc oxide, 50% or more of the filler is preferably spherical, and more preferably 75% or more. preferable. When the spherical filler is 50% or less, there is a possibility that the zinc oxide is subjected to strong local shearing during kneading and the yellowing degree is increased. The average particle diameter of the filler to which the present invention can be applied is 0.1 to 100 μm. When the particle size is less than this range, the particle size is too small, so that kneading becomes difficult. When the particle size is more than this range, the flow during compound kneading changes greatly, so that kneading becomes difficult. Preferably it is 1-50 micrometers, More preferably, it is 2-25 micrometers. If it is this range, the function as a binder of the liquid resin component at the time of kneading | mixing will not be impaired, the flow of the zinc oxide at the time of kneading | mixing will become smooth, and it will become difficult to apply a local shear.
About the usage fee for this component,

  In addition, the compound of the present invention contains the above-mentioned compound as a main component, and contains a solvent, a stabilizer, a plasticizer, a mold release agent, and other components as needed within a range that does not impair the object of the present invention. Can do.

<Mixing ratio of each component>
It describes about the ratio of each component with respect to a compound.
The upper limit ratio of the component (A) may be 60% by weight or less, preferably 40% by weight or less, and more preferably 20% by weight or less based on the entire compound. When the ratio exceeds the above upper limit ratio, the contents of the component (B) and the component (C) are relatively reduced, which affects the whiteness and strength of the molded body and the linear expansion coefficient, and desirable physical properties are obtained. Disappear.

  The lower limit ratio of the component (A) may be 5% by weight or more, preferably 7% by weight or more, and more preferably 9% by weight or more with respect to the entire compound. When the ratio is not more than the above lower limit ratio, the function of the liquid component as a binder is remarkably impaired, and uniform dispersion by kneading becomes impossible. Moreover, since the flow of particles in the compound is disadvantageous, local shearing to the acid value zinc is applied, and the discoloration described later occurs.

The upper limit ratio of component (B) may be 90% by weight or less, preferably 70% by weight or less, and more preferably 50% by weight or less, based on the entire compound. When the ratio exceeds the above upper limit ratio, the contents of the component (A) and the component (C) are relatively reduced, which affects the strength, linear expansion coefficient, and kneadability of the molded product, and desirable physical properties are obtained. Disappear.
The lower limit ratio of the component (B) is preferably 35% by weight or more, and more preferably 40% by weight or more based on the entire compound. When the ratio is not more than the above lower limit ratio, the whiteness of the compound is not ensured.

  The upper limit ratio of the component (C) may be 60% by weight or less, preferably 50% by weight or less, based on the entire compound. When the above upper limit is exceeded, the contents of the component (A) and the component (B) are relatively reduced, which affects the strength, linear expansion coefficient, and whiteness of the molded product, and provides desirable physical properties. Disappear.

  The lower limit ratio of component (C) is preferably 5% by weight or more, more preferably 15% by weight or more, and further preferably 25% by weight or more based on the entire compound. When it becomes below the said lower limit ratio, the intensity | strength and linear expansion coefficient of a preferable molded object are not ensured.

  From the above contents, it is possible to mix 5 to 60% by weight of component (A), 35 to 90% by weight of component (B), and 5 to 60% by weight of component (C). It can be said that the composition is balanced in terms of fluidity, whiteness, strength, and linear expansion coefficient.

<Moisture content of curable resin composition>
The moisture content of the present invention was determined by Karl Fischer moisture measurement with a moisture vaporization method using a Karl Fischer moisture meter (MKA-650, manufactured by Kyoto Electronics Industry) and a moisture vaporizer (ADP-611, manufactured by Kyoto Electronics Industry). Value. 2 to 5 g of a compound was prepared, heated at 230 ° C. using a moisture vaporizer, purged with nitrogen for 3 minutes, then the vaporized gas was sent to a moisture meter together with nitrogen, and measured for 30 minutes for measurement.

  It was found that the SF value was shortened as a result of removing the water content of the raw material. Specifically, 250 ppm or more is preferable, and 300 ppm or more is more preferable. In the present invention, YI was not lowered by adding water, and the SF value was improved. However, an excessive amount of water showed a decrease in mold release during molding. Specifically, 3000 ppm or less is preferable, and 2500 ppm or less is more preferable.

<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. 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.

  In the case where the semiconductor is a light emitting diode element, it is preferably designed so that light emitted from the light emitting diode element is irradiated, and more preferably, the light emitted from the light emitting diode element is reflected and taken out to the outside. It is designed. In that case, when the yellow index (hereinafter referred to as YI) of the present invention is less than 8.0, the effect can be remarkable. More preferably, YI is less than 7.0. There are no particular restrictions on the shape of the light emitting diode package. For example, it may have a shape having a recess for mounting a light emitting diode element, or may simply have a flat plate shape. The surface of the light emitting diode package of the present invention may be smooth or may have a non-smooth surface such as embossing.

<Light emitting diode element>
The various light emitting diode elements of the light emitting diode referred to in the present invention are not particularly limited, and the light emitting diode elements used in conventionally known light emitting diodes can be used. The size and number of the light emitting diode elements can be used without any particular limitation. One type of light emitting diode element may be used for single color emission, or a plurality of light emitting diode elements may be used for single color or multicolor emission.

<Transparent encapsulant for light-emitting diode>
There is no restriction | limiting in particular as a semiconductor sealing material of this invention, It is possible to select and use 1 type (s) or 2 or more types in arbitrary combinations among various well-known thermosetting resins. is there. On the other hand, it is possible to cover with glass or the like and seal with hermetic sealing without using resin sealing. Examples of resin sealing include, but are not limited to, conventionally used epoxy resins, silicone resins, cyanate resins, phenol resins, polyimide resins, polyurethane resins, acrylic fats, urea resins, and modified resins thereof. is not. Of these, transparent epoxy resins, silicon-based thermosetting resins containing silicon in the molecule, and transparent polyimide resins are preferred from the viewpoint of high transparency and excellent practical properties such as adhesiveness.

  Embodiments and effects of the present invention will be described below with reference to examples, but the present invention is not limited thereto.

(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. ^{By 1} H-NMR measurement, it was found that this had the following structure in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane reacted with triallyl isocyanurate.

<(A) Component formulation example>
Composition 1 was prepared by blending each component according to the contents of Table 1.

<Yellow Index (YI)>
YI in the present invention means a yellow index.
The yellow index is measured by converting the compound 6.3g to be measured into a φ13mm tablet and compressing and heating it with a transfer molding machine (G-LINE Manual System 60TON manufactured by Apic Yamada) into a flat plate of 5cm x 5cm x 1cm. It can measure in the reflectance measurement mode (made by Nippon Denshoku Industries Co., Ltd.). The YI value is preferably less than 8.0, and more preferably less than 7.5. If it deviates from this range, the reflectance decreases, and the luminance necessary for the reflector cannot be maintained.

<Spiral flow (SF value)>
In this invention, in order to evaluate the fluidity | liquidity of a compound, it evaluated using the spiral flow. Spiral flow is measured by measuring the flow length when a 17 g compound is transferred to a mosquito coil with a 5 cm tablet at 4.5 MPa at 170 ° C for 2 minutes (ETA-D type, manufactured by Shindo Metal Industries). It is to measure.
The measured flow length is preferably 30 cm or more from the viewpoint of subsequent moldability, and more preferably 35 cm or more. When the flow length is less than 30 cm, an unfilled portion may occur in the molded product.

<Method for measuring moisture>
Using a Karl Fischer moisture meter (MKA-650, manufactured by Kyoto Electronics Industry) and a moisture vaporizer (ADP-611, manufactured by Kyoto Electronics Industry), Karl Fischer moisture was measured by the moisture vaporization method. 2 to 5 g of a compound was prepared, heated at 230 ° C. using a moisture vaporizer, purged with nitrogen for 3 minutes, then the vaporized gas was sent to a moisture meter together with nitrogen, and measurement was performed for 30 minutes.

Example 1
The mixture of (A) to (C) was kneaded to prepare a compound.
The amount of raw material input is 1.0 kg, and details of the raw material are shown below.
(A) The blended product shown in Component Composition 1 was used at 9.34% by weight. As for the component (a), a component which was placed in a hot air dryer at 50 ° C. for 1 hour and melted was added.
Component (B) 42.57% by weight of first kind zinc oxide (average particle size 0.60 μm) manufactured by Sakai Chemical was used.
Component (C) MSR-SF650 (average particle size 10.6 μm) manufactured by Tatsumori Chemical was used at 47.88% by weight.
Further, 0.20% by weight of calcium stearate was used as an additive.
The water content of the compound according to the water content measuring method described above was 250 ppm.
The compound was molded on a flat plate (5 cm × 5 cm × 1 cm) with a compression molding machine (G-LINE Manual System 60TON manufactured by Apic Yamada), and YI was measured. As a result, YI was 7.5 or less. Moreover, there was no problem in the releasability at the time of molding. The spiral flow of the compound was 35cm.

(Example 2)
100 ppm of water was added to the mixture of Example 1 to prepare a compound. The moisture content of the compound was 350 ppm.
The compound was molded on a flat plate (5 cm × 5 cm × 1 cm) with a compression molding machine (G-LINE Manual System 60TON manufactured by Apic Yamada), and YI was measured. As a result, YI was 7.5 or less. Moreover, there was no problem in the releasability at the time of molding. The spiral flow of the compound was 40 cm.

(Example 3)
A compound was prepared by adding 500 ppm of water to the mixture of Example 1. The water content of the compound was 750 ppm.
The compound was molded on a flat plate (5 cm × 5 cm × 1 cm) with a compression molding machine (G-LINE Manual System 60TON manufactured by Apic Yamada), and YI was measured. As a result, YI was 7.5 or less. Moreover, there was no problem in the releasability at the time of molding. The spiral flow of the compound was 38 cm.

Example 4
1000 ppm of water was added to the mixture of Example 1 to prepare a compound. The water content of the compound was 1250 ppm.
The compound was molded on a flat plate (5 cm × 5 cm × 1 cm) with a compression molding machine (G-LINE Manual System 60TON manufactured by Apic Yamada), and YI was measured. As a result, YI was 7.5 or less. Moreover, there was no problem in the releasability at the time of molding. The spiral flow of the compound was 78 cm.

(Example 5)
A compound was prepared by adding 2000 ppm of water to the mixture of Example 1. The moisture content of the compound was 2250 ppm.
The compound was molded on a flat plate (5 cm × 5 cm × 1 cm) with a compression molding machine (G-LINE Manual System 60TON manufactured by Apic Yamada), and YI was measured. As a result, YI was 7.5 or less. Moreover, there was no problem in the releasability at the time of molding. The spiral flow of the compound was 115 cm.

(Comparative Example 1)
The components (B) and (C) of the mixture of Example 1 were dried by heating in an oven (DH610 manufactured by Yamato Kagaku) at 300 degrees, and the raw material was Karl Fischer moisture meter (MKA-650 manufactured by Kyoto Electronics Industry Co., Ltd.). ) Was 100 ppm less than the raw material used in Example 1. The moisture content of the compound was 150 ppm.
A compound was prepared by kneading using this raw material.

  The compound was molded on a flat plate (5 cm × 5 cm × 1 cm) with a compression molding machine (G-LINE Manual System 60TON manufactured by Apic Yamada), and YI was measured. As a result, YI was 7.5 or more. There was no problem in releasability during molding. The spiral flow of the compound was 31cm.

(Comparative Example 2)
A compound was prepared by adding 3000 ppm of the mixture water of Example 1. The water content of the compound was 3250 ppm.
The compound was molded on a flat plate (5 cm × 5 cm × 1 cm) with a compression molding machine (G-LINE Manual System 60TON manufactured by Apic Yamada), and YI was measured. As a result, YI was 7.5 or less. There was a problem in mold release during molding, and destruction occurred. The spiral flow of the compound was 64cm.

In Examples 1 to 5, the spiral flow and YI were satisfactory results, but in Comparative Examples 1 and 2, satisfactory results were not obtained in either the spiral flow or the releasability during molding. .
About the comparative example 1, since there is little water content, it is estimated that the flow length became short.
About the comparative example 2, it is thought that a mold release property worsened because moisture was discharge | released by the excessive heating at the time of shaping | molding, and sclerosis | hardenability fell.

Claims (8)

A curable resin composition containing (A) a curable resin, (B) zinc oxide, and (C) an inorganic filler as essential components, and having a moisture content of 250 to 3000 ppm. Resin composition. The curable resin composition according to claim 1, wherein the moisture content is 350 to 2500 ppm. The curable resin composition according to claim 1 or 2, wherein the (A) curable resin is an epoxy resin containing triglycidyl isocyanurate and an aliphatic acid anhydride. The curable resin composition according to claim 1 or 2, wherein the (A) curable resin is a silicone compound having the following components (a) to (d) as essential components.
(A) an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(B) a silicon compound containing at least two SiH groups in one molecule;
(C) a hydrosilylation catalyst,
(D) A silicone compound having a molecular weight of 1000 or more and containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule. The tablet obtained by pressure-molding the curable composition of any one of Claims 1-4. A package for a light-emitting diode, which is molded using the curable composition according to any one of claims 1 to 4 or the tablet according to claim 5. Water is added to a curable resin composition containing (A) a curable resin, (B) zinc oxide, and (C) an inorganic filler as essential components, and the curable resin composition having a moisture content of 350 to 2500 ppm ppm is added. The manufacturing method of the curable composition characterized by obtaining. The method for producing a curable composition according to claim 7, wherein the spiral flow value is 35 cm or more by adding water to the curable composition having a spiral flow value of 35 cm or less.