JP2018123286A - Method for producing thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for stably kneading a curable resin composition by preventing insufficient kneading and dispersion failure caused by the occurrence of a retained portion of the composition during kneading in a batch type kneader.SOLUTION: The method for producing a thermosetting resin composition using a kneader is provided. The thermosetting resin composition is a curable resin composition containing, as essential components, a curable resin (A), a white pigment (B) and an inorganic filler (C). The kneader is a biaxial kneader in which biaxial kneading blades revolve and each shaft rotates, and a kneading part is subjected to surface treatment providing a Vickers hardness of 500 or more and a surface roughness Ra of the kneading part has a relationship of surface roughness of a kneading pot<surface roughness of the kneading blade. The surface roughness of the kneading pot is Ra=0.1-6 μm, surface roughness of the kneading blade rotating in the same direction as revolution direction is Ra=0.3-7 μm, (Ra of blade-Ra of pot)>0.2. It is preferred that the method for producing a thermosetting resin composition uses the kneading pot in which the kneading blade has a different direction biaxial screw kneading blade.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a curable resin composition.

  Conventionally, various shapes of packages using a curable resin are applied to semiconductors. For these packages, various metal materials are used for electrical connection between the semiconductor and the outside of the package, for maintaining the strength of the package, or for transferring heat generated from the semiconductor to the outside of the package, and hardening. In many cases, it is integrally formed with a functional resin.

  At present, there is a tendency to increase the amount of light of the semiconductor, and the heat generated therewith is increasing. Therefore, the heat resistance and light resistance of the resin for the semiconductor package have been further demanded. In response to these requirements, resins that cure by a hydrosilylation reaction with high heat resistance, such as Patent Documents 1 and 2, have been applied as resins for semiconductor packages.

  From the background as described above, a curable resin described in Patent Document 3 has been developed, and a batch type kneader that can be efficiently kneaded with little risk of contamination is used.

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

  When a batch-type kneader that can be efficiently kneaded is used, there is a concern that a stagnant portion is generated during kneading, which may result in insufficient kneading or poor dispersion. The development of a method for producing a resin composition is an issue.

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 comprising (A) a curable resin, (B) a white pigment, and (C) an inorganic filler as essential components, wherein biaxial kneading blades revolve and each axis Each is a kneading machine with rotation, surface treatment of Vickers hardness of 500 or more is performed, and the kneading part surface roughness Ra is kneaded by a kneading machine having a kneading pot <kneading blade size relationship. A method for producing a thermosetting resin composition.

2). At the temperature at which the components (A), (B), and (C) are mixed, the component (A) is liquid,
It is a curable resin composition in which 5 to 60% by weight of component (A), 10 to 90% by weight of component (B), and 5 to 60% by weight of component (C) are mixed. 1) The manufacturing method of the thermosetting resin composition as described in 1).

  3). The method for producing a thermosetting resin composition according to 1) or 2), wherein the surface roughness of the kneading pot is Ra = 0.1 to 6 µm.

  4). The surface roughness of the kneading pot is Ra = 0.1-6 μm, the surface roughness of the kneading blade rotating in the same direction as the revolution is Ra = 0.3-7 μm, (Ra- of the kneading blade rotating in the same direction as the revolution) The method for producing a thermosetting resin composition according to any one of 1) to 3), wherein Ra)> 0.2 of the kneading pot.

  5). A curable resin composition comprising (A) a curable resin, (B) a white pigment, and (C) an inorganic filler as essential components, wherein biaxial kneading blades revolve and each axis Each kneading machine with rotation has a kneading blade rotating in the opposite direction to the revolution and a kneading blade rotating in the same direction as the revolution, and has been subjected to a surface treatment with a Vickers hardness of 500 or more, and the surface of the kneading part is rough. The degree Ra is kneaded in a kneading machine having a size relationship of a kneading pot <a kneading blade rotating in the opposite direction to the revolution <a kneading blade rotating in the same direction as the revolution. The manufacturing method of the thermosetting resin composition of description.

  In the present invention, in order to solve the above problem, by setting the wetted part to an appropriate surface roughness, the kneaded product can be prevented from staying and kneading shortage and poor dispersion can be solved.

  Hereinafter, the present invention will be described in detail.

<Thermosetting resin composition>
The thermosetting resin composition referred to in the present invention is a composition comprising (A) a curable resin, (B) a white pigment, and (C) an essential component of an inorganic filler.

<(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 are mixed with hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyl. Examples thereof include those cured with aliphatic acid anhydrides such as tetratetrahydrophthalic anhydride and hydrogenated methyl nadic acid 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.
The silicone resin is a resin having, as a skeleton, an organic group such as an alkyl group, an aryl group, an aralkyl group, and an epoxy group, a hydrogen atom, and a siloxane bond in which silicon atoms directly bonded to a hydroxyl group are bonded to oxygen atoms alternately. In particular, it is not limited to these.

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.
Among the silicone resins, silicone resins that are thermoset by hydrosilylation are more preferable.

  The component (A) may be liquid or solid at room temperature (25 ° C.), but at the temperature at which the components (A), (B), and (C) are mixed (kneaded), (A) The component is preferably liquid.

Among the silicon-based thermosetting resins,
(A) a 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,
It is particularly preferred that it is composed of a compound comprising
The components (a) to (c) will be described below.

<(A) component>
The component (a) is not particularly 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. Further, 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. Moreover, (a) component may be used independently and may be used in combination of 2 or more types.

  The compound (a) can be classified into a polymer compound and a 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 a monomer type compound, For example, Aromatic hydrocarbon type, such as a phenol type, a bisphenol type, benzene, and naphthalene; Aliphatic hydrocarbon type, such as a chain | strand shape and a ring; A mixture etc. are mentioned.

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 it does not specifically limit as said bivalent or more substituent, A C1-C10 substituent is preferable.

  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 compound of the 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.

  As component (a), bisphenol A diallyl ether, 2,2′-diallyl bisphenol A, novolak phenol allyl ether, diallyl phthalate, vinylcyclohexene, divinylbenzene, divinylbiphenyl, triallyl from the viewpoint of availability and reactivity Isocyanurate, diallyl monoglycidyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, and 1,2,4-trivinylcyclohexane are preferred, and triallyl isocyanurate is preferred from the viewpoint of heat resistance and light resistance. Further, diallyl monoglycidyl isocyanurate is particularly preferable from the viewpoint of adhesion to a substrate.

  The case where the component (a) is a polysiloxane containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule will be described.

  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. A polysiloxane containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule is a compound whose skeleton is substantially formed of Si—O—Si bonds, Various types such as a ring, a ring, a branch, and a partial network 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.

An example of a polysiloxane containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule may be represented by the following formula.
Rn (CH2 = CH) mSiO (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). It is.

  Examples of polysiloxanes containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule include polydimethylsiloxane, polydiphenylsiloxane, polypolysiloxane having vinyl groups as end groups or side groups. Mention may be made of methylphenylsiloxane and these two or three random or block copolymers. As the component (a), 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.

<(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 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.

<(B) component>
Component (B) is a white pigment and has the effect of increasing the light reflectance of the resulting cured product. Various components can be used as the component (B), such as titanium oxide, zinc oxide, magnesium oxide, antimony oxide, sirconia oxide, strontium oxide, niobium oxide, boron nitride, barium titanate, zinc sulfide, barium sulfate. , Magnesium carbonate, hollow glass particles, and the like. Of these, titanium oxide or zinc oxide is preferable, and titanium oxide is more preferable from the viewpoint of high light reflectance, ease of handling, availability, and cost. In addition, various average particle diameters are used, but the light reflectance of the obtained cured product is likely to be high, and from the viewpoint that the curable resin composition tablet becomes harder, 100 μm or less is preferable, More preferable is 50 μm or less, and most preferable is 25 μm or less. On the other hand, in terms of high fluidity of the curable resin composition, it is preferably 0.01 μm or more, and more preferably 0.1 μm or more.

<(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 and the like excluding the component (B), 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 Mohs hardness 4, it is preferable that 50% or more of the filler is spherical, and more preferably 75% or more. Further, the curable resin composition of the present invention contains the above-mentioned compound as a main component, and does not impair the object of the present invention, so that the solvent, the stabilizer, the antioxidant, the plasticizer, the mold release agent, and other components. Can be contained as required.

<Mixing ratio of each component>
It describes about the ratio of each component with respect to curable resin composition.
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 with respect to the entire curable resin composition. 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 component (A) may be 5% by weight or more, preferably 7% by weight or more, and more preferably 9% by weight or more based on the entire curable resin composition. 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.

  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 with respect to the entire curable resin composition. 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 10% by weight or more, more preferably 30% by weight or more based on the entire curable resin composition. When it becomes below the said lower limit ratio, the whiteness of curable resin composition will not be ensured.

  The upper limit ratio of component (C) may be 60% by weight or less, and preferably 50% by weight or less, based on the entire curable resin composition. 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 curable resin composition. 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 blend the component (A) in the ratio of 5 to 60% by weight, the component (B) in the range of 10 to 90% by weight, and the component (C) in the ratio of 5 to 60% by weight. It can be said that the composition is balanced in terms of fluidity, whiteness, strength, and linear expansion coefficient of the inner particles.

<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. 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 light emission, or a plurality of light emitting diode elements may be used for single color or multicolor light emission.

<Transparent encapsulant for light-emitting diode>
The semiconductor encapsulant of the present invention is not particularly limited, and can be used by selecting one or two or more kinds in any combination as required from 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.

<Kneading machine>
The kneader used in the examples of the present invention is a mixing stirrer 5XDMV-Qr (manufactured by Shinagawa Kogyo), but 1) the kneading blade revolves, 2) the kneading blade rotates, and 3) the kneading blade is 1 It is not particularly limited as long as it is a biaxial kneader that satisfies at least one of the above conditions 1) to 3).

  The rotational speed and the internal volume are not particularly limited, but the rotational speed is preferably 1 to 300 rpm and the internal volume is 1 to 200 L from the viewpoint of productivity. The revolving direction of the kneading blade may be one direction or may rotate in both forward and reverse directions. The rotation direction of the kneading blades is not particularly limited regardless of whether the kneading blades are in the same direction or different directions.

  The kneading blade that rotates in the same direction as the revolution direction does not have a strong kneading force, but has a function of pressing the kneaded material in a wide range against the kettle, and thus can apply a wide range of shear. The kneading blade rotating in the reverse direction of the revolution direction has a narrow kneading range but a strong kneading force and has an action of scraping off the kneaded material adhering to the kettle. In the case where the two kneading blades rotate in the same direction as the revolution direction, the kneading material adhering to the hook wall surface is not scraped off and may adhere to the wall surface. On the other hand, when the two kneading blades rotate in the direction opposite to the revolution direction, the range in which the kneading can be carried out is narrow. Therefore, it is necessary to spend sufficient time to uniformly knead the entire kneaded product, and the productivity is poor. Based on the above, the two kneading blades each have a kneading blade that rotates in the same direction as the revolution direction and a kneading blade that rotates in the opposite direction to the revolution direction, and has the effect of applying shear and scraping the kneaded material. Is preferable.

  The material of the kneading blade and the kneading pot is not particularly limited, but SUS304, SCS13, and SS400 are preferable in terms of workability, rust resistance, and cost. The surface treatment of the kneading blade and the kneading pot is not limited. However, in order to prevent the kneading blade and the kneading pot from being worn by the raw material used, it is preferable to perform a surface treatment having a higher hardness than the raw material used. The instrument for measuring the Vickers hardness is not particularly limited, but in the examples of the present invention, the Vickers hardness was measured using a micro hardness tester MXT30 manufactured by Matsuzawa Co., Ltd. The Vickers hardness is preferably 500 or more, and more preferably 600 or more. If the Vickers hardness is less than 500, the kneaded product wears the kneading pot, causing discoloration of the kneaded product and contamination of foreign matter. As the surface treatment having such hardness, a hard chrome plating treatment is preferable, and an aluminum sprayed one is more preferable. Surface roughness (Ra) refers to the arithmetic average roughness measured by the small surface roughness measuring machine Surf Test SJ-210 manufactured by Mitutoyo Corporation. The surface roughness Ra preferably has a kneading pot <a kneading blade rotating in a direction different from the revolution> <a kneading blade rotating in the same direction as the revolution. Further, when the surface roughness of the kneading kettle is high, a retention portion is formed in the kneading kettle. Therefore, the surface roughness of the kneading kettle is preferably Ra = 0.1 to 6 µm, more preferably Ra = 0.15 to 5 µm, particularly preferably Ra = 0.2 to 4 μm. If the surface roughness is smaller than the above range, the kneaded material cannot be slip kneaded on the surface of the kneading kettle, and if it is larger, the kneaded material stays in the kneading kettle.

  If the kneading blade has a surface roughness lower than that of the kneading kettle, the kneaded material cannot be scraped off from the kneading kettle. Therefore, the surface roughness must be higher than that of the kneading kettle, and Ra = 0.3 to 7 μm is preferable.

  The relationship between the Ra of the kneading vessel and the Ra of the kneading blade rotating in the same direction as the revolution is preferably (Ra of the kneading blade rotating in the same direction as the revolution−Ra of the kneading vessel)> 0.2, preferably (revolving) Of the kneading blade rotating in the same direction as that of the kneading vessel Ra)> 0.5, more preferably (Ra of the kneading blade rotating in the same direction as the revolution-Ra of the kneading vessel)> 0.9, more preferably (revolving) Of the kneading blade rotating in the same direction as that of the ra-kneading pot Ra)> 1.0. If the relationship of the surface roughness is smaller than the above range, the kneaded product tends not to be scraped off from the kneading pot by the kneading blade, so the above range is preferable.

  The shape of the hook is not particularly limited, but a shape with a curved corner is preferred so that there is no stagnant portion as much as possible. The kneading blade is preferably 0.5% to 90%, more preferably 1% to 70% of the kneading volume. When the proportion of the kneading blade increases with respect to the kneading volume, the processing amount decreases. On the other hand, if the proportion of the kneading blades decreases with respect to the kneading volume, the kneading space is reduced and the kneading becomes insufficient. As the kneading blade shape, there are a kneading mechanism and a lifting mechanism, a screw beater having a three-dimensional structure in which the screw is twisted, a two-dimensional structure beater, a spiral hook having a structure in which the screw beater is halved, There are hooks with a half-beater structure. In the case of a screw having a two-dimensional structure, a portion where the kneading blades do not pass through the kneading pot increases, and the staying portion increases, which may not be suitable for kneading. Therefore, from the viewpoint of kneadability, it is preferable to use a screw beater having at least one kneading mechanism. When using the kneading blades of the same shape, once the kneaded material stays in contact with the kneaded material in the same cycle, the kneaded material continues to be caught in the staying portion and cannot be kneaded. Therefore, by using a kneading blade having a different shape, the period at which the kneading blade collides with the kneaded product is changed, and the kneaded material in the staying part is updated, so that the kneaded material can be continuously kneaded without being retained.

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.

Example 1
A mixture of (A) to (C) was kneaded to prepare a curable resin composition.
(A) 10.0% by weight of the blend shown in Component Composition 1 was used. 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.
(B) Component Titanium oxide (average particle size 0.21 μm) manufactured by Ishihara Sangyo Co., Ltd. was used at 23.3% by weight.
(C) Component 66.4% by weight of spherical silica (average particle size 10.6 μm) manufactured by Tatsumori Co., Ltd. was used.
Further, 0.27% by weight of zinc stearate and 0.03% by weight of antioxidant were used as additives.
As a kneader, a mixing agitator 5XDMV-Qr manufactured by Shinagawa Kogyo was used. The biaxial kneading blade revolves, and has a kneading blade that rotates in the same direction as the revolution and a kneading blade that rotates in the same direction as the revolution, and the wetted part is subjected to alumina spraying with a Vickers hardness of about 900, The surface roughness of the kneading pot with Ra = 0.3μm, the surface roughness of the kneading blade rotating in the direction different from the revolution with Ra = 3μm, and the surface roughness of the kneading blade rotating in the same direction with the revolution with Ra = 3μm The kneading kettle temperature was set at 35 ° C. with a rotation speed of 30 rpm.

(Example 2)
When kneading the mixture of Example 1, Ra = 0.1 μm for the kneading pot of the kneader, Ra = 0.3 μm for the kneading blade rotating in the direction different from the revolution, and Ra = 3 μm for the kneading blade rotating in the same direction as the revolution. The sample was prepared at a rotation speed of 30 rpm. As a result, the kneaded product did not adhere to the kneading pot during kneading, and a good kneaded product was obtained.

(Comparative Example 1)
When kneading the mixture of Example 1, the surface roughness of the kneading pot of the kneader is Ra = 8 μm, the surface roughness of the kneading blade rotating in the direction different from the revolution is Ra = 8 μm, and the kneading rotating in the same direction as the revolution. The blade surface roughness was Ra = 8 μm and produced at a rotation speed of 30 rpm. As a result, the kneaded material was fixed in a layered manner to the bottom of the kneading vessel during kneading, and the appearance of the kneaded material was different between the kneading vessel contact portion and the inside of the kneading vessel, so that a good kneaded material could not be obtained.

(Comparative Example 2)
When the mixture of Example 1 is kneaded, the surface roughness of the kneading pot of the kneader is Ra = 3 μm, the surface roughness of the kneading blade rotating in the direction different from the revolution is Ra = 0.3 μm, and the rotation is the same direction as the revolution. A kneading blade having a surface roughness of Ra = 0.3 μm was prepared at a rotation speed of 30 rpm. As a result, the kneaded material was fixed in a layered manner to the bottom of the kneading vessel during kneading, and the appearance of the kneaded material was different between the kneading vessel contact portion and the inside of the kneading vessel, so that a good kneaded material could not be obtained.

In Examples 1 and 2, the kneading could be continuously performed without a decrease in torque during the kneading.
In Comparative Examples 1 and 2, the kneaded material stayed and adhered to the kneading pot, and a good kneaded material could not be obtained. This is thought to be because the kneaded material that contacted the kneading pot with the kneading blade could not be scraped off.

Claims (5)

A curable resin composition comprising (A) a curable resin, (B) a white pigment, and (C) an inorganic filler as essential components, wherein biaxial kneading blades revolve and each axis Each is a kneading machine with rotation, surface treatment of Vickers hardness of 500 or more is performed, and the kneading part surface roughness Ra is kneaded by a kneading machine having a kneading pot <kneading blade size relationship. A method for producing a thermosetting resin composition.
At the temperature at which the components (A), (B), and (C) are mixed, the component (A) is liquid,
It is a curable resin composition in which 5 to 60% by weight of component (A), 10 to 90% by weight of component (B), and 5 to 60% by weight of component (C) are mixed. The method for producing a thermosetting resin composition according to claim 1.
The method for producing a thermosetting resin composition according to claim 1 or 2, wherein the surface roughness of the kneading pot is Ra = 0.1 to 6 µm.
The surface roughness of the kneading pot is Ra = 0.1-6 μm, the surface roughness of the kneading blade rotating in the same direction as the revolution is Ra = 0.3-7 μm, (Ra- of the kneading blade rotating in the same direction as the revolution) The method for producing a thermosetting resin composition according to any one of claims 1 to 3, wherein Ra of the kneading pot> 0.2.
  A curable resin composition comprising (A) a curable resin, (B) a white pigment, and (C) an inorganic filler as essential components, wherein biaxial kneading blades revolve and each axis Each kneading machine with rotation has a kneading blade rotating in the opposite direction to the revolution and a kneading blade rotating in the same direction as the revolution, and has been subjected to a surface treatment with a Vickers hardness of 500 or more, and the surface of the kneading part is rough. The degree Ra is kneaded in a kneader having a size relationship of kneading pot <kneading blade rotating in a different direction from revolution <kneading blade rotating in the same direction as revolution. The manufacturing method of the thermosetting resin composition of description.