JP2017197595A - Curable resin composition, curable resin composition tablet, molded body, semiconductor package, semiconductor component, light-emitting diode, and method for manufacturing semiconductor package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition which suppresses moisture intrusion by reducing a reactive functional group on a resin surface after a curable resin has been cured, and can suppress wetting and spreading of a sealing agent in a light-emitting diode, and to provide a curable resin composition tablet, a molded body, a semiconductor package, a semiconductor component, and a light-emitting diode.SOLUTION: A curable resin composition has a contact angle to a surface of a plate-like molded body of a cured product of a curable resin composition of 35° or more, and has a contact angle of water to the surface of the plate-like molded body of 105° or more, at the lapse of time of 60 seconds after dropping of a phenyl silicone-based sealing agent having a viscosity of 5.3-6.3 Pa s. The curable resin composition contains (A) an organic compound containing two or more carbon-carbon double bonds having reactivity with an SiH group in one molecule, (B) a compound containing two or more SiH groups in one molecule, (C) a hydrosilylation catalyst, (D) a silicone compound having hydrocarbon having 1-5 carbon atoms in its side chain and terminal, and a siloxane unit in its main chain, and (E) an inorganic filler.SELECTED DRAWING: None

Description

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

  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.

  A semiconductor package in which the metal material and the curable resin are integrally formed has a risk of deterioration of the semiconductor due to moisture entering from a boundary portion between the metal portion and the resin portion (Patent Documents 1 and 2). Therefore, the curable resin is required to increase the adhesion to the semiconductor element or the metal material, and a curable resin having many reactive functional groups on the resin surface at the time of curing has been adopted. In recent years, due to high power and downsizing, reliability has become more important than ever, and having many reactive functional groups in terms of heat resistance and water resistance of semiconductor packages. It can be a problem.

  In light emitting diodes, demands for surface mounting type light emitting diodes using a curable resin as a light reflecting material called a reflector are increasing due to demands for higher luminance and lower costs. A semiconductor element is mounted in the package, and in order to protect the semiconductor element, the semiconductor element is sealed with a resin called a sealing agent such as epoxy or silicone in which a phosphor is dispersed. The reflector and sealant need to have high adhesion, but if the affinity between the two is too high, the sealant overflows outside the reflector in the sealing process, which can lead to instability / decrease of the emission intensity. There is sex.

  On the other hand, the heat generated from the semiconductor (and light when the semiconductor is a light emitting diode) has been increasing, and the heat resistance (light resistance) of the resin for the semiconductor package has been further demanded. Responding to these requirements, a resin that has high heat resistance and is cured by a hydrosilylation reaction has been applied as a resin for semiconductor packages (Patent Documents 1 and 3).

JP 2010-62272 A JP 2009-302241 A JP 2005-146191 A

  An object of the present invention is to provide a curable resin capable of suppressing moisture penetration by reducing reactive functional groups on the resin surface after curing of the curable resin, and suppressing the wetting and spreading of the sealing agent in a light emitting diode. It is providing a composition, a curable resin composition tablet, a molded object, a semiconductor package, a semiconductor component, and a light emitting diode.

  In order to solve such a problem, the present inventors have conducted intensive research, and as a result, a curable resin composition having a contact angle of 35 ° or more after 60 seconds from the dropping of the phenylsilicone-based sealant on the surface of the plate-like molded body. As a result, the inventors have found that the above-described problems can be achieved, and have reached the present invention.

That is, the present invention has the following configuration.
1). The contact angle with respect to the surface of the plate-like molded body, which is a cured product of the curable resin composition, is 35 at the time when 60 seconds have elapsed after the phenyl silicone sealant having a viscosity of 5.3 Pa · s to 6.3 Pa · s was dropped. A curable resin composition that is at least ° C.

  2). Curable resin composition as described in 1) whose contact angle of water with respect to the plate-shaped molded object surface which is a hardened | cured material of the said curable resin composition is 105 degrees or more.

  3). The curable resin composition according to 1) or 2), wherein the curable resin composition is for a semiconductor package.

  4). (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) a compound containing at least two SiH groups in one molecule, (C) It contains a hydrosilylation catalyst, (D) a silicone compound having 1 to 5 carbon atoms in the side chain and terminal, and a siloxane unit in the main chain, and (E) an inorganic filler. The curable resin composition according to any one of 1) to 3).

  5). (D) The curable resin composition as described in 4) whose average molecular weight of a component is 200 or more and 1,000,000 or less.

  6). (D) The curable resin composition according to 4) or 5), wherein the component contains one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule.

  7). (D) The curable resin composition according to 4) or 5), wherein the component does not contain a carbon-carbon double bond having reactivity with the SiH group in one molecule.

  8). (D) The curable resin composition according to any one of 4) to 7), wherein the component is a linear or cyclic silicone compound.

  9). Curable resin composition in any one of 4) -8) whose weight of (D) component with respect to the total weight of (A) component and (B) component is 1 weight% or more.

  10). Furthermore, the curable resin composition in any one of 1) -9) containing a white pigment (F).

11). 10) a tablet comprising the curable resin composition of
At least one of the component (A) and the component (B) is a liquid having a viscosity at 23 ° C. of 50 Pa seconds or less,
The total content of the component (E) and the component (F) is 70 to 95% by weight,
The ratio of the particle | grains of 12 micrometers or less to the sum total of (E) component and (F) component is 40 volume% or more, The curable resin composition tablet characterized by the above-mentioned.

  12). It is a cured product of the curable resin composition according to any one of 1) to 10) or the curable resin composition tablet of 11), and the light reflectance at a surface wavelength of 470 nm is 90% or more. Characteristic molded body.

  13). A semiconductor package, which is a curable resin composition according to any one of 1) to 10) or a curable resin composition tablet of 11).

  14). A semiconductor package comprising a curable resin composition according to any one of 1) to 10) or an integrally formed body of a curable resin composition tablet of 11) and a metal.

  15). A method for producing a semiconductor package, wherein the curable resin composition according to any one of 1) to 10) or the curable resin composition tablet of 11) and a lead frame are integrally formed by transfer molding.

  16). The semiconductor package according to any one of 13) or 14), wherein the semiconductor package is a package formed by substantially molding a resin on one side of a metal.

  17). The semiconductor package according to any one of 13), 14), and 16), wherein the semiconductor package is a surface-mount type light emitting diode package.

  18). A semiconductor component manufactured using the semiconductor package according to any one of 13), 14) and 16).

  19). A light-emitting diode manufactured using the semiconductor package according to any one of 13), 14), and 16).

  20). The light-emitting diode according to 19), wherein the encapsulant covering the semiconductor element is a phenyl silicone-based encapsulant.

  If the curable resin composition of this invention is used, a reactive functional group can be decreased on the resin surface after hardening of curable resin, and the penetration | invasion of the water | moisture content in a semiconductor package can be suppressed. In addition, in the light emitting diode, wetting and spreading of the sealing agent can be suppressed.

Hereinafter, the present invention will be described in detail.
The curable resin composition of the present invention has a contact angle with respect to the surface of the plate-shaped molded body of 35 at the time when 60 seconds elapses after the phenyl silicone-based sealant having a viscosity of 5.3 Pa · s to 6.3 Pa · s is dropped. It is more than °. The angle is desirably 37 ° or more, and more desirably 40 ° or more. When the angle is less than 35 °, it becomes difficult to suppress the ingress of moisture into the semiconductor package and the spread of the sealant of the light emitting diode.
The molding method of the plate-shaped molded body is not particularly limited, and a molding method such as transfer molding or compression molding that is generally used for molding a curable resin composition can be used. The surface of the plate-like molded body is required to be horizontal and smooth, desirably Rz 6.3 or less, and more desirably Rz 0.8 or less.
Phenylsilicone is a polysiloxane compound that always contains a phenylsiloxane unit as a siloxane unit, and is a compound having at least one of a linear, branched, cyclic, or three-dimensional crosslinked structure. For example, methylphenylsiloxane and diphenylsiloxane can be mentioned. The phenyl silicone-based sealant is a curable resin for semiconductor encapsulation made of the above-described phenyl silicone, and specific examples include, for example, OE-6630, OE-6635, OE- manufactured by Toray Dow Corning. 7651 and the like. For the measurement of the contact angle, there is no particular designation as long as it is a phenyl silicone sealant having a viscosity of 5.3 Pa · s to 6.3 Pa · s.
The contact angle can be measured as follows.
In an atmosphere at room temperature of 25 ° C. and a relative humidity of 50%, 1 to 4 μL of phenyl silicone sealant is dropped with a syringe. By using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., contact angle meter DM-501), the droplet is observed from a horizontal cross section, and the angle formed by the tangent of the droplet edge and the plane is determined.
Since the contact angle of the phenyl silicone-based sealant changes with time, it is defined as the contact angle when 60 seconds have elapsed after dropping.

In the curable resin composition of the present invention, the contact angle of water with respect to the surface of the plate-like molded body is preferably 105 ° or more. The angle is desirably 107 ° or more, and more desirably 110 ° or more. When the angle is less than 105 °, it becomes difficult to suppress the ingress of moisture into the semiconductor package and the spread of the sealant of the light emitting diode.
The plate-shaped molded body and the measurement of the contact angle are as described above. In the case of water, the contact angle is measured when the water droplet is stabilized immediately after dropping.

(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 formed on one side of a metal (MAP type).
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 sealant, for example, conventionally used epoxy resin, silicone resin, acrylic Sealing resins such as resins, urea resins, and imide resins 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, the moldability is good, and the metal (lead frame) can be easily integrally molded. 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.

(Curable resin composition component)
The present invention relates to (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) a compound containing at least two SiH groups in one molecule. , (C) a hydrosilylation catalyst, (D) a silicone compound whose side chain and terminal are hydrocarbons having 1 to 5 carbon atoms, and whose main chain is a siloxane unit, and (E) an inorganic filler. It is preferable that it is a curable resin composition characterized by these.
Hereinafter, each component will be described.

((D) component)
The component (D) of the present invention is a silicone compound whose side chain and terminal are hydrocarbons having 1 to 5 carbon atoms and whose main chain is a siloxane unit. By using the component (D), it is possible to reduce the amount of reactive functional groups on the cured resin surface of the curable resin to suppress the ingress of moisture, and to suppress the spread of the encapsulant in the light emitting diode. .
Moreover, when it contains (D) component, when it mixes with the inorganic filler of (E) component, it can be set as the curable resin composition which gives the hardened | cured material which has a smaller linear expansion coefficient.
Examples of the substituent bonded to the skeleton include hydrocarbon groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Among these, a methyl group is more preferable in that heat resistance tends to be high. When the carbonization number is 6 or more, it becomes difficult to suppress the wetting and spreading of the sealant.

  As the molecular weight of the component (D), the average molecular weight (Mn) is preferably 200 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 average molecular weight (Mn) of the component (D) is preferably 1,000,000 or less, and more preferably 100,000 or less. When the molecular weight is large, the strength of the curable resin composition after curing becomes low.

The component (D) may or may not contain one or more carbon-carbon double bonds having reactivity with the SiH group in one molecule.
In addition, when a substituent having a carbon-carbon double bond having reactivity with the SiH group is contained, the substituent having a carbon-carbon double bond having reactivity with the SiH group includes a vinyl group, an allyl group, Although a propenyl group etc. can be mentioned, A vinyl group is preferable at the point that reactivity is good among these.

The silicone compound of component (D) is a compound whose skeleton is substantially formed of Si—O—Si bonds, and various compounds such as linear, cyclic, branched, and partial networks are available. Used.
The component (D) is more preferably a linear or cyclic siloxane, and even more preferably a linear siloxane. From the viewpoint that the effects of the present invention can be obtained more easily, linear polydimethylsiloxane having vinyl groups at the ends is preferable, and linear polydimethylsiloxane having vinyl groups at both ends is more preferable.

  As the amount of the component (D), the weight of the component (D) is preferably 1% by weight to 200% by weight with respect to the total weight of the components (A) and (B), and preferably 5% by weight to 150% by weight. % Or less is more preferable, and 10% by weight or more and 100% by weight or less is more preferable. If it is less than 1% by weight, it becomes difficult to suppress the wetting and spreading of the sealant.

((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 SiH groups in one molecule.

(Skeleton of component (A))
Organic compounds do not contain siloxane units (Si-O-Si), such as polysiloxane-organic block copolymers and polysiloxane-organic graft copolymers, and elements other than C, H, N, O, S and halogen A compound containing no element is more preferable.
In the case of containing a siloxane unit, there is a problem that the adhesion between the semiconductor package and the lead frame or the sealing resin tends to be low.
The organic compound (A) can be classified into an organic polymer compound and an organic monomer compound.

(Example when component (A) is a polymer)
As the component (A) of the organic polymer system, for example, polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based, polyacrylate ester-based, polyamide-based, phenol-formaldehyde Examples thereof include those having a skeleton of a system (phenolic resin system) or a polyimide system.
Among these, examples of the polyether polymer include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and the like. More specific examples:

(In the formula, R ¹ and R ² are C 1 -C 6 divalent organic groups containing no elements other than C, H, N, O, S and halogen as constituent elements, n, m, and l are 1 to 1; Represents a number of 300.)
Etc.

  Examples of other polymers include dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrophthalic acid, and glycols such as ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, and neopentyl glycol. Polyester polymers obtained by condensation of lactones or ring-opening polymerization of lactones, ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, Copolymers with styrene, etc., polybutadiene, copolymers with butadiene and styrene, acrylonitrile, etc., polyisoprene, polybutadiene, isoprene or copolymers with butadiene and acrylonitrile, styrene, etc. Polyolefin (saturated hydrocarbon) polymers obtained by hydrogenating the body, polyacrylates obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate, acrylic esters such as ethyl acrylate and butyl acrylate, and Acrylate ester copolymer with vinyl acetate, acrylonitrile, methyl methacrylate, styrene, etc., graft polymer obtained by polymerizing vinyl monomer in the organic polymer, polysulfide polymer, ring opening of ε-aminocaprolactam Nylon 6 by polymerization, Nylon 66 by polycondensation of hexamethylenediamine and adipic acid, Nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, Nylon 11 by polycondensation of ε-aminoundecanoic acid, ε-aminolaurolacta Nylon 12 by ring-opening polymerization of the above, polyamide-based polymer such as copolymer nylon having two or more components among the above-mentioned nylons, for example, polycarbonate heavy polymer produced by polycondensation from bisphenol A and carbonyl chloride Examples of the polymer, diallyl phthalate polymer, and phenol-formaldehyde (phenolic resin) skeleton include novolak type phenolic resin, resol type phenolic resin, ammonia resol type phenolic resin, and benzylic ether type phenolic resin.

An alkenyl group having a carbon-carbon double bond can be introduced into these polymer skeletons to obtain the component (A).
In this case, the alkenyl group having a carbon-carbon double bond may be present anywhere in the molecule, but is preferably present in the side chain or the terminal in terms of reactivity.
Various methods for introducing an alkenyl group into the polymer skeleton can be used. However, the method can be roughly divided into a method for introducing an alkenyl group after polymerization and a method for introducing an alkenyl group during polymerization. Can do.

As a method for introducing an alkenyl group after polymerization, for example, an organic polymer having a functional group such as a hydroxyl group, an alkoxide group, a carboxyl group, or an epoxy group at the terminal, main chain, or side chain is reactive with the functional group. An alkenyl group can be introduced into the terminal, main chain or side chain by reacting an organic compound having both an active group and an alkenyl group. Examples of organic compounds having both an active group and an alkenyl group reactive to the functional group include C3-C20 unsaturated groups such as acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride, and acrylic acid bromide. fatty acids, acid halides, acid anhydrides or allyl chloroformate _{(CH 2 = CHCH 2 OCOCl)} , allyl bromo formate (CH ₂ = CHCH ₂ OCOBr) unsaturated aliphatic alcohol-substituted carbonic halide C3~C20 such, Allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1 -Hexenyl (chloromethoxy) benze , Allyloxy (chloromethyl) benzene, allyl isocyanate.

There is also a method of introducing an alkenyl group using a transesterification method. This method is a method of transesterifying an alcohol residue of an ester portion of a polyester resin or an acrylic resin with an alkenyl group-containing alcohol or an alkenyl group-containing phenol derivative using a transesterification catalyst. The alkenyl group-containing alcohol and alkenyl group-containing phenol derivative used for exchange with an alcohol residue may be any alcohol or phenol derivative having at least one alkenyl group and having at least one hydroxyl group. It is preferable to have it. A catalyst may or may not be used, but a titanium-based catalyst and a tin-based catalyst are preferable.
Examples of the above compounds are vinyl alcohol, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, and 7-octene-1. -Ol, 8-nonen-1-ol, 9-decen-1-ol, 2- (allyloxy) ethanol, neopentyl glycol monoallyl ether, glyceryl diallyl ether, trimethylolpropane triallyl ether, trimethylolethane triallyl ether , Pentaerythritol tetraallyl ether, 1,2,6-hexanetriol triallyl ether, sorbitan triallyl ether,

Etc. Among these, allyl alcohol, vinyl alcohol, 3-buten-1-ol, 2- (allyloxy) ethanol, and

Is preferred.

Furthermore, the ester residue of the above-mentioned alcohol or phenol derivative such as acetate ester and the ester part of the polyester resin or acrylic resin are transesterified using a transesterification catalyst, and the alcohol residue of the ester part of the produced polyester resin or acrylic resin is changed. There is also a method of introducing an alkenyl group by a method of distilling low molecular weight esterified products such as acetates out of the system by vacuum devolatilization or the like.
Moreover, after polymerizing methyl (meth) acrylate etc. by living polymerization, an alkenyl group can also be introduce | transduced into the terminal by the method of stopping a living terminal with the compound which has an alkenyl group.

  As a method for introducing an alkenyl group during the polymerization, for example, in the case of producing the organic polymer skeleton of the component (A) used in the present invention by radical polymerization, radical reactivity in the molecule of allyl methacrylate, allyl acrylate, etc. By using a vinyl monomer having a low alkenyl group or a radical chain transfer agent having a low alkenyl group such as allyl mercaptan, an alkenyl group can be introduced into the side chain or terminal of the organic polymer skeleton. .

  As the component (A), the molecular weight is not particularly limited, but any of 100 to 100,000 can be suitably used, and an alkenyl group-containing organic polymer is particularly preferably 500 to 20,000. When the molecular weight is 500 or less, characteristics due to the use of an organic polymer such as imparting flexibility are hardly exhibited, and when the molecular weight is 100,000 or more, the effect of crosslinking due to the reaction between the alkenyl group and the SiH group is hardly exhibited.

(Example when component (A) is a monomer)
Examples of the organic monomer-based component (A) include, for example, aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: heterocyclic compounds And mixtures thereof.

(Carbon-carbon double bond of component (A))
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) Although it does not specifically limit as a carbon-carbon double bond reactive with SiH group of a component, The following general formula (I)

A group represented by the formula (wherein R ¹ represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. In addition, from the availability of raw materials,

Is particularly preferred.
As the carbon-carbon double bond having reactivity with the SiH group of the component (A), the following general formula (II)

An alicyclic group represented by the formula (wherein R ² represents a hydrogen atom or a methyl group) is preferred from the viewpoint that the heat resistance of the cured product is high. In addition, from the availability of raw materials,

The alicyclic group represented by is particularly preferable.

((A) Component carbon-carbon double bond and skeleton bond group)
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. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, but preferably does not contain elements other than C, H, N, O, S and halogen as constituent elements. Examples of these substituents include

Is mentioned. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

  Examples of the group covalently bonded to the skeleton as described above 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 (allyl) Oxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

Is mentioned.

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

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

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

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

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

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

  Specific examples of the organic monomer component (A) include 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, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof,

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

  As the component (A), low molecular weight compounds that are difficult to express separately as described above for the skeleton portion and the alkenyl group can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

(Preferred requirements for component (A))
The component (A) preferably contains 0.001 mol or more of a carbon-carbon double bond having reactivity with the SiH group per 1 g of the component (A) from the viewpoint of further improving the heat resistance. What contains 0.005 mol or more per is more preferable, and what contains 0.008 mol or more is still more preferable.

  The number of carbon-carbon double bonds having reactivity with the SiH group of component (A) should be on average at least two per molecule, but may exceed 2 if it is desired to further improve the mechanical strength. Preferably, it is 3 or more. When the number of carbon-carbon double bonds having reactivity with the SiH group of component (A) is 1 or less per molecule, only a graft structure is formed even if it reacts with component (B). Don't be.

  From the viewpoint of good reactivity as the component (A), it is preferable that one or more vinyl groups are contained in one molecule, and two or more vinyl groups are contained in one molecule. Is more preferable. Further, from the viewpoint that the storage stability tends to be good, it is preferable that 6 or less vinyl groups are contained in one molecule, and it is more preferable that 4 or less vinyl groups are contained in one molecule.

  As the component (A), the viewpoint that the mechanical heat resistance is high, the viewpoint that the raw material liquid has little stringiness, the moldability and the handleability are good, and the powders such as the component (E) and the component (F) From the viewpoint of easy uniform mixing and good moldability when used as a curable resin composition tablet, those having a molecular weight of less than 900 are preferred, those having a molecular weight of less than 700 are more preferred, and less than 500 Are more preferred.

  As the component (A), in order to obtain uniform mixing with other components and good workability, the viscosity is preferably less than 1000 poise at 23 ° C., more preferably less than 300 poise, More preferred is less than 30 poise. The viscosity can be measured with an E-type viscometer.

  As the component (A), those having a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable from the viewpoint of higher light resistance. A phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group is preferable. What does not contain the compound which has is preferable. In the present invention, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and a phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxy group, or the like.

  Further, from the viewpoint of particularly good light resistance, the weight ratio of the component (A) in the aromatic ring is preferably 50% by weight or less, more preferably 40% by weight or less, and more preferably 30% by weight. The following are more preferable. Most preferred are those that do not contain an aromatic hydrocarbon ring.

  From the viewpoint that the resulting cured product is less colored and has high light resistance, the component (A) includes vinylcyclohexene, dicyclopentadiene, vinylnorbornene, triallyl isocyanurate, 2,2-bis (4-hydroxycyclohexyl). Preferred is diallyl ether of propane, 1,2,4-trivinylcyclohexane, particularly preferred is triallyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, and 1,2,4-trivinylcyclohexane. .

(Preferred structure 1 of component (A))
As the component (A), from the viewpoint of particularly high heat resistance and light resistance, the following general formula (III)

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same).
As R < ¹ > of the said general formula (III), it is preferable that it is a C1-C20 monovalent organic group from a viewpoint that the heat resistance of the hardened | cured material obtained can become higher, and C1-C1 10 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 4 carbon atoms are more preferable. Examples of these preferable R ¹ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

Etc.
The R ^{1 in the} general formula (III) includes three R ¹ from the viewpoint that the adhesiveness between the package and the lead frame or the sealing agent can be improved, or the mechanical strength of the obtained package can be increased. It is preferable that at least one of them is a monovalent organic group having 1 to 50 carbon atoms including one or more epoxy groups,

It is more preferable that it is a C1-C50 monovalent organic group containing 1 or more of epoxy groups represented by these. Examples of these preferable R ¹ include a glycidyl group,

Etc.
R ^{1 in the} general formula (III) is a carbon containing two or less oxygen atoms and containing only C, H, and O as constituent elements from the viewpoint that the heat resistance of the resulting cured product can be improved. A monovalent organic group having 1 to 50 carbon atoms is preferable, and a monovalent hydrocarbon group having 1 to 50 carbon atoms is more preferable. Examples of these preferable R ¹ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

Etc.
R ^{1 in the} general formula (III) is at least one of three R ¹ from the viewpoint of good reactivity.

It is preferable that it is a C1-C50 monovalent organic group containing 1 or more groups represented by general formula (IV) below.

More preferably (wherein R ² represents. A hydrogen atom or a methyl group) is a monovalent organic group having 1 to 50 carbon atoms containing at least one group represented, at least of the three R ¹ Two are the following general formula (V)

(Wherein R ³ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group) (a plurality of R ³ and R ⁴ are More preferably, they may be the same or different.

R ^{3 in the} general formula (V) is a direct bond or a divalent organic group having 1 to 48 carbon atoms. From the viewpoint that the heat resistance of the resulting package can be further increased, the direct bond or the carbon number It is preferably a divalent organic group having 1 to 20, more preferably a direct bond or a divalent organic group having 1 to 10 carbon atoms, and a direct bond or a divalent organic group having 1 to 4 carbon atoms. More preferably. Examples of these preferred R ³ include

Etc.
As R ^{3 in the} general formula (V), from the viewpoint that the heat resistance of the resulting package can be improved, only C, H, or O is included as a constituent element including a direct bond or two or less oxygen atoms. A divalent organic group having 1 to 48 carbon atoms is preferable, and a direct bond or a divalent hydrocarbon group having 1 to 48 carbon atoms is more preferable. Examples of these preferred R ³ include

Is mentioned.
R ^{4 in the} general formula (V) is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of good reactivity.
However, in the preferred examples of the organic compound represented by the general formula (III) as described above, it is necessary to contain at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule. is there. From the viewpoint that heat resistance can be further improved, an organic compound containing three or more carbon-carbon double bonds having reactivity with SiH groups in one molecule is more preferable. Preferable specific examples of the organic compound represented by the general formula (III) as described above include triallyl isocyanurate,

Etc.

(Preferred structure 2 of component (A))
In addition, from the viewpoint of having good compatibility with the component (B), and from the viewpoint that the volatility of the component (A) is low and the problem of outgas from the resulting package is less likely to occur, examples of the component (A) As described above, at least one compound selected from organic compounds containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule, and a compound having a SiH group (β) A reaction product with is also preferred.

((Β) component)
The component (β) is a compound having a SiH group, and a chain and / or cyclic polyorganosiloxane having a SiH group is an example.
Specifically, for example

Is mentioned.
Here, from the viewpoint that compatibility with an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule is likely to be improved, the following general formula (VI)

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

The substituent R ¹ in the compound represented by the general formula (VI) preferably does not contain a constituent element other than C, H, and O, more preferably a hydrocarbon group, and a methyl group. Further preferred.
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 an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH group in one molecule and (β) component)
Next, as component (A) of the present invention, an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule and (β) component are obtained by hydrosilylation reaction. The hydrosilylation reaction between an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule and the (β) component in the case of using a compound capable of reacting with SiH will be described.

  A hydrosilylation reaction of an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule and the (β) component results in a plurality of compounds containing the component (A) of the present invention. However, the curable resin composition of the present invention can also be prepared by using the mixture as it is without separating the component (A).

  Carbon-carbon double having reactivity with SiH group when hydrosilylation reaction of organic compound containing at least two carbon-carbon double bonds reactive with SiH group in one molecule and (β) component The mixing ratio of the organic compound containing at least two bonds in one molecule and the (β) component is not particularly limited, but generally is reactive with the SiH group to be mixed in that gelation during the reaction can be suppressed. In the (β) component to be mixed with the total number (X) of carbon-carbon double bonds having reactivity with SiH groups in an organic compound containing at least two carbon-carbon double bonds in one molecule The ratio of the total number of SiH groups (Y) is preferably X / Y ≧ 2, more preferably X / Y ≧ 3. Moreover, it is preferable that it is 10> = X / Y from the point that compatibility with (B) component of (A) component becomes easy, and it is more preferable that it is 5> = X / Y.

In the case of hydrosilylation reaction of an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH group in one molecule and the (β) component, 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 as a method of mixing the organic compound containing at least two carbon-carbon double bonds reactive with the SiH group in the case of reaction, the (β) component, and the catalyst. However, a method in which a catalyst is mixed with an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule is mixed with the (β) component. Organic containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule

  It is difficult to control the reaction when the catalyst is mixed with the mixture of the compound and the (β) component. In the case of adopting a method of mixing an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups into a mixture of component (β) and a catalyst, in the presence of the catalyst ( Since β) is reactive with moisture mixed therein, it may be altered.

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 (β) component with an organic compound containing at least two carbon-carbon double bonds reactive with SiH group in one molecule, it has reactivity with solvent and / or unreacted SiH group Organic compounds containing at least two carbon-carbon double bonds per molecule and / or (β) component can also be removed. By removing these volatile components, the obtained component (A) does not have a volatile component, so that in the case of curing with the component (B), problems of voids and cracks due to the volatilization of the volatile components are less likely to occur. 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.

  Examples of the component (A) which is a reaction product of the organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule and the component (β) are bisphenol. A reaction product of diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, divinylbenzene and 1,3,5, Reaction product of 7-tetramethylcyclotetrasiloxane, reaction product of dicyclopentadiene and 1,3,5,7-tetramethylcyclotetrasiloxane, triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane Reaction of diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane Applied Physics, mention may be made of reaction products of vinyl norbornene and bis dimethylsilyl benzene.

(Other reactive groups of component (A))
(A) As a component, you may have another reactive group. 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.

(Mixing of component (A))
(A) component can be used individually or in mixture of 2 or more types.

((B) component)
The component (B) is a compound containing at least two SiH groups in one molecule.
The component (B) 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 WO 96/15194 is at least two SiH groups in one molecule. Those having a group can be used.
Among these, from the viewpoint of availability, a chain and / or cyclic organopolysiloxane having at least two SiH groups in one molecule is preferable, and from the viewpoint of good compatibility with the component (A), Furthermore, the following general formula (VI)

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

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

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

  The molecular weight of the component (B) is not particularly limited, and any one can be suitably used. However, the viewpoint that the fluidity is more easily expressed and the powder such as the component (E) and the component (F) is easily mixed uniformly. Are preferably those having a low molecular weight. In this case, the lower limit of the preferred molecular weight is 50, and the upper limit of the preferred molecular weight is 100,000, more preferably 1,000, and still more preferably 700.

As component (B), in order to facilitate uniform mixing with other components, particularly powders such as component (E) and component (F), more specifically, heating above the melting point for uniform mixing. The liquid is preferably liquid at 23 ° C., and its viscosity is preferably 50 Pa seconds or less at 23 ° C., more preferably 20 Pa seconds or less, and more preferably 5 Pa seconds or less. Further preferred. The viscosity can be measured with an E-type viscometer.
Component (B) can be used alone or in combination of two or more.

(Preferred structure of component (B))
From the viewpoint of having good compatibility with the component (A), and from the viewpoint that the problem of outgas from the curable resin composition that can be reduced in volatility of the component (B) is less likely to occur, the component (B) An organic compound (α) containing at least one carbon-carbon double bond reactive with a SiH group in one molecule and a compound (β) having at least two SiH groups in one molecule are hydrosilylated. It is preferable that the compound is obtained by a chemical reaction.

((Α) component)
Here, the component (α) is the component (A) described above, and the same component (α1) as the organic compound containing at least two carbon-carbon double bonds reactive with the SiH group in one molecule is used. Can do. When the component (α1) is used, the resulting cured product has a high crosslink density and tends to be a cured product having high mechanical strength.
In addition, an organic compound (α2) containing one carbon-carbon double bond having reactivity with the SiH group in one molecule can also be used. When the (α2) component is used, the obtained cured product tends to have low elasticity.

((Α2) component)
The component (α2) is not particularly limited as long as it is an organic compound containing one carbon-carbon double bond having reactivity with the SiH group in one molecule, but the component (B) is in phase with the component (A). In terms of improved solubility, the compound does not contain a siloxane unit (Si—O—Si) such as a polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, and C, H, N as constituent elements. , O, S, and halogen are preferred.
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.

The (α2) component compound can be classified into a polymer compound and a monomer compound.
Examples of the polymer compound include polysiloxane, polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde ( Phenol resin type) and polyimide type compounds can be used.
Examples of monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as straight-chain and alicyclics: heterocyclic compounds, and silicon-based compounds. Examples thereof include compounds and mixtures thereof.
Although it does not specifically limit as a carbon-carbon double bond which has the reactivity with SiH group of ((alpha) 2) component, The following general formula (I)

A group represented by the formula (wherein R ¹ represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. In addition, from the availability of raw materials,

Is particularly preferred.
As the carbon-carbon double bond having reactivity with the SiH group of the component (α2), the following general formula (II)

An alicyclic group represented by the formula (wherein R ² represents a hydrogen atom or a methyl group) is preferred from the viewpoint that the heat resistance of the cured product is high. In addition, from the availability of raw materials,

The alicyclic group represented by is particularly preferable.
The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the (α2) component, or may be covalently bonded via a divalent or higher substituent. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms. However, in terms that the component (B) is easily compatible with the component (A), C, Those containing only H, N, O, S and halogen are preferred. Examples of these substituents include

Is mentioned. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.
Examples of the group covalently bonded to the skeleton as described above 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 (allyl) Oxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group,

Is mentioned.

  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 (VI)

(Wherein R ¹ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10). Cyclic polyorganosiloxane having at least three SiH groups in one molecule. Is preferred.
The substituent R ¹ in the compound represented by the general formula (VI) is preferably composed of C, H, and O, more preferably a hydrocarbon group, and a methyl group. Is more preferable.
In view of availability, 1,3,5,7-tetramethylcyclotetrasiloxane is preferable.

Other examples of the (β) component include compounds having a SiH group such as bisdimethylsilylbenzene.
Various (β) components as described above can be used alone or in admixture of two or more.

(Reaction of (α) component and (β) component)
Next, hydrosilylation of (α) component and (β) component in the case of using a compound obtained by hydrosilylation reaction of (α) component and (β) component as component (B) of the present invention The 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 containing the (B) component of the present invention may be obtained, but without separating the (B) component therefrom. The curable resin composition of the present invention can also be prepared using the mixture as it is.

  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 hydrosilylation of the obtained (B) component and (A) component is not limited. In view of the strength of the cured product due to the above, since it is preferable that the component (B) has a larger amount of SiH groups, the total number of carbon-carbon double bonds having reactivity with the SiH groups in the component (α) to be mixed ( The ratio of X) to the total number of SiH groups (Y) in the (β) component to be mixed is preferably Y / X ≧ 2, and more preferably Y / X ≧ 3. Moreover, it is preferable that it is 10> = Y / X from the point that compatibility with the (A) component of (B) 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 component (B) obtained does not have volatile components, so that the problem of voids and cracks due to volatilization of the volatile components hardly occurs in the case of curing with the component (A). 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.

  Examples of the component (B) that is a reaction product of the component (α) and the component (β) as described above include a reaction product of bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, Reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, dicyclopentadiene and 1,3,5, Reaction product of 7-tetramethylcyclotetrasiloxane, reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclo Reactant of tetrasiloxane, allyl glycidyl ether and 1,3,5,7-tetramethylcyclotetrasilo A reaction product of xane, 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.

(Mixing of component (A) and component (B))
Regarding combinations of component (A) and component (B), various combinations of those listed as examples of component (A) and their various mixtures / examples of component (B) and their various mixtures are listed. be able to.

  The mixing ratio of the component (A) and the component (B) is not particularly limited as long as the necessary strength is not lost, but the number of SiH groups in the component (B) (Y) is the carbon-carbon in the component (A). In the ratio to the number of double bonds (X), the lower limit of the preferred range is Y / X ≧ 0.3, more preferably Y / X ≧ 0.5, and even more preferably Y / X ≧ 0.7, which is preferable. The upper limit of the range is 3 ≧ Y / X, more preferably 2 ≧ Y / X, and even more preferably 1.5 ≧ Y / X. If it is out of the preferred range, sufficient strength may not be obtained, or thermal deterioration may easily occur.

((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 groups of the component (B) in order to have sufficient curability and keep the cost of the curable resin composition relatively low. 10 ⁻⁸ mol, more preferably 10 ⁻⁶ mol, and the upper limit of the preferable addition amount is 10 ⁻¹ mol, more preferably 10 ⁻² mol, relative to 1 mol of SiH group of the component (β).
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.

((E) component)
The component (E) is an inorganic filler.
The component (E) has an effect of increasing the strength and hardness of the obtained cured product and reducing the linear expansion coefficient.

  As the inorganic filler of the component (E), 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, titanium oxide, zinc oxide, silicon nitride, boron 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, magnesium carbonate, barium sulfate, barium titanate, potassium titanate, calcium silicate, inorganic balloons, conventional fillers such as epoxy, as well as silver powder Inorganic fillers that are generally used and / or proposed as fillers for That. 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. Titanium oxide is preferred in that the light reflectance of the package resin is high and the light extraction efficiency of the resulting light emitting diode tends to be high. 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.

  As the order of mixing the inorganic filler of the component (E), various methods can be used, but in the point that the storage stability of the intermediate raw material of the curable resin composition tends to be good, the component (A) A method of mixing the component (C) and the inorganic filler with the component (B) is preferable. When the method of mixing the component (A) with the component (B) mixed with the component (C) and / or the inorganic filler, the component (B) is present in the presence and / or absence of the component (C). Has a reactivity with moisture and / or inorganic fillers in the environment, and may be altered during storage. In addition, (A) component, (B) component, (C) in that (A) component, (B) component, and (C) component which are reaction components are well mixed and a stable molded product is easily obtained. It is preferable to mix a mixture of components and an inorganic filler.

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

((F) component)
The curable resin composition of the present invention preferably contains a white pigment (component (F)).
The component (F) 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 (F), for example, titanium oxide, zinc oxide, magnesium oxide, antimony oxide, zirconia oxide, strontium oxide, niobium oxide, boron nitride, barium titanate, zinc sulfide, barium sulfate. , Magnesium carbonate, hollow glass particles, and the like. Among these, titanium oxide or zinc oxide is preferable from the viewpoint of ease of handling, availability, and cost.

  Various components can be used as the component (F) titanium oxide, which may be anatase type or rutile type, but it is not photocatalytic and the curable resin composition is likely to be stable. A rutile type is preferred.

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

On the other hand, in terms of high fluidity of the curable resin composition, it is preferably 0.05 μm or more, and more preferably 0.1 μm or more.
The average particle diameter can be measured using a laser diffraction / scattering particle size distribution analyzer.
As the method for producing the component (F) titanium oxide, those produced by any method such as sulfuric acid method and chlorine method can be used.
The component (F) may be subjected to surface treatment.

  In the surface treatment of the component (F), the surface of the component (F) 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 (F) 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 dry pulverizing titanium oxide, when slurrying, or when wet pulverizing. It can be carried out. In addition, there are various methods such as a liquid phase method and a gas phase method.
Among these, the cured product obtained is preferably treated with an organic siloxane treatment because the light reflectance is high and the heat and light resistance is improved. In addition, the inclusion of an organosiloxane-treated titanium oxide is suitable for producing an excellent light-emitting diode that has high light extraction efficiency and does not decrease light extraction efficiency even when used for a long period of time.

In this case, various organic siloxane treating agents are used. For example, polysiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, or copolymers thereof, hexamethylcyclotrisiloxane, heptamethylcyclotetrasiloxane, 1,3,5,7-tetra Cyclosiloxanes such as methylcyclotetrasiloxane, chlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and other silanes having an epoxy functional group, 3-methacryloxypropyltrimethyl Xysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, Silanes having a methacrylic group or an acrylic group such as acryloxymethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, etc. Silanes, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane and other mercaptosilanes, γ-aminopropyltriethoxy Γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, Silanes having amino groups, such as N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, isocyanate Silanes having an isocyanate group such as propyltrimethoxysilane and isocyanatepropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxy Silane coupling agents exemplified by various silanes such as silanes having alkyl groups such as silane and octyltriethoxysilane, and other silanes such as γ-chloropropyltrimethoxysilane and γ-anilinopropyltrimethoxysilane And hexamethyldisiloxane and hexamethyldisilazane. These surface treatment agents preferably contain no carbon-carbon double bonds, and if they contain carbon-carbon double bonds, the heat resistance tends to decrease. Further, a surface treatment other than the organic siloxane can be used in combination, and treatment with Al, Zr, Zn, or the like can also be performed.
Moreover, it may be surface-treated with an inorganic compound.

The surface treatment with an inorganic compound is not particularly limited, and various surface treatments such as an aluminum compound, a silicon compound, and a zirconium compound are used. Titanium oxide may be surface-treated with an inorganic compound or an organic compound for the purpose of improving durability, improving affinity with the medium, or preventing the collapse of the particle shape, but the component (F) is inorganic. 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 (F) in 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 (F) is not particularly limited, but the amount of the component (F) 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.

(Amount of component (E) and component (F))
The total amount of the component (E) and the component (F) is not particularly limited, but the total amount of the component (E) and the component (F) in the entire curable resin composition is preferably 70% by weight or more. It is more preferably 85% by weight or more, and further preferably 90% by weight or more. The maximum amount of the total amount of component (E) and component (F) is preferably 98% by weight or less.
When the total amount of the component (E) and the component (F) is small, it is difficult to obtain the effect of increasing the strength and hardness or reducing the linear expansion coefficient.
As the mixing order of the component (F), various methods can be used, but the preferred embodiment is the same as (E) described above. Moreover, you may add (F) component and (E) component simultaneously.
As means for mixing the component (F), the same means as the means for mixing the component (E) can be used.

((G) component)
The curable resin composition of the present invention desirably contains a metal soap (component (G)).
(G) A component is added in order to improve the moldability including the mold release property of a curable resin composition.
Examples of the component (G) include various conventionally used metal soaps. The metal soap here is generally a combination of long-chain fatty acids and metal ions. The nonpolar or low polarity part based on fatty acids and the polar part based on the metal binding part are combined in one molecule. Can be used. Examples of the long chain fatty acid include saturated fatty acids having 1 to 18 carbon atoms, unsaturated fatty acids having 3 to 18 carbon atoms, and aliphatic dicarboxylic acids. Among these, saturated fatty acids having 1 to 18 carbon atoms are preferable from the viewpoint of easy availability and high industrial feasibility, and 6 to 18 carbon atoms from the viewpoint of high effect of releasability. The saturated fatty acid is more preferable. Examples of metal ions include zinc, cobalt, aluminum, strontium, and the like in addition to alkali metals and alkaline earth metals. Specific examples of metal soaps include lithium stearate, lithium 12-hydroxystearate, lithium laurate, lithium oleate, lithium 2-ethylhexanoate, sodium stearate, sodium 12-hydroxystearate, lauric acid Sodium, sodium oleate, sodium 2-ethylhexanoate, potassium stearate, potassium 12-hydroxystearate, potassium laurate, potassium oleate, potassium 2-ethylhexanoate, magnesium stearate, magnesium 12-hydroxystearate, Magnesium laurate, magnesium oleate, magnesium 2-ethylhexanoate, calcium stearate, calcium 12-hydroxystearate, calcium laurate , Calcium oleate, calcium 2-ethylhexanoate, barium stearate, barium 12-hydroxystearate, barium laurate, zinc stearate, zinc 12-hydroxystearate, zinc laurate, zinc oleate, 2-ethylhexane Examples include zinc acid, lead stearate, lead 12-hydroxystearate, cobalt stearate, aluminum stearate, manganese oleate, barium ricinoleate, and the like. Among these metal soaps, metal stearates are preferred from the viewpoint of easy availability, safety and industrial feasibility, and calcium stearate, magnesium stearate, stearin are particularly preferred from the viewpoint of economy. Most preferred is one or more selected from the group consisting of zinc acid.
Although there is no restriction | limiting in particular as addition amount of this metal soap, The minimum of a preferable amount is 0.01 weight part with respect to 100 weight part of the whole curable resin composition, More preferably, it is 0.025 weight part, More preferably, it is 0. The upper limit of the preferable amount is 5 parts by weight, more preferably 4 parts by weight with respect to 100 parts by weight of the entire curable resin composition. When the addition amount is too large, the physical properties of the cured product are deteriorated. When the addition amount is too small, mold releasability may not be obtained.

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

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

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

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

The addition amount of the curing retarder can be selected at various levels, the preferred amount of the lower limit is 10 ^-1 moles with respect to hydrosilylation catalyst 1mol used, more preferably 1 mol, the upper limit of the preferable amount is 10 ³ mol, more preferably Is 50 moles.
Moreover, these hardening retarders may be used independently and may be used together 2 or more types.

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

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

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

Although the addition amount of the epoxy compound can be variously set, the lower limit of the preferable addition amount with respect to 100 parts by weight of [(A) component + (B) component] is preferably 1 part by weight, more preferably 3 parts by weight. The upper limit of the addition amount is 50 parts by weight, more preferably 25 parts by weight. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.
These coupling agents, silane coupling agents, epoxy compounds, etc. may be used alone or in combination of two or more.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.
Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.
Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

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

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

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

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

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

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

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

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

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

(Curable resin composition tablet)
When the curable resin composition of the present invention contains at least the component (F) in addition to the components (A) to (E), the curable resin composition tablet can be formed.
Specifically, at least one of the curable resin composition tablet cures the component (A) and the component (B), the component (A) and the component (B) that are liquids having a viscosity at 23 ° C. of 50 Pa seconds or less. Therefore, it is preferable to contain (C) component, (E) component and (F) component which are both powder, and also (D) component.

  This curable resin composition tablet is capable of flowing the entire curable resin composition due to a decrease in viscosity of the component (A) and the component (B) at a high temperature. It can be formed into a shape.

  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.
The total ratio of the component (E) and the component (F) in the curable resin composition tablet of the present invention (hereinafter sometimes referred to as a filling rate) is preferably 70 to 95% by weight. The distribution of the (E) component and the (F) component in the filling rate is not particularly limited and can be set freely.

  When the filling rate is 70% by weight or less, the coefficient of thermal expansion of the resulting cured product becomes large, causing a problem of dimensional change of the molded product, and the resulting curable resin composition becomes a hard paste or clay. There is a problem that can not be tableted. When the filling rate is 95% by weight or more, the viscosity at high temperature becomes too high and the moldability may be lowered, and the resulting tablet may become too brittle.

  In the curable resin composition of the present invention, when at least one of the component (A) and the component (B) is liquid at room temperature, it tends to be in the form of a paste or clay when the filling rate is low. In this case, the tablet does not become a tablet, but the moldability at high temperature tends to be good. On the other hand, when the filling rate is high, since there are few components to be flowed, it tends to be flaky or powdery. These can be compressed into a tablet shape by being compressed, but they tend to have poor fluidity at high temperatures and easily deteriorate moldability. Until now, it has been difficult to achieve both tableting and moldability by simply increasing the filling rate.

  However, in the curable resin composition according to the present invention, the proportion of particles of 12 μm or less in the total powder of the component (E) and the component (F) is 40% by volume or more, and tableting and molding are performed. Since it becomes a curable resin composition excellent in property, it is preferable.

  The reason for this is speculated as follows. In the mixed system of liquid and particles, it is considered that the liquid component covers the surface of the particle, and the extra liquid component covering all the particles seems to contribute to the deformation. For this reason, even if the filling rate is the same, the larger the proportion of small particles, the larger the total surface area and the more liquid components that are consumed for coating. Since the viscosity of the liquid decreases significantly at high temperatures, the change in fluidity with respect to the proportion of small particles is small at high temperatures, but the viscosity is high at low temperatures, so when there are many small particles, it flows like paste or clay. It can be considered that the flakes or powders cannot be obtained.

(470 nm light reflectance of the molded product)
As a molded product (cured molded product) obtained by curing the curable resin composition of the present invention, the light reflectance at a surface wavelength of 470 nm is preferably 90% or more, and more preferably 95% or more. Preferably, it is 97% or more, more preferably 99% or more.
The light reflectance of the surface can be measured as follows.

  Using a PET film as a release film, a 0.5 mm-thick molded body without voids is prepared by press molding under a predetermined temperature condition. The obtained molded body is subjected to predetermined post-curing as necessary. It can obtain | require by measuring the total reflection of 470 nm using the spectrophotometer which installed the integrating sphere about the obtained molded object.

From the viewpoint that the light extraction efficiency of the light emitting diode tends to be high, 75% or more is preferable in the wavelength band of 420 to 700 nm, and 80% or more is more preferable. The light reflectance at 470 nm on the surface is 90% or more.
Moreover, it is desirable that the retention ratio of the spectral reflectance after the heat resistance test at 180 ° C. for 72 hours (spectral reflectance after the heat resistance test / initial spectral reflectance × 100) is 90% or more.
The light reflectance of the package is examined as follows.
Spectral reflectances at wavelengths of 400 nm to 700 nm (20 nm intervals) were measured using a micro-surface spectral color difference meter (Nippon Denshoku Industries Co., Ltd. VSS400). Here, the average value of the measurement values at any four locations (measurement area 0.1 mmφ) on the surface of the molded body was adopted as the measurement values at each wavelength.

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

(warp)
The semiconductor package molded using the curable resin composition according to the present invention is preferably a package formed by molding a resin substantially on one side of a metal. When the curable resin composition of the present invention is molded on one side of a lead frame (metal) for a light-emitting diode to form a package (integrated molded body), the warp of the package can be as low as ± 1.0 mm or less. It is.

The warpage in this case is measured based on the maximum warpage measuring method described in JIS C 6481. A semiconductor package is suspended vertically at the center of one side, and a straight ruler is applied parallel to that side. The straight ruler is applied to the concave surface of the semiconductor package, and the maximum distance between the straight ruler and the substrate surface of the semiconductor package is measured to a unit of 1.0 mm with a metal straight scale. If the resin is molded on the concave surface of the semiconductor package, measure the maximum distance between the straight ruler and the resin surface molded on the semiconductor package to a unit of 1.0 mm with a metal linear scale. The value obtained by subtracting the thickness is rounded off to the nearest 1.0 mm.
The other sides are also measured sequentially, and the greatest gap is warped. In addition, the semiconductor package shown by the (molding method) of an Example was used for the semiconductor package used for the measurement of curvature.

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)

(Formulation example)
According to the content of Table 1, each component was mix | blended and the composition A was prepared.

(Examples 1-2, Comparative Example 1)
Table 2 shows the blending ratio of each component of the curable resin composition.

Component (D), KF-96H-60,000 cs, is a polydimethylsiloxane having a molecular weight of about 100,000. PDV-2331 is polydimethyldiphenylsiloxane having a molecular weight of about 13,000.

(Formulation of curable resin composition)
A mixed powder of the component (F) and the component (E), which had been mixed in advance, was added little by little to a mixture of the composition A and the component (D) prepared separately, and kneaded. When the obtained curable resin composition was pasty, it was kneaded with a stirring bar to make it uniform. In the case of clay, it was homogenized by repeating the work of stretching with a round bar-shaped jig and then folding and stretching again. In the case of flakes or powders, they were crushed with a mortar and made uniform.

(Molding of plate-shaped compact)
The curable resin composition of Table 2 is made of a PET film as a release film, a rectangular mold made of stainless steel (SUS304) having an inner dimension of 80 mm × 50 mm and a thickness of 0.5 mm, and a condition of 150 ° C./5 minutes. And press-molded. The produced rectangular plate-shaped press-molded body was post-cured in an oven at 150 ° C./1 hour and 180 ° C./0.5 hour.

(Light reflectance at a wavelength of 470 nm)
About the obtained molded object, the light reflectance of wavelength 470nm was measured using the spectrophotometer (JASCO Corporation Co., Ltd. make, ultraviolet visible spectrophotometer V-560) which installed the integrating sphere. The reflectance was measured using a Spectralon plate manufactured by Labsphere as a standard plate. The measurement results are shown in Table 4.

(Measurement of contact angle)
In an atmosphere at room temperature of 25 ° C. and a relative humidity of 50%, 1 to 4 μL of phenylsilicone sealant and water were dropped with a syringe. Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., contact angle meter DM-501), the droplet was observed from a horizontal cross section, and the angle formed by the tangent of the droplet edge and the plane was determined. The contact angle at 60 seconds after dropping was measured for the phenyl silicone sealant, and the contact angle at 1 second after dropping was measured for water.

  In Examples 1 and 2, a curable resin composition having a viscosity of 35 ° or more after a lapse of 60 seconds after dropping a phenyl silicone sealant having a viscosity of 5.3 Pa · s to 6.3 Pa · s was used as a semiconductor package. In the case of a light-emitting diode using a phenyl silicone-based sealant as the sealant, it is shown that wetting and spreading of the sealant can be suppressed.

Claims (20)

The contact angle with respect to the surface of the plate-like molded body, which is a cured product of the curable resin composition, is 35 at the time when 60 seconds have elapsed after the phenyl silicone sealant having a viscosity of 5.3 Pa · s to 6.3 Pa · s was dropped. A curable resin composition that is at least ° C. The curable resin composition according to claim 1, wherein a contact angle of water with respect to a surface of the plate-like molded body, which is a cured product of the curable resin composition, is 105 ° or more. The curable resin composition according to claim 1 or 2, wherein the curable resin composition is for a semiconductor package. (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) a compound containing at least two SiH groups in one molecule, (C) It contains a hydrosilylation catalyst, (D) a silicone compound having 1 to 5 carbon atoms in the side chain and terminal, and a siloxane unit in the main chain, and (E) an inorganic filler. The curable resin composition according to any one of claims 1 to 3. The average molecular weight of (D) component is 200 or more and 1,000,000 or less, The curable resin composition of Claim 4. The curable resin composition according to claim 4 or 5, wherein the component (D) contains at least one carbon-carbon double bond having reactivity with the SiH group in one molecule. The curable resin composition according to claim 4 or 5, wherein the component (D) does not contain a carbon-carbon double bond having reactivity with the SiH group in one molecule. (D) Component is a linear or cyclic silicone compound, The curable resin composition of any one of Claims 4-7 characterized by the above-mentioned. The weight of (D) component with respect to the total weight of (A) component and (B) component is 1 weight% or more, The curable resin composition of any one of Claims 4-8. Furthermore, the curable resin composition of any one of Claims 1-9 containing a white pigment (F). A tablet comprising the curable resin composition according to claim 10,
At least one of the component (A) and the component (B) is a liquid having a viscosity at 23 ° C. of 50 Pa seconds or less,
The total content of the component (E) and the component (F) is 70 to 95% by weight,
The ratio of the particle | grains of 12 micrometers or less to the sum total of (E) component and (F) component is 40 volume% or more, The curable resin composition tablet characterized by the above-mentioned. It is a cured product of the curable resin composition according to any one of claims 1 to 10 or the curable resin composition tablet of claim 11, and has a light reflectance of 90% or more at a surface wavelength of 470 nm. A molded product characterized by. A curable resin composition according to any one of claims 1 to 10, or a curable resin composition tablet of the curable resin composition tablet according to claim 11, which is a semiconductor package. A semiconductor package, wherein the curable resin composition according to any one of claims 1 to 10 or the curable resin composition tablet according to claim 11 and a metal are integrally formed. A method for producing a semiconductor package, wherein the curable resin composition according to claim 1 or the curable resin composition tablet according to claim 11 and a lead frame are integrally formed by transfer molding. . The semiconductor package according to any one of claims 13 and 14, wherein the semiconductor package is a package formed by substantially molding a resin on one side of a metal. The semiconductor package according to claim 13, wherein the semiconductor package is a surface-mount type light emitting diode package. A semiconductor component manufactured using the semiconductor package according to claim 13, 14 or 16. The light emitting diode manufactured using the semiconductor package of any one of Claim 13, 14, or 16. The light-emitting diode according to claim 19, wherein the sealing agent covering the semiconductor element is a phenyl silicone-based sealing agent.