JP2013203798A - Thermosetting resin composition tablet improved in tuck property and package of semiconductor by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable material composition tablet giving a cured article capable of satisfying both of handling property in normal temperatures and meltability in high temperatures, having high spectral reflectances at 460 and 480 nm and having a good heat resistance and light fastness.SOLUTION: A thermosetting resin composition tablet obtained by the tablet formation of a thermosetting resin composition selected from the group consisting of an epoxy resin, a modified epoxy resin, a silicone resin, a modified silicone resin, an acrylate resin and a urethane resin is characterized by covering the surface of the tablet with an inorganic filler such as silica, aluminum hydroxide, magnesium hydroxide, alumina, zinc oxide, titanium oxide, etc., or an organic filler obtained by crushing a polymer selected from the group consisting of polymethyl methacrylate (PMMA), polyethyl methacrylate, etc.

Description

  The present invention relates to a thermosetting resin composition tablet, a semiconductor package using the same, and a semiconductor component manufactured using the same. More specifically, the present invention relates to a heat-resistant and easy-to-handle heat during transportation and molding. The present invention relates to a curable resin composition tablet, a package for a light emitting diode using the tablet, and a light emitting diode manufactured using the same.

  Conventionally, as a light emitting diode, a surface-mount type using a package has been manufactured. As a material for the package, ceramic, polyamide resin, polyester resin, or the like is mainly used.

  However, when ceramic is used as a packaging material, industrial applicability is generally narrow because ceramic moldability is not good. In addition, for the manufacture of light emitting diodes, it is common to fill a package with a sealing agent (mold material) such as an epoxy resin. In that case, the linear expansion coefficient between the ceramic and the sealing agent such as an epoxy resin Therefore, there is also a problem that the reliability of the light emitting diode is lowered due to the occurrence of cracks in the sealant due to thermal stress or the like. Further, ceramic has a problem that light reflectance is low and light extraction efficiency as a light emitting diode is lowered.

  When a polyamide resin is used as a packaging material, there is a problem that the polyamide resin is colored due to light resistance deterioration, and therefore, when used for a long time, there is a problem that the reflectance on the package surface is lowered and the luminance of the light emitting diode is lowered. . In addition, there is also a problem that the reliability of the light emitting diode is lowered due to a decrease in adhesiveness with the sealing agent due to light resistance deterioration of the polyamide resin.

  When a polyester resin is used as a packaging material, the heat resistance is not sufficient, so that there is a problem that the solder reflow resistance is poor and the industrial applicability is limited.

  In order to solve these problems, a thermosetting resin composition in which an inorganic filler and a white pigment are blended with a thermosetting resin has been reported. For example, Patent Document 1 describes a light reflecting resin composition tablet composed of an epoxy resin, an inorganic filler, and a white pigment, and a light emitting diode package obtained by transfer molding using the tablet. However, since the heat resistance of the epoxy resin is not sufficient, there is a problem with the heat resistance and light resistance of the resulting package.

  On the other hand, Patent Documents 2 and 3 report white thermosetting resin compositions using a silicone-based resin that is superior in heat resistance and light resistance to an epoxy resin. Patent Document 2 describes a curable resin composition comprising a thermosetting silicone having a melting point of 40 to 130 ° C., a white pigment, and an inorganic filler. Since the curable resin composition can be maintained in a solid state by setting the melting point of the thermosetting silicone to 40 ° C. or more, application of transfer molding is facilitated. However, in order to uniformly mix the thermosetting silicone with the white pigment and the inorganic filler, it is necessary to cool and pulverize after melting and kneading at a melting point or higher, which complicates the process and increases the load on the equipment. In addition to problems, there were problems such as curing progressed by heat and moldability decreased. In addition, when blended with a white pigment and an inorganic filler below the melting point of the thermosetting silicone, there is a problem that mixing is uneven because all the components are solid.

  Patent Document 3 proposes a light emitting diode package using a thermosetting resin composition in which a white pigment and an inorganic filler are blended with a silicone-based resin. Since this silicone resin is liquid at room temperature, uniform mixing of the white pigment and the inorganic filler is facilitated, but the resulting thermosetting resin composition is in the form of a paste. Therefore, in order to apply the thermosetting resin composition to transfer molding, it is very difficult to handle, measure, transport, and supply the paste to a molding machine. Met.

JP 2008-112977 A JP 2009-155415 A JP 2005-146191 A

  Accordingly, an object of the present invention is to provide a method for producing a thermosetting resin composition tablet that does not have surface tackiness at room temperature, has good handling properties, and gives a cured product having good moldability, and the heat produced by this method. It is providing the package of the light emitting diode using a curable resin composition, and the light emitting diode manufactured using the same.

  In order to solve the above problems, the inventors have intensively studied, and after tablet production, the surface tackiness of the tablet at room temperature is eliminated by dusting with an inorganic filler and / or an organic filler, and handling during transport and molding. The inventors have found that the characteristics can be greatly improved, and have completed the invention.

That is, the present invention has the following configuration.
(1) A tablet obtained by tableting a thermosetting resin composition, wherein the tablet surface is covered with a filler, and the thermosetting resin composition tablet.
(2) The thermosetting resin composition tablet according to (1), wherein the filler includes an inorganic filler and / or an organic filler.
(3) The inorganic filler is a silica-based inorganic filler such as quartz, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, aluminum hydroxide, magnesium hydroxide, barium sulfate, It is at least one selected from the group consisting of calcium carbonate, magnesium carbonate, barium carbonate, alumina, zinc oxide, antimony oxide, zirconium oxide, titanium oxide, magnesium oxide, carbon black, and hollow particles ( The thermosetting resin composition tablet according to 2).
(4) The organic filler is a filler obtained by pulverization of a polymer, and is polymethyl methacrylate (PMMA), polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate (PBMA), polyacetic acid The thermosetting resin according to (2), which is at least one selected from the group consisting of vinyl (PVAc), polyethylene glycol (PEG), polypropylene glycol (PPG), and polyvinyl alcohol (PVA). Composition tablet.
(5) The thermosetting resin composition is at least one selected from the group consisting of epoxy resin, modified epoxy resin, silicone resin, modified silicone resin, acrylate resin, and urethane resin (1) The thermosetting resin composition tablet according to any one of (4) to (4).
(6) A thermosetting resin composition tablet for semiconductor packages, comprising the thermosetting resin composition tablet according to any one of (1) to (5).
(7) A thermosetting resin composition tablet for a light emitting diode package, comprising the thermosetting resin composition tablet according to any one of (1) to (5).
(8) The thermosetting resin composition tablet according to any one of (1) to (5) or the thermosetting resin composition tablet for semiconductor package according to (6) or the light emitting diode package according to (7) A molded product obtained by molding a thermosetting resin composition tablet for use, and having a spectral reflectance of 80 R% or more at wavelengths of 460 and 480 nm on the surface.
(9) A package for a light emitting diode obtained by transfer molding the thermosetting resin composition tablet for a light emitting diode package according to (7).
(10) A light emitting diode manufactured using the light emitting diode package according to (9).
(11) The thermosetting resin composition tablet according to any one of (1) to (5) or the thermosetting resin composition tablet for semiconductor package according to (6) or the light-emitting diode according to (7) A method for producing a tablet of a thermosetting resin composition for a package, the step of molding the thermosetting resin composition under pressure to form a tablet, and the inorganic tablet and / or organic filling of the tablet thus formed The manufacturing method of the thermosetting resin composition tablet characterized by having the process of coat | covering a material.
(12) A method for producing a tablet of the thermosetting resin composition according to (11), wherein the molded tablet is coated with an inorganic filler and / or an organic filler. A method for producing a thermosetting resin composition tablet, comprising the step of rolling the thermosetting resin composition tablet mechanically or manually and applying the filler.

  If the thermosetting resin composition tablet of the present invention is used, since there is no tackiness of the tablet at room temperature, handling at the time of conveyance and molding becomes easy, and productivity is greatly improved. Moreover, the mechanical strength of a tablet improves by grind | pulverizing a thermosetting resin composition tablet, and the handling property at the time of conveyance and tablet loading improves.

  Hereinafter, the present invention will be described in detail with reference to embodiments, but the present invention is not limited to the following embodiments.

The thermosetting resin composition tablet of the present invention is a tablet obtained by tableting a thermosetting resin composition for a semiconductor package, wherein the surface is covered with a filler. It is a thermosetting resin composition tablet, Comprising: A filler is an inorganic filler and / or an organic filler, It is a thermosetting resin composition tablet characterized by the above-mentioned.
(Inorganic filler)
The inorganic filler for tablet surface coating is not particularly limited. For example, silica-based inorganic fillers such as quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultra fine powder amorphous silica , Alumina, zinc oxide, antimony oxide, zirconium oxide, titanium oxide, magnesium oxide, magnesium hydroxide, barium carbonate, carbon black, hollow particles, zircon, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, alumina fiber Conventional semiconductors such as epoxy fiber, inorganic fillers such as carbon fiber, mica, diatomaceous earth, clay, talc, aluminum hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, and inorganic balloon Generally used or / and proposed as a filler for sealing materials It can be mentioned inorganic fillers such as being. Of these, silica, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, magnesium carbonate, barium carbonate, alumina, zinc oxide, antimony oxide, zirconium oxide, titanium oxide, magnesium oxide, carbon black, and hollow particles are preferably used. be able to.

  Among these, silica-based inorganic fillers are preferable from the viewpoint of hardly inhibiting the curing reaction. 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. In addition, glass fiber and calcium silicate are preferable in that the reinforcing effect is high and the strength of the package tends to be high. These inorganic fillers may be used alone or in combination of two or more.

  Among these, from the viewpoint of improving moldability and the uniformity of the composition of a cured product formed by thermosetting the thermosetting resin composition, inorganics contained in the thermosetting resin composition described below. It is particularly desirable to use the same filler.

  The shape of the inorganic filler is not particularly limited, and a crushed shape, a piece shape, a spherical shape, a rod shape, and the like can be used, but the moldability is good even when the content in the thermosetting resin composition tablet is increased. Therefore, it is preferably spherical or rounded and more preferably spherical.

  The particle size of the inorganic filler is not particularly limited, but can be used as a filler for a conventional semiconductor sealing material such as an epoxy-based material and / or a material in the proposed range. From the standpoint of easy moldability, the preferred average particle size is 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less.

  Moreover, you may surface-treat an inorganic filler suitably. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a coupling agent, and the like. 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.

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

(Organic filler)
As an organic filler for tablet surface coating, a filler obtained by polymerizing a polymerized monomer containing a filler or a crosslinking agent of a powder polymer obtained by pulverization or dispersion polymerization of a polymer, and then pulverizing the filler Can be mentioned. The polymer used as a raw material for the filler usable here is not particularly limited. For example, polymethyl methacrylate (PMMA), polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate (PBMA), polyacetic acid. Examples thereof include vinyl (PVAc), polyethylene glycol (PEG), polypropylene glycol (PPG), and polyvinyl alcohol (PVA). From the viewpoint of availability and heat resistance, crosslinked polymethyl methacrylate is preferred. Although it does not specifically limit as a particle size of an organic filler, From the point that a moldability tends to become favorable, as a preferable average particle diameter, it is 100 micrometers or less, More preferably, it is 50 micrometers or less, More preferably, it is 30 micrometers or less. is there.

  These organic fillers may be used alone or in combination of two or more. Two or more inorganic fillers and organic fillers can be used in combination.

  Among inorganic fillers and / or organic fillers, a silica-based filler is particularly preferable from the viewpoint of being resistant to heat resistance and curing reaction.

(Thermosetting resin)
The thermosetting resin is not particularly limited, and examples thereof include epoxy resins, modified epoxy resins, silicone resins, modified silicone resins, acrylate resins, and urethane resins.

<Epoxy resin and modified epoxy resin>
As the epoxy resin, those generally used for epoxy resin molding materials for electronic component sealing can be used, and are not particularly limited. Examples thereof include phenol novolac epoxy resins and orthocresol novolac epoxy resins. Obtained by the reaction of epichlorohydrin with epoxidized novolak resin of phenol and aldehyde, diglycidyl ether such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted biphenol, diaminodiphenylmethane, isocyanuric acid and the like. There are glycidylamine-type epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, and alicyclic epoxy resins, which may be used alone or in combination of two or more. Good. In addition, it is preferable that the epoxy resin used is relatively uncolored, and examples of such an epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and triglycidyl isocyanate. Nurate can be mentioned.

  A modified epoxy resin can also be suitably used. Examples of such modified epoxy resins include modified bisphenol A type epoxy resins and modified alicyclic epoxy resins modified with an organopolysiloxane having at least one amino group per molecule having good reactivity with an epoxy group. .

  Moreover, you may use a hardening | curing agent and a hardening accelerator together with an epoxy resin. Any curing agent can be used without particular limitation as long as it reacts with the epoxy resin. For example, an acid anhydride curing agent, a phenol curing agent, and the like can be given. Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride. Examples thereof include acid, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like. These may be used alone or in combination of two or more. Among these acid anhydride curing agents, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride are preferably used. The acid anhydride curing agent preferably has a molecular weight of about 140 to 200, and is preferably a colorless or light yellow acid anhydride.

  Moreover, the said hardening | curing agent is set so that the active group (an acid anhydride group or a hydroxyl group) which can react with the epoxy group in a hardening | curing agent will be 0.5-1.5 equivalent with respect to 1 equivalent of epoxy groups in an epoxy resin. It is preferable to mix | blend and it is more preferable to mix | blend so that it may become 0.7-1.2 equivalent. When the active group is less than 0.5 equivalent, the curing rate of the epoxy resin composition is slowed, and the glass transition temperature of the resulting cured product may be lowered. The moisture resistance may be reduced.

  The curing accelerator is not particularly limited. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine, tri-2,4,6-dimethylaminomethylphenol Tertiary amines such as 2-ethyl-4-methylimidazole, imidazoles such as 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphoro Examples thereof include phosphorus compounds such as dithioate, quaternary ammonium salts, organometallic salts, and derivatives thereof. These may be used alone or in combination. Among these curing accelerators, it is preferable to use tertiary amines, imidazoles, and phosphorus compounds.

  Moreover, it is preferable that the content rate of a hardening accelerator is 0.01 to 8.0 weight% with respect to an epoxy resin, More preferably, it is 0.1 to 3.0 weight%. When the content of the curing accelerator is less than 0.01% by weight, a sufficient curing acceleration effect may not be obtained. When the content exceeds 8.0% by weight, discoloration is observed in the obtained cured product. There is.

<Silicone resin>
Silicone resins can be classified into condensation-type silicone resins and addition-type silicone resins as follows.

<Condensation type silicone resin>
The thermosetting organopolysiloxane according to the present invention is a silanol group-containing organopolysiloxane, particularly the following average composition formula (1):
R ¹ _a Si (OR ² ) _b (OH) _c O _(4-abc) / 2 (1)
(Wherein R ¹ is the same or different organic group having 1 to 20 carbon atoms, R ² is the same or different organic group having 1 to 4 carbon atoms, 0.8 ≦ a ≦ 1.5, 0 ≦ (b ≦ 0.3, 0.001 ≦ c ≦ 0.5, 0.801 ≦ a + b + c <2)
It is the silicone polymer represented by these.

Examples of the organic group represented by R ^1, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, the number of carbon atoms of an aralkyl group having 7 to 20 carbon atoms 1-20 unsubstituted or substituted monovalent hydrocarbon group is mentioned, As said alkyl group, a C1-C10 alkyl group is more preferable, and any of linear, branched, and cyclic may be sufficient as it. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl Groups and the like.

  As said alkenyl group, a C2-C10 alkenyl group is more preferable, for example, a vinyl group, an aryl group, a propenyl group etc. are mentioned.

  As said aryl group, a C6-C10 thing is more preferable, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group etc. are mentioned.

  As said aralkyl group, a C7-C10 thing is more preferable, for example, a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group etc. are mentioned.

  Moreover, the substituted monovalent hydrocarbon group which substituted one or more of the hydrogen atoms of the said unsubstituted monovalent hydrocarbon group by the halogen atom, the cyano group, etc. may be sufficient.

Among these, R ¹ in the average composition formula (1) is particularly preferably a methyl group or a phenyl group.

In the average composition formula (1), R ² is the same or different organic group having 1 to 4 carbon atoms, and examples thereof include an alkyl group and an alkenyl group. OR ² represents a portion other than the silanol group (Si—OH) in the terminal group of the siloxane resin, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. A methoxy group and an isopropoxy group are easily available.

In the average composition formula (1), a, b and c are 0.8 ≦ a ≦ 1.5, 0 ≦ b ≦ 0.3, 0.001 ≦ c ≦ 0.5, 0.801 ≦ a + b + c < 2, more preferably 0.9 ≦ a ≦ 1.3, 0.001 ≦ b ≦ 0.2, 0.01 ≦ c ≦ 0.3, 0.911 ≦ a + b + c ≦ 1.8. It is. When the content a of R ¹ is less than 0.8, it becomes hard and the crack prevention property is lowered, and when it exceeds 1.5, the organic group is increased, the hydrophobicity is increased, and it becomes soft and the crack prevention effect is lost. . When the content b of OR ² exceeds 0.3, the amount of terminal groups increases and the molecular weight tends to decrease, so that crack prevention performance does not appear. When the OH content c exceeds 0.5, the ratio involved in the condensation reaction at the time of heat curing is increased, and the hardness is high but the crack resistance is poor. When c is less than 0.001, the melting point tends to be high, which causes a problem in workability. As a condition for controlling c, the complete condensation rate of the alkoxy group is preferably 86 to 96%. If it is less than 86%, the melting point becomes low, and if it exceeds 96%, the melting point tends to be too high.

Such thermosetting organopolysiloxanes having the above average composition formula (1) are generally Q units derived from tetrafunctional silane [SiO _4/2 ], T units derived from trifunctional silane [R ¹ SiO _3/2 (R ¹ is the same as described above.)] It can be expressed by a combination of D unit [R ¹ SiO _2/2 ] derived from bifunctional silane [R ¹ SiO _1/2 ] derived from monofunctional silane. However, when the thermosetting organopolysiloxane is represented by this notation, the ratio of the number of moles of T units represented by R ¹ SiO _3/2 to the total number of moles of all siloxane units is 70 moles. % Or more, desirably 75 mol% or more, and particularly desirably 80 mol% or more. If the T unit is less than 70 mol%, the overall balance of hardness, adhesion, and appearance may be lost. The balance may be M, D, and Q units, and the sum of these is preferably 30 mol% or less. Regarding the melting point, the melting point increases as the Q and T units increase, and the melting point tends to decrease as the D and M units increase. It is more preferable that the ratio of the number of moles of the T unit represented by R ¹ SiO _3/2 is 70 mol% or more and the remaining 30 mol% or less is the D unit.

  The melting point of the thermosetting organopolysiloxane is 40 to 130 ° C, preferably 70 to 80 ° C. When the temperature is lower than 40 ° C., the solid is not solid and the solid surface becomes more sticky and transfer molding becomes difficult. When the temperature exceeds 130 ° C., fluidity is lost and transfer molding becomes difficult.

Such thermosetting organopolysiloxane has the following general formula (2)
R ¹ _n SiX _4-n (2)
(Wherein R ¹ is as described above. X is a halogen atom such as chlorine or an alkoxy group, particularly an alkoxy group having 1 to 4 carbon atoms, and n is 1, 2 or 3.) It can be obtained as a hydrolytic condensate of silane.

  In this case, X is preferably a halogen atom, particularly a chlorine atom, from the viewpoint of obtaining a solid organopolysiloxane.

Moreover, n in the said General formula (2) represents the integer of 1-3. When n is 2 or 3, that is, when R ¹ is more, each R ¹ may be different may be identical or different. n is preferably n = 1 in that a solid polysiloxane can be obtained.

  Examples of the silane compound represented by the general formula (2) include methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, methylvinyldichlorosilane, diphenyldichlorosilane, methyltrimethoxysilane, and ethyltrimethoxy. Organotrichlorosilanes and organotrialkoxysilanes such as silane, phenyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, Diorgans such as diphenyldiethoxysilane, methylvinyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane Dialkoxysilane, and the like. In particular, it is preferable to use methyltrichlorosilane. It is also effective to use phenyltrichlorosilane in combination.

  In addition, it is preferable to select the usage-amount of trichlorosilane and trialkoxysilane from the point which obtains the silanol group containing organopolysiloxane which contains 70 mol% or more of T units for these silane compounds.

  The hydrolysis and condensation of the silane compound having a hydrolyzable group may be performed by an ordinary method. For example, an acid catalyst such as acetic acid, hydrochloric acid or sulfuric acid, or sodium hydroxide, potassium hydroxide or tetramethylammonium hydroxide. It is preferable to carry out in presence of alkali catalysts, such as. For example, when a silane containing a chloro group as a hydrolyzable group is used, a desired hydrolysis condensate having an appropriate molecular weight can be obtained using hydrochloric acid generated by addition of water as a catalyst.

  The amount of water added at the time of hydrolysis and condensation is usually 0.9 to 1 mol per total amount of hydrolyzable groups (for example, in the case of chloro groups) in the silane compound having a hydrolyzable group. 1.6 mol, preferably 1.0-1.3 mol. When this addition amount satisfies the range of 0.9 to 1.6 mol, the composition described later has excellent workability, and the cured product has excellent toughness.

  The silane compound having a hydrolyzable group is usually preferably used after being hydrolyzed in an organic solvent such as alcohols, ketones, esters, cellosolves, and aromatic compounds. Specifically, alcohols such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, n-butanol and 2-butanol, and toluene and xylene are preferable as aromatic compounds, and the curability of the composition and the toughness of the cured product are excellent. Therefore, a combination system of isopropyl alcohol and toluene is more preferable.

  In this case, the reaction temperature for hydrolysis and condensation is preferably 10 to 120 ° C, more preferably 20 to 100 ° C. When the reaction temperature satisfies this range, a solid hydrolysis condensate that can be used in the next step is obtained without gelation.

  As a specific synthesis method, when methyltrichlorosilane is used, water and isopropyl alcohol are added to methyltrichlorosilane dissolved in toluene and subjected to partial hydrolysis (reaction temperature of -5 to 100 ° C.). A solid silicone polymer having a melting point of 76 ° C. can be obtained by adding water that hydrolyzes the entire amount and reacting.

  Thus, the desired organopolysiloxane is obtained. The melting point of this organopolysiloxane is 50 to 100 ° C., preferably 70 to 80 ° C. When the temperature is lower than 50 ° C. and exceeds 100 ° C., there arises a problem that kneading becomes difficult due to the mixing workability in the next step.

  When the organopolysiloxane of the present invention is cured, it is necessary to prepare a composition by mixing with a curing catalyst (condensation catalyst). This condensation catalyst is selected in consideration of the stability of the organopolysiloxane, the hardness of the coating, non-yellowing, curability and the like. For example, as an organic metal catalyst, an organic acid zinc, a Lewis acid catalyst, an organic aluminum compound, an organic titanium compound, or the like is preferably used. Specifically, zinc octylate, zinc benzoate, zinc p-tert-butylbenzoate, Zinc laurate, zinc stearate, aluminum chloride, aluminum perchlorate, aluminum phosphate, aluminum triisopropoxide, aluminum acetylacetonate, ethyl acetoacetate aluminum di (normal butyrate), aluminum-n-butoxydiethylacetoacetate , Tetrabutyl titanate, tetraisopropyl titanate, tin octylate, cobalt naphthenate, tin naphthenate and the like.

  The addition amount of the curing catalyst is preferably 0.0001 to 10 parts by mass, particularly preferably 0.001 to 1.0 part by mass with respect to 100 parts by mass of the organopolysiloxane. When the added amount satisfies this range, the curability is good and stable.

  Moreover, an internal mold release material can be mix | blended to such an extent that the sclerosis | hardenability of the organopolysiloxane of this invention and the hardness of hardened | cured material are not impaired. The internal mold release material is blended in order to improve the mold release property at the time of molding, and is added so as to contain 0.2 to 5% by mass with respect to the entire composition. Examples of the internal mold release material include natural waxes such as carnauba wax, acid waxes, polyethylene waxes, synthetic waxes such as fatty acid esters, among which it is desirable to use calcium stearate having a melting point of 120 to 140 ° C. Even when left at high temperature or under light irradiation, yellowing is suppressed and good releasability is continuously maintained for a long time.

<Additional silicone resin>
The addition-type silicone resin according to the present invention is an addition-curable silicone resin containing (A) an organosilicon compound having a double bond group, (B) an organohydrogenpolysiloxane, and (C) a platinum-based catalyst as essential components. Compositions are preferably used.

(A) component:
The component (A) includes the following general formula (3):
R ¹ R ² R ³ SiO— (R ⁴ R ⁵ SiO) _a — (R ⁶ R ⁷ SiO) _b —SiR ¹ R ² R ³ (3) (wherein R ¹ is a monovalent carbon containing a double bond group) R ^{2 to} R ⁷ each represent the same or different monovalent hydrocarbon group, among which R ^{4 to} R ⁷ preferably represent a monovalent hydrocarbon group excluding an aliphatic unsaturated bond, R ⁶ and / or R ⁷ represents an aromatic monovalent hydrocarbon group, and is an integer of 0 ≦ a + b ≦ 500, preferably 10 ≦ a + b ≦ 500, and 0 ≦ a ≦ 500, preferably 10 ≦ a ≦. 500, 0 ≦ b ≦ 250, preferably 0 ≦ b ≦ 150.)
Can be used.

In this case, R ¹ has an aliphatic unsaturated bond represented by an alkenyl group having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and R ^{2 to} R ⁷ have 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms. Are preferably alkyl groups, alkenyl groups, aryl groups, aralkyl groups, etc., among which R ^{4 to} R ⁷ are preferably alkyl groups other than aliphatic unsaturated bonds such as alkenyl groups, An aryl group, an aralkyl group, etc. are mentioned. R ⁶ and / or R ⁷ is preferably an aromatic monovalent hydrocarbon group such as an aryl group having 6 to 12 carbon atoms such as a phenyl group or a tolyl group.

  The organopolysiloxane of the general formula (3) includes, for example, cyclic diorganopolysiloxanes such as cyclic dimethylpolysiloxane, cyclic diphenylpolysiloxane, and cyclic methylphenylpolysiloxane constituting the main chain, and divinyltetramethyl constituting the terminal group. It can be obtained by alkali equilibration reaction with disiloxanes such as disiloxane, dimethyltetravinyldisiloxane, hexavinyldisiloxane, diphenyltetravinyldisiloxane, divinyltetraphenyldisiloxane, etc. No chloro content.

  Specific examples of the organopolysiloxane of the general formula (3) include the following.

(In the above formula, k and m are integers satisfying 0 ≦ k + m ≦ 500, preferably 5 ≦ k + m ≦ 250, and integers satisfying 0 ≦ m / (k + m) ≦ 0.5.)
The component (A) has a three-dimensional network structure including a trifunctional siloxane unit, a tetrafunctional siloxane unit, etc., as necessary, in addition to the organopolysiloxane having the linear structure of the general formula (3). Organopolysiloxane can also be used in combination.

  (A) Content of the double bond group in a component is 1-50 mol% of all the monovalent hydrocarbon groups, Preferably it is 2-40 mol%, More preferably, it is 5-30 mol%. If the content of the double bond group is less than 1 mol%, a cured product cannot be obtained, and if it is more than 50 mol%, the mechanical properties may be deteriorated.

  Moreover, content of the aromatic group in (A) component is 0-95 mol% of all the monovalent hydrocarbon groups, Preferably it is 10-90 mol%, More preferably, it is 20-80 mol%. When an appropriate amount of the aromatic group is contained in the resin, there is an advantage that the mechanical properties are good and the production is easy. Another advantage is that the refractive index can be controlled by introducing an aromatic group.

(B) component:
As the component (B), an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule is used. Such an organohydrogenpolysiloxane acts as a crosslinking agent, and an SiH group in the component and a double bond-containing group (typically an alkenyl group) such as a vinyl group in the component (A) undergo an addition reaction. Thus, a cured product is formed.

  In addition, the organohydrogenpolysiloxane has an aromatic hydrocarbon group, thereby improving compatibility when the organosilicon compound having a double bond group as the component (A) has a high refractive index, and is a transparent cured product. Can be given. Therefore, in the organohydrogenpolysiloxane of the component (B), the organohydrogenpolysiloxane having an aromatic monovalent hydrocarbon group can be included as a part or all of the component (B).

  In addition, in the organohydrogenpolysiloxane of the component (B), the organohydrogenpolysiloxane having a glycidyl structure can be included as part or all of the component (B), and the organohydrogenpolysiloxane has a glycidyl structure. By having the containing group, a thermosetting resin composition having high adhesion to the substrate can be provided.

Examples of the organohydrogenpolysiloxane include, but are not limited to, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (dimethylhydrogen Siloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1-glycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-glycidoxypropyl-1,3,5 7-tetramethylcyclotetrasiloxane, 1-glycidoxypropyl-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends Trimethylsiloxy group-blocked dimethylsiloxa・ Methyl hydrogensiloxane copolymer, dimethylpolysiloxane blocked with dimethylhydrogensiloxy at both ends, dimethylsiloxane blocked with dimethylhydrogensiloxy group at both ends ・ Methylhydrogensiloxane copolymer, methylhydrogensiloxane blocked at both ends with trimethylsiloxy group・ Diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane at both ends ・ Diphenylsiloxane ・ dimethylsiloxane copolymer, trimethoxysilane polymer, (CH ₃ ) ₂ HSiO _1/2 unit and SiO _4/2 unit And a copolymer composed of (CH ₃ ) ₂ HSiO _1/2 units, SiO _4/2 units, and (C ₆ H ₅ ) SiO _3/2 units.

  Moreover, the organohydrogenpolysiloxane obtained using the unit shown by the following structure can also be used.

  Examples of such organohydrogenpolysiloxanes include the following.

  The molecular structure of such an organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms (or the degree of polymerization) in one molecule is 2. One or more, preferably 2 to 1,000, more preferably about 2 to 300 can be used.

  The amount of such an organohydrogenpolysiloxane is such that the silicon atom-bonded hydrogen atoms (SiH groups) in the component (B) are 0 per one double bond group (typically an alkenyl group) in the component (A). It is preferable to contain an amount sufficient to give .75 to 2.0 pieces.

(C) component:
As the component (C), a platinum-based catalyst is used. Examples of the platinum-based catalyst include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum complexes having a chelate structure, and the like. These can be used alone or in combination of two or more.
The blending amount of these catalyst components is a curing effective amount, and may be a so-called catalytic amount.
And it is used in the range of 0.1 to 500 ppm, particularly 0.5 to 100 ppm in terms of the mass of platinum group metal per 100 parts by mass of the total amount of component (B).

  (D) Other components: The addition-curable silicone resin composition used in the present invention contains the above-described components (A) to (C) as essential components, and various silane coupling agents as necessary. May be added. For example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, N-2 (amino Ethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxy Run, 3-aminopropyltriethoxysilane, N- phenyl-3-aminopropyl trimethoxysilane, and 3-mercaptopropyl trimethoxysilane, trimethoxysilane, tetramethoxysilane and oligomers thereof, and the like. These silane coupling agents can be used alone or in combination of two or more.

  The blending amount of the silane coupling agent is preferably 10% by mass or less (0 to 10% by mass), particularly 5% by mass or less (0 to 5% by mass) of the entire composition.

<Modified silicone resin>
The modified silicone resin according to the present invention includes (E) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (F) at least two SiH in one molecule. A group-containing compound, (G) a hydrosilylation catalyst, (H) a SiH group or a silicone compound containing at least one carbon-carbon double bond reactive with the SiH group in one molecule. The curable resin composition is characterized. Hereinafter, each component will be described in detail.

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

(Skeleton of (E) component)
The skeleton of the component (E) may be siloxane. In this case, specifically, a siloxane compound having a vinyl group and polysiloxane can be exemplified.
R _n (CH ₂ ═CH) _m SiO _{(4-nm) / 2}
(Wherein R is a group selected from a hydrogen atom, a hydroxyl group, a methyl group or a phenyl group, and n and m are numbers satisfying 0 ≦ n <4, 0 <m ≦ 4, and 0 <n + m ≦ 4). More specifically, polydimethylsiloxane having a vinyl group as a terminal group or side chain group, polymethylhydrogensiloxane, polydiphenylsiloxane, polymethylphenylsiloxane, 1,3-divinyltetramethyl, and the like. Examples thereof include disiloxane and 1,3,5,7-tetravinylcyclotetrasiloxane.

  From the viewpoint that the strength tends to increase and the adhesiveness tends to increase, the component (E) preferably has an organic skeleton.

  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.

The organic compound (E) can be classified into an organic polymer compound and an organic monomer compound.
(Example when component (E) is a polymer)
Examples of the component (E) of the organic polymer system include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, 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 or ring-opening polymerization of lactones, ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, styrene Copolymer, polybutadiene, butadiene and styrene, acrylonitrile, etc., polyisoprene, polybutadiene, isoprene or butadiene and acrylonitrile, styrene, etc. Polyolefins obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate, and acrylic acid esters such as ethyl acrylate and butyl acrylate, and acetic acid. Acrylate ester copolymer with vinyl, acrylonitrile, methyl methacrylate, styrene, etc., graft polymer obtained by polymerizing vinyl monomer in the organic polymer, polysulfide polymer, ring-opening polymerization of ε-aminocaprolactam Nylon 6 by polycondensation, 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-aminolaurolactam Nylon 12 by ring-opening polymerization, a polyamide polymer such as copolymer nylon having two or more components among the above nylons, for example, a polycarbonate polymer produced by polycondensation from bisphenol A and carbonyl chloride, Examples of the diallyl phthalate polymer and the phenol-formaldehyde (phenolic resin) skeleton include novolac 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 (E).

  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 that are reactive with 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,

And so on. 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 an organic polymer skeleton of the component (E) 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 (E), 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 (E) is a monomer)
Examples of the organic monomer type (E) component include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as linear and alicyclics: heterocyclic compounds And mixtures thereof.

(Carbon-carbon double bond of component (E))
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.

  (E) 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,

The groups shown are particularly preferred.

  As the carbon-carbon double bond having reactivity with the SiH group of the component (E), 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 groups shown are particularly preferred.

((E) 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 of the component (E), or may be covalently bonded through 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, 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 (E))
Specific examples of the (E) component 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 represent numbers from 1 to 300.)
Etc.

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

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

  As the component (E), low molecular weight compounds that are difficult to express separately as described above for the skeleton and alkenyl groups 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 (E))
The component (E) preferably contains 0.001 mol or more of a carbon-carbon double bond having reactivity with the SiH group per gram of the component (E), from the viewpoint that heat resistance can be further improved. 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 (E) should be on average at least two per molecule, but it 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 the component (E) is 1 or less per molecule, only a graft structure is formed even if it reacts with the component (F). Don't be.

  From the viewpoint of good reactivity as the component (E), 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 (E), the viewpoint that the mechanical heat resistance is high, the viewpoint that the raw material liquid has little stringiness and the handleability is good, and uniform mixing with powders such as a white pigment and an inorganic filler described later From the viewpoint of being easy and the moldability of the thermosetting resin composition tablet being good, the molecular weight is preferably less than 900, more preferably less than 700, and even more preferably less than 500.

  As the component (E), in order to facilitate uniform mixing with other components, particularly powders such as white pigments and inorganic fillers described later, more specifically, heating above the melting point for uniform mixing. Since it does not need to be liquefied, it 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 even more preferably 5 Pa seconds or less. preferable. The viscosity can be measured with an E-type viscometer.

  The component (E) preferably has a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group 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 component weight ratio in the component (E) of 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 (E) is 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 (E))
As the component (E), 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.

(Wherein R ² represents a hydrogen atom or a methyl group) is more preferably a monovalent organic group having 1 to 50 carbon atoms and containing at least one group represented by:
At least two of the three R ¹ are represented by 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 (E))
In addition, from the viewpoint of having good compatibility with the component (F), and from the viewpoint that the volatility of the component (E) is reduced and the problem of outgas from the resulting package is less likely to occur, examples of the component (E) 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 (E) 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 (E) of the present invention. However, the curable composition of the present invention can also be prepared by using the mixture as it is without separating the component (E).

  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 the (F) component of (E) 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.

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is sufficient with respect to 1 mole of SiH group of the (β) component in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ^-8 mol, more preferably 10 ^-6 mole, preferable amount of the upper limit is 10 ^-1 moles per mole of the SiH group (beta) component, more preferably 10 ^-2 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 maleate, 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. If the catalyst is mixed with a mixture of an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule and the (β) component, it is difficult to control the reaction. 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 (E) does not have a volatile component, so that the problem of voids and cracks due to the volatilization of the volatile components hardly occurs in the case of curing with the component (F). 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 (E) component, which is a reaction product of the organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group as described above, and the (β) component include 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 (E))
(E) 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 resulting curable composition tends to be high, and the strength of the resulting 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 (E))
(E) A component can be used individually or in mixture of 2 or more types. In particular, when the component (E) is an organic compound, a smaller linear expansion coefficient can be obtained by using a silicone compound containing at least one carbon-carbon double bond reactive with the SiH group in one molecule. It can be set as the curable resin composition which gives the hardened | cured material which has. In this case, a silicone compound containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule is particularly used as the component (H).

((H) component)
The (H) component silicone compound 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.

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

  Examples of the component (H) may be those represented by the following formula.

R _n (CH ₂ ═CH) _m SiO _{(4-nm) / 2}
(In the formula, R is a group selected from a hydroxyl group, a methyl group or a phenyl group, and n and m are numbers satisfying 0 ≦ n <4, 0 <m ≦ 4, and 0 <n + m ≦ 4)
Examples of the component (H) include polydimethylsiloxane having a vinyl group as a terminal group or side chain group, polydiphenylsiloxane, polymethylphenylsiloxane, 1,3-divinyltetramethyldisiloxane, 1,3,5, Examples thereof include 7-tetravinylcyclotetrasiloxane. As the component (H), a plurality of components may be mixed and used.

  Of these, linear polysiloxanes having vinyl groups at the ends are preferable, linear polysiloxanes having vinyl groups at both ends are more preferable, and both ends are more preferable in that the effects of the present invention are more easily obtained. A linear polymethylphenylsiloxane having a vinyl group is more preferable, and a linear polymethylphenylsiloxane having a vinyl group at both ends, wherein the amount of phenyl groups with respect to all substituents is 20 mol% or more. It is particularly preferred that

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

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

(F component)
The component (F) is a compound containing at least two SiH groups in one molecule.

  The component (F) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule. For example, the compound described in International Publication WO96 / 15194 is at least two 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 (E), 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.

As a compound represented by the general formula (VI), from the viewpoint of availability, 1,3
, 5,7-tetramethylcyclotetrasiloxane is preferred.

  The molecular weight of the component (F) is not particularly limited and can be suitably used. However, it has a low molecular weight from the viewpoint of high fluidity and easy mixing with powders such as white pigments and inorganic fillers described later. Those are preferably used. 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 (F), in order to facilitate uniform mixing with other components, particularly powders such as white pigments and inorganic fillers described later, more specifically, heating above the melting point for uniform mixing. Since it does not need to be liquefied, it 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 even more preferably 5 Pa seconds or less. preferable. The viscosity can be measured with an E-type viscometer.

  Component (F) can be used alone or in combination of two or more.

(Preferred structure of component (F))
From the viewpoint of having good compatibility with the component (E), and from the viewpoint that the problem of outgas from the composition that can lower the volatility of the component (F) is less likely to occur, the component (F) is a SiH group. Hydrosilylation reaction of an organic compound (α) containing at least one carbon-carbon double bond having reactivity with a compound (β) having at least two SiH groups in one molecule is carried out. It is preferable that it is a compound which can be obtained.
((Α) component)
Here, the component (α) is also the component (E) 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 (F) is in phase with the component (E). 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,

The groups shown are 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 (F) component is easily compatible with the (E) component, 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 resulting curable composition tends to be high, and the strength of the resulting 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 (V)

(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 (V) is preferably composed of 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 (α) component and (β) component)
Next, hydrosilylation of the (α) component and the (β) component when using a compound obtained by hydrosilylation reaction of the (α) component and the (β) component as the (F) component 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 (F) component of the present invention may be obtained, but without separating the (F) component therefrom. The curable composition of the present invention can 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 (F) component and the (E) component is not limited. In view of the strength of the cured product due to the above, since it is preferable that the component (F) 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 (E) component of (F) 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.

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is sufficient with respect to 1 mole of SiH group of the (β) component in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ^-8 mol, more preferably 10 ^-6 mole, preferable amount of the upper limit is 10 ^-1 moles per mole of the SiH group (beta) component, more preferably 10 ^-2 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 maleate, 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 obtained component (F) does not have a volatile component, so that the problem of voids and cracks due to the volatilization of the volatile components hardly occurs in the case of curing with the component (E). 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 (F) component that is a reaction product of the (α) component and the (β) component 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 (E) component and (F) component)
Regarding the combination of the component (E) and the component (F), various combinations of those listed as examples of the component (E) and various mixtures thereof / examples of the component (F) and various mixtures thereof are listed. be able to.

  The mixing ratio of the component (E) and the component (F) is not particularly limited as long as the required strength is not lost, but the number of SiH groups in the component (F) (Y) is the carbon-carbon in the component (E). 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. When it deviates from the preferred range, sufficient strength may not be obtained or thermal deterioration may easily occur.

((G) component)
Component (G) is a hydrosilylation catalyst.

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

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

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

Although the addition amount of the catalyst is not particularly limited, the lower limit of the preferable addition amount is sufficient with respect to 1 mol of SiH group of the component (F) in order to have sufficient curability and keep the cost of the curable composition relatively low. 10 ^-8 mol, more preferably 10 ^-6 mole, preferable amount of the upper limit is 10 ^-1 moles per mole of the SiH group (beta) component, more preferably 10 ^-2 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 maleate, 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.

<Acrylate resin>
The acrylate resin according to the present invention is an acrylate resin containing polybutylene glycol di (meth) acrylate (I) and alicyclic (meth) acrylate (J).

<Polybutylene glycol di (meth) acrylate (I)>
Polybutylene glycol di (meth) acrylate (I) is a component that suppresses curing shrinkage and contributes to a decrease in the elastic modulus and water absorption rate of the resulting cured product. Polybutylene glycol di (meth) acrylate (I) is obtained by sealing both ends of polybutylene glycol with (meth) acrylic acid. The number of repeating units n of the butylene glycol group in the polybutylene glycol part is preferably 5 to 16. However, since polybutylene glycol di (meth) acrylate is generally a mixture of compounds having different numbers of repeating units in a normal distribution, the number of repeating units n here means a median value. When the number of repeating units n is 5 or more, the resulting cured product has a good elastic modulus. In the case of 16 or less, the water absorption rate is good. Moreover, heat resistance becomes favorable.

<Alicyclic (meth) acrylate (J)>
The alicyclic (meth) acrylate (J) is a component that suppresses the curing shrinkage rate and contributes to the improvement of the heat resistance and transparency of the resulting cured product. Specific examples of the alicyclic (meth) acrylate (J) include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate. 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meta ) Acrylate, Dicyclopentenyloxyethyl (meth) acrylate, Fentyl (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, Tricyclodecane dimethanol di (meth) acrylate DOO, norbornane dimethanol di (meth) acrylate. An alicyclic (meth) acrylate (J) may be used individually by 1 type, and may use 2 or more types together. The alicyclic (meth) acrylate (J) is preferably a mono (meth) acrylate represented by the following general formula (4). By using mono (meth) acrylate, workability during molding is improved.

(Wherein R ¹ represents hydrogen or a methyl group, and R ² represents a hydrocarbon group containing an alicyclic hydrocarbon structure.)

R ^{2 in the} general formula (4) is preferably an alicyclic hydrocarbon group having 5 to 12 carbon atoms. When the number of carbon atoms of R ^{2 in} the general formula (4) is 5 or more, curing shrinkage is suppressed. Moreover, the heat resistance of the hardened | cured material obtained becomes favorable. In the case of 12 or less, the strength is good. From the viewpoints of heat resistance, low curing shrinkage, and transparency, isobornyl (meth) acrylate and fentyl (meth) acrylate are preferred. From the viewpoint of heat resistance, isobornyl methacrylate and fentyl methacrylate are more preferable.

  The content ratio of polybutylene glycol di (meth) acrylate (I) and alicyclic (meth) acrylate (J) in the curable resin composition is 25 to 65 for polybutylene glycol di (meth) acrylate (I). It is preferable that 35 mass% and alicyclic (meth) acrylate (J) are 35-75 mass%, polybutylene glycol di (meth) acrylate (I) is 35-55 mass%, and alicyclic (meth) acrylate. (J) More preferably, it is 45-65 mass%. When the content of the alicyclic (meth) acrylate (J) is 35% by mass or more, transparency and heat resistance of the cured product are improved. The elastic modulus of the cured product is preferably lower than 75% by mass.

(Other ingredients)
As a component other than (I) and (J) constituting the acrylic resin in the present invention, other radical polymerizable vinyl monomers may be used within the range not impairing the characteristics of the present invention. Specific examples of other radical polymerizable vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl ( (Meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) Acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxylate 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate , Mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) acid phosphate, (meth) acrylic acid, (meth) acryloylmorpholine, styrene, vinyltoluene, vinyl acetate, etc. Is mentioned. Moreover, you may use the (meth) acrylic-type radically polymerizable monomer which has a 2 or more double bond in 1 molecule as needed. Specific examples thereof include ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylic acid adduct, etc. are mentioned.

  The content of the other radical polymerizable vinyl monomer is preferably 20% by mass or less, more preferably 10% by mass or less, in total with the components (I) and (J).

  The curing agent used for curing the acrylate resin of the present invention is not particularly limited, and any conventional curing method can be used. For example, thermal polymerization may be performed using a polymerization initiator such as an organic peroxide or an azo compound as a curing agent, or photopolymerization may be performed using a photopolymerization initiator. These may be used in combination.

  Specific examples of the organic peroxide used as a polymerization initiator used in the acrylate resin of the present invention include ketone peroxides such as methyl ketone peroxide, 1,1-di (tert-hexylperoxy) -3, Peroxyketals such as 3,5-trimethylcyclohexane, 1,1-di (tert-hexylperoxy) cyclohexane, 1,1-di (tert-butylperoxy) cyclohexane, 1,1,3,3, -tetra Diacyl peroxides such as methyl peroxide, cumene hydroperoxide, hydroperoxide such as p-menthane hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide , Di (4-te t-butylcyclohexyl) peroxydicarbonate, peroxydicarbonate such as di (2-ethylhexyl) peroxydicarbonate, tert-butylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropylmonocarbonate, tert -Peroxyesters such as butyl peroxybenzoate.

  Specific examples of the azo compound used as the polymerization initiator used in the acrylate resin of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyano Valeric acid, 2,2′-azobis- (2-amidinopropane) dihydrochloride and the like can be mentioned.

  Specific examples of the photopolymerization initiator used in the acrylate resin of the present invention include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-methyl-1-phenyl- Examples include propan-1-one and oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone.

  The blending amount of the thermal polymerization initiator or photopolymerization initiator per 100 parts by mass of the acrylate resin is preferably 0.01 parts by mass to 5 parts by mass, and 0.1 parts by mass to 2 parts by mass. More preferred. When the amount is 0.01 parts by mass or more, the curability is good, and when it is 5 parts by mass or less, the heat resistance and transparency of the cured product are good.

  The polymerization temperature and polymerization time when the acrylate resin of the present invention is cured by thermal polymerization are not particularly limited because the optimum value varies depending on the type and content of the curing agent, but the polymerization temperature is preferably 40 ° C to 140 ° C. . When it is 40 ° C. or higher, the curability is good and the curing time can be shortened, so that productivity is improved. The crack and foaming of hardened | cured material by rapid hardening can be suppressed as it is 140 degrees C or less. The polymerization time is preferably 0.5 hours to 5 hours. If it is 0.5 hours or longer, the curability is good, and if it is 5 hours or less, the curing time is shortened and the productivity is improved. Moreover, photopolymerization by light irradiation can be performed in a shorter time in order to obtain a cured product.

  In addition, the acrylate resin of the present invention has, for example, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a lubricant, a release agent, a dye, a pigment, an antifoaming agent, in order to improve various properties. Various additives such as a polymerization inhibitor and a filler may be added.

<Urethane resin>
The urethane resin according to the present invention comprises (K) a urethane oligomer, (L) a polymerizable compound having at least one unsaturated double bond, (M) a radical polymerization initiator, and (N) a phenolic antioxidant. Is a curable resin composition. Hereinafter, the (meth) acryl group means an acryl group and a methacryl group corresponding thereto. The same applies to (meth) acryl modification.

  Here, (K) urethane oligomer includes (a) diisocyanate, (b) polycarbonate diol represented by the following general formula (5), and (c) hydroxyl group-containing (meta) represented by the following general formula (6). ) Acrylate, a caprolactone-modified (meth) acrylate represented by the following general formula (7) or a trifunctional hydroxyl group-containing (meth) acrylate represented by the following general formula (8).

(In the formula, R ¹ and R ² are each independently a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 50.)

(In the formula, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a linear or branched hydrocarbon group having 1 to 10 carbon atoms.)

(In the formula, R ⁵ is a hydrogen atom or a methyl group, R ⁶ is a linear or branched hydrocarbon group having 2 to 4 carbon atoms, and n is an integer of 1 to 50.)

(In the formula, R ⁷ is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 50.)
(A) Diisocyanate is a compound having two isocyanate groups in one molecule. Specific examples thereof include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylene diisocyanate. , Isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like. These can be used alone or in combination. Of these, isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are preferred because the resulting urethane oligomer has good yellowness and handling properties.

  (B) As the polycarbonate diol represented by the general formula (5), for example, a polycarbonate diol having a weight average molecular weight of 500 (manufactured by Daicel Chemical Industries, Ltd .; trade name: Plaxel CD CD205) and having a weight average molecular weight of 1,000. Examples include polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd .; trade name: Plaxel CD CD210), polycarbonate diol having a weight average molecular weight of 2,000 (trade name: Plaxel CD CD220, manufactured by Daicel Chemical Industries, Ltd.), and the like. These can be used alone or in combination. Among these, a polycarbonate diol having a weight average molecular weight of 500 is preferable because the handleability of the resulting urethane oligomer is good.

  (C) Hydroxyl group-containing (meth) acrylate represented by general formula (6), caprolactone-modified (meth) acrylate represented by general formula (7) or trifunctional hydroxyl group-containing (meta) represented by general formula (8) The acrylate may be a compound having one or more radically polymerizable functional groups in the molecule and one hydroxyl group capable of reacting with an isocyanate group to form a urethane bond. The radical polymerizable functional group may be any functional group capable of radical polymerization, and may be, for example, a (meth) acryl group.

  Examples of the hydroxyl group-containing (meth) acrylate represented by the general formula (6) include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. It is done. These can be used alone or in combination.

  The caprolactone-modified (meth) acrylate represented by the general formula (7) is an unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone in which one (meth) acrylate is introduced into a polycaprolactone oligomer. For example, 2-hydroxyethyl Ε-caprolactone 1 mol addition product of (meth) acrylate, ε-caprolactone 2 mol addition product of 2-hydroxyethyl (meth) acrylate, ε-caprolactone 3 mol addition product of 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meta ) Ε-caprolactone 5 mol addition product of acrylate, ε-caprolactone 10 mol addition product of 2-hydroxyethyl (meth) acrylate, and the like. These can be used alone or in combination. In these, the 2 mol epsilon caprolactone addition product of 2-hydroxyethyl (meth) acrylate is more preferable. Further, as the (meth) acrylate to be introduced, in addition to 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3 -Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. can also be used. These can be used alone or in combination.

  Examples of the trifunctional hydroxyl group-containing (meth) acrylate represented by the general formula (8) include pentaerythritol triacrylate.

  The equivalent ratio of the isocyanate group in the component (a) to the hydroxyl group in the component (b) and the component (c) is 0.8 to 1.2.

  When synthesizing (K) urethane oligomer (hereinafter also referred to as component (K)), a known polymerization inhibitor or catalyst may be added in addition to the components (a) to (c).

  The weight average molecular weight of the (K) urethane oligomer is preferably in the range of 2,000 to 10,000, more preferably in the range of 3,000 to 9,000, and 4,000 to 8,000. It is particularly preferable that the range is When the weight average molecular weight is less than 2,000, sufficient toughness tends to be difficult to obtain, and when it exceeds 10,000, the cured product tends to be soft.

  As the polymerization inhibitor, a known polymerization inhibitor can be used, and examples thereof include p-methoxyquinone, p-methoxyphenol, and p-tert-butylcatechol. Moreover, as a catalyst, the well-known catalyst used for urethane oligomer synthesis | combination can be used, For example, dibutyltin dilaurate, dibutyltin diacetate, triethylenediamine, etc. are mentioned.

  In the (K) urethane oligomer synthesis reaction, a mercaptan compound, thioglycol, carbon tetrachloride, α-methylstyrene dimer, or the like can be added as necessary as a molecular weight modifier.

  (L) A polymerizable compound having at least one unsaturated double bond (hereinafter also referred to as (L) component) is a monomer curable by heat and has an ether structure from the viewpoint of heat resistance. Those having no aromatic ring are preferred from the viewpoint of light resistance. Specific examples thereof include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl. (Meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, ethoxyethyl (meth) acrylate, Butoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methyl Xoxyethoxy (meth) acrylate, 2-ethoxyethoxy (meth) acrylate, pyrenoxide adduct (meth) acrylate, octafluoropentyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( (Meth) acrylate, cyclohexyl mono (meth) acrylate, mono (meth) acrylate having tricyclodecane, ethylene glycol di (meth) acrylate, methanediol di (meth) acrylate, 1,2-ethanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1 6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10- Decanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, neopentyl di (meth) acrylate, Bifunctional (meth) acrylates such as dimethylol tricyclodecane di (meth) acrylate, zinc di (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, caprolactone-modified tricyclodecane dimethanol di (meth) acrylate , One end (meth) acrylic variation Silicone oil, both-end (meth) acryl-modified silicone oil, and the like. These can be used alone or in combination of two or more. Among these, dimethylol-tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexaacrylate are preferable.

  As the (M) radical polymerization initiator (hereinafter also referred to as the (M) component), a radical thermal polymerization initiator can be used. As the radical thermal polymerization initiator, any one that can be used for ordinary radical polymerization, such as an azo initiator and a peroxide initiator, can be used.

  Examples of the azo initiator include azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, azodibenzoyl, and the like.

  Examples of peroxide-based initiators include benzoyl peroxide, lauroyl peroxide, di-tert-butylperoxyhexahydroterephthalate, tert-butylperoxy-2-ethylhexanoate, 1,1-tert-butylperoxide. Examples include oxy-3,3,5-trimethylcyclohexane, tert-butylperoxyisopropyl carbonate, di-tert-hexyl peroxide and the like.

  The (N) phenolic antioxidant (hereinafter also referred to as the (N) component) is limited as long as it is a main radical scavenger generally used for suppressing thermal oxidative degradation and imparting a long life to the polymer. It can be used without Specifically, for example, 1,3,5-tris (4-tert-butyl-4-hydroxy-2,6-dimethylbenzene) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy) -5-tert-butylphenyl) butane, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol, n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-tert-butyl) Phenyl) propionate, tetrakis {methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate} methane, triethylene glycol bis {3- (3′-tert-butyl-4 ′) -Hydroxyphenol) propionate, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylpheny ) Propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxapyro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5'-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5, -di-butyl-4-hydroxybenzyl) isocyanurate, 2,2'-methylenebis (4-methyl-6-tert-) Butylphenol), 2,6-di-tert-butyl-4-methylphenol, etc. Among them, 4,4′-butylidenebis (3 -Methyl-6-tert-butylphenol, n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate , Tetrakis {methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate} methane, 3,9-bis [2- {3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxapyro [5.5] undecane and the like are more preferred.

  Moreover, these (N) phenolic antioxidants may improve the antioxidant effect when used in combination with phosphite antioxidants or thioether antioxidants. For example, phosphite antioxidants include tris (phenyl) phosphite, tris (isodecyl) phosphite, diphenylisooctyl phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tris (2 , 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. As the thioether-based antioxidant, tetrakis {methylene-3- (laurylthio) propionate} methane, bis [methyl-4- {3-n-alkyl (C12 or C14) thiopropioniodyl} -5-tert- Butylphenyl] sulfide, ditridecyl-3,3′-thiodipropionate, and the like.

  The mass ratio of the (K) component and the (L) component in the urethane resin is preferably in the range of 1: 9 to 9: 1, and more preferably in the range of 2: 8 to 8: 2. When the content of the (L) component is less than 10 parts by mass with respect to 90 parts by mass of the (K) component, the viscosity of the urethane resin becomes high and tends to be difficult to handle. On the other hand, when the content of the (L) component is larger than 90 parts by mass with respect to 10 parts by mass of the (K) component, the mounting reliability tends to be lowered.

  The content of the (M) component in the urethane resin is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of the (K) and (L) components, and 0.05 to 0.5 It is particularly preferable to use parts by mass. When the content of the component (M) exceeds 1 part by mass, the cured product tends to be colored by heat or near ultraviolet rays, and the curing rate becomes too fast, making it difficult to handle the resin composition. On the other hand, when the content of the component (M) is less than 0.01 parts by mass, it tends to be difficult to cure. Even when a plurality of thermal radical polymerization initiators having different half-life temperatures are used, the total content is preferably within the above range.

  The content of the (N) component in the urethane resin is preferably 0.001 to 5 parts by mass, and 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of the (K) and (L) components. It is more preferable to set it as 0.1-1 mass part. When the content of the (N) component exceeds 5 parts by mass, the cured product tends to be colored, and when it is less than 0.001 part by mass, the effect of suppressing coloring tends to be small.

  In addition to the above components (K) to (N), an ultraviolet absorber, HALS, an inorganic filler, an organic filler, a coupling agent, a polymerization inhibitor, and the like can be added to the urethane resin. Moreover, a mold release agent, a plasticizer, an antistatic agent, a flame retardant, etc. may be added from the viewpoint of moldability.

The urethane resin preferably has a gelation time at 165 ° C. of 25 to 200 seconds. When the gelation time is shorter than 25 seconds, the resin solution is hardened before it sufficiently flows through the flow path in the molding die, and an unfilled portion is generated in the molded product, thereby obtaining a molded product having a desired shape. Tend to be difficult. Moreover, when it has 200 seconds or more for gelatinization, there exists a tendency for it to become difficult to fully harden a molded object.
(Thermosetting resin composition)
The thermosetting resin is kneaded with a white pigment and an inorganic filler as described below to obtain a thermosetting resin composition. The kneading method and kneading apparatus for the white pigment and the inorganic filler are not particularly limited, and a lykai machine, a kneader, a roll, a ball mill, a planetary mixer, an extruder, an extruder, and the like can be used. In addition, depending on the resin composition, a method of cooling and pulverizing and kneading may be used as necessary.
(White pigment)
The white pigment has an effect of increasing the light reflectance of the obtained cured product. Various white pigments can be used, such as titanium oxide, zinc oxide, magnesium oxide, antimony oxide, zirconia oxide, strontium oxide, niobium oxide, boron nitride, barium titanate, zinc sulfide, barium sulfate, carbonic acid. Examples include magnesium and hollow glass particles. Among these, titanium oxide or zinc oxide is preferable from the viewpoint of ease of handling, availability, and cost. Titanium oxide is preferable from the viewpoint of increasing the reflectance of the cured product of the resulting thermosetting resin composition. Various types of titanium oxide can be used as the white pigment, which may be anatase type or rutile type, but is rutile type in that it has no photocatalytic action and the composition tends to be stable. Is preferred. As a method for producing white pigment titanium oxide, those produced by any method such as sulfuric acid method and chlorine method can be used.

  Zinc oxide is preferred from the viewpoint of high thermal conductivity of the cured product of the resulting thermosetting resin composition.

  Various average particle diameters of the white pigment are used, but from the viewpoint that the light reflectance of the obtained cured product tends to be high, those having a thickness of 1.0 μm or less are preferable, and those having a particle diameter of 0.80 μm or less are more preferable. The most preferable one is 0.60 μm or less. The average particle diameter can be measured using a laser diffraction / scattering particle size distribution analyzer.

  The white pigment may be subjected to a surface treatment.

  In the surface treatment of the white pigment, the surface of the white pigment 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 white pigment 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 the white pigment, when it is slurried, or when wet pulverized. Can do. 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 a white pigment that has been treated with organosiloxane 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. White pigments, especially 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 particle shape collapse. By surface-treating the pigment with an inorganic compound, the affinity with the components contained in the thermosetting resin composition is improved, the dispersibility of the white pigment in the thermosetting resin composition is improved, and the strength of the cured product is improved. I think that.

  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 white pigment is not particularly limited, but the amount of the white pigment in the entire thermosetting resin composition is preferably 10% by weight or more, more preferably 15% by weight or more, and 20% by weight. More preferably, it is the above. If it is less than 10% by weight, the light reflectance of the resulting cured product may be lowered.

(Inorganic filler)
The inorganic filler is different from the white pigment used as the white pigment. The inorganic filler has the effect of increasing the strength and hardness of the resulting cured product and reducing the linear expansion coefficient.

  The inorganic filler is not particularly limited. For example, silica-based inorganic fillers such as quartz, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine powder amorphous silica, alumina, zircon, titanium oxide, nitriding Silicon, boron nitride, aluminum nitride, silicon carbide, magnesium hydroxide, barium carbonate, hollow particles, glass fiber, alumina fiber, carbon fiber, mica, graphite, carbon black, graphite, diatomaceous earth, white clay, clay, talc, hydroxylation Generally used as a filler for conventional semiconductor encapsulants such as epoxy, including inorganic fillers such as aluminum, calcium carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloon, silver powder, etc. And proposed inorganic fillers. Among them, silica-based inorganic fillers such as quartz, precipitated silica, anhydrous silica, fused silica, crystalline silica, ultrafine powder amorphous silica, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, magnesium carbonate, Barium carbonate, alumina, zinc oxide, antimony oxide, zirconium oxide, titanium oxide, magnesium oxide, carbon black, and hollow particles can be suitably used.

  Among these, silica-based inorganic fillers are preferable from the viewpoints that the curing reaction is not easily inhibited, the effect of reducing the linear expansion coefficient is large, and the adhesiveness to the lead frame is likely to be high. Furthermore, fused silica is preferable in terms of a good balance of physical properties such as moldability and electrical characteristics, and crystalline silica is preferable in terms of easy package thermal conductivity and high heat dissipation. Alumina is preferable in that heat dissipation tends to be higher. In addition, glass fiber, potassium titanate, and calcium silicate are preferable in that the reinforcing effect is high and the strength of the package tends to be high. These inorganic fillers may be used alone or in combination of two or more.

  The shape of the inorganic filler is not particularly limited, and a crushed shape, a piece shape, a spherical shape, a rod shape, and the like can be used, but the moldability is good even when the content in the thermosetting resin composition tablet is increased. Therefore, it is preferably spherical or round and crushed, and more preferably spherical.

  The particle size of the inorganic filler is not particularly limited, but can be used as a filler for a conventional semiconductor sealing material such as an epoxy-based material and / or a material in the proposed range. The upper limit of the preferable average particle diameter is 100 μm, and preferably 50 μm from the viewpoint that fluidity tends to be good.

  The specific surface area of the inorganic filler is not particularly limited, and can be set in various ways including those used and / or proposed as fillers for conventional sealing materials such as epoxy-based materials.

  The inorganic filler is preferably low radiation from the viewpoint that it is difficult to damage the semiconductor element.

  Moreover, you may surface-treat an inorganic filler suitably. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a coupling agent, and the like.

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

(Thermosetting resin composition tablet)
The molding method is not particularly limited, and a molding method such as transfer molding or compression molding that is generally used for molding a thermosetting resin composition can be used. When using these molding methods, if the thermosetting resin composition that is the raw material is in the form of a paste or clay, it will not be possible to maintain a constant shape, and it will be attached, integrated, or deformed. The 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 tablet molding conditions of the thermosetting resin composition of the present invention are not particularly limited, but are pressure-molded at room temperature (0 to 35 ° C.) under conditions of 0.5 to 20 MPa and about 1 to 5 seconds. It is desirable that the tablet can be molded.

(Coating of filler on thermosetting resin composition tablet)
The average particle diameter of the filler coated on the thermosetting resin composition tablet of the present invention is preferably 100 μm or less. 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 cannot be done, but it is considered that it becomes flakes or powders. In other words, by increasing the proportion of small particles in the particles, it is possible to harden the composition at room temperature while maintaining the fluidity of the composition at high temperature, and to obtain a tablet with excellent dimensional stability. .

  The coating amount of the filler can be arbitrarily determined according to the surface state such as the shape of the thermosetting resin composition tablet and the adhesiveness. The amount of the filler is not particularly limited, but the weight percent of the filler with respect to the tablet weight is preferably 0.5 to 1.5 wt%. When the amount used is more than 1.5 wt%, excess filler causes mold contamination, so it is preferable to remove excess filler adhering to the surface area of the adherend by vibration. Moreover, when the usage-amount of a filler is less than 0.5 wt%, sufficient surface tack inhibitory effect is not seen.

  The method for coating the adherend on the adherend is not particularly limited as long as the filler can be integrated with the thermosetting resin composition tablet. Suitable methods include a method in which a filler is placed in a container or a bag, and a thermosetting resin composition tablet is coated by vibration using a machine, or a method in which the filler is manually sprinkled.

  The filler for coating the tablet is not particularly limited, but the same filler as kneaded in the thermosetting resin composition tablet can be used to form and heat cure the thermosetting resin composition. It is preferable from the viewpoint that the uniformity of the composition of the cured product to be molded is improved.

(Properties of cured product)
If the thermosetting resin composition tablet of the present invention is molded and cured, a white molded body can be obtained, but the white molded body obtained by curing has a light reflectance of 80 at a surface wavelength of 460 nm and / or 480 nm. % Or more is preferable, and 85% or more is more preferable. The light reflectance of the surface can be measured as follows. Using a PET film as a release film, a 0.5 mm-thick molded body without voids is prepared by press molding under a predetermined temperature condition. The obtained molded body is subjected to predetermined post-curing as necessary. About the obtained molded object, it can obtain | require by measuring a diffuse reflectance of 460 nm and / or 480 nm using a spectral color difference meter (Nippon Denshoku VSS-400).

(Light emitting diode package)
The light emitting diode package referred to in the present invention is designed so that light emitted from the light emitting diode element is irradiated, and more preferably, the light emitted from the light emitting diode element is reflected and taken out to the outside. It is designed. There are no particular restrictions on the shape and the like. For example, it may have a shape having a recess for mounting a light emitting diode element, or may simply have a flat plate shape. The surface of the light emitting diode package of the present invention may be smooth or may have a non-smooth surface such as embossing.

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

(Light emitting diode package 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 and epoxy resins, such as injection molding, transfer molding, RIM molding, casting molding, and press molding, are used. Of these, transfer molding is preferred in that the molding cycle is short and the moldability is good. The molding conditions can be arbitrarily set, for example, the molding temperature is also arbitrary. However, in terms of fast curing and a short molding cycle, the moldability tends to be good, more preferably 100 ° C. or higher, more preferably 120 ° C. or higher. A temperature of 150 ° C. or higher is preferable. After molding by the various methods as described above, post-curing (after-curing) is optional as required. Heat resistance tends to increase by post-curing.

(Light-emitting diode element)
The various light emitting diode elements of the light emitting diode referred to in the present invention are not particularly limited, and the light emitting diode elements used in conventionally known light emitting diodes can be used.

  The size and number of the light emitting diode elements can be used without any particular limitation.

  Any light emitting output of the light emitting diode element can be used without any particular limitation. However, when a light emitting element of 1 mW or more is used at 20 mA, the effect of the present invention is remarkable, and a light emitting element of 4 mW or more at 20 mA is used. When used, the effect of the present invention is remarkable. When a light emitting element of 5 mW or more is used at 20 mA, the effect of the present invention is further remarkable.

  Various light emission wavelengths of the light emitting diode element can be used from the ultraviolet region to the infrared region, but the effect of the present invention is particularly remarkable when the main light emission peak wavelength is 550 nm or less.

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

(Lead)
The lead terminal used in the semiconductor of the present invention preferably has good adhesion with an electrical connecting member such as a bonding wire, electrical conductivity, etc., and the electrical resistance of the lead terminal is preferably 300 μΩ-cm or less, More preferably, it is 3 μΩ-cm or less. Examples of these lead terminal materials include iron, copper, iron-containing copper, tin-containing copper, and those plated with gold, silver, nickel, palladium, and the like. The glossiness of these lead terminals may be adjusted as appropriate in order to obtain a good light spread.

(Sealing agent)
Various semiconductor sealing agents of the present invention can be used. For example, conventionally used sealing resins such as epoxy resins, silicone resins, acrylic 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 sealing agent comprising a curable 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 sealing agent is used. In view of the fact that the effect is high 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.

(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.

  Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

(Formulation Example 1) Epoxy Resin First, a thermosetting light reflecting resin composition was prepared by roll kneading the components shown below under conditions of a kneading temperature of 20 to 30 ° C. and a kneading time of 10 minutes. .

(Curable resin composition for light reflection)
Epoxy resin:
100 parts by weight of triglycidyl isocyanurate
(Epoxy equivalent 100)
Curing agent:
Hexahydrophthalic anhydride 140 parts by weight Curing accelerator:
Tetra-n-butylphosphonium 2.4 parts by weight
o, o-Diethyl phosphorodithioate Inorganic filler:
600 parts by weight of fused silica (average particle size 20 μm)
Alumina (average particle size 1 μm) 890 parts by weight White pigment:
185 parts by weight of hollow particles (average particle size 27 μm)
("Glass Bubbles S60HS (trade name)" manufactured by 3M)
Coupling agent:
19 parts by weight of epoxy silane Antioxidant:
9,10-dihydro-9-oxa-10-1 part by weight
Phosphaphenanthrene-10-oxide Next, using a molding die for tablets, the above epoxy resin composition was tableted under conditions of room temperature and molding pressure of 2 МPa for 3 seconds, and a cylindrical tablet having a diameter of 13 mm and a height of 15 mm was obtained. Produced.

(Synthesis Example 1) Condensation Type Silicone Resin 100 parts by mass of methyltrichlorosilane and 200 parts by mass of toluene were placed in a 1 L flask, and a mixed solution of 8 parts by mass of water and 60 parts by mass of isopropyl alcohol was added dropwise in the liquid. The internal temperature was dropped at -5 to 0 ° C over 5 to 20 hours, then heated and stirred at reflux temperature for 20 minutes. Then, the mixture was cooled to room temperature, and 12 parts by mass of water was added dropwise at 30 ° C. or less over 30 minutes, followed by stirring for 20 minutes. Further, 25 parts by mass of water was added dropwise, followed by stirring at 40 to 45 ° C. for 60 minutes. Thereafter, 200 parts by mass of water was added to separate the organic layer. The organic layer was washed until neutral, and then azeotropic dehydration, filtration, and vacuum stripping were performed to obtain 36.0 parts by mass of an organopolysiloxane (colorless transparent solid (melting point 76 ° C.)) (yield) 80%).

(CH ₃ ) _1.0 Si (OC ₃ H ₇ ) _0.07 (OH) _0.10 O _1.4

(Formulation example 2) The raw material used was the composition shown below, and melt kneading was performed using a two-roll hot roll to obtain a condensation type silicone resin composition.
Thermosetting organopolysiloxane:
100 parts by weight of organopolysiloxane obtained in Synthesis Example 1 White pigment: Titanium dioxide (W-2568: manufactured by Sakai Chemical Co., Ltd., alumina-silica surface treatment, anatase type, average particle size 0.29 μm) 150 parts by weight inorganic Filler: Spherical fused silica A Average particle size 45 μm (MSR-4500TN: manufactured by Tatsumori Co., Ltd.) 200 parts by weight
Spherical fused silica B Average particle size 4 μm (N-MSR-04: manufactured by Tatsumori) 55 parts by weight
Spherical fused silica C Average particle size 0.5 μm (SO-25R: manufactured by Admatech) 30 parts by weight Curing catalyst: Zinc benzoate (manufactured by Wako Pure Chemical Industries, Ltd.) 1.1 parts by weight Release material: Calcium stearate (Wako Pure Chemical Industries, Ltd.) 0.8 parts by weight Silane coupling agent: 3-mercaptopropyltriethoxysilane (KBM-803: Shin-Etsu Chemical Co., Ltd. trade name) 1 part by weight

(Formulation example 3) Addition type silicone resin The used raw material was knead | mixed with the composition shown below, and the addition type silicone resin composition was obtained.
Both ends vinyldimethylsiloxy group-blocked dimethylpolysiloxane:
94 parts by weight of an organohydrogenpolysiloxane represented by the following formula (i):
Compound represented by the following formula (ii) 6 parts by weight white pigment:
Titanium dioxide (W-2568: Sakai Chemical Co., Ltd., alumina-silica surface treatment, anatase type, average particle size 0.29 μm) 150 parts by weight Inorganic filler:
Spherical fused silica A Average particle size 45 μm (MSR-4500TN: manufactured by Tatsumori Co., Ltd.) 200 parts by weight
Spherical fused silica B Average particle size 4 μm (N-MSR-04: manufactured by Tatsumori) 55 parts by weight
Spherical fused silica C Average particle size 0.5 μm (SO-25R: manufactured by Admatech) 30 parts by weight curing catalyst:
Zinc benzoate (Wako Pure Chemical Industries, Ltd.) 1.1 parts by weight release material:
Calcium stearate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.8 part by weight silane coupling agent:
3-mercaptopropyltriethoxysilane (KBM-803: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight

(Synthesis Example 2) A stirrer, a dropping funnel, and a condenser tube were set in a four-necked flask of 5 L of modified silicone resin. 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 3)
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

(Formulation Example 4 and Formulation Example 5)
According to the content of Table 1, each component was mix | blended and the thermosetting resin was obtained.

(Formulation example 6)
According to the content of Table 2, each component was mix | blended and the thermosetting composition was obtained.

(Formulation example 7) Acrylate resin polybutylene glycol dimethacrylate (n = 8-9, manufactured by Mitsubishi Rayon Co., Ltd.)
70 parts by weight isobornyl methacrylate 30 parts by weight Bis (4-tert-butylcyclohexyl) peroxydicarbonate (manufactured by NOF Corporation, Parroyl TCP, 10 hour half-life temperature: 40.8 ° C. (catalog value) ), White granular form) was mixed and stirred at room temperature to obtain an acrylate resin.

(Formulation example 8)
Moreover, the acrylate resin composition was obtained by knead | mixing with the composition shown below.
100 parts by weight of acrylate resin obtained in Formulation Example 7 White pigment: Titanium dioxide (W-2568: manufactured by Sakai Chemical Co., Ltd., alumina-silica surface treatment, anatase type, average particle size 0.29 μm) 150 parts by weight inorganic Filler: Spherical fused silica A Average particle size 45 μm (MSR-4500TN: manufactured by Tatsumori Co., Ltd.) 200 parts by weight
Spherical fused silica B Average particle size 4 μm (N-MSR-04: manufactured by Tatsumori) 55 parts by weight
Spherical fused silica C Average particle size 0.5 μm (SO-25R: manufactured by Admatech) 30 parts by weight Release material: Calcium stearate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.8 parts by weight Silane coupling agent: 3 -Mercaptopropyltriethoxysilane (KBM-803: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight

(Synthesis example 4) Urethane resin A stirrer, a thermometer, a cooling pipe and an air gas introduction pipe were attached to a 0.5 L three-necked flask, and after introducing air gas, a polycarbonate diol having a weight average molecular weight of 500 (manufactured by Daicel Chemical Industries, Ltd.) Trade name: Plaxel CD CD205) 50.0 g, 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .; trade name: light ester HOA) 23.2 g, p-methoxyquinone (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor 0.05 g, 0.03 g of dibutyltin dilaurate (manufactured by Tokyo Fine Chemical Co., Ltd .; trade name L101) was added as a catalyst, and after raising the temperature to 70 ° C., norbornane diisocyanate (made by Mitsui Chemicals Polyurethane Co., Ltd.) was stirred ; Product name COSMONATE NBDI) 41.2g for 2 hours The solution was uniformly dropped over the course of the reaction. When the reaction was completed for about 5 hours after the completion of the dropping, IR measurement was performed to confirm that the isocyanate had disappeared, and the reaction was terminated to obtain urethane oligomer 1 (UA1) having a weight average molecular weight of 5,500.

(Formulation example 9)
90 parts by weight of urethane oligomer 1 synthesized in Synthesis Example 4 dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: trade name Light Acrylate DCP-A) 10 parts by weight of lauroyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd .: commodity Name paroyl L) 0.1 part by weight 3,9-bis [2- {3- (tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 8,10-tetraoxapyro [5,5] undecane (manufactured by ADEKA: trade name ADK STAB AO-80) 0.5 part by weight white pigment: titanium dioxide (W-2568: manufactured by Sakai Chemical Co., Ltd., alumina-silica Surface treatment, anatase type, average particle size 0.29 μm) 150 parts by weight inorganic filler: spherical fused silica A average particle size 45 μm (MSR-4500TN) Ltd. Tatsumori) 200 parts by weight
Spherical fused silica B Average particle size 4 μm (N-MSR-04: manufactured by Tatsumori) 55 parts by weight
Spherical fused silica C Average particle size 0.5 μm (SO-25R: manufactured by Admatech) 30 parts by weight Release material: Calcium stearate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.8 parts by weight Silane coupling agent: 3 -Mercaptopropyltriethoxysilane (KBM-803: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight

(Tablet)
The prepared curable resin composition was compressed by 0.39 MPa using a tablet manufacturing jig made of a metal pestle and mortar having a diameter of 13 mm, and the amount charged was adjusted to a height of 7.5 mm.

(Filling material coating)
The prepared tablet was put in a container filled with spherical silica, and the tablet surface was coated by applying vibration. Excess silica was screened off on the bat.
Example 1 and Example 3: Spherical silica Average particle diameter: 22.5 μm (МSR-2212, manufactured by Tatsumori)
Example 2: Zinc oxide Average particle size 0.5 μm (first type, manufactured by Sakai Chemical Industry Co., Ltd.)
Example 4 to Example 7: Spherical silica Average particle size 45 μm (МSR-4500-TN, manufactured by Tatsumori)

(Measurement of tablet characteristics)
(1) Tackiness: A tablet was placed in a polyethylene bag (trade name Unipack, manufactured by Seinichi Co., Ltd.) and the adhesion of the composition was qualitatively determined.
A: 1 day after filler coating, no deposit on bag, ○: Immediately after filler coating, no deposit on bag, Δ: Immediately after filler coating, deposit on bag (2) Moldability: 50 mm × using transfer molding machine The moldability was determined by the fillability when a 50 mm × 1 mm plate was produced.
○: No problem in filling, Δ: Unfilled portion (3) Reflectivity: A 1 mm-thick flat plate molded in (2) was used using a micro-spectral color difference meter (Nippon Denshoku Co., Ltd. VSS-400). The diffuse reflectance was measured.
○: Reflectance at 460 nm and 480 nm is 80% or more, Δ: Reflectance at 460 nm and 480 nm is less than 80%

As shown in Table 3, the compositions of Formulation Examples 1, 2, 3, 6, 8 and Formulation Example 9 are tableted, and the inorganic filler contained in each composition is coated to obtain tablets without tackiness. (Examples 1 to 7). All of these have good transfer moldability, and the obtained cured product has high reflectance. Examples 1 and 2 are particularly good because the tackiness does not change with time even one day after coating with the inorganic filler.
Table 4 shows the weight percentage of the filler with respect to the tablet weight. Specifically, the weight of the tablet that is tableted and not coated with the filler (corresponding to the blank) is measured, the filler is coated, the weight is measured (corresponding to the inorganic filler after coating), and the following calculation is performed. It is obtained by the formula.
Weight% of filler relative to tablet weight = [(after coating with inorganic filler) − (blank)] ÷ (blank) × 100
In Table 4, weight% of the filler with respect to each tablet weight of Examples 1-5 was described. As a result, the coating amount of the inorganic filler is in the range of 0.8 to 1.2 wt% with respect to the tablet weight, and as described above, there is no tackiness and the surroundings may be contaminated with excess filler. There was no. Comparative Example 1 is a tablet of the composition of Formulation Example 6 and has tackiness, which may cause problems in an automatic conveying device of a molding machine. As described above, coating the thermosetting resin composition of the present invention with an inorganic filler eliminates the tackiness of the tablet without impairing the moldability, thereby facilitating handling during transport and molding and improving productivity. . Moreover, all the obtained hardened | cured materials have a high reflectance and are suitable for electronic material uses, such as a package for optical semiconductors.

Claims (12)

  A thermosetting resin composition tablet obtained by tableting a thermosetting resin composition, wherein the tablet surface is covered with a filler.   The thermosetting resin composition tablet according to claim 1, wherein the filler includes an inorganic filler and / or an organic filler.   The inorganic filler is silica-based inorganic filler such as quartz, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, 3. At least one selected from the group consisting of magnesium carbonate, barium carbonate, alumina, zinc oxide, antimony oxide, zirconium oxide, titanium oxide, magnesium oxide, carbon black, and hollow particles. The thermosetting resin composition tablet as described.   The organic filler is a filler obtained by pulverization of a polymer, and includes polymethyl methacrylate (PMMA), polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate (PBMA), polyvinyl acetate (PVAc) ), Polyethylene glycol (PEG), polypropylene glycol (PPG), polyvinyl alcohol (PVA), and at least one selected from the group consisting of polyvinyl alcohol (PVA). .   The thermosetting resin composition is at least one selected from the group consisting of epoxy resins, modified epoxy resins, silicone resins, modified silicone resins, acrylate resins, and urethane resins. The thermosetting resin composition tablet according to any one of the above.   The thermosetting resin composition tablet for semiconductor packages which consists of a thermosetting resin composition tablet in any one of Claim 1 to 5.   The thermosetting resin composition tablet for light emitting diode packages which consists of a thermosetting resin composition tablet in any one of Claim 1 to 5.   The thermosetting resin composition tablet according to any one of claims 1 to 5, or the thermosetting resin composition tablet for a semiconductor package according to claim 6, or the thermosetting resin for a light emitting diode package according to claim 7. A molded article obtained by molding a composition tablet and having a spectral reflectance at a surface wavelength of 460 and 480 nm of 80 R% or more.   The package for light emitting diodes obtained by transfer-molding the thermosetting resin composition tablet for light emitting diode packages of Claim 7.   The light emitting diode manufactured using the package for light emitting diodes of Claim 9.   The thermosetting resin composition tablet according to any one of claims 1 to 5, or the thermosetting resin composition tablet for semiconductor package according to claim 6, or the thermosetting resin package for a light emitting diode according to claim 7. A method for producing a tablet of a resin composition, the step of molding a thermosetting resin composition under pressure and molding the tablet, and the step of coating the thus-formed tablet with an inorganic filler and / or an organic filler The manufacturing method of the thermosetting resin composition tablet characterized by having.   It is a manufacturing method of the tablet of the thermosetting resin composition of Claim 11, Comprising: The method of coat | covering the shape | molded tablet with an inorganic filler and / or an organic filler puts a filler in a container or a bag, heat | fever A method for producing a thermosetting resin composition tablet, comprising a step of rolling the curable resin composition tablet mechanically or manually and applying a filler.