JP5805420B2 - Thermosetting resin composition using organopolysiloxane, encapsulant for optical semiconductor, die bond material for semiconductor, optical semiconductor package, optical semiconductor - Google Patents

Description

  The present invention relates to an organopolysiloxane, a thermosetting resin composition using the same, a sealing material for optical semiconductors, and a die bonding material for optical semiconductors.

  It is known that an epoxy resin composition using an acid anhydride curing agent forms a transparent cured product and is suitable as a sealing material for optical semiconductor elements such as light emitting diodes and photodiodes. For example, an epoxy resin mainly composed of an epoxy resin having an organic resin skeleton such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and (3 ′, 4′-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate The composition has been used in the field of optical semiconductor devices.

  However, as the performance of optical semiconductors in recent years has progressed, the sealing materials for optical semiconductor elements are required to have more excellent characteristics such as heat resistance and light resistance. Conventional epoxy resin compositions However, sufficient characteristics cannot be obtained.

  Then, the thermosetting resin composition for optical semiconductors which cures a specific silicone composition by hydrosilylation reaction is proposed (for example, refer patent document 1). In addition, application of a specific silicone composition with improved hardness to optical semiconductor applications has been proposed (see, for example, Patent Document 2). Furthermore, application of a methacryloxy group-containing silicone composition to optical semiconductor applications has been proposed (see, for example, Patent Document 3). On the other hand, a composition of an organopolysiloxane having a specific structure is disclosed (for example, see Patent Document 4).

JP 2010-1358 A JP 2008-274185 A JP 2008-131209 A Japanese Patent No. 4322949

  In the case of the composition disclosed in Patent Document 1, heat-resistant yellowing and light resistance are excellent, but since the hardness of the cured product is low, scratches easily occur and handling is difficult. In addition, the gas barrier property and adhesion to the substrate are low, and it cannot be suitably used for optical semiconductor sealing materials.

  The composition disclosed in Patent Document 2 uses a phenyl group to increase the hardness. However, since the phenyl group causes heat-resistant yellowing and light resistance to deteriorate, it cannot be suitably used for an optical semiconductor sealing material.

  In the case of the composition disclosed in Patent Document 3, although heat yellowing resistance and light resistance are excellent, since the hardness of the cured product is low, scratches easily occur and handling is difficult. Moreover, the gas barrier property and the adhesion to the base material have not yet been satisfied.

  In the case of the composition disclosed in Patent Document 4, although the gas barrier property and the adhesiveness are excellent, the heat yellowing resistance and the light resistance have not reached satisfactory levels, and it is difficult to adapt to the use of an optical semiconductor encapsulant.

  As described above, it has been difficult in the past to obtain a transparent cured product that sufficiently satisfies the level required in optical semiconductor applications in terms of heat-resistant yellowing, light resistance, gas barrier properties, and adhesion.

  The object of the present invention is to thermally cure capable of forming a transparent cured product that sufficiently satisfies the level required in optical semiconductor applications in terms of heat-resistant yellowing, light resistance, gas barrier properties and adhesion. It is in providing a conductive resin composition. Another object of the present invention is to provide an optical semiconductor sealing material and a die-bonding material, which are formed using such a thermosetting resin composition.

As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by a thermosetting resin composition containing a specific organopolysiloxane, and have completed the present invention. . That is, this invention relates to the following thermosetting resin compositions, the sealing material for optical semiconductors, and the die-bonding material for optical semiconductors.
1. General formula (1):

[Wherein R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group or an aralkyl group; R ² represents an acryloxy group or a methacryloxy group; Represents a divalent hydrocarbon group having 3 to 10 carbon atoms, a represents an integer of 1 or more, b represents an integer of 0 or more, and a + b represents an integer of 3 to 20. ) Cyclic organopolysiloxane represented by

2.1. A thermosetting resin composition containing 100 parts by mass of the cyclic organopolysiloxane described in 1 and 0.5 to 10 parts by mass of a thermal radical initiator.
3. Furthermore, it contains 0.5 to 10 parts by mass of a silane coupling agent with respect to 100 parts by mass of the cyclic organopolysiloxane. The thermosetting resin composition described in 1.
4). Furthermore, it contains 0 to 2000 parts by mass of an organopolysiloxane containing a (meth) acryloxy group having a structure different from that of the cyclic organopolysiloxane with respect to 100 parts by mass of the cyclic organopolysiloxane. Or 3. The thermosetting resin composition described in 1.
5. 1. The functional group equivalent of the (meth) acryloxy group is 180 to 900 g / mol. ~ 4. The thermosetting resin composition according to any one of the above.
6). 1. R ¹ is an alkyl group having 1 to 10 carbon atoms; ~ 5. The thermosetting resin composition according to any one of the above.
7). 1. R ¹ is a methyl group. ~ 6. The thermosetting resin composition according to any one of the above.
8.2. ~ 7. The sealing material for optical semiconductors containing the thermosetting resin composition in any one of.
9.2. ~ 7. The die-bonding material for optical semiconductors containing the thermosetting resin composition in any one of.
10.8. An optical semiconductor package, wherein the sealing material for an optical semiconductor according to item 1 is molded.
11.8. An optical semiconductor manufactured using the sealing material for optical semiconductors described in 1.

  According to the thermosetting resin composition of the present invention, a transparent cured product that sufficiently satisfies the level required in optical semiconductor applications in any of heat-resistant yellowing, light resistance, gas barrier properties, and adhesion is formed. It is possible.

  The thermosetting resin composition according to the present invention is suitable as a sealing material and a die bond material for optical semiconductors. An excellent optical semiconductor package can be provided by using the thermosetting resin composition according to the present invention as an optical semiconductor sealing material, a die bonding paste, or the like.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, this invention is not limited to the form shown below.

  The thermosetting resin composition according to this embodiment contains a cyclic organopolysiloxane represented by the following general formula (1).

  In the said General formula (1), a shows an integer greater than or equal to 1, b shows an integer greater than or equal to 0, and a + b is an integer of 3-20.

R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group. Examples of R ¹ having 10 or less carbon atoms include methyl group, ethyl group, propyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, cyclopentyl group, cyclohexyl group, and octyl group. An aryl group such as a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a mesityl group; an aralkyl group such as a benzyl group, a phenethyl group, and a phenylpropyl group; or a bond to a carbon atom of these groups A hydroxypropyl group, a cyanoethyl group, a 1-chloropropyl group, a 3,3,3-trifluoropyr group, etc., in which part or all of the hydrogen atoms are substituted with a hydroxy group, a cyano group, a halogen atom, etc. It is done. Of these, a methyl group is most preferred from the viewpoint of excellent heat yellowing and light resistance.

R ² in the formula (1) is an acryloxy group represented by the following formula (2) or a methacryloxy group represented by the following formula (3).

X represents a divalent hydrocarbon group having 3 to 10 carbon atoms. Examples of this divalent hydrocarbon group include — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, and — (CH ₂ ) ₈ —. , — (CH ₂ ) ₁₀ —, —CH (CH ₃ ) CH ₂ —, —C (CH ₃ ) ₂ — and the like, in particular — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ — and — (CH ₂ ) ₆ — are preferred from the standpoint of availability of raw materials and reactivity.

The functional group equivalent of the (meth) acryloxy group of the organopolysiloxane according to this embodiment is preferably 180 g / mol or more from the viewpoint of heat yellowing resistance and light resistance, and 900 g / mol or less from the viewpoint of gas barrier properties. From such a viewpoint, the functional group equivalent of the (meth) acryloxy group is more preferably 190 g / mol to 880 g / mol, and most preferably 200 g / mol to 850 g / mol.

  The cyclic organopolysiloxane represented by the general formula (1) includes a hydrogen polysiloxane (a) having at least one SiH group in one molecule represented by the following general formula (4) and an alkenyl group. The (meth) acrylate compound (b) can be produced by an addition reaction in the presence of a hydrosilylation reaction catalyst.

In Formula (4), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, or an aralkyl group, c represents an integer of 1 or more, d shows an integer greater than or equal to 0, and c + d is an integer of 3-20.

  The hydrogen polysiloxane (a) having at least one SiH group in one molecule represented by the general formula (4) is represented by the following formula (5), (6) or (7), for example. Things.

  The hydrogen polysiloxane (a) may be a combination of two or more kinds, or one kind alone.

  The alkenyl group-containing (meth) acrylate compound (b) is represented by the following general formula (8).

R ² in Formula (8) represents an acryloxy group or a methacryloxy group, and R ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms. In particular, the carbon number of R ³ is preferably 1 to 4. When R ³ has 0 carbon atoms, no hydrosilylation reaction occurs. On the other hand, when the number of carbon atoms is 9 or more, the boiling point becomes high, and it is difficult to distill off the excess alkenyl group-containing (meth) acrylate compound (b) from the reaction solution. These alkenyl group-containing (meth) acrylate compounds (b) may be a combination of two or more types, or may be a single type.

  The amount of the alkenyl group-containing (meth) acrylate compound (b) is excessively added with respect to the molar amount of SiH groups derived from the hydrogen polysiloxane (a) from the viewpoint of reacting to the end without leaving any SiH groups. It is preferable. Specifically, [molar amount of alkenyl group-containing (meth) acrylate compound] / [molar amount of SiH group derived from (a)] = 1.2 to 3.0 is preferable.

  The hydrosilylation reaction catalyst is not particularly limited, and any conventionally known catalyst can be used. For example, platinum black, second platinum chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of chloroplatinic acid and olefins, platinum-based catalyst such as platinum bisacetoacetate; palladium-based catalyst And platinum group metal catalysts other than platinum catalysts, such as rhodium catalysts. The hydrosilylation reaction catalyst (d) may be a combination of two or more kinds, or one kind alone.

  The amount of the hydrosilylation reaction catalyst is not particularly limited, but relative to the mass of the organopolysiloxane which is an addition reaction product of the hydrogen polysiloxane (a) and the alkenyl group-containing (meth) acrylate compound (b). 0.01-100 ppm is preferable. The amount of the reaction catalyst is preferably 0.01 ppm or more from the viewpoint of sufficiently obtaining the addition effect, and preferably 100 ppm or less from the viewpoint of performing the synthesis reaction safely and cost. The hydrosilylation reaction catalyst (d) can be removed by an adsorbent such as activated alumina or activated carbon after the reaction. From the viewpoint of heat-resistant yellowing and light resistance, the amount of hydrosilylation reaction catalyst in the thermosetting resin resin composition is the addition of hydrogen polysiloxane (a) and alkenyl group-containing (meth) acrylate compound (b). 0.001 mass part or less is preferable with respect to the reaction product.

  The above addition reaction can usually be performed at room temperature to 100 ° C. Since the (meth) acryloxy group easily reacts at high temperatures and may be gelled, the reaction temperature is preferably 40 ° C to 70 ° C.

  The above addition reaction can be performed in a solvent as necessary. Solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane and octane, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and isobutyl acetate, An ether solvent such as diisopropyl ether, 1,4-dioxane, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate, and an alcohol solvent such as isopropanol, or a mixed solvent thereof. Can be used.

  The atmosphere for the reaction may be either air or inert gas. The obtained organohydropolysiloxane is preferably in an inert gas such as nitrogen, argon, and helium because it is less colored, but a small amount of oxygen should be introduced for the purpose of preventing the polymerization reaction of the (meth) acryloxy group. You can also.

  For the purpose of preventing the polymerization reaction of the (meth) acryloxy group, it is preferable to add a polymerization inhibitor such as phenothiazine, a hindered phenol compound, an amine compound, and a quinone compound to the reaction system. The type and amount of such a polymerization inhibitor are particularly limited as long as the addition of them can prevent the polymerization reaction of (meth) acryloxy groups, that is, acryloxy groups or methacryloxy groups, without hindering the progress of the hydrosilylation reaction. Not.

  After completion of the addition reaction, the surplus alkenyl group-containing (meth) acrylate compound (b) and the solvent in the case of using the solvent are distilled off under heating and / or reduced pressure to obtain the cyclic organo of the above general formula (1). Siloxane can be obtained.

  The thermosetting resin composition according to the present embodiment contains a thermal radical polymerization initiator. The thermal radical polymerization initiator is not particularly limited as long as it can radically polymerize a (meth) acryloxy group by heat. Examples of the thermal radical polymerization initiator include organic peroxides such as benzoyl peroxide, lauryl peroxide, t-butyl peroxide, and cumene hydroperoxide; and azo compounds such as azobisisobutyronitrile. Specifically, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries), 2,2′-azobis (2,4-dimethylvaleronitrile) ( V-65, manufactured by Wako Pure Chemical) 2,2'-azobisisobutyronitrile (V-60, manufactured by Wako Pure Chemical), and 2,2'-azobis (2-methylbutyronitrile) (V-59) Azonitrile compounds such as Octanoyl peroxide (Perroyl O, manufactured by NOF Corporation), Lauroyl peroxide (Perroyl L, manufactured by NOF Corporation), stearoyl peroxide (Perroyl S, manufactured by NOF Corporation), Succinic Acid peroxide (Perroyl SA, manufactured by Nippon Oil & Fats), Benzoyl peroxide (Niper BW, manufactured by Nippon Oil & Fats), Isobutyryl peroxide (Perroyl IB, Nippon Oil) Diacyl peroxides such as 2,4-dichlorobenzoyl peroxide (Niper CS, manufactured by NOF Corporation) and 3,5,5-trimethylhexanoyl peroxide (Perroyl 355, manufactured by NOF Corporation); -Propyl peroxydicarbonate (paroyl NPP-50M, manufactured by NOF Corporation), diisopropyl peroxydicarbonate (paroyl IPP-50, manufactured by NOF Corporation), bis (4-t-butylcyclohexyl) peroxydicarbonate (paroyl TCP, Nippon Oil & Fats), di-2-ethoxyethyl peroxydicarbonate (Perroyl EEP, manufactured by Nippon Oil & Fats), di-2-ethoxyhexyl peroxydicarbonate (Perroyl OPP, manufactured by Nippon Oil & Fats), di-2-methoxybutyl per Oxydicarbonate (Parroyl MB Peroxydicarbonates such as di (3-methyl-3-methoxybutyl) peroxydicarbonate (Perroyl SOP, manufactured by Nippon Oil &Fats); t-butyl hydroperoxide (perbutyl H-69, Hydroperoxides such as Nippon Oil & Fats) and 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta H, manufactured by Nippon Oil &Fats); Di-t-butyl peroxide (Perbutyl D, manufactured by Nippon Oil & Fats) ), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (Perhexa 25B, manufactured by NOF Corporation); α, α′-bis (neodecanoylperoxy) diisopropyl Benzene (Dyper ND, manufactured by NOF Corporation), Cumylperoxyneodecanoate (Park Mill ND, manufactured by NOF Corporation) 1,1,3,3-tetramethylbutyl peroxyneodecanoate (Perocta ND, manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxyneodecanoate (PercycloND, manufactured by NOF Corporation), t -Hexyl peroxyneodecanoate (perhexyl ND, manufactured by NOF Corporation), t-butyl peroxyneodecanoate (perbutyl ND, manufactured by NOF Corporation), t-hexyl peroxypivalate (perhexyl PV, manufactured by NOF Corporation) , T-butyl peroxypivalate (perbutyl PV, manufactured by NOF Corporation), 1,1,3,3, -tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, manufactured by NOF Corporation) 2,5- Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane (Perhexa 250, manufactured by NOF Corporation), 1- Chlohexyl-1-methylethylperoxy-2-ethylhexanoate (Percyclo O, manufactured by NOF Corporation), t-hexylperoxy 2-ethylhexanoate (Perhexyl O, manufactured by NOF Corporation), t-butylperoxy-2 -Ethylhexanoate (perbutyl O, manufactured by NOF Corporation), t-butyl peroxyisobutyrate (perbutyl IB, manufactured by NOF Corporation), t-hexyl peroxyisopropyl monocarbonate (perhexyl I, manufactured by NOF Corporation), and t -Butyl peroxymaleic acid (Perbutyl MA, manufactured by NOF Corporation), t-amylperoxy 2-ethylhexanoate (Trigonox 121, manufactured by Kayaku Akzo), t-amylperoxy 3,5,5-trimethylhexa Peroxyesters such as Noate (Kaya Ester AN, Kayaku Akzo) Examples of the organic peroxide include, but are not limited to, organic peroxides. Moreover, these thermal radical polymerization initiators can be used alone or in combination of two or more.

  As for content of a thermal radical polymerization initiator, 0.5-10 mass parts is preferable with respect to 100 mass parts of cyclic organopolysiloxane of General formula (1). If the content of the thermal radical polymerization initiator is 0.5 parts by mass or more, the curability is excellent, and if it is 10 parts by mass or less, the heat-resistant yellowing is excellent. From such a viewpoint, the content of the thermal radical polymerization initiator is more preferably 1 part by mass or more and 8 parts by mass or less, and most preferably 2 parts by mass or more and 5 parts by mass or less.

  In the thermosetting resin composition according to this embodiment, a silane coupling agent can be blended with the cyclic organosiloxane of the general formula (1). A silane coupling agent is a reactive group that chemically bonds to an inorganic material such as glass, metal, or silica in one molecule, and a reactive group that chemically bonds to an organic material such as a synthetic resin or a substituent that is compatible with the organic material. If it is a compound which has this, it will not restrict | limit in particular. Examples of the reactive group chemically bonded to the inorganic material include a methoxy group and an ethoxy group. Examples of reactive groups that chemically bond with organic materials include vinyl groups, epoxy groups, amino groups, methacrylic groups, acrylic groups, mercapto groups, and isocyanate groups, and isocyanurates as substituents that are compatible with organic materials. Group and the like. Specifically, vinyltrimethoxysilane (KBM-1003, manufactured by Shin-Etsu Chemical), vinyltriethoxysilane (KBE-1003, manufactured by Shin-Etsu Chemical), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM- 303, manufactured by Shin-Etsu Chemical), 3-glycidoxypropylmethyldimethoxysilane (KBM-402, manufactured by Shin-Etsu Chemical), 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical), 3-glycidoxy Propylmethyldiethoxysilane (KBE-402, manufactured by Shin-Etsu Chemical), 3-glycidoxypropyltriethoxysilane (KBE-403, manufactured by Shin-Etsu Chemical), p-styryltrimethoxysilane (KBM-1403, manufactured by Shin-Etsu Chemical), 3-Methacryloxypropylmethyldimethoxysilane (KBM-502, manufactured by Shin-Etsu Chemical) 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical), 3-methacryloxypropylmethyldiethoxysilane (KBE-502, manufactured by Shin-Etsu Chemical), 3-methacryloxypropyltriethoxysilane (KBE-503, Shin-Etsu Chemical), 3-acryloxypropyltrimethoxysilane (KBM-5103, Shin-Etsu Chemical), N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602, Shin-Etsu Chemical), N 2- (aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Chemical), 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical), 3-aminopropyltriethoxysilane ( KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-triethoxysilyl 3-N- (1,3-dimethyl-butylidene) propylamine (KBE-9103, manufactured by Shin-Etsu Chemical), N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Chemical), N- (vinylbenzyl) -2 Aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (KBM-575, manufactured by Shin-Etsu Chemical), 3-ureidopropyltriethoxysilane (KBE-585, manufactured by Shin-Etsu Chemical), 3-mercaptopropylmethyldimethoxysilane (KBM) -802, manufactured by Shin-Etsu Chemical), 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical), bis (triethoxysilylpropyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical), 3-isocyanatopropyltriethoxy Silane (KBE-9007, manufactured by Shin-Etsu Chemical), Tris- ( 3-trimethoxysilylpropyl) isocyanurate (X-12-965, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are exemplified, but the invention is not particularly limited thereto. These silane coupling agents can be used alone or in combination of two or more.

  In addition, the thermosetting resin composition according to the present embodiment includes an organopolysiloxane containing a (meth) acryloxy group having a structure different from that of the cyclic organopolysiloxane in the cyclic organosiloxane of the general formula (1). Can be made. Examples of the organopolysiloxane containing a (meth) acryloxy group having a structure different from that of the cyclic organopolysiloxane include those represented by the following general formula (9) or (10), but are not limited thereto. Absent.

  The compounding amount of the organopolysiloxane containing a (meth) acryloxy group having a structure different from that of the cyclic organopolysiloxane is based on 100 parts by mass of the cyclic organosiloxane of the general formula (1). From a viewpoint, it can contain 0-2000 mass parts. From such a viewpoint, the blending amount of the organopolysiloxane containing the (meth) acryloxy group is more preferably 1000 parts by mass or less, and most preferably 200 parts by mass or less.

  The thermosetting resin composition according to this embodiment includes a dye, a deterioration inhibitor, a mold release agent, a diluent, an antioxidant, and a heat stabilizer within a quantitative and qualitative range that does not depart from the scope of the present invention. Additives such as flame retardants, plasticizers, and surfactants can be blended.

  For the purpose of improving heat resistance, light resistance, hardness, conductivity, thermal conductivity, thixotropy, and low thermal expansion, the thermosetting resin composition contains fillers typified by inorganic oxides as necessary. May be. Fillers include silica (fumed silica, colloidal silica, precipitated silica, etc.), silicon nitride, boron nitride, alumina, titania, barium titanate and other inorganic oxides or inorganic nitrides, glass, ceramics, silver powder, gold powder And copper powder.

  The filler can be used with or without a surface treatment. When the surface treatment is performed, the fluidity of the composition is increased and the filling rate can be increased, which is industrially preferable.

  When the average particle size of the filler is 500 nanometers or less, the transparency of the cured product is increased, which is industrially preferable. Become.

  The thermosetting resin composition according to the present embodiment is liquid or solid before curing and is cured by heating. The curing temperature is usually 100 to 250 ° C. The method for curing and molding the thermosetting resin composition is not particularly limited. For example, the thermosetting resin composition can be molded by casting, low-pressure transfer molding, potting, dipping, pressure molding, and injection molding. When the thermosetting resin composition is solid, it can be molded by heating and curing under pressure using a press, a low-pressure transfer molding machine or the like.

  A cured product formed by curing the thermosetting resin composition is suitably used as a sealing material for an optical semiconductor device. A thermosetting resin composition may be used as a die bonding paste, and the cured product may be formed as a die bond material. The cured product of the thermosetting resin composition can be suitably used for optical semiconductor device applications such as a chip coating material and a lens material that coat the periphery of the chip. In this case, examples of the optical semiconductor include an LED lamp, a chip LED, a semiconductor laser, a photocoupler, and a photodiode.

  The optical semiconductor device includes a housing material, a silicon chip provided in the housing, and a sealing material that is a cured product of the thermosetting resin composition according to the present embodiment and seals the silicon chip. The material of the housing material is not particularly limited, and examples thereof include aromatic polyamides such as polyphthalamide, engineering plastics such as 66 nylon, and ceramics. In the case of polyphthalamide, particularly high adhesion is exhibited.

  It is preferable that glass fiber is contained in the housing material because the adhesive strength increases. The content of the glass fiber is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass based on the mass of the housing material. When the content of the glass fiber is within these numerical ranges, the effect of the present invention is more remarkably exhibited.

  The cured product of the thermosetting resin composition takes advantage of its heat-resistant yellowing and high transparency, such as spectacle lenses, optical device lenses, CD and DVD pickup lenses, automotive headlamp lenses, projector lenses, etc. It is also suitably used for various optical members such as lens materials, optical fibers, optical waveguides, optical filters, optical adhesives, optical disk substrates, display substrates, and coating materials such as antireflection films.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In Examples and Comparative Examples, measurement and evaluation were performed by the following methods.

(1) Calculation of functional group equivalent The solution which melt | dissolved in the deuterated chloroform solvent in the ratio of 1 ml with respect to 30 mg of samples was made into the measurement sample. Using this measurement sample, ¹ H NMR measurement was performed with α-400 manufactured by JASCO Corporation at 200 integration times, and the obtained results were analyzed to determine the average composition in one molecule of organopolysiloxane.

A solution in which 8 wt% of Cr (acac) ₃ was added to silicone was dissolved in deuterated chloroform solvent at a rate of 1 g with respect to 0.15 g of sample. Using this measurement sample, ²⁹ Si NMR was measured with α-400 manufactured by JASCO Corporation at a total number of 4000 times, and the obtained results were analyzed to determine the average composition in one molecule of organopolysiloxane. ^The results obtained by ¹ H NMR and ²⁹ Si NMR were analyzed, and the functional group equivalent (mass per mole of functional group) of the (meth) acryloxy group was calculated.

(2) Heat-resistant yellowing Using a cured product having a thickness of 3 mm, YI (yellowness) was measured with a spectrocolorimeter CM-3600d (trade name) manufactured by Konica Minolta. Next, the cured product was wrapped in aluminum foil and heat-treated at 150 ° C. for 150 hours under air. Thereafter, YI (yellowness) was measured again with a spectrocolorimeter CM-3600d (trade name) manufactured by Konica Minolta. The change in YI before and after the heat treatment was ΔYI, and ΔYI was evaluated as ◎ when less than 1.0, ◯ when 1.0 or more and less than 3.0, and × when 3.0 or more.

(3) Light resistance Using a cured product having a thickness of 3 mm, YI (yellowness) was measured with a spectrocolorimeter CM-3600d (trade name) manufactured by Konica Minolta. Next, the cured product was set in a constant-temperature dryer at a constant temperature of 50 ° C., and an illuminance of 4 W at 365 nm using a UV irradiation device (trade name: SP-7, manufactured by USHIO INC.) Equipped with a 365 nm bandpass filter. Irradiated at / cm ² for 100 hours. Thereafter, YI (yellowness) was again measured with a spectrocolorimeter CM-3600d (trade name) manufactured by Konica Minolta. The change in YI before and after the UV irradiation was ΔYI, and ΔYI was evaluated as を when less than 1.0, ◯ when 1.0 or more and less than 3.0, and × when 3.0 or more.

(4) Gas barrier properties Using a 100 mm × 100 mm cured product having a thickness of 0.2 mm, an oxygen transmission rate was measured at 23 ° C. under dry conditions using an oxygen transmission rate measuring device Model 8001 manufactured by Illinois. Oxygen permeability of less than ^{500cc / m 2 / day ◎,} 500cc / m 2 / day or more 1000 cc ^/ m less than 2 / day ○, was evaluated as × least 1000cc ^/ m 2 ^/ day.

(5) Adhesion A thermosetting resin composition is placed in a mold of a polyphthalamide resin (Amodel 4122 manufactured by Solvay) in which a depression of 10 mmφ and a depth of 1 mm is formed in the center of a 20 mm × 20 mm × 2 mm flat plate. A test piece was obtained by casting and heat-curing. The number of times until peeling occurred was visually observed for the obtained test piece with a small thermal shock apparatus TSE-11 manufactured by Espec Corp. at room temperature to −40 ° C. (15 minutes) to 120 ° C. (15 minutes) to room temperature. Observed. The case where peeling did not occur for 100 cycles or more was evaluated as ◎, the case where peeling was generated 50 times or more and less than 100 times was evaluated as ◯, and the case where peeling occurred less than 50 times was rated as x.

[ Production Example 1]
<Production of methacryloxy group-containing organopolysiloxane (A1)>
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, 1,3,5,7-tetramethylcyclotetrasiloxane 40 g (SiH: 0.7 mol) as component (a), As component (b), 130 g (1.0 mol) of allyl methacrylate (allyl methacrylate), 200 g of toluene, and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were added, and the mixture was stirred at 60 ° C. in a nitrogen gas atmosphere. Warmed to. Thereafter, an isopropanol solution of chloroplatinic acid was added in an amount such that the platinum metal was 10 ppm relative to the mass of the organopolysiloxane that was the addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 55 to 65 ° C. by heat insulation, water cooling or air cooling. When the contents of the flask were analyzed, the characteristic absorption at 2130 cm ⁻¹ by infrared absorption (FT-IR) of the SiH group disappeared. Then, the activated carbon treatment was performed, and volatile components were distilled off to obtain 110 g of methacryloxy group-containing organopolysiloxane (A1) as an addition reaction product. The functional group equivalent of the obtained methacryloxy group-containing organopolysiloxane (A1) was 186 g / mol.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of methacryloxy group-containing organopolysiloxane (A1) and 2.5 parts by mass of tert-amylperoxy-2-ethylhexanoate (manufactured by Kayaku Akzo, trade name: Trigonox 121-50E, 50% by mass solution) Were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition. The curable composition was poured into a mold made of SUS316 and cured at 100 ° C. for 4 hours and further at 150 ° C. for 1 hour to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[ Production Example 2]
<Production of methacryloxy group-containing organopolysiloxane (A2)>
In a 0.5 L three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 25 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.4 mol) as component (a), As component (b), 140 g (1.0 mol) of 3-butenyl methacrylate (3-butenyl methacrylate), 200 g of toluene, and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) are added and stirred under a nitrogen gas atmosphere. While warming to 60 ° C. Then, the quantity which becomes 10 ppm with respect to the mass of the organopolysiloxane which a platinum metal is an addition reaction product was added to the isopropanol solution of chloroplatinic acid. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 55 to 65 ° C. by heat insulation, water cooling or air cooling. When the contents of the flask were analyzed, the characteristic absorption at 2130 cm ⁻¹ by infrared absorption (FT-IR) of the SiH group disappeared. Thereafter, the resultant was treated with activated carbon, and volatile components were distilled off to obtain 124 g of methacryloxy group-containing organopolysiloxane (A2) as an addition reaction product. The functional group equivalent of the obtained methacryloxy group-containing organopolysiloxane (A2) was 200 g / mol.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of methacryloxy group-containing organopolysiloxane (A2) and 2.5 parts by mass of tert-amylperoxy-2-ethylhexanoate (manufactured by Kayaku Akzo, trade name: Trigonox 121-50E, 50% by mass solution) Were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition. The curable composition was poured into a mold made of SUS316 and cured at 100 ° C. for 4 hours and further at 150 ° C. for 1 hour to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[ Production Example 3]
<Production of methacryloxy group-containing organopolysiloxane (A3)>
To a 0.7 L three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 40 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.7 mol) as component (a), As component (b), 140 g (0.8 mol) of 5-hexenyl methacrylate (5-hexenyl methacrylate), 200 g of toluene, and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) are added and stirred under a nitrogen gas atmosphere. The mixture was heated to 60 ° C. Thereafter, an isopropanol solution of chloroplatinic acid was added in an amount such that the platinum metal was 10 ppm relative to the mass of the organopolysiloxane that was the addition reaction product. After confirming the start of the hydrosilylation reaction, the reaction system was stirred for 72 hours while being kept at 55 to 65 ° C. by heat insulation, water cooling or air cooling. When the contents of the flask were analyzed, the characteristic absorption at 2130 cm ⁻¹ by infrared absorption (FT-IR) of the SiH group disappeared. Then, the activated carbon treatment was performed, and the volatile component was distilled off to obtain 134 g of methacryloxy group-containing organopolysiloxane (A3) as an addition reaction product. The functional group equivalent of the obtained methacryloxy group-containing organopolysiloxane (A3) was 228 g / mol.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of methacryloxy group-containing organopolysiloxane (A3) and 2.5 parts by mass of tert-amylperoxy-2-ethylhexanoate (manufactured by Kayaku Akzo, trade name: Trigonox 121-50E, 50% by mass solution) Were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition. The curable composition was poured into a mold made of SUS316 and cured at 100 ° C. for 4 hours and further at 150 ° C. for 1 hour to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 4]
<Production of methacryloxy group-containing organopolysiloxane (A2)>
The methacryloxy group-containing organopolysiloxane (A2) was produced in the same manner as in Production Example 2.

<Manufacture and characteristic evaluation of cured product>
To 100 parts by mass of the methacryloxy group-containing organopolysiloxane (A2), 5 parts by mass of 3-methacryloxypropylmethyldimethoxysilane (KBM-502, manufactured by Shin-Etsu Chemical) was mixed. The functional group equivalent of this composition was 191 g / mol. Furthermore, 2.5 parts by mass of tert-amylperoxy-2-ethylhexanoate (manufactured by Kayaku Akzo, trade name: Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, and the whole was uniform. The mixture was stirred until defoaming to obtain a curable composition. The curable composition was poured into a mold made of SUS316 and cured at 100 ° C. for 4 hours and further at 150 ° C. for 1 hour to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[ Production Example 5]
<Production of methacryloxy group-containing organopolysiloxane (A2)>
The methacryloxy group-containing organopolysiloxane (A2) was produced in the same manner as in Production Example 2.

<Acryloxy group-containing organopolysiloxane (A4)>
As the acryloxy group-containing organopolysiloxane (A4), an acryloxy group-containing organopolysiloxane represented by the following general formula (11) having a structure different from that of (A2) was used. The functional group equivalent of the acryloxy group-containing organopolysiloxane (A4) was 920 g / mol.

  In the formula, l is 83 and m is 8.

<Manufacture and characteristic evaluation of cured product>
To 100 parts by mass of the methacryloxy group-containing organopolysiloxane (A2), 2000 parts by mass of the acryloxy group-containing organopolysiloxane (A4) represented by the general formula (11) was mixed. The functional group equivalent of this composition was 885 g / mol. Furthermore, 2.5 parts by mass of tert-amylperoxy-2-ethylhexanoate (manufactured by Kayaku Akzo, trade name: Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, and the whole was uniform. The mixture was stirred until defoaming to obtain a curable composition. The curable composition was poured into a mold made of SUS316 and cured at 100 ° C. for 4 hours and further at 150 ° C. for 1 hour to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[ Production Example 6]
<Production of methacryloxy group-containing organopolysiloxane (A2)>
The methacryloxy group-containing organopolysiloxane (A2) was produced in the same manner as in Production Example 2.

<Methacryloxy group-containing organopolysiloxane (A5)>
As the methacryloxy group-containing organopolysiloxane (A5), a methacryloxy group-containing organopolysiloxane made by Shin-Etsu Chemical Co., Ltd. represented by the following general formula (12) having a structure different from that of (A2) was used. The functional group equivalent of the acryloxy group-containing organopolysiloxane (A5) was 893 g / mol.

  In the formula, n is 20.

<Manufacture and characteristic evaluation of cured product>
200 parts by mass of the methacryloxy group-containing organopolysiloxane (A5) represented by the general formula (12) was mixed with 100 parts by mass of the methacryloxy group-containing organopolysiloxane (A2). The functional group equivalent of this composition was 657 g / mol. Furthermore, 2.5 parts by mass of tert-amylperoxy-2-ethylhexanoate (manufactured by Kayaku Akzo, trade name: Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, and the whole was uniform. The mixture was stirred until defoaming to obtain a curable composition. The curable composition was poured into a mold made of SUS316 and cured at 100 ° C. for 4 hours and further at 150 ° C. for 1 hour to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Comparative Example 1]
<Acryloxy group-containing organopolysiloxane (A4)>
As the acryloxy group-containing organopolysiloxane (A4), an acryloxy group-containing organopolysiloxane having a structure different from that of (A2) and represented by the above general formula (11) was used. The functional group equivalent of the acryloxy group-containing organopolysiloxane (A4) was 920 g / mol.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of methacryloxy group-containing organopolysiloxane (A4) and 2.5 parts by mass of tert-amylperoxy-2-ethylhexanoate (manufactured by Kayaku Akzo, trade name: Trigonox 121-50E, 50% by mass solution) Were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition. The curable composition was poured into a mold made of SUS316 and cured at 100 ° C. for 4 hours and further at 150 ° C. for 1 hour to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Comparative Example 2]
<Methacryloxy group-containing organopolysiloxane (A5)>
As the methacryloxy group-containing organopolysiloxane (A5), a methacryloxy group-containing organopolysiloxane made by Shin-Etsu Chemical Co., Ltd. represented by the general formula (12) having a structure different from that of (A2) was used. The functional group equivalent of the acryloxy group-containing organopolysiloxane (A5) was 893 g / mol.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of methacryloxy group-containing organopolysiloxane (A5) and 2.5 parts by mass of tert-amylperoxy-2-ethylhexanoate (manufactured by Kayaku Akzo, trade name: Trigonox 121-50E, 50% by mass solution) Were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition. The curable composition was poured into a mold made of SUS316 and cured at 100 ° C. for 4 hours and further at 150 ° C. for 1 hour to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Comparative Example 3]
<Epoxy group-containing organopolysiloxane (A6)>
As the epoxy group-containing organopolysiloxane (A6), an epoxy group-containing organopolysiloxane represented by the following general formula (13) was used.

<Manufacture and characteristic evaluation of cured product>
Mix 100 parts by mass of the epoxy group-containing organopolysiloxane (A6) with 60.5 parts by mass of methylhexahydrophthalic anhydride and 1 part by mass of diazabicycloundecene octylate, and stir until the whole becomes uniform. Foamed to obtain a curable composition. The curable composition was poured into a mold and subjected to a curing reaction at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Comparative Example 4]
<Curable resin composition (A7)>
As the curable resin composition (A7), KER-2500 manufactured by Shin-Etsu Chemical Co., Ltd., which is commercially available as a curable resin for optical semiconductor encapsulants, was used.
<Manufacture and characteristic evaluation of cured product>
Commercially available KER-2500A and KER-2500B were mixed in an amount of 100 parts by mass, stirred until the whole became uniform, and then defoamed to obtain a curable composition. The curable composition was poured into a mold made of SUS316 and cured at 100 ° C. for 1 hour and further at 150 ° C. for 5 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Comparative Example 5]
<Curable resin composition (A8)>
As the curable resin composition (A8), ASP-1010 manufactured by Shin-Etsu Chemical Co., Ltd., which is commercially available as a curable resin for optical semiconductor encapsulants, was used.

<Manufacture and characteristic evaluation of cured product>
Commercially available ASP-1010A and ASP-1010B were mixed by 100 parts by mass, stirred until the whole became uniform, and then defoamed to obtain a curable composition. The curable composition was poured into a mold made of SUS316 and cured at 100 ° C. for 1 hour and further at 150 ° C. for 5 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

  According to the thermosetting resin composition of the present invention, a tough cured product having high transparency, heat-resistant yellowing, light resistance, gas barrier properties and adhesion can be obtained. The thermosetting resin composition according to the present invention can be suitably used for forming optical members such as a sealing material for optical semiconductors and a die bonding material.

Claims (7)

General formula (1):

[Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents an acryloxy group or a methacryloxy group, and X represents — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ -,-(CH ₂ ) ₆ -,-(CH ₂ ) ₈ -,-(CH ₂ ) _10- , -CH (CH ₃ ) CH _2- , and -C (CH ₃ ) _2- A divalent hydrocarbon group having 3 to 10 carbon atoms selected, a represents an integer of 1 or more, b represents an integer of 0 or more, and a + b represents an integer of 3 to 20; 100 parts by mass of a cyclic organopolysiloxane represented by the formula:
0.5 to 10 parts by mass of a thermal radical initiator,
Containing 0.5 to 10 parts by mass of a silane coupling agent ,
The thermosetting resin composition whose functional group equivalent of the (meth) acryloxy group in the said cyclic organopolysiloxane is 180-900 g / mol .   Furthermore, it contains 0 to 2000 parts by mass of an organopolysiloxane containing a (meth) acryloxy group having a structure different from that of the cyclic organopolysiloxane with respect to 100 parts by mass of the cyclic organopolysiloxane. Thermosetting resin composition. Wherein R ¹ is a methyl group, according to claim 1 or a thermosetting resin composition according to 2. The sealing material for optical semiconductors containing the thermosetting resin composition of any one of Claims 1-3 . The die-bonding material for optical semiconductors containing the thermosetting resin composition of any one of Claims 1-3 . An optical semiconductor package, wherein the optical semiconductor sealing material according to claim 4 is molded. The optical semiconductor manufactured using the sealing material for optical semiconductors of Claim 4 .