JP2012211237A - Organopolysiloxane and thermosetting resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition from which a transparent cured product can be formed, the product sufficiently satisfying a required level to be used for photo-semiconductors, in any properties of resistance against yellowing by heat, light resistance, scratch resistance and adhesiveness.SOLUTION: The thermosetting resin composition contains organopolysiloxane including a specific methacryloyloxy group-containing cyclic siloxane compound and a specific methacryloyloxy group-containing cyclic siloxane in which adjoining silicon atoms are substituted with a cyclic substituent containing siloxane, in which a molar fraction of hydrosilyl groups included in organosiloxane including the above two compounds is 0.020 or less.

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 the cured product is easily scratched and difficult to handle. Moreover, since adhesion is also low, it cannot be used suitably for a sealing material for optical semiconductors.

In the composition disclosed in Patent Document 2, an attempt is made to improve scratch resistance by increasing the hardness of a cured product by introducing phenyl into the molecular structure. 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. Also, the level of adhesion is not satisfactory.

  In the case of the composition disclosed in Patent Document 4, although scratch resistance and adhesion are excellent, the heat yellowing resistance and light resistance are not yet satisfactory, and it is difficult to adapt to use as 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, scratch resistance, and adhesion. .

  The object of the present invention is to provide a heat that can form a transparent cured product that sufficiently satisfies the level required in optical semiconductor applications in terms of heat-resistant yellowing, light resistance, scratch resistance, and adhesion. The object is to provide a curable 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. An organopolysiloxane represented by an average composition formula (3), comprising at least a compound represented by the following general formula (1) and a compound represented by the following general formula (2), wherein [g / (a + b + c + d + e + f + g + h + i + j) ] Is a range of 0.020 or less.

[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, Y represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and Z represents a bond with the divalent hydrocarbon group Y. In the formula, t is each independently an integer of 0 or more, u is each independently an integer of 3 or more, and v is an integer of 0 to 20. A, b, c, d, e, f, g, h, i, and j represent the number of moles of each structural unit present in 1 mole of organopolysiloxane, and a, e, and f exceed 0. B, c, d, g, h, i, and j are values that are 0 or more and satisfy e = a + d + i. The chain in the general formulas (1) and (2) may be random or block. ]

2. The general formula for the content [WA] of the compound represented by the general formula (1), which is calculated by the following formula (I) from the peak intensity obtained when measured by matrix-assisted ionization time-of-flight mass spectrometry The ratio [WB] / [WA] of the content [WB] of the compound represented by the formula (2) is 0.1 or more and 20.0 or less. The organopolysiloxane described.

3.1. Or 2. A thermosetting resin composition containing 100 parts by mass of the organopolysiloxane described in 1 and 0.5 to 10 parts by mass of a thermal radical initiator.
4). Furthermore, 0.5 to 10 parts by mass of a silane coupling agent is contained with respect to 100 parts by mass of the organopolysiloxane. The thermosetting resin composition described in 1.
5. 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 organopolysiloxane with respect to 100 parts by mass of the organopolysiloxane. Or 4. The thermosetting resin composition described in 1.
6). 2. The functional group equivalent of the (meth) acryloxy group is 180 to 900 g / mol. ~ 5. The thermosetting resin composition according to any one of the above.
7). 2. R ¹ is an alkyl group having 1 to 10 carbon atoms; ~ 6. The thermosetting resin composition according to any one of the above.
8). 2. R ¹ is a methyl group; ~ 7. The thermosetting resin composition according to any one of the above.
9.3. ~ 8. The sealing material for optical semiconductors containing the thermosetting resin composition of any one of these.
10.3. ~ 8. The die-bonding material for optical semiconductors containing the thermosetting resin composition of any one of these.
11.9. An optical semiconductor package, wherein the sealing material for an optical semiconductor according to item 1 is molded.

  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 terms of heat-resistant yellowing, light resistance, scratch resistance, and adhesion is formed. 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 the present embodiment is represented by an average composition formula (3) including at least a compound represented by the following general formula (1) and a compound represented by the following general formula (2). An organopolysiloxane, characterized in that the value of [g / (a + b + c + d + e + f + g + h + i + j)] is in the range of 0.020 or less.

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. Among these, a methyl group is most preferable from the viewpoint of heat-resistant yellowing and light resistance.

R ² is an acryloxy group represented by the following formula (4) or a methacryloxy group represented by the following formula (5).

X represents a divalent hydrocarbon group having 3 to 10 carbon atoms. For example, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₈ —, — (CH ₂ ) ₁₀ —, —CH (CH ₃ ) CH ₂ —, —C (CH ₃ ) ₂ — and the like are mentioned, and in particular, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — ( CH ₂ ) ₆ — is preferable from the viewpoint of availability of raw materials and reactivity.

Y represents a divalent hydrocarbon group having 2 to 10 carbon atoms. For example, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₈ —, -(CH ₂ ) _10- , -CH (CH ₃ ) CH _2- , -C (CH ₃ ) _2- and the like, and in particular,-(CH ₂ ) ₂ -,-(CH ₂ ) ₃ -,-( CH ₂ ) ₄ — is preferable from the viewpoint of availability of raw materials and reactivity.
Furthermore, Z represents a bond with a divalent hydrocarbon group Y.

In the formula, t is each independently an integer of 0 or more, u is each independently an integer of 3 or more, and v is an integer of 0 to 20. A, b, c, d, e, f, g, h, i, and j represent the number of moles of each structural unit present in 1 mole of organopolysiloxane, and a, e, and f exceed 0. B, c, d, g, h, i, and j are values that are 0 or more and satisfy e = a + d + i.
The values of t and u in the general formulas (1) and (2) represent the number of chains, and the chains may be random or block. In the present invention, t is each independently an integer of 0 or more, and u is each independently an integer of 3 or more.

  In the organopolysiloxane according to the present embodiment, the viscosity is reduced and the handleability is increased, or the heat discoloration of the cured product obtained using the organopolysiloxane tends to be improved. Therefore, the general formula (1) and The value of (t + u) in the general formula (2) is preferably 10 or less, t is 1 or less, more preferably u is 3 or more and 7 or less, t is 0, and u is 3 or more. More preferably, it is 7 or less, and it is especially preferable that t is 0 and u is 3 or more and 5 or less.

  The values of t and u in the above general formulas (1) and (2) can be calculated by the MALDI-TOF / MS measurement.

  In the organopolysiloxane of this embodiment, v is an integer of 0-20. The heat resistance of the cured product obtained using organopolysiloxane is improved, the compatibility with the curing agent is good, a transparent and uniform cured product is obtained, and the adhesion tends to be good. It is preferably 0 or more and 20 or less, more preferably 0 or more and 15 or less, and particularly preferably 0 or more and 10 or less.

  In the organopolysiloxane of the present embodiment, in order to show an excellent storage stability without showing a modification reaction or a viscosity change at the time of storage, it represents the remaining amount of unreacted SiH groups remaining in the organopolysiloxane [ g / (a + b + c + d + e + f + g + h + i + j)] is required to be 0.020 or less, preferably 0.015 or less, more preferably 0.010 or less, and 0.005 or less. Further preferred.

  Here, in the average composition formula (3), when h, i, and j satisfy the following formulas (1) and (2), the above a, b, h, i, and j It is a numerical value selected from a range satisfying 3).

h + i ≠ 0 Formula (1)
j ≠ 0 Expression (2)
0 ≦ b ≦ a + (h + i) + 2j + 2 (3)
Moreover, when said h, i, j satisfy | fills following formula (4) and formula (5) simultaneously, said a and b are numerical values selected from the range which satisfies following formula (6). .

h + i = 0 Formula (4)
j = 0 Expression (5)
0 ≦ b ≦ a + 2 (6)
When h, i, and j satisfy the following expressions (1) and (5), a, b, h, and i are selected from a range that satisfies the following expression (7). It is a numerical value.

h + i ≠ 0 Formula (1)
j = 0 Expression (5)
0 ≦ b ≦ a + (h + i) +2 (7)
Further, when h, i, and j satisfy the following expressions (4) and (2), a, b, and j are numerical values selected from a range that satisfies the following expression (8). .

h + i = 0 Formula (4)
j ≠ 0 Expression (2)
0 ≦ b ≦ a + 2j + 2 (8)

  The bicyclo structure represented by the general formula (2) is a component that plays an important role when the cured product obtained by curing the organopolysiloxane of the present invention exhibits excellent light resistance, scratch resistance and adhesion. It is. With only the monocyclic structure represented by the general formula (1), it is difficult to obtain sufficient light resistance, scratch resistance and adhesion after curing. In order to further improve the light resistance, scratch resistance and adhesion of the cured product, the content of the compound having a monocyclic structure represented by the general formula (1) is set to [WA] and the general formula (2). When the content of the compound having a bicyclo structure represented by is [WB], the ratio [WB] / [WA] is preferably in a specific range.

  In the present invention, matrix-assisted ionization time-of-flight mass spectrometry (hereinafter referred to as MALDI-) is used as a method for calculating the content ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2). (TOF / MS) is used, and the peak intensity of the compounds of the general formula (1) and the general formula (2) obtained by measuring the organopolysiloxane of the present invention by MALDI-TOF / MS is used. ] / [WA] is calculated by the following formula (I).

  In the present invention, the value of [WB] / [WA] is preferably 0.1 or more and 20.0 or less. When the value of [WB] / [WA] is less than 0.1 or exceeds 20.0, light resistance, scratch resistance, or adhesion tends to be insufficient. The light resistance, scratch resistance and adhesion of the cured product obtained by curing the resulting organopolysiloxane tend to increase, and the heat resistance tends to increase, so the value of [WB] / [WA] is 0. It is more preferably 12 or more and 17.0 or less, and further preferably 0.15 or more and 15.0 or less.

In the above formula (I), the mass corresponding to each structure of the general formula (1) and the general formula (2) is an isotope of each element when the elements constituting the structure have isotopes. This is a value calculated using the mass of the isotope having the largest abundance among the masses of.
In the present invention, when there are a plurality of peaks corresponding to the general formulas (1) and (2), the value of [WB] / [WA] is a plurality of peak intensities corresponding to each structure. Calculate using the total value. However, in the present invention, 3% or less of the maximum intensity of the peak corresponding to the total mass of the mass corresponding to each structure of the general formula (1) and the general formula (2) and the mass 23 of sodium. Peaks having intensity are excluded from the calculation of the total peak intensity.
Below, the specific method of the measuring method by MALDI-TOF / MS is described.

  A solution of 0.1 g of organopolysiloxane dissolved in 100 mL of tetrahydrofuran at room temperature and a solution of 10 mg of dithranol dissolved in 1 mL of tetrahydrofuran were uniformly mixed at a volume ratio of 1: 1 at room temperature. To prepare solution a. Next, 1 μL of solution a was dropped on a sample plate on which 1 μL of 10 mg sodium iodide dissolved in 10 mL of acetone was placed, and the solvent was evaporated at room temperature. Do.

<Measurement conditions>
Equipment: Shimadzu AXIMA CFRplus
Laser: Nitrogen laser (337 nm)
Detector type: Linear mode Ion detection: Positive ion (positive mode)
Integration count: 500 times

  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-resistant yellowing 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 organopolysiloxane of this embodiment includes a hydrogen polysiloxane (a) represented by the following general formula (4) and a vinyl group-containing organopolysiloxane (b) having two or more vinyl groups bonded directly to silicon atoms. And an alkenyl group-containing (meth) acrylate compound (c) can be produced by a method in which the addition reaction is carried out in the presence of a hydrosilylation reaction catalyst (d).

In the 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, p represents an integer of 1 or more, q represents an integer of 0 or more, and p + q is an integer of 3 to 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.
Examples of vinyl group-containing organopolysiloxane (b) having two or more vinyl groups directly bonded to silicon atoms are given below.

For example,
_{CH 2 = CHSi (Me) 2} O-Si (Me) 2 CH = CH 2,
_{CH 2 = CHSi (Me) 2} O-Si (Me) 2 O-Si (Me) 2 CH = CH 2,
_{CH 2 = CHSi (Me) 2} O- (Si (Me) 2 O) 2 -Si (Me) 2 CH = CH 2
_{CH 2 = CHSi (Me) 2} O- (Si (Me) 2 O) 3 -Si (Me) 2 CH = CH 2,
_{CH 2 = CHSi (Me) 2} O- (Si (Me) 2 O) 6 -Si (Me) 2 CH = CH 2,
_{CH 2 = CHSi (Me) 2} O- (Si (Me) 2 O) 8 -Si (Me) 2 CH = CH 2,
_{CH 2 = CHSi (Me) 2} O- (Si (Me) 2 O) 11 -Si (Me) 2 CH = CH 2,
_{CH 2 = CHSi (Me) 2} O- (Si (Me) 2 O) 12 -Si (Me) 2 CH = CH 2,
_{CH 2 = CHSi (Me) 2} O- (Si (Me) 2 O) 20 -Si (Me) 2 CH = CH 2,
_{CH 2 = CHCH 2 Si (Me} ) 2 O-Si (Me) 2 CH 2 CH = CH 2, and _{CH 2 = CHCH 2 Si (Me} ) 2 O-Si (Me) 2 O-Si (Me) 2 CH ₂ CH═CH ₂ is mentioned.

The vinyl group-containing organopolysiloxane (b) having two or more vinyl groups directly bonded to silicon atoms may be a combination of two or more types, or may be a single type.
The alkenyl group-containing (meth) acrylate compound (c) 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 becomes difficult to distill off the excess alkenyl group-containing (meth) acrylate compound (c) from the reaction solution. These alkenyl group-containing (meth) acrylate compounds (c) 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 (c) is from the viewpoint of reacting to the end without leaving any SiH group.
For the difference between the molar amount of SiH groups derived from the hydrogen polysiloxane (a) and the molar amount of vinyl groups in the vinyl group-containing organopolysiloxane (b) having two or more vinyl groups bonded directly to silicon atoms Therefore, it is preferable to add excessively.

  Specifically, [molar amount of alkenyl group-containing (meth) acrylate compound (c)] / [(molar amount of SiH group derived from (a)) − (molar amount of vinyl group derived from (b)) ] = 1.2 to 3.0 is preferable.

  The hydrosilylation reaction catalyst (d) 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 hydrogen polysiloxane (a), vinyl group-containing organopolysiloxane (b) having two or more vinyl groups directly bonded to silicon atoms, and alkenyl 0.01-100 ppm is preferable with respect to the mass of the organopolysiloxane which is an addition reaction product with group containing (meth) acrylate compound (c). 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 composition has hydrogen polysiloxane (a) and two or more vinyl groups bonded directly to silicon atoms. 0.001 mass part or less is preferable with respect to the addition reaction product of vinyl group containing organopolysiloxane (b) and an alkenyl group containing (meth) acrylate compound (c).

  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 excess alkenyl group-containing (meth) acrylate compound (c) and the solvent in the case of using the solvent are distilled off under heating and / or reduced pressure, and are represented by the above general formula (1). The organopolysiloxane represented by the average composition formula (3), which contains at least the compound represented by formula (2) and the compound represented by the general formula (2), 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.

  The content of the thermal radical polymerization initiator includes hydrogen polysiloxane (a), vinyl group-containing organopolysiloxane (b) having two or more vinyl groups bonded directly to silicon atoms, and alkenyl group-containing (meta ) 0.5 to 10 parts by mass is preferable with respect to 100 parts by mass of the addition reaction product with the acrylate compound (c). 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.

  The thermosetting resin composition according to this embodiment includes a hydrogen polysiloxane (a), a vinyl group-containing organopolysiloxane (b) having two or more vinyl groups bonded directly to silicon atoms, and an alkenyl group. A silane coupling agent can be blended with the addition reaction product with the containing (meth) acrylate compound (c). A silane coupling agent is compatible with a reactive group chemically bonded to an inorganic material such as glass, metal, or silica and a reactive group or organic material chemically bonded to an organic material such as a synthetic resin in one molecule. If it is a compound which has a substituent, 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 hydrogen polysiloxane (a), vinyl group-containing organopolysiloxane (b) having two or more vinyl groups bonded directly to silicon atoms, An organopolysiloxane containing a (meth) acryloxy group having a structure different from that of the organopolysiloxane can be added to the addition reaction product with the alkenyl group-containing (meth) acrylate compound (c). Examples of the organopolysiloxane containing a (meth) acryloxy group having a structure different from that of the organopolysiloxane include those represented by the following general formula (9) or (10), but are not limited thereto. .

  The amount of the organopolysiloxane containing the (meth) acryloxy group is such that the hydrogen polysiloxane (a) and a vinyl group-containing organopolysiloxane having two or more vinyl groups bonded directly to silicon atoms (b) ) And 100 parts by mass of the addition reaction product of the alkenyl group-containing (meth) acrylate compound (c), from the viewpoint of scratch resistance and adhesion, 0 to 2000 parts by mass can be contained. 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. When the average particle diameter is 0.1 nanometers or more, the viscosity of the resin composition is low, and the moldability is good. Become.

The curable resin composition of the present embodiment is liquid or solid before curing, and a cured product can be produced by performing a predetermined treatment. When a thermal radical generator is contained in the curable resin composition, a cured product is obtained by performing a heat treatment. The curing temperature is usually 100 to 250 ° C. The curing method and molding method of the curable resin composition are not particularly limited.
When the curable resin composition is a liquid, it can be molded by, for example, casting, low-pressure transfer molding, potting, dipping, pressure molding, and injection molding.

  When the curable resin composition is solid, it can be molded by heating and curing under pressure using a press machine, 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.

  Further, the optical semiconductor device using the cured product of the curable resin composition of the present embodiment as a sealing material for the optical semiconductor includes a housing material, a silicon chip provided in the housing, It is the hardened | cured material of curable resin composition, and has the structure which comprises the sealing material which seals the said 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, ceramics, and the like. Adhesiveness is expressed.

  By including glass fiber in the housing material, the adhesive strength is preferably increased. 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 adhesion 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 content ratio of compound represented by general formula (1) and compound represented by general formula (2) ([WB] / [WA]) [WA] and [WB] in the present invention The values correspond to the structures of the general formula (1) and the general formula (2) obtained by measuring with an organopolysiloxane matrix-assisted ionization time-of-flight mass spectrometry (hereinafter referred to as MALDI-TOF / MS). The intensity of the peak corresponding to the total mass of the mass to be added and the mass 23 of sodium is expressed.

  In addition, the mass corresponding to each structure of the general formula (1) and the general formula (2) is the mass of the isotope of each element when the elements constituting the structure have isotopes. The value calculated using the mass of the isotope having the highest abundance.

In the present invention, when a plurality of peaks corresponding to the general formulas (1) and (2) are present, the content [WA] of the compound having the structure of the general formula (1) and the general formula (2) The content [WB] of the compound represented by the formula was the total peak intensity corresponding to each structure.
However, the peak having an intensity of 3% or less with respect to the maximum intensity of the peak corresponding to the total mass of the mass corresponding to each structure of the general formula (1) and the general formula (2) and the mass 23 of sodium. The intensity of was excluded from the calculation of the total peak intensity.
The measurement method of MALDI-TOF / MS was performed by the following method.

<Measurement method of MALDI-TOF / MS>
A solution of 0.1 g of organopolysiloxane dissolved in 100 mL of tetrahydrofuran at room temperature and a solution of 10 mg of dithranol dissolved in 1 mL of tetrahydrofuran were uniformly mixed at a volume ratio of 1: 1 at room temperature. Thus, solution a was prepared. Next, 1 μL of solution a was dropped on a sample plate on which 1 μL of 10 mg sodium iodide dissolved in 10 mL of acetone was placed, the solvent was evaporated at room temperature, and measurement was performed with MALDI-TOF / MS under the following measurement conditions. went.

(Measurement condition)
Equipment: Shimadzu AXIMA CFRplus
Laser: Nitrogen laser (337 nm)
Detector type: Linear mode Ion detection: Positive ion (positive mode)
Integration count: 500 times

(2) Calculation of functional group equivalent A solution dissolved in a deuterated chloroform solvent at a rate of 1 ml with respect to 30 mg of the sample was used as a 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.

(3) 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.

(4) 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.

(5) Scratch resistance
An abrasion resistance tester “IMC-1557 type” manufactured by Imoto Seisakusho was used. The measurement conditions were a vertical load of 1 kg, a reciprocating speed of 30 times / minute, a reciprocating distance of 100 mm, a reciprocating number of 1000 times, and the shape of the worn cloth attachment part being 10 mm in diameter. Steel wool (# 0000) was used as an abrasion cloth.
The scratches on the coating film surface after 50 reciprocations were visually evaluated. The case where no scratch was confirmed was evaluated as ◎, and the case where scratch was confirmed was evaluated as ×.

(6) 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 1 mm depth 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 150 cycles or more was evaluated as ◎, the case where peeling was generated 100 times or more and less than 150 times was evaluated as ◯, and the case where peeling occurred less than 100 times was rated as x.

[Example 1]
<Production of methacryloxy group-containing organopolysiloxane (A1)>
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), 12 g (0.06 mol) of vinyldimethylsiloxy-terminated polydimethylsiloxane having a weight average molecular weight of 186 represented by the following average composition formula (b-1), and allyl methacrylate (allyl methacrylate) as component (c): 56 g (0.4 mol), 300 g of toluene, and 0.02 g of a hydroquinone monomethyl ether (polymerization inhibitor) were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen gas atmosphere.
_{CH 2 = CHSi (Me) 2} O-Si (Me) 2 CH = CH 2 ··· (b-1)

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 70 g of a methacryloxy group-containing organopolysiloxane (A1) containing an organopolysiloxane represented by the following general formulas (11) and (12).
[WB] / [WA] of the obtained methacryloxy group-containing organopolysiloxane (A1) was 0.7. The functional group equivalent was 252 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.

[Example 2]
<Production of methacryloxy group-containing organopolysiloxane (A2)>
To a 0.5 L three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 15 g of 1,3,5,7-tetramethylcyclotetrasiloxane (SiH: 0.25 mol) as component (a), As component (b), 29 g (0.04 mol) of vinyldimethylsiloxy-terminated polydimethylsiloxane having a weight average molecular weight of 780 represented by the following average composition formula (b-2) and 37 g of 3-butenyl methacrylate as component (c) ( 0.3 mol), 275 g of toluene, and 0.02 g of a hydroquinone monomethyl ether (polymerization inhibitor) were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen gas atmosphere.
_{CH 2 = CHSi (Me) 2} O- (Si (Me) 2 O) 8 -Si (Me) 2 CH = CH 2 ··· (b-2)

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 63 g of a methacryloxy group-containing organopolysiloxane (A2) containing an organopolysiloxane represented by the following general formulas (13) and (14).
The value of [WB] / [WA] of the obtained methacryloxy group-containing organopolysiloxane (A2) was 0.8. The functional group equivalent was 398 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.

[Example 3]
<Production of methacryloxy group-containing organopolysiloxane (A3)>
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), (B) 19 g (0.1 mol) of vinyldimethylsiloxy-terminated polydimethylsiloxane having a weight-average molecular weight of 186 represented by the following average composition formula (b-3) as component, and allyl methacrylate (allyl methacrylate) as component (c) 40 g (0.3 mol), 280 g of toluene, and 0.02 g of a hydroquinone monomethyl ether (polymerization inhibitor) were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen gas atmosphere.
_{CH 2 = CHSi (Me) 2} O-Si (Me) 2 CH = CH 2 ··· (b-3)

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, activated carbon treatment was performed, and volatile components were distilled off to obtain 65 g of a methacryloxy group-containing organopolysiloxane (A3) containing organopolysiloxanes represented by the following general formulas (11) and (12).
[WB] / [WA] of the obtained methacryloxy group-containing organopolysiloxane (A3) was 1.7. The functional group equivalent was 354 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 (A4)>
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), 19 g (0.1 mol) of vinyldimethylsiloxy-terminated polydimethylsiloxane having a weight average molecular weight of 186 represented by the following average composition formula (b-4), and 45 g of 3-butenyl methacrylate as component (c) ( 0.3 mol), 295 g of toluene, and 0.02 g of a hydroquinone monomethyl ether (polymerization inhibitor) were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen gas atmosphere.
_{CH 2 = CHSi (Me) 2} O-Si (Me) 2 CH = CH 2 ··· (b-4)
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 63 g of a methacryloxy group-containing organopolysiloxane (A4) containing an organopolysiloxane represented by the following general formulas (13) and (15).
[WB] / [WA] value of the obtained methacryloxy group-containing organopolysiloxane (A4) was 1.7. The functional group equivalent was 354 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 1 shows the performance of the obtained cured product.

[Example 5]
<Production of methacryloxy group-containing organopolysiloxane (A5)>
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), 19 g (0.1 mol) of vinyldimethylsiloxy-terminated polydimethylsiloxane having a weight average molecular weight of 186 represented by the following average composition formula (b-5) and 54 g of 5-hexenyl methacrylate (0) as component (c) 3 mol), 318 g of toluene, and 0.02 g of a hydroquinone monomethyl ether (polymerization inhibitor) were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen gas atmosphere.
_{CH 2 = CHSi (Me) 2} O-Si (Me) 2 CH = CH 2 ··· (b-5)

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, activated carbon treatment was performed, and volatile components were distilled off to obtain 75 g of a methacryloxy group-containing organopolysiloxane (A5) containing organopolysiloxanes represented by the following general formulas (16) and (17).
The obtained [methacryloxy group-containing organopolysiloxane (A5)] had a [WB] / [WA] value of 1.6. The functional group equivalent was 382 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 1 shows the performance of the obtained cured product.

[Example 6]
<Production of methacryloxy group-containing organopolysiloxane (A6)>
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), 31 g (0.17 mol) of vinyldimethylsiloxy-terminated polydimethylsiloxane having a weight average molecular weight of 186 represented by the following average composition formula (b-6), and 18 g of 3-butenyl methacrylate as component (c) ( 0.13 mol), 270 g of toluene, and 0.02 g of a hydroquinone monomethyl ether (polymerization inhibitor) were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen gas atmosphere.
_{CH 2 = CHSi (Me) 2} O-Si (Me) 2 CH = CH 2 ··· (b-4)

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 62 g of a methacryloxy group-containing organopolysiloxane (A6) containing an organopolysiloxane represented by the following general formulas (13) and (15).
The value of [WB] / [WA] of the obtained methacryloxy group-containing organopolysiloxane (A6) was 10.1. The functional group equivalent was 814 g / mol.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of methacryloxy group-containing organopolysiloxane (A6) 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.

[Example 7]
<Production of methacryloxy group-containing organopolysiloxane (A4)>
The methacryloxy group-containing organopolysiloxane (A4) was produced in the same manner as in Example 4.

<Manufacture and characteristic evaluation of cured product>
To 100 parts by mass of the methacryloxy group-containing organopolysiloxane (A4), 5 parts by mass of 3-methacryloxypropylmethyldimethoxysilane (KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed. The functional group equivalent of this composition was 350 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 2 shows the performance of the obtained cured product.

[Example 8]
<Production of methacryloxy group-containing organopolysiloxane (A2)>
The methacryloxy group-containing organopolysiloxane (A2) was produced in the same manner as in Example 4.

<Acryloxy group-containing organopolysiloxane (A7)>
As the acryloxy group-containing organopolysiloxane (A7), an acryloxy group-containing organopolysiloxane represented by the following general formula (18) having a structure different from that of (A2) was used. The functional group equivalent of the acryloxy group-containing organopolysiloxane (A7) 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 (A4), 2000 parts by mass of the acryloxy group-containing organopolysiloxane (A7) represented by the general formula (18) was mixed. The functional group equivalent of this composition was 893 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 2 shows the performance of the obtained cured product.

[Example 9]
<Production of methacryloxy group-containing organopolysiloxane (A4)>
The methacryloxy group-containing organopolysiloxane (A4) was produced in the same manner as in Example 4.

<Methacryloxy group-containing organopolysiloxane (A8)>
As the methacryloxy group-containing organopolysiloxane (A8), a methacryloxy group-containing organopolysiloxane made by Shin-Etsu Chemical Co., Ltd. represented by the following general formula (19) having a structure different from that of (A4) was used. The functional group equivalent of the acryloxy group-containing organopolysiloxane (A8) 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 (A8) represented by the general formula (19) was mixed with 100 parts by mass of the methacryloxy group-containing organopolysiloxane (A4). The functional group equivalent of this composition was 713 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 2 shows the performance of the obtained cured product.

[Comparative Example 1]
<Production of methacryloxy group-containing organopolysiloxane (A9)>
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 (c), 90 g (0.6 mol) of 3-butenyl methacrylate, 295 g of toluene, and 0.02 g of a hydroquinone monomethyl ether (polymerization inhibitor) were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen gas atmosphere. Warm up.

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, activated carbon treatment was performed, and volatile components were distilled off to obtain 45 g of a methacryloxy group-containing organopolysiloxane (A9) containing an organopolysiloxane represented by the following general formula (13).
The value of [WB] / [WA] of the obtained methacryloxy group-containing organopolysiloxane (A9) was 0. The functional group equivalent was 200 g / mol.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of methacryloxy group-containing organopolysiloxane (A9) and 2.5 parts by mass of tert-amylperoxy-2-ethylhexanoate (trade name: Trigonox 121-50E, 50 mass% solution, manufactured by Kayaku Akzo) 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 3 shows the performance of the obtained cured product.

[Comparative Example 2]
<Acryloxy group-containing organopolysiloxane (A7)>
As the acryloxy group-containing organopolysiloxane (A7), the acryloxy group-containing organopolysiloxane represented by the general formula (18) was used. The functional group equivalent of the acryloxy group-containing organopolysiloxane (A7) was 920 g / mol.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of a methacryloxy group-containing organopolysiloxane (A7) 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 3 shows the performance of the obtained cured product.

[Comparative Example 3]
<Methacryloxy group-containing organopolysiloxane (A8)>
As the methacryloxy group-containing organopolysiloxane (A8), the methacryloxy group-containing organopolysiloxane shown by the general formula (19) was used. The functional group equivalent of the acryloxy group-containing organopolysiloxane (A8) was 893 g / mol.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of methacryloxy group-containing organopolysiloxane (A8) 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 3 shows the performance of the obtained cured product.

[Comparative Example 4]
<Epoxy group-containing organopolysiloxane (A10)>
As the epoxy group-containing organopolysiloxane (A10), an epoxy group-containing organopolysiloxane represented by the following general formula (20) was used.

<Manufacture and characteristic evaluation of cured product>
To 100 parts by mass of the epoxy group-containing organopolysiloxane (A10), 60.5 parts by mass of methylhexahydrophthalic anhydride and 1 part by mass of diazabicycloundecene octylate are mixed and stirred 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 3 shows the performance of the obtained cured product.

[Comparative Example 5]
<Curable resin composition (A11)>
As the curable resin composition (A11), 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 3 shows the performance of the obtained cured product.

[Comparative Example 6]
<Curable resin composition (A12)>
As the curable resin composition (A12), 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 3 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, scratch resistance 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 (11)

An organopolysiloxane represented by the average composition formula (3), comprising at least a compound represented by the following general formula (1) and a compound represented by the following general formula (2), wherein [g / (a + b + c + d + e + f + g + h + i + j) ] Is a range of 0.020 or less.

[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, Y represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and Z represents a bond with the divalent hydrocarbon group Y. In the formula, t is each independently an integer of 0 or more, u is each independently an integer of 3 or more, and v is an integer of 0 to 20. A, b, c, d, e, f, g, h, i, and j represent the number of moles of each structural unit present in 1 mole of organopolysiloxane, and a, e, and f exceed 0. B, c, d, g, h, i, and j are values that are 0 or more and satisfy e = a + d + i. The chain in the general formulas (1) and (2) may be random or block. ] The general formula for the content [WA] of the compound represented by the general formula (1), which is calculated by the following formula (I) from the peak intensity obtained when measured by matrix-assisted ionization time-of-flight mass spectrometry The ratio [WB] / [WA] of the content [WB] of the compound represented by the formula (2) is 0.1 or more and 20.0 or less, the organopoly according to claim 1 Siloxane.

  The thermosetting resin composition containing 100 mass parts of organopolysiloxane as described in any one of Claim 1 or 2, and 0.5-10 mass parts of thermal radical initiators.   Furthermore, the thermosetting resin composition of Claim 3 which contains 0.5-10 mass parts of silane coupling agents with respect to 100 mass parts of said organopolysiloxane.   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 organopolysiloxane with respect to 100 parts by mass of the organopolysiloxane. Thermosetting resin composition.   The thermosetting resin composition according to any one of claims 3 to 5, wherein the functional group equivalent of the (meth) acryloxy group is 180 to 900 g / mol. The thermosetting resin composition according to any one of claims 3 to 6, wherein R ¹ is an alkyl group having 1 to 10 carbon atoms. The thermosetting resin composition according to claim 3, wherein R ¹ is a methyl group.   The sealing material for optical semiconductors containing the thermosetting resin composition of any one of Claims 3-8.   The die-bonding material for optical semiconductors containing the thermosetting resin composition of any one of Claims 3-8.   An optical semiconductor package, wherein the optical semiconductor sealing material according to claim 9 is molded.