TW201602174A - Branched-chain polyorganosiloxycyl alkylene, method for producing same, curable resin composition, and semiconductor device - Google Patents

Abstract

Provided are a branched-chain polyorganosiloxycyl alkylene, a method for producing same, a curable resin composition, and a semiconductor device. This method for producing a branched-chain polyorganosiloxycyl alkylene has the steps below. Step 1: a step for causing an addition reaction in a manner such that for every mole of vinyl silyl groups of a siloxane compound (A) having a vinylsilyl group, there is greater than one mole of vinyl silyl groups of a siloxane compound (B) having a hydrosilyl group, thus obtaining a polyorganosiloxylcyl alkylene (H) having a hydrosilyl group. Step 2: a step for causing an addition reaction in a manner such that for every mole of hydrosilyl groups in the polyorganosiloxycyl alkylene (H), there is greater than one mole of a siloxane compound (C) having a vinyl silyl group, thus forming a branched-chain polyorganosiloxycyl alkylene having a vinyl silyl group.

Description

Branched chain polyorganodecyloxydecane alkylene, process for producing the same, curable resin composition and semiconductor device

The present invention relates to a branched-chain polyorgano siloxy silalkylene, a method for producing the same, a curable resin composition comprising the same, and a semiconductor device using the curable resin composition. The priority of Japanese Patent Application No. 2014-106786, filed on May 23, 2014 in Japan, is hereby incorporated by reference.

The polyorganoquinoloxyalkylene alkylene is a polymer compound having a decane bond and a decyl olefin bond. The polyorganoquinoloxyalkylene alkylene is known to be used as a raw material for a sealing material for a semiconductor, like an epoxy resin or an anthrone resin.

Patent Document 1 discloses a method for producing a polyorganodecyloxydecylalkylene, which comprises adding a pyridoxane compound containing a vinyl fluorenyl group and a hydrazine group containing a hydroquinone group in the presence of a platinum catalyst. The method of reaction.

In addition, high heat resistance is required. In a high withstand voltage semiconductor device, heat resistance of 150 ° C or higher is generally required for a material covering a semiconductor element. In particular, heat resistance is required for a material (sealing material) of an optical material such as an optical semiconductor element.

In Patent Document 2, as a material having excellent heat dissipation properties and excellent heat resistance, it is disclosed that at least one first organic ruthenium polymer and at least one second organic ruthenium polymer are linked by a ruthenium oxide bond. a composition of a third organic ruthenium polymer having a molecular weight of 20,000 to 800,000, wherein the first organic ruthenium polymer has a crosslinked structure due to a siloxane (Si-O-Si bond). The second organic ruthenium polymer has a linear connection structure due to siloxane.

Further, Patent Document 3 discloses a liquid silsesquioxane containing a composition comprising an aliphatic carbon-carbon double bond and an H-Si bond-free cage structure, and A liquid sesquioxane having a cage structure containing an H-Si bond and not containing an aliphatic carbon-carbon double bond. However, since the cured product of the composition of the sesquisestamer containing the cage structure lacks flexibility, there is a problem that cracks are likely to occur.

Further, Patent Document 4 discloses a chain-like and/or cyclic polyorganosiloxane containing at least two carbon-carbon double bonds in one molecule and at least two SiH groups in one molecule. And a composition of a hydroquinone alkylation catalyst, but the cured product of the above composition is not satisfactory in terms of flexibility.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1]: JP-A-2012-140617

[Patent Document 2]: Japanese Laid-Open Patent Publication No. 2006-206721

[Patent Document 3]: JP-A-2007-031619

[Patent Document 4]: JP-A-2002-314140

In the case of producing a branched-chain polyorganomethoxyalkylene alkylene, it is known that the production method described in Patent Document 1 has a plurality of vinyl fluorenyl groups in the branched chain portion, so that the addition reaction proceeds promptly. It is easy to gel and there is a problem at the point of productivity or quality.

Further, the metal material such as an electrode in the optical semiconductor device is easily corroded by the corrosive gas, and the electric conduction characteristics (for example, the energization characteristics in a high-temperature environment) are deteriorated with the passage of time. Therefore, the sealing material for optical semiconductors requires high barrier properties against corrosive gases. However, the sealing material of the conventional anthrone-based resin material disclosed in Patent Documents 2 to 4 is known to have insufficient barrier properties against corrosive gases.

Accordingly, an object of the present invention is to provide a method for producing a branched chain polyorganomethoxyalkylene alkylene excellent in quality with excellent productivity.

Another object of the present invention is to provide a branched chain polyorganoalkyloxy decylalkylene obtained by the above method.

Another object of the present invention is to provide a curable resin composition which is excellent in heat resistance and flexibility, and has barrier properties against hydrogen sulfide (H ₂ S) gas (H ₂ S corrosion resistance) and sulfur oxidation. A cured product excellent in barrier properties (SO _X corrosion resistance) of a substance (SO _X ) gas.

Another object of the present invention is to provide a cured product of the curable resin composition and an optical semiconductor device including the cured product as a constituent element.

As a result of intensive review in order to solve the above problems, the present inventors have found that a certain amount of a siloxane compound having three or more vinyl fluorenyl groups in one molecule can be used for a polyorganodecyloxy decyl olefin having a hydroquinone group. By carrying out the reaction, it is possible to produce a branched chain polyorganodecyloxydecylalkylene having a vinyl fluorenyl group excellent in quality with excellent productivity.

Further, it has been found that a curable resin composition comprising a branched chain polyorganomethoxyalkylene alkylene having a vinyl fluorenyl group obtained by the method is excellent in heat resistance and flexibility, and is excellent in corrosive gas. Barrier hardening. The present invention has been completed based on these findings.

That is, the present invention provides a method for producing a branched chain polyorganoalkyloxydecanealkylene having the following steps.

Step 1: A fluorenyl compound having two or more hydrofluorenyl groups in one molecule with respect to a vinyl fluorenyl group 1 mole of a methoxy siloxane compound (A) having one or more vinyl fluorenyl groups in one molecule ( The hydroquinolyl group of B) is in a manner of more than 1 mole, and the addition reaction of the oxoxane compound (A) and the oxoxane compound (B) to obtain a polyorganodecyloxy decylalkylene having a hydroquinone group ( a step of H); a step 2: a hydroxyl group 1 (mol) having 1 or more vinyl fluorenyl groups in one molecule with respect to the hydroquinone alkyl 1 mol of the polyorganodecyloxyalkylene (H) The polyorganoquinolyloxyalkylene (H) and the decane compound (C) are subjected to an addition reaction in a manner of more than 1 mole to obtain a branched chain polyorganoalkyloxyalkyl group having a vinyl fluorenyl group. Alkene (V) steps.

Further, the present invention provides a process for producing a branched chain polyorganodecyloxydecanealkylene as described above, wherein in step 2, a polyorganodecyloxydecylalkylene (H) is added to a decane compound (C) In order to carry out an addition reaction of a polyorganoquinolyloxyalkylene (H) and a siloxane compound (C).

Further, the present invention provides a process for producing a branched chain polyorganoalkyloxy decylalkylene as described above, wherein in step 1, a oxoxane compound (A) and a siloxane compound (B) are reacted to a vinyl decane The base disappears.

Furthermore, the present invention provides a method for producing a branched chain polyorganodecyloxydecanealkylene as described above, wherein the oxirane compound (A) is a compound represented by the following formula (a),

(wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and s represents an integer of 0 or more).

Furthermore, the present invention provides a method for producing a branched chain polyorganoalkyloxy decylalkylene as described above, wherein the oxirane compound (B) is a compound represented by the following formula (b),

(wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and t is an integer of 0 or more).

Furthermore, the present invention provides a process for producing a branched chain polyorganoalkyloxy decylalkylene as described above, wherein the oxirane compound (C) is a compound represented by the following formula (c),

(wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and u is an integer of 1 to 10).

Further, the present invention provides a process for producing a branched chain polyorganodecyloxydecanealkylene as described above, wherein the branched chain polyorganoalkyloxydecylalkylene (V) having a vinyl fluorenyl group has the following The compound of the structure: a structure in which all or a part of hydrogen atoms of the hydroquinone group of the polyorganoquinolyloxyalkylene (H) having a hydroquinone group is substituted with a group represented by the following formula (d),

(wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and u is an integer of 1 to 10. The left end of the formula (d) is agglomerated Si bonding of an organodecyloxydecylalkylene).

Further, the present invention provides a branched chain polyorganoalkyloxy decylalkylene having a vinyl fluorenyl group which is obtained by the aforementioned production method.

In addition, the present invention provides a branched chain polyorganomethoxyalkoxyalkylene having a vinyl fluorenyl group as described above, and has a viscosity [at 25 ° C, a shear rate of 20 (l/s)] of 1500 to 100 000 mPa. s.

Further, the present invention provides a branched chain polyorganodecyloxydecanealkylene having a vinyl fluorenyl group as described above, wherein the content of the linear polyorganodecyloxydecanealkylene having a vinyl fluorenyl group is zero.

Further, the present invention provides the aforementioned branched-chain alkoxy polyorganosiloxane Silicon Silicon alkenyl group having a vinyl group silicon, wherein the resonant frequency by a ¹ H 500MHz, ¹ H-NMR measurement under the measurement conditions of temperature 25 ℃ The hydrogen atom bonded to the ruthenium atom is below the detection limit.

Further, the present invention provides a curable resin composition comprising the following (A1) component, (B1) component, (C1) component, and (D1) component.

(A1): the above-mentioned branched chain polyorganomethoxyalkoxyalkylene having a vinyl fluorenyl group; (B1): a polyorgano group having one or more hydroalkylalkyl groups in the molecule and having no aliphatic unsaturation (C1): a branched chain polyorganosiloxane having one or more alkenyl groups in the molecule; (D1): a hydroquinone alkylation catalyst containing a platinum group metal.

Further, the present invention provides the curable resin composition as described above, which further comprises the following (E1) component: (E1): a decane coupling agent.

Further, the present invention provides a cured product obtained by hardening the above-mentioned curable resin composition.

Further, the present invention provides the curable resin composition as described above, which is a resin composition for sealing a photo-semiconductor.

Furthermore, the present invention provides a curable resin composition as described above, which is a resin composition for forming a lens for an optical semiconductor.

Moreover, the present invention provides an optical semiconductor device comprising an optical semiconductor element and a sealing material for sealing the optical semiconductor element, wherein the sealing material is a cured product of the curable resin composition.

Further, the present invention provides an optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is a cured product of the curable resin composition.

That is, the present invention relates to the following.

[1] A process for producing a branched chain polyorganoalkyloxy decylalkylene having the following steps: Step 1: a oxoxane compound having one or more vinyl fluorenyl groups in one molecule (A) a vinyl fluorenyl group 1 mole, a hydroxanyl group of a fluorinated alkane compound (B) having two or more hydrofluorenyl groups in one molecule, in a manner of more than 1 mol, such that the oxoxane compound (A) and hydrazine a step of performing an addition reaction of an oxyalkyl compound (B) to obtain a polyorganomethoxyalkoxyalkylene (H) having a hydroquinone group; and a step 2: a hydrogen relative to a polyorganodecyloxyalkylene (H) a mercaptoalkyl group, a polyoxonium alkylene compound (C) having a polyoxyalkylene alkylene group (C) having a molecular weight of more than 1 mole in one molecule and having a polyoxonium alkylene group (C) (C) performing an addition reaction to obtain A step of a branched chain polyorganomethoxyalkoxyalkylene (V) having a vinyl fluorenyl group.

[2] The method for producing a branched chain polyorganodecyloxydecanealkylene according to [1], wherein in the step 2, a polyorganodecyloxydecylalkylene (H) is added to the decane compound ( In C), an addition reaction of a polyorganoquinolyloxyalkylene (H) and a siloxane compound (C) is carried out.

[3] The method for producing a branched chain polyorganoalkyloxy decylalkylene according to [1] or [2], wherein, in the step 1, the oxoxane compound (A) and the decane compound (B) are provided. The reaction is until the vinyl sulfonyl group disappears.

[4] The method for producing a branched chain polyorganoalkyloxy decylalkylene according to any one of [1] to [3] wherein the oxirane compound (A) is represented by the following formula (a) compound of,

(wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and s represents an integer of 0 or more).

[5] The method for producing a branched chain polyorganoalkyloxy decylalkylene according to any one of [1] to [4] wherein the oxirane compound (B) is represented by the following formula (b) compound of,

(wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and t is an integer of 0 or more).

[6] The method for producing a branched chain polyorganoalkyloxy decylalkylene according to any one of [1] to [5] wherein the oxirane compound (C) is represented by the following formula (c) compound of,

(wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and u is an integer of 1 to 10).

[7] The method for producing a branched chain polyorganoalkyloxy decylalkylene according to any one of [1] to [6] wherein the branched chain polyorganoalkyloxyalkylene group having a vinyl fluorenyl group The alkene (V) is a compound having a structure in which all or a part of hydrogen atoms of a hydrofluorenyl group of a polyorganodecyloxydecylalkylene (H) having a hydroquinone group are substituted with a group represented by the following formula (d); Construction,

(wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and u is an integer of 1 to 10. The left end of the formula (d) is agglomerated Si bonding of an organodecyloxydecylalkylene).

[8] A branched chain polyorganodecane oxygen having a vinyl fluorenyl group The alkylene group is obtained by the production method according to any one of [1] to [7].

[9] The branched chain polyorganoalkyloxy decylalkylene having a vinyl fluorenyl group as described in [8], wherein the viscosity [at 25 ° C, shear rate 20 (l / s)] is 1500 ~ 100000 mPa. s.

[10] The branched chain polyorganoalkyloxy decylalkylene having a vinyl fluorenyl group as described in [8] or [9], wherein the content of the linear polyorganodecyloxydecylalkylene having a vinyl fluorenyl group Zero.

[11] The branched chain polyorganoalkyloxy decylalkylene having a vinyl fluorenyl group according to any one of [8] to [10], wherein the temperature is 25 ° C at a resonance frequency of 500 MHz at ¹ H. The ¹ H-NMR measurement under the conditions is such that the hydrogen atom bonded to the ruthenium atom is below the detection limit.

[12] A curable resin composition comprising the following (A1) component, (B1) component, (C1) component, and (D1) component: (A1): as in any one of [8] to [11] A branched chain polyorganomethoxyalkoxyalkylene having a vinyl fluorenyl group; (B1): a polyorganosiloxane having one or more hydroalkylalkyl groups in the molecule and having no aliphatic unsaturation (C1): a branched chain polyorganosiloxane having one or more alkenyl groups in the molecule; (D1): a hydroquinone alkylation catalyst containing a platinum group metal.

[13] The curable resin composition according to [12], which further comprises the following (E1) component: (E1): a decane coupling agent.

[14] A cured product which is made to have curability as described in [12] or [13] The resin composition is obtained by hardening.

[15] The curable resin composition according to [12] or [13], which is a resin composition for sealing a photo-semiconductor.

[16] The curable resin composition according to [12] or [13], which is a resin composition for forming a lens for an optical semiconductor.

[17] An optical semiconductor device comprising: an optical semiconductor element; and a sealing material for sealing the optical semiconductor element, wherein the sealing material is a cured product of the curable resin composition according to [15].

[18] An optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is a cured product of the curable resin composition according to [16].

According to the production method of the present invention, a branched chain polyorganodecyloxydecylalkylene having a vinyl fluorenyl group excellent in quality can be obtained with high efficiency. Further, the branched chain polyorganodecyloxydecanealkylene having a vinyl fluorenyl group obtained by the production method of the present invention has higher curing reactivity than a linear one, and is advantageous for optimizing the viscosity. In addition, the curable resin composition containing the branched chain polyorganomethoxyalkylene alkylene having a vinyl fluorenyl group of the present invention is excellent in curability, and when it contains a filler or a fluorescent material, etc., such dispersion Excellent stability. Therefore, a cured product excellent in toughness, heat resistance, flexibility, and sulfur barrier property (SO _X , H ₂ S) can be formed. Therefore, the branched chain polyorganodecyloxydecane alkylene having a vinyl fluorenyl group of the present invention can be used as a raw material for a sealing material for a semiconductor (particularly, a sealing material for an optical semiconductor) or a lens for an optical semiconductor.

100‧‧‧Reflector (resin composition for light reflection)

101‧‧‧Metal wiring (electrode)

102‧‧‧Optical semiconductor components

103‧‧‧welding line

104‧‧‧ hardened material (sealing material)

Fig. 1 is a view showing the results of ¹ H-NMR measurement of the reaction product after completion of the step 1 in Example 1.

Fig. 2 is a view showing the results of ¹ H-NMR measurement of the reaction product after completion of the step 2 in Example 1.

Fig. 3 is a schematic view showing an example of an optical semiconductor device in which an optical semiconductor device is sealed by a cured product (sealing material) of the curable resin composition of the present invention. Figure (a) is a perspective view, and Figure (b) is a cross-sectional view.

[Formation of the Invention]

[Method for Producing Branched Chain Polyorganoalkyloxyalkylene Alkene]

The method for producing a branched chain polyorganomethoxyalkylene alkylene of the present invention is characterized by having the following steps.

Step 1: A fluorenyl compound having two or more hydrofluorenyl groups in one molecule with respect to a vinyl fluorenyl group 1 mole of a methoxy siloxane compound (A) having one or more vinyl fluorenyl groups in one molecule ( The hydroquinolyl group of B) is in a manner of more than 1 mole, and the addition reaction of the oxoxane compound (A) and the oxoxane compound (B) to obtain a polyorganodecyloxy decylalkylene having a hydroquinone group ( a step of H); a step 2: a hydroxyl group 1 (mol) having 1 or more vinyl fluorenyl groups in one molecule with respect to the hydroquinone alkyl 1 mol of the polyorganodecyloxyalkylene (H) a polyorganodecyloxydecylalkylene (H) and a decane compound (C) are subjected to an addition reaction in a manner of more than 1 mole to obtain A step of a branched chain polyorganomethoxyalkoxyalkylene (V) having a vinyl fluorenyl group.

(step 1)

Step 1 of the present invention is characterized in that the hydroquinone group is made more than 1 mol (preferably more than 1.0 mol and less than 5.0 mTorr) with respect to the vinyl fluorenyl group 1 mol of the oxoxane compound (A). The amount of the oxoxane compound (B), particularly preferably in an amount of more than 1.0 mol and not more than 1.4 mol, is reacted with the oxoxane compound (A). Thereby, at least one polyorganodecyloxydecylalkylene having a hydroquinone group at the terminal can be selectively produced.

The oxirane compound (A) having one or more vinyl fluorenyl groups in one molecule includes a fluorinated alkane compound having one vinyl fluorenyl group in one molecule and two vinyl fluorenyl groups in one molecule. A siloxane compound or the like. In the present invention, a compound having two vinyl fluorenyl groups in one molecule is preferred, and a compound represented by the following formula (a) is particularly preferred.

(wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and s represents an integer of 0 or more).

R ¹ and R ² in the formula (a) are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms. The 2s R ¹ in the formula (a) may be the same or different. The four R ² in the formula (a) may be the same or different.

Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, and a pentyl group. An alkyl group having a carbon number of 1 to 8 (preferably 1 to 6, particularly preferably 1 to 3) such as a hexyl group or an octyl group. The aryl group may, for example, be an aryl group having 6 to 10 (preferably 6) carbon atoms such as a phenyl group or a naphthyl group. R ^{1 is} preferably an aryl group having 6 to 10 carbon atoms (particularly preferably a phenyl group), and R ^{2 is} preferably an alkyl group having 1 to 8 carbon atoms (particularly preferably a methyl group).

The s in the formula (a) is an integer of 0 or more, for example, 0 to 10, preferably 1 to 5.

The oxoxane compound (B) having two or more hydroalkylene groups in one molecule includes a fluorinated alkane compound having two hydrofluorenyl groups in one molecule and three hydroalkylene groups in one molecule. A siloxane compound or the like. In the present invention, a decyl alkane compound having two hydrofluorenyl groups in one molecule is preferable, and a decane compound represented by the following formula (b) is particularly preferable.

(wherein R ¹ and R ² are the same as defined above. t represents an integer of 0 or more).

The 2t R ¹ in the formula (b) may be the same or different. Further, the four R ² in the formula (b) may be the same or different.

The t in the formula (b) is an integer of 0 or more, for example, 0 to 10, preferably 1 to 5.

In the present invention, the reaction of the oxirane compound (A) and the oxirane compound (B) is preferably carried out until the disappearance of the vinyl fluorenyl group. Thereby, it is possible to selectively produce only a polyorganodecyloxydecylalkylene having a hydroquinone group at both terminals. In addition, the disappearance of the vinyl fluorenyl group can be confirmed, for example, by the measurement result of ¹ H-NMR under the conditions of a ¹ H resonance frequency of 500 MHz and a measurement temperature of 25 ° C, and the signal derived from the vinyl group is below the detection limit value. .

The reaction of step 1 is preferably carried out in the presence of a catalyst (for example, a hydroquinone alkylation catalyst), particularly a platinum-vinyl oxirane complex (for example, platinum-1,3-divinyl four). Methyldioxane complex, platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetraoxane complex, etc.) due to reactivity It is preferable because it is excellent in storage stability, compatibility with a oxoxane compound, and the like.

The amount of the catalyst (in terms of metal) is, for example, 1 × 10 ^-8 to 1 × 10 ^-2 mol, preferably 1 × 10 ^-6 to 1 × 10 with respect to the oxime compound (A) 1 mol. ^-4 moles.

The reaction in the step 1 is preferably carried out in the presence of a solvent. For the solvent, for example, one or two or more kinds of saturated or unsaturated hydrocarbon solvents such as pentane, hexane, heptane, octane or petroleum ether can be used. An aromatic hydrocarbon solvent such as benzene, toluene or xylene; a halogenated hydrocarbon solvent such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene or bromobenzene; diethyl ether and diisopropyl ether , dibutyl ether, tetrahydrofuran, two An ether-based solvent such as dioxane, 1,2-dimethoxyethane or cyclopentylmethyl ether; a nitrile-based solvent such as acetonitrile or benzonitrile; an anthraquinone solvent such as dimethyl hydrazine; An isobutyl sulfonium-based solvent; a guanamine-based solvent such as dimethylformamide; a high-boiling solvent such as an oxime oil.

The amount of the solvent to be used is, for example, 50 to 300% by weight based on the total amount of the siloxane compound (A). If the amount of solvent exceeds In the above range, the concentration of the reaction component becomes low, and the reaction rate tends to decrease.

The reaction gas atmosphere is not particularly limited as long as it does not interfere with the reaction, and may be, for example, an air atmosphere, a nitrogen atmosphere, or an argon atmosphere.

The reaction temperature (= temperature at the time of dropping) is, for example, 40 to 120 ° C, preferably 50 to 100 ° C. The reaction time (= dropping time) is, for example, 0.1 to 3.0 hours, preferably 0.5 to 1.5 hours. After the reaction (= dripping) is completed, the ripening step can also be set. In the case where the ripening step is provided, the ripening temperature is, for example, 40 to 120 ° C, preferably 50 to 110 ° C, and the ripening time is, for example, 1 hour or longer, preferably 3 to 8 hours. Further, the reaction can be carried out in any one of a batch type, a semi-batch type, a continuous type, and the like, and a continuous type is preferred. In the case of the continuous type, since the dropping speed can be arbitrarily adjusted, the molecular weight or molecular weight distribution of the reaction product can be optimized by controlling the reaction temperature, which is advantageous in the production steps and quality management.

After completion of the reaction, the obtained reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, or the like.

The polyorganodecyloxydecylalkylene (H) having a hydrofluorenyl group obtained in the first step is represented, for example, by the following formula (1). In the following ^{formulas, R 1, R 2, s} , t with the same system. n represents an integer of 1 or more (for example, 1 to 100).

(Step 2)

Step 2 of the present invention is characterized in that a decane compound (C) having three or more vinyl fluorenyl groups in one molecule with respect to the hydroquinone alkyl group 1 mole of the polyorganodecyloxydecylalkylene (H) a compound of more than 1 mole (preferably more than 1.0 mole, and 10.0 mole or less, particularly preferably 1.1 to 5.0 moles), a polyorganoquinoloxyalkylene (H) and a decane compound (C) An addition reaction is carried out to obtain a branched chain polyorganodecyloxydecylalkylene (V) having a vinyl fluorenyl group. Thereby, it is possible to prevent the polyorganoquinolyloxyalkylene having a hydrofluorenyl group and the siloxane compound (C) from reacting in an indefinite manner and gelling, and to produce the target compound selectively and efficiently.

The siloxane compound (C) having three or more vinyl fluorenyl groups in one molecule is preferably a oxoxane compound represented by the following formula (c).

(wherein R ¹ and R ² are the same as defined above. u represents an integer of 1 or more).

The u R ¹ in the formula (c) may be the same or different. Further, (4 + 2u) R ² in the formula (c) may be the same or different.

The u in the formula (c) is an integer of 1 or more, for example, 1 to 10, preferably 1 to 5.

The addition reaction of the above polyorganodecyloxydecylalkylene (H) and the decane compound (C) is preferably added or dropped in an excess of the oxoxane compound (C) (may be continuous, It can also be carried out as an intermittent poly(polyalkylene alkoxyalkylene) (H). Further, it is not preferable to add or drop the oxoxane compound (C) in an excess amount of the polyorganomethoxyalkylene alkylene (H) to gel.

The reaction of step 2 is preferably carried out in the presence of a catalyst (e.g., a hydroquinone alkylation catalyst), particularly a platinum-vinyl alkane complex (e.g., platinum-1,3-divinyl four). Methyldioxane complex, platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetraoxane complex, etc.) due to reactivity It is preferable because it is excellent in storage stability, compatibility with a oxoxane compound, and the like. According to the present invention, the same catalyst can be used in steps 1 and 2. Step 2 can directly use the catalyst of step 1, or can be added as needed.

The amount of the catalyst (in terms of metal) is, for example, 1 × 10 ^-8 to 1 × 10 ^-2 mol, preferably 1 × 10 ^-6 with respect to the polyorganodecyloxydecylalkylene (H) 1 mol. ~1×10 ^-4 moles.

The reaction gas atmosphere is not particularly limited as long as it does not interfere with the reaction, and may be, for example, an air atmosphere, a nitrogen atmosphere, or an argon atmosphere.

The reaction temperature (=addition or temperature at the time of dropping) is, for example, 40 to 120 ° C, preferably 50 to 100 ° C. The reaction time (=addition or dripping time) is, for example, 0.1 to 3.0 hours, preferably 0.5 to 1.5 hours. After the reaction (=addition or dripping) is completed, the ripening step can also be set. In the case where the ripening step is set, the ripening temperature is, for example, 40 to 120 ° C, preferably. For the temperature of 50 to 110 ° C, the ripening time is, for example, 1 to 10 hours, preferably 3 to 8 hours.

After completion of the reaction, the obtained reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, or the like.

The branched chain polyorganoalkyloxy decylalkylene (V) having a vinyl fluorenyl group obtained in the second step is represented, for example, by the following formula (2). In the following formula, R ¹ , R ² , s, t, and u are the same as described above. m represents an integer of 1 or more (for example, 1 to 50).

According to the above method, a branched chain polyorganoalkyloxy decylalkylene (V) having a vinyl fluorenyl group can be selectively produced, and a linear chain represented by the following formula (3) is not mixed in the reaction product. Polyorganotinoalkylene alkylene. R ¹ , R ² , s, and t in the formula (3) are the same as described above. k represents an integer of 1 or more.

The branched chain polyorganoalkyloxy decylalkylene of the present invention obtained by the above method (=branched chain polyorganoalkyloxy decylalkylene (V) having a vinyl fluorenyl group) having polyorganodecane The hydrogen atom of the hydrofluorenyl group of the oxonium alkylene (H) is substituted with a branched chain group represented by the following formula (d).

(wherein R ¹ , R ² and u are the same as defined above. The left end of the formula (d) is bonded to the Si of the polyorganodecyloxydecylalkylene), and thus is represented by the above formula (3). The linear polyorganoalkyloxyalkylene alkylene of the compound is superior in reactivity. In addition, it has a moderate viscosity [viscosity at 25 ° C, shear rate 20 (l / s), for example, 500 ~ 100000 mPa. s, preferably 1500~10000mPa. s, especially good is 2000~9000mPa. s]. Therefore, when a curable resin composition (for example, a resin composition for photo-semiconductor sealing) containing the branched chain polyorganomethoxyalkylene alkylene of the present invention contains a filler or a fluorescent material, such a Excellent dispersion stability.

Further, the branched chain polyorganoalkyloxy decylalkylene of the present invention obtained by the above method does not contain a linear polyorganodecyloxydecylalkylene. Further, linear polyethylene organosilane silicon group content is zero alkylene group, for example, can be from the measurement results of ¹ H-NMR under conditions of a ¹ H resonance frequency 500MHz, the measured temperature 25 ℃ to and from silicon The signal of the atom-bonded hydrogen atom is confirmed below the detection limit value.

[Curable resin composition]

The curable resin composition of the present invention contains the following (A1) component, (B1) component, (C1) component, and (D1) component.

(A1): a branched chain polyorganoalkyloxy decylalkylene having a vinyl fluorenyl group; (B1): a polyorganoquinone having one or more hydroalkylalkyl groups in the molecule and having no aliphatic unsaturation (C1): a branched chain polyorganosiloxane having one or more alkenyl groups in the molecule; (D1): a hydroquinone alkylation catalyst containing a platinum group metal.

[(A1) ingredient]

The component (A1) is a branched chain polyorganodecyloxydecylalkylene having a vinyl fluorenyl group as described above. In the curable resin composition of the present invention, the component (A1) can be used singly or in combination of two or more.

The content (the blending amount) of the component (A1) in the curable resin composition of the present invention is preferably from 1 to 30% by weight, more preferably from 5 to 25, based on the curable resin composition (100% by weight). The weight %, more preferably 10 to 30% by weight. When the content of the component (A1) is 1% by weight or more, the thermal shock resistance of the cured product tends to be further improved. The curable property of the curable resin composition is further improved. On the other hand, when the content of the component (A1) is 30% by weight or less, the sulfur barrier property tends to be further improved.

[(B1) ingredients]

The component (B1) has one or more (preferably two or more) hydroalkylene groups (Si-H) in the molecule, and has -Si-O-Si-(a decane bond) as a main chain, and does not have An aliphatic unsaturated group (for example, an aliphatic hydrocarbon group having a non-aromatic carbon-carbon double bond such as an ethylenically unsaturated group or an acetylene unsaturated group) and a polyorganosiloxane having a decylalkylene bond (having only Polyorgano In the case of oxyalkylene (B1). In the curable resin composition of the present invention, the component (B1) and the component having an alkenyl group (for example, the component (A1) and the component (C1)) are hydroquinone-alkylated. When the curable resin composition of the present invention contains the component (B1), the hydroquinone alkylation reaction can be efficiently carried out, and a cured product having excellent sulfur barrier properties can be obtained.

The component (B1) is not particularly limited as long as it has one or more hydroquinone groups in the molecule, but it is preferably two or more from the viewpoint of curability of the curable resin composition (for example, 2~) 50).

The polyorganosiloxane (B1) may, for example, be a molecular structure having a linear or branched chain shape (a linear chain having a partial branch, a branched chain, a mesh, or the like). These can be used alone or in combination of two or more.

The polyorganosiloxane (B1) has one or more hydroalkylene groups (Si-H) in the molecule, but as a group bonded to the ruthenium atom, in addition to a hydrogen atom, for example, a monovalent substitution may be mentioned. Or an unsubstituted hydrocarbyl group (however, an aliphatic unsaturation group is excluded).

Examples of the monovalent substituted or unsubstituted hydrocarbon group described above and the following include an alkyl group [e.g., a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc.], a cycloalkyl group [e.g. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclododeyl, etc.], cycloalkyl-alkyl [for example, cyclohexylmethyl, methylcyclohexyl, etc.], one or more of the hydrocarbon groups a halogenated hydrocarbon group in which a hydrogen atom is substituted by a halogen atom [for example, a halogenated alkyl group such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc.], and an aryl group [for example, phenyl, toluene a substituted or unsubstituted C _6-14 aryl group or the like of a group, a xylyl group, a naphthyl group, an aralkyl group (for example, a benzyl group, a phenethyl group, etc.).

Among them, an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group) is preferred.

Further, the component (B1) may have a hydroxyl group or an alkoxy group as a group bonded to a ruthenium atom.

The nature and state of the polyorganosiloxane (B1) are not particularly limited, and may be, for example, liquid at 25 ° C or solid. Wherein, it is preferably liquid, more preferably having a viscosity of 0.1 to 1 billion mPa at 25 ° C. s liquid.

As the polyorganosiloxane (B1), it is preferred to have the following average unit formula: (R ²¹ SiO _3/2 ) _b1 (R ²¹ ₂ SiO _2/2 ) _b2 (R ²¹ ₃ SiO _1/2 ) _b3 (SiO _4/2 ) _b4 (X ¹ O _1/2 ) _b5

The polyorganosiloxane is represented. In the above average unit formula, R ²¹ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (however, an aliphatic unsaturated group is excluded).

However, a part of R ^{21 is} a hydrogen atom (a hydrogen atom constituting a hydrofluorenyl group), and the ratio thereof is controlled to be one or more (preferably two or more) in the molecule. For example, the ratio of the hydrogen atom to the total amount of R ²¹ (100 mol%) is preferably 0.1 to 40 mol%. When the ratio of the hydrogen atoms is controlled to the above range, the curability of the curable resin composition tends to be further improved. Further, R ²¹ other than a hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

In the above average unit formula, X ¹ is a hydrogen atom or an alkyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, and particularly preferably a methyl group.

In the above average unit formula, b1 is 0 or a positive number, b2 is 0 or a positive number, b3 is 0 or a positive number, b4 is 0 or a positive number, b5 is 0 or a positive number, and (b1+b2+b3) is a positive number.

An example of the polyorganosiloxane (B1) is a linear polyorganosiloxane having one or more (preferably two or more) hydroalkylene groups in the molecule. Examples of the group bonded to the ruthenium atom other than the hydrogen atom in the linear polyorganosiloxane may, for example, be the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (however, the aliphatic unsaturated group is excluded). Specific examples, but among them, an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group) is preferred.

In the above linear polyorganosiloxane, the ratio of a hydrogen atom (a hydrogen atom bonded to a ruthenium atom) to a total amount (100 mol%) of a group bonded to a ruthenium atom is not particularly limited, but Good is 0.1~40%. Further, the ratio of the alkyl group (particularly methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but is preferably from 20 to 99 mol%. Further, the ratio of the total amount (100 mol%) of the aryl group (particularly phenyl group) to the group bonded to the ruthenium atom is not particularly limited, but is preferably 40 to 80 mol%. In particular, as the linear polyorganosiloxane, the ratio of the total amount (100 mol%) of the group bonded to the ruthenium atom by using an aryl group (particularly phenyl group) is 40 mol% or more. (For example, 45 to 70 mol%), there is a tendency that the sulfur barrier property of the cured product is further improved. Further, by using an alkyl group (particularly a methyl group), the ratio of the total amount (100 mol%) of the group bonded to the ruthenium atom is 90 mol% or more (for example, 95 to 99 mol%), There is a tendency that the thermal shock resistance of the cured product is further improved.

The above linear polyorganosiloxane is, for example, of the following formula (b-1) indicates.

[In the above formula, R ²¹ is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (however, an aliphatic unsaturated group is excluded). However, at least one (preferably at least two) of R ²¹ is a hydrogen atom. M1 is an integer from 1 to 1000]

Further, in the linear polyorganosiloxane represented by the above formula (b1), the above R ²¹ may be a hydroxyl group or an alkoxy group. Further, the monovalent substituted or unsubstituted hydrocarbon group in the above R ²¹ (however, the aliphatic unsaturated group is excluded) may have a hydroxyl group or an alkoxy group.

Other examples of the polyorganosiloxane (B1) include a branched chain polyorganosiloxane having one or more (preferably two or more) hydroalkylene groups in the molecule. The branched chain polyorganosiloxane contains at least a oxoxane unit (T unit) represented by [R ²¹ SiO _3/2 ] in the above average unit formula. The branched chain polyorganosiloxane also contains a polyorganosiloxane having a three-dimensional structure such as a mesh shape.

Examples of the group bonded to the ruthenium atom other than the hydrogen atom in the branched chain polyorganosiloxane include the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (however, the aliphatic unsaturated group is excluded). Specific examples, but among them, an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group) is preferred. Further, R ²¹ in the above T unit may, for example, be a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (however, an aliphatic unsaturated group is excluded), but among them, an alkyl group is preferred. It is a methyl group, an aryl group (especially a phenyl group). The ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of R ²¹ in the above T unit is not particularly limited, but is preferably 30 mol from the viewpoint of sulfur barrier property of the cured product. %the above.

In the above branched chain polyorganosiloxane, the ratio of the alkyl group (particularly methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but is preferably 70. ~95 moles %. Further, the ratio of the total amount (100 mol%) of the aryl group (particularly phenyl group) to the group bonded to the ruthenium atom is not particularly limited, but is preferably from 10 to 70 mol%. In particular, as the above-mentioned branched chain polyorganosiloxane, the ratio of the total amount (100 mol%) of the group bonded to the ruthenium atom by using an aryl group (particularly a phenyl group) is 10 mol% The above (for example, 10 to 70 mol%) tends to have a higher sulfur barrier property of the cured product. Further, by using an alkyl group (particularly a methyl group), the ratio of the total amount (100 mol%) of the group bonded to the ruthenium atom is 50 mol% or more (for example, 50 to 90 mol%), There is a tendency that the thermal shock resistance of the cured product is further improved.

The branched chain polyorganosiloxane is, for example, a compound represented by the above average unit formula and having a positive b1 number. In this case, there is no particular limitation, but b2/b1 is preferably a number from 0 to 10, b3/b1 is preferably a number from 0 to 0.5, and b4/(b1+b2+b3+b4) is preferably 0~. The number of 0.3, b5/(b1+b2+b3+b4) is preferably a number from 0 to 0.4. Further, the molecular weight of the branched chain polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 300 to 10,000, more preferably 500 to 3,000.

Further, in the curable resin composition of the present invention, (B1) The components may be used alone or in combination of two or more.

In addition, the content (mixing amount) of the component (B1) in the curable resin composition of the present invention is preferably from 1 to 60% by weight, more preferably from 5 to 60% by weight, based on the curable resin composition (100% by weight). ~55% by weight, more preferably 10~50% by weight. When the content of the component (B1) is 1% by weight or more, the curability of the curable resin composition is further improved, and the sulfur barrier property tends to be further improved. On the other hand, when the content of the component (B1) is 60% by weight or less, the thermal shock resistance of the cured product tends to be further improved.

[(C1) component]

The component (C1) is a branched chain polyorganosiloxane having one or more alkenyl groups in the molecule. In the curable resin composition of the present invention, the component (C1) is hydroquinone-alkylated with a component having a hydroquinone group (for example, a component (B1), etc.) together with the component (A1). Since the curable resin composition of the present invention contains the component (C1), a cured product excellent in heat resistance, thermal shock resistance, and sulfur barrier property can be obtained.

The component (C1) is a branched chain polyorganosiloxane having one or more alkenyl groups in the molecule and having -Si-O-Si-(decane oxide bond) as a main chain and having no decylalkylene bond. An alkane (polyorganosiloxane having a branched chain backbone). Further, the branched chain shape also includes a three-dimensional structure such as a mesh shape.

The alkenyl group which is contained in the molecule as the component (C1) may, for example, be a vinyl group, an allyl group, a butenyl group, a pentenyl group or a hexenyl group, and among them, a vinyl group is preferred. Further, the component (C1) may be one having only one type of alkenyl group, or may be one having two or more kinds of alkenyl groups. The alkenyl group which the (C1) component has is preferably a bond to a ruthenium atom. That is, as the component (C1), it is preferably a branched chain having one or more vinyl fluorenyl groups in the molecule. Polyorganosiloxane.

The (C1) component is not particularly limited as long as the number of the alkenyl groups in the molecule is one or more, but it is preferably two or more from the viewpoint of the curability of the curable resin composition (for example, 2~) 50).

The group bonded to the ruthenium atom other than the alkenyl group which the (C1) component has is not particularly limited, and examples thereof include a hydrogen atom and an organic group. The organic group may, for example, be a specific example of the above monovalent substituted or unsubstituted hydrocarbon group (however, the aliphatic unsaturated group is excluded).

Further, the component (C1) may have a hydroxyl group or an alkoxy group as a group bonded to a ruthenium atom.

The nature and state of the component (C1) are not particularly limited, and may be, for example, a liquid state or a solid state at 25 ° C.

As the component (C1), it is preferred to have the following average unit formula: (R ⁴ SiO _3/2 ) _d1 (R ⁴ ₂ SiO _2/2 ) _d2 (R ⁴ ₃ SiO _1/2 ) _d3 (SiO _4/2 ) _{Polyorganosiloxane} which is represented by _d4 (X ² O _1/2 ) _d5 . In the above average unit formula, R ⁴ is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, and an alkenyl group (for example, a vinyl group, an alkene group) may be mentioned. a substituted or unsubstituted alkenyl group such as a propyl group, a butenyl group, a pentenyl group or a hexenyl group). However, a part of R ⁴ is an alkenyl group (especially a vinyl group), and the ratio thereof is controlled to be one or more (preferably two or more) in the molecule. For example, the ratio of the alkenyl group to the total amount of R ⁴ (100 mol%) is preferably from 0.1 to 40 mol%. When the ratio of the alkenyl group is controlled to the above range, the curability of the curable resin composition tends to be further improved. Further, R ⁴ other than the alkenyl group is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).

In the above average unit formula, X ² is a hydrogen atom or an alkyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, and particularly preferably a methyl group.

In the above average unit formula, d1 is 0 or a positive number, d2 is 0 or a positive number, d3 is 0 or a positive number, d4 is 0 or a positive number, d5 is a 0 or a positive number, and (d1+d2+d3) and (d1+d4) They are positive numbers.

Specific examples of the component (C1) include two or more alkenyl groups in the molecule and a fluorene oxide unit (T unit) represented by (R ⁴ SiO _3/2 ) in the above average unit formula. Branched chain polyorganosiloxane. Specific examples of the alkenyl group of the branched chain polyorganosiloxane include the above-described alkenyl group, and among them, a vinyl group is preferred. Further, it may be one having only one type of alkenyl group, or one having two or more kinds of alkenyl groups. Further, examples of the group bonded to the ruthenium atom other than the alkenyl group in the branched chain polyorganosiloxane may, for example, be a specific example of the above monovalent substituted or unsubstituted hydrocarbon group, but among them, preferred It is an alkyl group (especially a methyl group), an aryl group (especially a phenyl group). Further, as R ⁴ in the above T unit, an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group) is preferred.

The ratio of the alkenyl group in the branched chain polyorganosiloxane to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but the curability of the curable resin composition is not limited. Preferably, it is 0.1 to 40% by mole. Further, the ratio of the alkyl group (particularly methyl group) to the total amount (100 mol%) of the group bonded to the ruthenium atom is not particularly limited, but is preferably 10 to 40 mol%. Further, the ratio of the total amount (100 mol%) of the aryl group (especially phenyl group) to the ruthenium atom-bonded group is not particularly limited, but is preferably from 5 to 70 mol%. In particular, as the above-mentioned branched chain polyorganosiloxane An alkane having a ratio of a total amount (100 mol%) of a group bonded to a ruthenium atom by an aryl group (particularly a phenyl group) of 40 mol% or more (for example, 45 to 60 mol%), There is a tendency for the sulfur barrier property of the hardened material to be further improved. Further, by using an alkyl group (particularly a methyl group), the ratio of the total amount (100 mol%) of the group bonded to the ruthenium atom is 50 mol% or more (for example, 60 to 99 mol%), There is a tendency that the thermal shock resistance of the cured product is further improved.

The above branched chain polyorganosiloxane can be represented by the above average unit formula in which d1 is a positive number. In this case, there is no particular limitation, but d2/d1 is preferably a number from 0 to 10, d3/d1 is preferably a number from 0 to 0.5, and d4/(d1+d2+d3+d4) is preferably 0~. The number of 0.3, d5/(d1+d2+d3+d4) is preferably a number from 0 to 0.4. Further, the molecular weight of the branched chain polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 500 to 10,000, more preferably 700 to 3,000.

Specific examples of the component (C1) include, for example, the following average unit formula in which d1 and d2 are 0 and X ³ is a hydrogen atom in the above average unit formula: (R ^4a ₂ R ^4b SiO _1/2 ) _d6 ( R ^4a ₃ SiO _1/2 ) _d7 (SiO _4/2 ) _d8 (HO _1/2 ) _d9

The polyorganosiloxane is represented. In the above average unit formula, R ^4a is the same or different and represents an alkyl group, a cycloalkyl group or an aryl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. A group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and the like, among which a methyl group is preferred. Further, R ^4b is the same or different and represents an alkenyl group, of which a vinyl group is preferred. In addition, d6, d7, d8 and d9 all satisfy d6+d7+d8=1, d6/(d6+d7)=0.15~0.35, d8/(d6+d7+d8)=0.53~0.62, d9/(d6 +d7+d8) A positive number of 0.0005~0.03. Also, d7 can be 0. From the viewpoint of the curability of the curable resin composition, d6/(d6+d7) is preferably 0.2 to 0.3. Further, d8/(d6+d7+d8) is preferably from 0.55 to 0.60 from the viewpoint of hardness or mechanical strength of the cured product. Further, d9/(d6+d7+d8) is preferably from 0.01 to 0.025 from the viewpoint of adhesiveness or mechanical strength of the cured product. Examples of such a polyorganosiloxane include a polyorganosiloxane having a SiO _4/2 unit and a (CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 unit, and SiO _{4/. 2} units and a polyorganosiloxane such as a (CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 unit and a (CH ₃ ) ₃ SiO _1/2 unit.

In addition, the (C1) component of the curable resin composition of the present invention can be used singly or in combination of two or more.

The content (mixing amount) of the component (C1) in the curable resin composition of the present invention is not particularly limited, but is preferably, for example, the total amount of the component (A1), the component (B1), and the component (C1). 30 to 80% by weight, more preferably 40 to 70% by weight, still more preferably 45 to 75% by weight. When the content of the component (C1) is controlled within the above range, the thermal shock resistance, sulfur barrier property, and heat resistance of the cured product may be further improved.

[(D1) ingredients]

The (D1) component is a hydroquinone alkylation catalyst containing a platinum group metal. That is, the (D1) component includes a hydroquinone alkylation catalyst of at least one metal (platinum group metal) selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, and platinum. Since the curable resin composition of the present invention contains the component (D1), the hydroquinonelation reaction between the alkenyl group (including the vinyl sulfonyl group) and the hydrofluorenyl group in the curable resin composition can be efficiently performed by heating. get on.

As the component (D1), well-known or conventional hydroquinone can be used. Specific examples of the catalyst (for example, a platinum-based catalyst, a ruthenium-based catalyst, and a palladium-based catalyst) include platinum fine powder, platinum black, ruthenium oxide fine powder carrying platinum, and platinum supported thereon. A carbonyl complex of platinum such as activated carbon, chloroplatinic acid, chloroplatinic acid and a complex of an alcohol, an aldehyde or a ketone, an olefin complex of platinum, or a platinum-carbonylvinylmethyl complex. Platinum-vinylmethyl oxime complex, platinum-phosphine complex, platinum-divinyltetramethyl dioxane complex or platinum-cyclovinylmethyl oxime complex A platinum-based catalyst such as a platinum-phosphite complex or a palladium-based catalyst or a ruthenium-based catalyst containing a palladium atom or a ruthenium atom instead of a platinum atom in the platinum-based catalyst. Among them, as the component (D1), a platinum-based catalyst (hydroquinone alkylation catalyst containing platinum), particularly a platinum-vinyl methyl oxime complex or a platinum-carbonyl vinyl methyl methoxide is preferred. The complex or the complex of chloroplatinic acid with an alcohol or an aldehyde is preferred because of its good reaction rate.

In the curable resin composition of the present invention, the component (D1) can be used singly or in combination of two or more.

The content (the amount of blending) of the component (D1) in the curable resin composition of the present invention is not particularly limited, but the total amount of the alkenyl group (including a vinylidene group) contained in the curable resin composition is 1 mol. The ear (per 1 m) is preferably 1 x 10 ^-8 to 1 x 10 ^-2 mol, more preferably 1.0 x 10 ^-6 to 1.0 x 10 ^-3 mol. By setting the content of the component (D1) to 1 × 10 ^-8 mol or more, the cured product can be formed more efficiently. On the other hand, when the content of the component (D1) is 1 × 10 ^-2 mol or less, a cured product having a more excellent hue (less coloration) can be obtained.

In addition, the content (mixing amount) of the component (D1) in the curable resin composition of the present invention is not particularly limited, but is, for example, by weight The amount of the platinum group metal in the hydroquinone-based catalyst is preferably in the range of 0.01 to 1000 ppm, and more preferably in the range of 0.1 to 500 ppm. When the component (D1) is contained in the above range, the cured product can be formed more efficiently, and a cured product having a more excellent hue can be obtained.

[(E1) component]

The curable resin composition of the present invention may contain a decane coupling agent (a case referred to as "(E1) component"). In the curable resin composition of the present invention, the (E1) component is contained, and the adhesion of the cured product to the adherend is improved, and the sulfur barrier property tends to be further improved.

The component (E1) has good compatibility with the components (A1) to (D1) described above, and it is easy to obtain a uniform curable resin composition by containing the component (E1).

The (E1) component can be a known or customary decane coupling agent, and is not particularly limited, and examples thereof include 3-glycidoxypropyltrimethoxydecane and 2-(3,4- Epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, etc. Mixture; N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N -2-(Aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxy Base alkyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-amine Amino group-containing decane such as hydrochloride of ethyl ethyl-3-aminopropyltrimethoxydecane or N-(β-aminoethyl)-γ-aminopropylmethyldiethoxydecane Coupling agent Base decane, tetraethoxy decane, methyl triethoxy decane, dimethyl diethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, vinyl ginseng (methoxy ethoxylate) Base decane), phenyltrimethoxydecane, diphenyldimethoxydecane, vinyltriethoxydecane, gamma-(meth)acryloxypropyl (meth)acryloxypropyltriethoxy Baseline, γ-(meth)acryloxypropyltrimethoxydecane, γ-(meth)acryloxypropylmethyldimethoxydecane, γ-(meth)acryloxyloxy Propylmethyldiethoxydecane, decyl-propyltrimethoxydecane, decyl-propyltriethoxydecane, and the like. Among them, a cyclodecane coupling agent containing an epoxy group (particularly 3-glycidoxypropyltrimethoxydecane) is preferred. Further, the component (E1) can be used singly or in combination of two or more.

The content (the blending amount) of the component (E1) in the curable resin composition of the present invention is preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the siloxane compound contained in the curable resin composition. It is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 2 parts by weight.

In addition, the content (mixing amount) of the component (E1) in the curable resin composition of the present invention is preferably 0.01 to 15% by weight, more preferably 0.1%, based on the curable resin composition (100% by weight). ~10% by weight, more preferably 0.5 to 5% by weight. When the content of the component (E1) is 0.01% by weight or more, the adhesion to the adherend tends to be improved. On the other hand, when the content of the component (E1) is 15% by weight or less, the curing tends to be insufficient, and the sulfur barrier property and the thermal shock resistance of the cured product tend to be further improved.

[Other ingredients]

The curable resin composition of the present invention may contain the above components The ingredients (there are cases called "other ingredients"). The other components are not particularly limited, and examples thereof include a solvent, an inorganic filler, a surface-treated inorganic filler, an organic resin fine powder, a conductive metal powder, a stabilizer, a flame retardant, and a flame retardant. Reinforcing material, nucleating agent, coupling agent other than (E1) component, crosslinking agent, lubricant, wax, plasticizer, mold release agent, impact resistance improver, hue improver, fluidity improver, colorant A well-known additive such as a phosphor, a surface conditioner, a dispersant, an antifoaming agent, a defoaming agent, an antibacterial agent, a preservative, a viscosity modifier, a tackifier, and other functional additives. These can be used alone or in combination of two or more. Further, the content (doping amount) of the other components is not particularly limited and may be appropriately selected.

The curable resin composition of the present invention is not particularly limited, but is preferably a composition having a hydroquinolyl group of 1 mol and an alkenyl group present in the curable resin composition of 0.2 to 4 mol (blending composition). More preferably, it is 0.5 to 1.5 m, and even more preferably 0.8 to 1.2 m. When the ratio of the hydroquinone group and the alkenyl group is controlled to the above range, the thermal shock resistance and the sulfur barrier property of the cured product tend to be further improved.

The total amount (total content) of the oxirane compound [(A1) component, (B1) component, (C1) component) contained in the curable resin composition of the present invention is not particularly limited, but is preferably relative to hardening. The resin composition (100% by weight) is 70% by weight or more (for example, 70% by weight or more and less than 100% by weight), more preferably 80% by weight or more (for example, 80 to 99% by weight), still more preferably 90% by weight. More than weight% (for example, 90 to 99% by weight). When the total amount is 70% by weight or more, the heat resistance and transparency of the cured product tend to be further improved.

The total amount (total content) of the component (A1) and the component (C1) contained in the curable resin composition of the present invention is not particularly limited, but is preferably 40% with respect to the curable resin composition (100% by weight). ~90% by weight, more preferably 50 to 85% by weight, still more preferably 60 to 80% by weight. When the component (A1) and the component (C1) are contained in the above range, the durability and transparency of the cured product tend to be improved. On the other hand, when the total amount is 90% by weight or less, the curing property tends to be further improved.

The ratio of the component (A1) contained in the curable resin composition of the present invention to the total amount (total content; 100% by weight) of the component (A1) and the component (C1) is not particularly limited, but is preferably 10% by weight. The above (for example, 10 to 100% by weight), more preferably 15% by weight or more (for example, 15 to 90% by weight), still more preferably 20% by weight or more (for example, 20 to 80% by weight, preferably 20%) 50% by weight, particularly preferably 20 to 40% by weight). When the component (A1) is contained in the above range, the adhesion of the cured product is further lowered, and the sulfur barrier property and the thermal shock resistance tend to be improved.

The ratio of the (C1) component to the total amount (total content; 100% by weight) of the component (A1) and the component (C1) contained in the curable resin composition of the present invention is not particularly limited, but is preferably 20 to 80. %, more preferably 40 to 80% by weight, still more preferably 60 to 80% by weight. When the component (C1) is contained in the above range, thermal shock resistance tends to be improved.

The content (mixing amount) of the component (B1) in the curable resin composition of the present invention is not particularly limited, but is preferably 100% by weight based on the total amount (total content) of the component (A1) and the component (C1). The serving is 1 to 200 parts by weight, particularly preferably 10 to 100 parts by weight, most preferably 20 to 50 parts by weight. Hardening of the curable resin composition by containing the component (B1) within the above range The sex is further improved and the tendency to form a hardened material can be efficiently formed.

The ratio of the component (A1) contained in the curable resin composition of the present invention to the total amount (total content; 100% by weight) of the siloxane compound [(A1) component, (B1) component, and (C1) component] Although it is not particularly limited, it is preferably 5% by weight or more (for example, 5 to 100% by weight), more preferably 10% by weight or more, still more preferably 15 to 50% by weight, particularly preferably 15 to 30% by weight.

The total amount of the (B1) component and the (C1) component to the oxoxane compound [(A1) component, (B1) component, and (C1) component) contained in the curable resin composition of the present invention (total content; 100%) The ratio (total ratio) of the weight %) is not particularly limited, but is preferably 50% by weight or more (for example, 50 to 90% by weight), more preferably 60% by weight or more, still more preferably 65 to 85% by weight.

The ratio of the component (B1) contained in the curable resin composition of the present invention to the total amount (total content; 100% by weight) of the siloxane compound [(A1) component, (B1) component, and (C1) component] It is not particularly limited, but is preferably 10 to 40% by weight, more preferably 15 to 35% by weight, still more preferably 20 to 30% by weight.

The ratio of the component (C1) contained in the curable resin composition of the present invention to the total amount (total content; 100% by weight) of the siloxane compound [(A1) component, (B1) component, and (C1) component] It is not particularly limited, but is preferably 40 to 70% by weight, more preferably 45 to 65% by weight, still more preferably 50 to 60% by weight.

The curable resin composition of the present invention is not particularly limited, but can be stirred, for example, at room temperature (or while heating as needed). The above components are mixed to prepare. Moreover, the curable resin composition of the present invention can be used as a one-liquid system in which each component is previously mixed. For example, the composition can be used as a composition of a multi-liquid system (for example, a two-liquid system) which is used by mixing two or more components prepared in a predetermined ratio before use.

The curable resin composition of the present invention is not particularly limited, but is preferably a liquid at normal temperature (about 25 ° C). More specifically, the viscosity of the curable resin composition of the present invention at 25 ° C is preferably 300 to 20,000 mPa. s, more preferably 500~10,000 mPa. s, more preferably 1000~8000mPa. s. By the above viscosity is 300mPa. Above s, there is a tendency that the heat resistance of the cured product is further improved. On the other hand, the above viscosity is 20,000 mPa. s or less, the preparation of the curable resin composition is easy, the productivity and handleability are further improved, and the bubbles become hard to remain in the cured product, so that the productivity or quality of the cured product (especially the sealing material) is more improved. The tendency to ascend.

<hardened matter>

By curing the curable resin composition of the present invention (particularly by curing with a hydroquinone alkylation reaction), a cured product (in the case of "the cured product of the present invention") can be obtained. The condition at the time of hardening is not particularly limited, and can be appropriately selected from the conventionally known conditions. However, for example, the temperature (hardening temperature) is preferably from 25 to 180 ° C (more preferably from 60 to 150 ° C) at the point of the reaction rate. (hardening time) is preferably from 5 to 720 minutes. In addition to the heat resistance and transparency peculiar to the polyoxyalkylene-based material, the cured product of the present invention is excellent in flexibility, adhesion to the adherend, and sulfur barrier properties.

<sealing material, optical semiconductor device>

The curable resin composition of the present invention can be particularly preferably used as a sealing resin for an optical semiconductor element (LED element) in an optical semiconductor device. (a resin composition for optical semiconductor sealing) (the case of "the sealing agent of this invention" is called). The optical semiconductor device is sealed by using the sealing material of the present invention to obtain an optical semiconductor device (the case of "the optical semiconductor device of the present invention"). In other words, the optical semiconductor device of the present invention includes at least an optical semiconductor element and a sealing material for sealing the optical semiconductor element, and the sealing material is a cured product of the curable resin composition (sealing material of the present invention) of the present invention ( An optical semiconductor device of the cured product of the present invention. In addition, the sealing of the optical semiconductor element can be carried out by a known method or a conventional method, and is not particularly limited. For example, the sealing material of the present invention can be infused into a predetermined molding die and heated and cured under predetermined conditions. . The hardening temperature and the hardening time are not particularly limited, and can be appropriately set in the same range as in the case of curing the cured product.

An example of the optical semiconductor device of the present invention is shown in FIG. In Fig. 3, 100 denotes a reflector (resin composition for light reflection), 101 denotes a metal wiring (electrode), 102 denotes an optical semiconductor element, 103 denotes a bonding wire, and 104 denotes a cured product (sealing material).

<Composition for forming a lens for optical semiconductors, optical semiconductor device>

In addition, the curable resin composition of the present invention can be preferably used as a composition for forming a lens (a lens for an optical semiconductor) provided in an optical semiconductor device (a composition for forming a lens for an optical semiconductor). The case of "the composition for forming a lens of the present invention"). An optical semiconductor device can be obtained by using the composition for forming a lens of the present invention. That is, the optical semiconductor device of the present invention includes at least an optical semiconductor element and a lens, and the lens is a curable resin composition of the present invention (the lens of the present invention) An optical semiconductor device in which a cured product (cured product of the present invention) of the composition (formation) is formed. In addition, the production of the optical semiconductor lens using the lens forming composition of the present invention can be carried out by a known or customary method, and is not particularly limited. However, for example, the lens forming composition of the present invention can be injected. It is carried out by a method of heat-hardening under a predetermined condition in a predetermined molding die, or a method of heating and hardening under a predetermined condition by coating with a dispenser or the like. The hardening temperature and the hardening time are not particularly limited, and can be appropriately set in the same range as in the case of preparing the cured product. The optical semiconductor device of the present invention is not particularly limited as long as it has the above-described lens. For example, when the optical semiconductor device of the present invention has a sealing material, some or all of the aspects of the surface of the sealing material may be disposed. The aspect of the optical semiconductor element of the optical semiconductor device is sealed (that is, the cured product of the present invention doubles as a sealing material and a lens). More specifically, for example, the aspects disclosed in, for example, International Publication No. 2012/147342, JP-A-2012-188627, JP-A-2011-233605, and the like can be cited.

The curable resin composition of the present invention is not limited to the above-mentioned sealing material application (use of sealing material for optical semiconductor element) and lens forming application (for lens forming use in optical semiconductor device), and can be preferably used for, for example, an optical semiconductor. A sealing agent for a semiconductor element in a semiconductor device other than the device, a functional coating agent, a heat-resistant plastic lens, a transparent device, an adhesive (such as a heat-resistant transparent adhesive), an electrical insulating material (such as an insulating film), a laminate, and a coating agent , ink, paint, sealant, resist, composite, transparent substrate, transparent sheet, transparent film, optical component, optical lens, optical component, optical shape, electronic paper, touch panel, too Optically related or semiconductor-related applications such as solar cell substrates, optical waveguides, light guide plates, and holographic memories.

In particular, the curable resin composition of the present invention can be preferably used in current resin materials which are difficult to correspond to, and have high brightness. A short-wavelength optical semiconductor device in which a sealing material of an optical semiconductor element is coated with high heat resistance. Use of a sealing material for covering a semiconductor element in a high-voltage-resistant semiconductor device (such as a power semiconductor).

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples.

Production Example 1 (Production of Branched Chain Polyorganoalkyloxyalkylene Alkene Containing Vinylalkyl Group)

(step 1)

In a 100 mL flask equipped with a reflux tube, 6.53 g (20 mmol) of 3,3-diphenyl-1,1,5,5-tetramethyltrioxane (manufactured by Eternal Co., Ltd.) was placed in a nitrogen atmosphere. Hydroxanthene: 40 millimolar), toluene (a reagent manufactured by Wako Pure Chemical Industries, Ltd., special grade) 7.020 g, platinum (2%)-divinyltetramethyldioxane complex xylene The solution was stirred at 60 ° C and maintained at 0.0018 g [1.9 × 10 ^-4 mmol (in terms of Pt); and Wako Pure Chemical Industries, Ltd.].

Using a dropping funnel, 1.155 g (16 mmol) of ethylene, 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrioxane (manufactured by Eternal Co., Ltd.)矽alkyl: 32 millimoles) spent 50 minutes dropping.

After completion of the dropwise addition, the mixture was kept at 60 ° C for 6 hours to obtain a reaction liquid containing "linear polyorganodecyloxydecylalkylene having a hydroquinone at both ends". The obtained reaction liquid was sampled in a small amount, and the structure of the reaction product was confirmed by ¹ H-NMR. As a result, it was confirmed that there was no ¹ H-NMR signal derived from a vinyl group in the vicinity of 6 ppm (see Fig. 1).

After that, it was cooled to room temperature.

(Step 2)

In a 100 mL flask equipped with a reflux tube, 2.4800 g (5.9 mmol) and platinum (0.02%)-two were placed in a 100 mL flask equipped with a reflux tube under a nitrogen gas atmosphere (manufactured by Eternal Co., Ltd.). A solution of the vinyltetramethyldioxane complex in a xylene solution of 0.0744 g [8 × 10 ^-5 mmol (in terms of Pt); and Wako Pure Chemical Industries, Ltd.] was kept at 100 °C.

The reaction liquid obtained in the step 1 (hydroperalkyl group in the reaction liquid: 2.7 mmol) was dropped for 50 minutes using a dropping funnel.

After the completion of the dropwise addition, the reaction liquid obtained for 6 hours was sampled in a small amount, and the structure of the reaction product was confirmed by ¹ H-NMR. As a result, it was confirmed that there was no ¹ H-NMR signal derived from a hydrofluorenyl group in the vicinity of 5.02 ppm (see Fig. 2).

After that, it was cooled to room temperature.

After cooling, the solvent was removed from the reaction liquid by an evaporator, and concentrated until it was unable to detect toluene by a gas chromatograph (product name "GC-2010", manufactured by Shimadzu Corporation), and 14.2 g of a vinylidene group-containing fraction was obtained. Branch-chain polyorganoalkyloxyalkylene alkylene (completely branched polyorganoalkyloxyalkylene alkylene containing vinyl decyl group, viscosity [at 25 ° C, shear rate 20 (l / s)]: 13600 mPa. s, linear polyorganomethoxy alkoxyalkylene content: below the detection limit).

Production Example 2 (Linear polyorganoindole containing vinyl fluorenyl group) Manufacture of alkoxy decylalkylene)

In a 100 mL flask equipped with a reflux tube, 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrioxane (manufactured by Eternal Co., Ltd.) was placed under a nitrogen atmosphere. 7.694g (20 millimolar), toluene (and reagents of Wako Pure Chemical Industries, Ltd., special grade) 7.020g, platinum (2%)-divinyltetramethyldioxane complex in xylene solution (Wako Pure Chemical Industries, Ltd.) 1.9 × 10 ^-4 mmol (in terms of Pt), and stirred and maintained at 60 °C. Using a dropping funnel, 5.3221 g (16 mmol) of 3,3-diphenyl-1,1,5,5-tetramethyltrioxane (manufactured by SiSiB SILICONES Co., Ltd.) was dropped for 50 minutes.

After completion of the dropwise addition, the mixture was kept at 100 ° C for 3 hours to obtain a reaction liquid containing "linear polyorganodecyloxydecylalkylene having a vinyl fluorenyl group at both ends".

After cooling to room temperature, the solvent was removed from the reaction liquid by an evaporator, and the mixture was concentrated until it was unable to detect toluene by a gas chromatograph (product name "GC-2010" manufactured by Shimadzu Corporation). Linear polyorganoalkyl alkoxyalkylene.

Production Example 3 (Production of Branched Chain Polyorganosiloxane Containing Vinylalkyl Group)

In a 100 mL flask (reaction vessel), a thermometer, a stir bar, a reflux condenser, and a nitrogen introduction tube were installed, and 20.00 g (100 mmol) of phenyltrimethoxydecane and divinyltetramethyldioxane were introduced under a nitrogen stream. The alkane was 2.26 g (16.8 mmol) and 6.16 g of methyl isobutyl ketone, and the mixture was heated to 70 °C. 5.74 g (319 mmol) of water and 0.32 g of 5N hydrochloric acid (4.8 mmol of hydrogen chloride) were dropped for 1 hour while dropping to the above mixture, and a polycondensation reaction was carried out at 70 ° C for 6 hours. After cooling, add 50g of water and wash until water After the lower aqueous layer was made neutral, the organic layer of the upper layer was separated, and the solvent was distilled off under reduced pressure at 1 mmHg and 40 ° C to obtain 10 g of a solid product. The above product had a number average molecular weight of 600 and a weight average molecular weight of 1,300.

Example 1 (Production of Branched Chain Polyorganoalkyloxyalkylene Alkene Containing Vinylalkyl Group)

(step 1)

In a 200 mL 4-neck flask equipped with a cooling tube, a magnetic stirrer, and a thermocouple, 1,1,3,3,5,5-hexamethyltrioxane (25.10 g, 120.4 m) was added under a nitrogen atmosphere. Mole), toluene (79.10g, 858.8 millimolar), platinum (2%)-divinyltetramethyldioxane complex in xylene solution 0.0108g [1.107×10 ^-3 millimolar ( Pt conversion); Wako Pure Chemical Industries Co., Ltd.], maintaining 1,3-divinyl-1,1,3,3-tetramethyldioxane (17.89 g, 95.98 mmol) while maintaining It was dripped at 80 ° C for 50 minutes. After stirring at 80 ° C for 6 hours, a reaction liquid containing "linear polyorganodecyloxydecylalkylene having a hydroquinone at both ends" was obtained. The obtained reaction liquid was sampled in a small amount, and the structure of the reaction product was confirmed by ¹ H-NMR. As a result, it was confirmed that there was no ¹ H-NMR signal derived from a vinyl group. It was then cooled to room temperature.

(Step 2)

Under a nitrogen atmosphere, a 200 mL four-necked flask equipped with a cooling tube, a magnetic stirrer, and a thermocouple was placed with ginseng (vinyl dimethyl decyl) methyl decane (11.67 g, 33.66 mmol), a solution of platinum (2%)-divinyltetramethyldioxane complex in a solution of 0.0037 g [3.973 × 10 ^-4 mmol (in terms of Pt); and Wako Pure Chemical Industries, Ltd.] 113.2 g of the reaction liquid obtained in the step 1 (hydroquinolyl group in the reaction liquid: 39.51 mmol) was dropped while maintaining the temperature at 100 ° C for 50 minutes. After stirring at 100 ° C for 6 hours, a reaction liquid containing "branched chain polyorganodecyloxydecylalkylene having a vinyl fluorenyl group at both ends" was obtained. The obtained reaction liquid was sampled in a small amount, and the structure of the reaction product was confirmed by ¹ H-NMR. As a result, it was confirmed that there was no ¹ H-NMR signal derived from hydroquinone. The low boiling point fraction was distilled off under reduced pressure to give 44.90 g of a colorless, transparent liquid, a branched chain polyorganomethoxyalkylene alkylene group containing a vinylidene group. The content of the vinyl group was 2.52% by weight and the ethylene content was 13.4% by weight as a result of ¹ H-NMR measurement. The weight average molecular weight (Mw) was 9573 and the number average molecular weight (Mn) was 3008 by GPC measurement.

The ¹ H-NMR spectrum of the above polyorganodecyloxydecylalkylene is as follows.

¹ H-NMR (JMN ECA-500 (500 MHz, CDCl ₃ )) δ: -0.10 - 0.19 (br), 0.39 - 0.57 (br), 0.98 - 1.1 (br), 5.7 - 6.2 (br)

As an analysis machine, a nuclear magnetic resonance apparatus JNM ECA-500 (manufactured by JEOL Ltd.) was used.

Example 2

[Manufacture of Curable Resin Composition]

First, as shown in Table 1, the fully branched polyorganodecyloxydecylalkylene (20 parts by weight) containing a vinyl decyl group obtained in Production Example 1 and a decane coupling agent (3-glycidoxypropyl group) were mixed. Trimethoxy decane, trade name "XIAMETER OF S-6040", manufactured by Dow-Corning Co., Ltd.) (0.1 part by weight), and platinum (2%)-divinyltetramethyldioxane complex xylene 0.0744 g [8 × 10 ^-5 mmol (Pt conversion); Wako Pure Chemical Industries, Ltd.] (5 parts by weight) was stirred at room temperature for 1 hour to prepare a reagent.

Next, the A-based agent (25.1 parts by weight) obtained above was mixed with the branched alkyl polyorganosiloxane (60 parts by weight) and diphenyldivinyl containing the vinyl fluorenyl group obtained in Production Example 3. Tetramethyltrioxane (manufactured by Eternal Co., Ltd.) (20 parts by weight) was used as a reagent B, and the mixture was stirred at room temperature for 1 hour to obtain a curable resin composition.

[Manufacture of hardened materials and optical semiconductor devices]

The LED package (InGaN element, 3.5 mm × 2.8 mm) shown in Fig. 1 was injected into the curable resin composition obtained above, and heated at 60 ° C for 1 hour, followed by heating at 80 ° C. In the hour, the film was further heated at 150 ° C for 4 hours to produce an optical semiconductor device in which the optical semiconductor element was sealed by the cured product of the curable resin composition.

Comparative example 1

[Manufacture of Curable Resin Composition]

The completely branched polyorganodecane containing the vinyl fluorenyl group obtained in Production Example 1 was replaced with the linear polyorganoalkyloxy decylalkylene (20 parts by weight) containing a vinyl fluorenyl group obtained in Production Example 2. A curable resin composition was obtained in the same manner as in Example 2 except that the oxonium alkylene (20 parts by weight) was used.

[Manufacture of hardened materials and optical semiconductor devices]

A cured product and an optical semiconductor device were produced in the same manner as in Example 2, except that the curable resin composition obtained above was used instead of the curable resin composition obtained in Example 2.

Comparative example 2

[Manufacture of Curable Resin Composition]

The completely branched polyorganodecyloxydecylalkylene having a vinyl decyl group obtained in Production Example 1 was used instead of the phenyl siloxane having a vinyl fluorenyl group at both ends (trade name: PMV9925, manufactured by Gelest Co., Ltd.). A cured product and an optical semiconductor device were produced in the same manner as in Example 2 except for the parts by weight.

(Evaluation)

The following evaluations were performed on the curable resin composition and the optical semiconductor device obtained in Example 2, Comparative Example 1, and Comparative Example 2. The evaluation results are shown in Table 1.

(Shore D hardness)

The obtained curable resin composition is heated by a hot press to a thickness of about 3 mm. It was hardened to obtain a circular test piece (2 pieces) having a diameter of 13 mm.

For the obtained test piece (thickness: 3 mm), after 4 hours of postcure in a thermostat at 150 ° C, two test pieces were overlapped, and rubber was used. The plastic hardness tester "KORI Durometer KR-25D" measures the Shore D hardness near the center of the test piece in accordance with JIS K6753.

(SO _X barrier test)

The obtained optical semiconductor device and 0.3 g of sulfur powder (manufactured by Kishida Chemical Co., Ltd.) were placed in a 450 mL glass bottle, and the glass bottle was further placed in an aluminum case. Then, the aluminum box was placed in an oven (manufactured by Yamato Scientific Co., Ltd., model "DN-64") set at 80 ° C, and after 24 hours, the corrosion state of the silver electrode in the optical semiconductor device was observed. The color of the above electrode was silvery white before the test, but it changed to brownish brown with the progress of corrosion, and even changed to black.

In the evaluation criteria of the SO _X barrier property, the case where the silver electrode is almost invisible to discoloration is "◎", and the case where the color is slightly changed to brown or black is "○", and the color is completely changed to brown or black. Set to "△".

[Industrial availability]

The branched chain polyorganodecyloxydecanealkylene having a vinyl fluorenyl group of the present invention can be used as a raw material for an adhesive, a coating agent, a sealing material or the like in the field of electronic devices and the like.

The curable resin composition containing the branched chain polyorganodecyloxydecylalkylene having a vinyl fluorenyl group of the present invention can be used particularly as a gas barrier requiring heat resistance, transparency, flexibility, and corrosive gas. A sealing material for an optical semiconductor element (for example, an LED element, a semiconductor laser element, a solar power generation element, a CCD element, or the like).

Further, according to the method for producing a branched chain polyorganomethoxyalkylene alkylene according to the present invention, it is possible to efficiently produce a branched chain polyorganodecyloxydecanealkylene having a vinyl fluorenyl group as described above. .

Claims (18)

A method for producing a branched polyorgano siloxy silalkylene having the following steps: Step 1: a oxoxane compound having one or more vinyl fluorenyl groups in one molecule The vinyl fluorenyl group (1) of (A), the hydrofluorenyl group of the oxoxane compound (B) having two or more hydrofluorenyl groups in one molecule is more than 1 mol, and the oxoxane compound (A) is used. a step of performing an addition reaction with a oxoxane compound (B) to obtain a polyorganodecyloxy decylalkylene (H) having a hydroquinone group; and a step 2: a decyloxyalkylene (H) relative to the polyorganoalkylene oxide a hydroquinoneyl group 1 mole, a oxoxane compound (C) having 3 or more vinyl fluorenyl groups in one molecule in a manner of exceeding 1 mol, and a polyorganoquinoloxy decylalkylene (H) and a ruthenium oxide The alkyl compound (C) is subjected to an addition reaction to obtain a branched chain polyorganoalkyloxydecylalkylene (V) having a vinyl fluorenyl group. A method for producing a branched chain polyorganoalkyloxy decylalkylene according to claim 1, wherein in step 2, a polyorganodecyloxydecylalkylene (H) is added to the oxirane compound (C). An addition reaction of a polyorganoquinolyloxyalkylene (H) and a siloxane compound (C) is carried out. A method for producing a branched chain polyorganoalkyloxy decylalkylene according to claim 1 or 2, wherein in step 1, the oxirane compound (A) and the oxirane compound (B) are reacted to a vinyl decyl group. Disappeared. The method for producing a branched chain polyorganoalkyloxy decylalkylene according to any one of claims 1 to 3, wherein the oxoxane compound (A) is a compound represented by the following formula (a), (wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and s represents an integer of 0 or more). The method for producing a branched chain polyorganoalkyloxy decylalkylene according to any one of claims 1 to 4, wherein the oxoxane compound (B) is a compound represented by the following formula (b), (wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and t is an integer of 0 or more). The method for producing a branched chain polyorganoalkyloxy decylalkylene according to any one of claims 1 to 5, wherein the oxoxane compound (C) is a compound represented by the following formula (c), (wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and u is an integer of 1 to 10). The method for producing a branched chain polyorganoalkyloxy decylalkylene according to any one of claims 1 to 6, wherein the branched chain polyorganoalkyloxy decylalkylene (V) having a vinyl fluorenyl group is a compound having a structure in which all or a part of hydrogen atoms of a hydrofluorenyl group of a polyorganoquinolyloxyalkylene (H) having a hydroquinone group is substituted with a group represented by the following formula (d), (wherein R ¹ and R ² are the same or different and represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and u is an integer of 1 to 10; and the left end of the formula (d) is agglomerated Si bonding of an organodecyloxydecylalkylene). A branched chain polyorganomethoxyalkoxyalkylene having a vinyl fluorenyl group obtained by the production method according to any one of claims 1 to 7. The branched chain polyorganoalkyloxy decylalkylene having the vinyl fluorenyl group of claim 8 has a viscosity [at 25 ° C, shear rate of 20 (l/s)] of 1500 to 100 000 mPa. s. A branched chain polyorganoalkyloxy decylalkylene having a vinyl fluorenyl group as claimed in claim 8 or 9, wherein the linear polyorganoalkyloxy decylalkylene having a vinyl fluorenyl group has a content of zero. ¹ H- the requested item as ethylene having 8-10 branched chain alkyl poly silicon organosilane silicon group alkenyl group any of which by a ¹ H resonance frequency of 500MHz, the measurement conditions of temperature 25 ℃ The hydrogen atom bonded to the ruthenium atom was below the detection limit by NMR. A curable resin composition comprising the following (A1) component, (B1) component, (C1) component, and (D1) component: (A1): having a vinyl decane according to any one of claims 8 to 11. Branched chain polyorganoalkyloxyalkylene alkene; (B1): polyorganooxynonane having one or more hydrofluorenyl groups in the molecule and having no aliphatic unsaturation; (C1): molecule a branched chain polyorganosiloxane having one or more alkenyl groups; (D1): a hydroquinone alkylation catalyst containing a platinum group metal. The curable resin composition of claim 12, which further comprises the following (E1) component: (E1): a decane coupling agent. A cured product obtained by hardening a curable resin composition as claimed in claim 12 or 13. The curable resin composition of claim 12 or 13, which is a resin composition for sealing a photo-semiconductor. The curable resin composition of claim 12 or 13, which is a resin composition for forming a lens for an optical semiconductor. An optical semiconductor device comprising an optical semiconductor element and a sealing material for sealing the optical semiconductor element, the sealing material being a cured product of the curable resin composition of claim 15. An optical semiconductor device comprising an optical semiconductor element and a lens which is a cured product of the curable resin composition of claim 16.