TWI475050B - Organopolysiloxane, method for producing the same and curable resin composition containing the same - Google Patents

Description

Organic polyoxane, method for producing the same, and curable resin composition containing organic polyoxyalkylene

The present invention relates to an organopolysiloxane, a method for producing the same, and a curable resin composition containing the above organopolysiloxane.

Conventionally, it has been known that an epoxy resin composition using an acid anhydride-based curing agent can form a transparent cured product, and is suitable as a sealing material for an optical semiconductor element such as a light-emitting diode or a photodiode.

It is organic, for example, with a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a methyl-3,4-epoxycyclohexanecarboxylic acid (3',4'-epoxycyclohexyl) ester. An epoxy resin composition containing an epoxy resin as a main component of the resin skeleton can be used in the field of optical semiconductor elements.

However, in recent years, with the advancement of the high performance of the optical semiconductor, the sealing material for the optical semiconductor element is required to have more excellent heat resistance, light resistance, and the like, and the epoxy resin composition generally known in the prior art is The characteristics are not sufficient.

In view of the above problems, various proposals have been made in various resin compositions for optical semiconductor applications.

For example, a thermosetting resin composition for photo-semiconductor use in which a specific polyoxymethylene composition is hardened by a hydrogenation reaction is proposed (refer to Patent Document 1).

At the same time, a technique of using a specific polyoxyl composition having improved hardness as a photo-semiconductor is also proposed (refer to Patent Document 2).

Further, there has been proposed a composition containing an organic polysiloxane having a specific structure as an optical semiconductor (refer to Patent Document 3).

In addition, there has also been proposed a technique of using a polyoxymethylene composition containing a methacryloxy group as a photo-semiconductor (refer to Patent Document 4).

In addition, there has been proposed a technique in which an epoxy resin composition is used as a photosensitive coating material and ink, and an alicyclic epoxy compound and a vinyl ether compound are used in this technique (see, for example, Patent Documents 5 and 6).

In addition, there is a proposal to control the mechanical properties of the cured product by using a specific phenol resin in a material in which an epoxy compound and a vinyl ether compound are used in combination (refer to Patent Document 7).

[Previous Technical Literature]

Patent literature

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-1358

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-274185

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-201851

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-131009

[Patent Document 5] Japanese Patent Laid-Open No. Hei 6-298911

[Patent Document 6] Japanese Patent Laid-Open No. Hei 9-328634

[Patent Document 7] Japanese Patent No. 4235698

However, the techniques of the previously proposed above still have the following problems.

The thermosetting resin composition proposed in Patent Document 1 is resistant Although the heat yellowing property and the light resistance are good, the hardness of the cured product is still low, so that it is liable to be damaged and difficult to use. At the same time, since the gas barrier properties and the adhesion to the substrate are also low, it is not applicable to the use of the sealing material for optical semiconductors.

In the polyfluorene composition proposed in Patent Document 2, a phenyl group is used to increase the hardness thereof, but the phenyl group is responsible for reducing heat yellowing resistance and light resistance, and therefore, the use of the sealing material for an optical semiconductor is also Not suitable for use.

The composition proposed in Patent Document 3 is excellent in hardness, adhesion, and gas barrier properties, but the hetero-cyanate forming the basic skeleton is a cause of reducing heat-resistant yellowing and light resistance, and thus is in the light. The use of a semiconductor sealing material is not necessarily satisfactory.

The polyfluorene-oxygen composition proposed in Patent Document 4 is excellent in heat-resistant yellowing and light resistance, and has no stress-relieving stress in the molecular structure, and is subjected to an environmental change test such as a thermal shock test. When the hardened material is broken. That is, in the use of optical semiconductors, the resin is broken when the ON-OFF of the switch is repeatedly operated, which is related to the disconnection problem. At the same time, it has not been able to meet the degree of gas barrier properties and adhesion to the substrate.

The materials proposed in Patent Documents 5 to 7 are excellent in gas barrier properties and adhesion, but are all epoxy resin compositions which are prone to yellowing, so they have not been able to reach the point of heat yellowing and light resistance. The degree of satisfaction.

As described above, the resin composition previously proposed has not been able to sufficiently satisfy the optical semiconductor in terms of hardness, gas barrier properties, heat yellowing resistance, light resistance, thermal shock resistance, and adhesion to a substrate. Use and A hardened material that is well balanced to the extent required in the field of coating materials and the like.

That is, the object of the present invention is to provide all the characteristics that can sufficiently satisfy the hardness, gas barrier properties, heat yellowing resistance, light resistance, thermal shock resistance, and adhesion to a substrate, particularly in optical semiconductor applications. An organic polysiloxane having a cured product which is well balanced, a method for producing the same, a curable resin composition using the same, and a die-bonding material for optical semi-conducting, which are required for the above characteristics, A coating material, a curable resin composition for nano-imprinting, and an ink.

As a result of deliberate review of the above problems, the present inventors have found that the above object can be attained by a curable resin composition containing an organic polysiloxane having a specific structure, and the present invention has been completed.

That is, the present invention is as follows.

〔1〕

An organopolyoxane having one or more unsaturated bond-containing groups in one molecule and having the constituent units F1, M1, and T represented by the following general formulae (1) to (3) (i) A constituent unit of any combination of F1 and M1, (ii) F1 and T, (iii) F1, M1, and T.

(In the above formulae (1) to (3), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or not Any one selected from the group consisting of a substituted aryl group and a substituted or unsubstituted aralkyl group; R ² represents a group having 2 to 10 carbon atoms and an unsaturated bond; and X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; Y represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and a, b, and c each independently represent an integer of 1 or more. Among them, F1 represents a constituent unit of a cyclic organopolyoxane.

〔2〕

The organopolyoxane according to the above [1], wherein a, b, and c satisfy the following formula (I) in the above formulae (1) to (3).

0.1≦a/(b+c)≦5.........(I)

[3]

The organopolyoxane according to the above [1] or [2], wherein R ² is an acryloxy group or a methacryloxy group in the constituent unit F1 represented by the above formula (1).

[4]

The organopolyoxane according to any one of the above-mentioned items (1) to (3), which comprises any of the constituent units represented by the following general formulae (4) to (6): D1, D2, and D3. .

D1: (R ¹ ₂ SiO ₂ / ₂ ).........(4)

D3: (R ¹ ₂ SiO ₂ / ₂ ) (6) (In the above formulae (4) to (6), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted Or any one selected from the group consisting of an unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group; X represents a carbon number of 2 to 10 Hydrocarbyl group.

Here, D1 and D2 represent a constituent unit of a cyclic organopolyoxane, and D3 represents a constituent unit of a chain organopolysiloxane. )

[5]

The organopolyoxane according to any one of the above [1] to (4), which comprises a constituent unit S represented by the following formula (7), and the composition represented by the formula (7) The content of the unit can satisfy the following formula (II) with respect to the content of the constituent unit F1 represented by the above formula (1).

d/a≦0.1.........(II)

(In the above formula (7), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. And any one selected from the group consisting of a substituted or unsubstituted aralkyl group, wherein the constituent unit S represents a constituent unit of a cyclic or chain organopolyoxane.

[6]

The organic polyoxosiloxane according to any one of the above aspects, wherein the constituent unit F1 represented by the above (1) is contained as the constituent unit containing the above R ² .

[7]

The organopolyoxane according to any one of the above-mentioned [1], wherein the composition unit F1 represented by the above formula (1) and the composition represented by the following formula (8) are contained. The unit F2 is a constituent unit containing the above R ² . (In the following general formula (8), R ²¹ is contained in the above R ² .)

(In the above formula (8), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. And any one selected from the group consisting of substituted or unsubstituted aralkyl groups; R ²¹ represents an acryloxy group or a methacryloxy group; and Y represents a divalent hydrocarbon group having 2 to 10 carbon atoms.

Wherein F2 represents a constituent unit of a chain organopolyoxane. )

〔8〕

An organopolyoxane which further contains 0.1 to 100 parts by mass of the following formula with respect to 100 parts by mass of the organopolyoxane according to any one of the above [1] to [7] ( 9) A cyclic organopolyoxane as shown.

(In the above formula (9), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. And any one selected from the group consisting of substituted or unsubstituted aralkyl groups; R ²¹ represents an acryloxy group or a methacryloxy group; X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and e represents 1 or more An integer; f represents an integer greater than 0; e+f represents an integer from 3 to 20.)

〔9〕

An organopolyoxane which further contains 0.01 to 1000 parts by mass of the following formula with respect to 100 parts by mass of the organopolyoxane shown in any one of the above [1] to [8] ( 10) The compound shown.

(In the above formula (10), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. And any one selected from the group consisting of a substituted or unsubstituted aralkyl group; R ²¹ represents an acryloxy group or a methacryloxy group; X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and g represents 1 or more An integer; h represents an integer greater than 0; i represents an integer from 0 to 20.)

[10]

The organopolyoxane according to any one of the above [1] to (9), which contains a cyclic organopolyoxane represented by the following formula (9) and a formula (10) The compound shown, (In the above formula (9), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. And any one selected from the group consisting of substituted or unsubstituted aralkyl groups; R ²¹ represents an acryloxy group or a methacryloxy group; X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and e represents 1 or more An integer; f represents an integer greater than 0; e+f represents an integer from 3 to 20.)

(In the above formula (10), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. And any one selected from the group consisting of a substituted or unsubstituted aralkyl group; R ²¹ represents an acryloxy group or a methacryloxy group; X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and g represents 1 or more An integer; h represents an integer greater than 0; i represents an integer from 0 to 20.)

The peak intensity obtained by the matrix-assisted free time-of-flight mass spectrometry is calculated by the following formula (III), and the obtained compound (WB) represented by the above formula (10) is compared with the above formula (9). The ratio of the compound content [WA] shown: the value of [WB] / [WA] is 0.1 or more and 20.0 or less.

[Number 1] [WB] / [WA] = the intensity of the peak corresponding to the mass of the structure of the general formula (10) and the total mass of the sodium mass 23 / the mass of the structure conforming to the formula (9) and the sodium mass 23 The intensity of the peak corresponding to the total mass.........(III)

[11]

The organopolyoxane according to any one of the above aspects, wherein the above R ¹ is an alkyl group having 1 to 10 carbon atoms.

[12]

The organopolyoxane according to any one of the above [1], wherein the above R ¹ is a methyl group.

[13]

The organopolyoxane according to any one of the above [1], wherein the above R ² contains an acryloxy group or a methacryloxy group, and the propylene oxime group or the methacrylium group The functional group equivalent of the oxy group is from 210 to 2100 g/mole.

[14]

The organopolyoxane according to any one of the above [1] to [13], which has a weight average molecular weight of 700 to 5,000,000 and a viscosity at 25 ° C of 50 to 1,000,000 mPa. s.

[15]

A method for producing an organopolyoxane according to any one of the above [1] to [14], which has the following steps: the following formula (11) The hydrogenated polyoxyalkylene (a1) and the hydrogenated polyoxyalkylene (a2) and i) having one or more hydrogen atoms directly bonded to a halogen atom are directly bonded to the ruthenium. a vinyl group-containing vinyl polyorganosiloxane (b1) of an atom or a polyoxyalkylene (b2) having two or more hydroxyl groups directly bonded to a ruthenium atom, and ii) having two or more in one molecule The addition reaction of the saturated bond organic compound (c) is carried out in the presence of a hydrazine hydrogenation catalyst (d). (In the above formula (11), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. And any one selected from the group consisting of substituted or unsubstituted aralkyl groups; j represents an integer of 1 or more; k represents an integer of 0 or more; and j+k represents an integer of 3 to 20.).

[16]

The method for producing an organopolyoxane according to the above [15], wherein the step of performing the addition reaction comprises the steps of: preparing a reaction liquid; and adding a rhodium hydrogenation catalyst (d) to the reaction liquid. And the reaction solution contains the hydrogenated polyoxyalkylene (a1) represented by the above formula (11), and the above-mentioned hydrogenated polyfluorene having one or more hydrogen atoms directly bonded to the above-mentioned germanium atom. An alkane (a2), the above-mentioned vinyl group-containing organopolyoxane (b1) having two or more vinyl groups bonded directly to a ruthenium atom, and an organic compound having two or more unsaturated bonds in one molecule (c) Or an organic compound (c) having two or more polyoxyalkylenes (b2) directly bonded to a hydroxyl group of a halogen atom and two or more unsaturated bonds in one molecule.

[17]

The method for producing an organopolyoxane according to the above [15], wherein the step of performing the addition reaction is carried out in the following steps: a step of preparing a reaction liquid containing the above formula (11) The hydrogenated polyoxyalkylene (a1) shown, which has two or more hydrogenated polyoxyalkylenes (a2) having one or more hydrogen atoms bonded directly to the above-mentioned germanium atom, and one or more molecules Saturated bond of organic compound (c); In the step of forming an adduct, the hydrogenation catalyst (d) is added to the reaction liquid to form a hydrogenated polyoxyalkylene (a1) represented by the above formula (11), and one or more of the above-mentioned ones are required. a step of directly bonding a hydrogenated polyoxyalkylene (a2) to a hydrogen atom of a halogen atom and an addition product of an organic compound (c) having two or more unsaturated bonds in one molecule; and an addition step in the above reaction The above-mentioned vinyl group-containing organopolyoxane (b1) having two or more vinyl groups directly bonded to a ruthenium atom or a polyoxyxane having two or more hydroxyl groups directly bonded to a ruthenium atom is added to the liquid ( B2).

[18]

A curable resin composition containing 100 parts by mass of the organopolysiloxane according to any one of the above [1] to [14] and 0.5 to 10 parts by mass of a thermal radical generator.

[19]

A curable resin composition containing 100 parts by mass of the organic polysiloxane of any one of the above [1] to [14] and 0.5 to 20 parts by mass of a photo radical generator.

[20]

The sclerosing resin composition according to any one of the above-mentioned [1] to [14], wherein the organopolysiloxane according to any one of the above [1] to [14], It contains 0.1 to 10 parts by mass of a decane coupling agent.

〔twenty one〕

The curable resin group according to any one of the above [18] to [20] The (d) hydrazine hydrogenation catalyst is further contained in an amount of 0.001 part by mass or less based on 100 parts by mass of the organopolysiloxane of any one of the above [1] to [14].

〔twenty two〕

The sclerosing resin composition according to any one of the above [1] to [14], wherein the organic polyoxo oxide according to any one of the above [1] to [14] The alkane further contains 0.1 to 500 parts by mass of an inorganic oxide.

〔twenty three〕

A sealing material for a photo-semiconductor, which comprises the curable resin composition according to any one of the above [18] to [22].

〔twenty four〕

A die bonding material for an optical semiconductor, comprising the curable resin composition according to any one of the above [18] to [22].

[25]

A coating material comprising the curable resin composition according to any one of the above [18] to [22].

[26]

A curable resin composition for a nano-imprint, comprising the curable resin composition according to any one of the above [18] to [22].

[27]

An ink composition comprising the curable resin composition according to any one of the above [18] to [22], and a coloring agent.

[28]

An optical semiconductor package is formed by using a sealing material for an optical semiconductor according to the above [23].

According to the present invention, it is possible to obtain all the characteristics required for the use of the optical semiconductor in terms of hardness, gas barrier properties, heat yellow resistance, light resistance, thermal shock resistance, and adhesion to the substrate. An organic polyoxyalkylene which is well-balanced and sufficiently satisfactorily cured, and a curable resin composition using the same.

According to the present invention, it is also possible to provide a sealing material for an optical semiconductor having the above characteristics, a wafer bonding material for an optical semiconductor, a coating material, a curable resin composition for nanoimprint printing, a material useful in the field of ink printing, and the like. An optical semiconductor package formed of a sealing material for an optical semiconductor.

Hereinafter, embodiments of the present invention (hereinafter referred to as "this embodiment") will be described in detail.

However, the present invention is not limited to the following description, and various modifications may be made without departing from the spirit and scope of the invention.

[organic polyoxane]

The organopolyoxane of the present embodiment has a group containing one or more unsaturated bonds in one molecule, and has constituent units F1, M1 and T represented by the following general formulae (1) to (3). (i) F1 and M1, (ii) F1 and T, (iii) an organic polyoxane of a constituent unit of any combination of F1, M1 and T.

In the above formulae (1) to (3), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted group. Any one selected from the group consisting of an aryl group and a substituted or unsubstituted aralkyl group; R ² represents a group having 2 to 10 carbon atoms and an unsaturated bond; and X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; A divalent hydrocarbon group having 2 to 10 carbon atoms; a, b, and c each independently represent an integer of 1 or more. Wherein F1 represents a constituent unit of the cyclic organopolyoxane.

The organopolyoxane of the present embodiment is an organic polyoxoxane containing any constituent units represented by the following general formulae (4) to (6): D1, D2, and D3 from the viewpoint of light resistance. It is better.

D1: (R ¹ ₂ SiO ₂ / ₂ ).........(4)

D3: (R ¹ ₂ SiO ₂ / ₂ ).........(6)

In the above formulae (4) to (6), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted group. Any one selected from the group consisting of an aryl group and a substituted or unsubstituted aralkyl group; X represents a divalent hydrocarbon group having 2 to 10 carbon atoms.

Here, D1 and D2 represent a constituent unit of a cyclic organopolyoxane, and D3 represents a constituent unit of a chain organopolysiloxane.

The organopolysiloxane of the present embodiment is preferably a constituent unit S represented by the following formula (7), and the content of the constituent unit S represented by the formula (7) is relative to the above formula (1). The content of the constituent unit F1 shown is an organic polyoxane of the following formula (II).

d/a≦0.1.........(II)

When many of the constituent units S represented by the following formula (7) are contained, there is a concern that the SiH reacts with the unsaturated bond to colloidal upon storage of the solvent or during storage, and the product is stable in productivity and storage stability. From the viewpoint of the nature, it is preferred to satisfy the above formula (II).

In the above formula (7), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, and Any of the group of substituted or unsubstituted aralkyl groups.

The constituent unit S represents a constituent of a cyclic or chain organopolyoxane Bit.

In addition, the organic polysiloxane of the present embodiment contains the organic component of the constituent unit F1 represented by the above formula (1) as a constituent unit containing the above R ² from the viewpoint of the hardness of the cured product. A siloxane is preferred. This is because the crosslinking density of the cured product can be increased only when the unit F1 is formed.

Further, the above-mentioned "constituting unit containing R ² " includes a constituent unit of R ²¹ in the subordinate concept of R ² and also includes the following general formulae (8) to (10). In other words, the above-mentioned "constituting unit constituting the above-mentioned R ² includes only the constituent unit F1 represented by the above formula (1)", and means "having a constituent unit F1 represented by the general formula (1). However, the formula (8) to (10)" containing the constituent units of the following R ^{21 is} not contained.

In addition, the organic polysiloxane of the present embodiment contains the composition represented by the above formula (1) from the viewpoint of workability at a low viscosity of the curable resin composition containing the organopolysiloxane. The organopolysiloxane having the unit F1 and the constituent unit F2 represented by the following formula (8) is preferred.

This is because when one part of the tetrafunctional SiH is substituted with the difunctional SiH, the formation of the crosslinked structure of the decane can be suppressed, so that the viscosity can be reduced.

In the above formula (8), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, and Any one selected from the group consisting of substituted or unsubstituted aralkyl groups; R ²¹ represents an acryloxy group or a methacryloxy group; and Y represents a divalent hydrocarbon group having 2 to 10 carbon atoms. Wherein F2 represents a constituent unit of a chain organopolyoxane.

The organopolysiloxane of the present embodiment is a cyclic organopolyoxane represented by the following formula (9), and when the organopolyoxane component other than the following formula (9) is 100 parts by mass It is preferably further contained in an amount of 0.1 to 100 parts by mass. The structure containing the following general formula (9) can increase the crosslinking density of the cured product, thereby improving hardness and gas barrier properties.

The content of the cyclic organopolyoxane represented by the following formula (9) is preferably from 1 to 90 parts by mass, more preferably from 5 to 80 parts by mass.

In the above formula (9), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, and Any of the group of substituted or unsubstituted aralkyl groups. R ²¹ represents an acryloxy group or a methacryloxy group. X represents a divalent hydrocarbon group having 2 to 10 carbon atoms. e represents an integer of 1 or more. f represents an integer of 0 or more. e+f represents an integer from 3 to 20.

Meanwhile, the organopolyoxane of the present embodiment is further a compound represented by the following formula (10), wherein the organopolyoxane component is 100 mass. When it is a part, it is preferable to contain 0.01 to 1000 mass parts.

When the compound of the formula (10) is contained therein, flexibility can be imparted to the cured product, so that the thermal shock resistance can be improved.

The content of the compound represented by the following formula (10) is preferably from 0.03 to 900 parts by mass, more preferably from 0.05 to 750 parts by mass.

In the formula (10), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group and a substitution. Any one selected from the group consisting of unsubstituted aralkyl groups. R ²¹ represents an acryloxy group or a methacryloxy group. X represents a divalent hydrocarbon group having 2 to 10 carbon atoms. g represents an integer of 1 or more; h represents an integer of 0 or more. i represents an integer from 0 to 20.

Further, the organopolysiloxane of the present embodiment contains the cyclic organopolyoxane represented by the above formula (9) and the above-mentioned viewpoint from the viewpoint of balance between hardness, gas barrier properties and cold shock resistance. a compound represented by the formula (10), and the peak intensity obtained by the matrix-assisted free time-of-flight mass spectrometry is calculated by the following formula (III), and the compound represented by the above formula (10) The ratio of [WB] to the compound content [WA] represented by the above formula (9): [WB] / [WA] is 0.1 or more and 20.0 or less. Preferably, it is more preferably 0.3 or more and 18 or less, and more preferably 0.5 or more and 15 or less.

[Number 2] [WB] / [WA] = the intensity of the peak corresponding to the mass of the structure of the general formula (10) and the total mass of the sodium mass 23 / the sum of the mass of the structure of the general formula (9) and the mass of the sodium 23 The intensity of the peak corresponding to the quality.........(III)

Wherein R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or Any one selected from the group of unsubstituted aralkyl groups.

Examples of R ¹ include methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclopentyl, cyclohexyl and octyl groups. An alkyl group having 1 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group or a cyclodecyl group; a phenyl group, a tolyl group, and a second group; An aryl group such as a tolyl group, a cumyl group or a trimethylphenyl group; an aralkyl group such as a benzyl group, a phenethyl group or a phenylpropyl group; or a part or all of a hydrogen atom bonded to a carbon atom of the group; A hydroxypropyl group, a cyanoethyl group, a 1-chloropropyl group, a 3,3,3-trifluoropropyl group or the like substituted with a hydroxyl group, a cyano group, a halogen atom or the like.

In the case of R ¹ , from the viewpoint of light resistance, an alkyl group having 1 to 10 carbon atoms is preferred.

Meanwhile, R ¹ is more preferably a methyl group from the viewpoints of heat-resistant yellowing and light resistance of the organopolysiloxane and the curable resin composition of the present embodiment.

As described above, R ² represents a group having 2 to 10 carbon atoms and containing an unsaturated bond.

Examples thereof include vinyl, allyl, isopropenyl, 3-butenyl, 2-methylpropenyl, 4-pentenyl, 5-hexenyl, 6-heptenyl, 7- An unsaturated chain hydrocarbon group such as an octenyl group, an 8-alkenyl group or a 9-nonenyl group; an unsaturated cyclic hydrocarbon group such as a cyclohexenyl group or a nortenyl group; and an ether bond such as a vinyl ether group or an allyl ether group; An unsaturated hydrocarbon group such as a cyclohexenyl group; an unsaturated fatty acid group such as an acryloxy group or a methacryloxy group;

In the viewpoint of the reactivity in the formation of a curable resin composition to be described later, that is, the thermal curing or the photocuring is easy to carry out and the reaction proceeds rapidly, the acryloxy group represented by the following formula (12), Or a methacryloxy group represented by the following formula (13) (these are collectively referred to as (meth) acryloxy).

As described above, X represents a divalent hydrocarbon group having 2 to 10 carbon atoms.

Examples thereof include: -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ -, -(CH ₂ ) ₆ -, -(CH _{2 8} -, -(CH ₂ ) ₁₀ -, -CH(CH ₃ )CH ₂ -, -C(CH ₃ ) ₂ -, etc., especially from -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ - The material of -(CH ₂ ) ₄ - is preferred because it is easy to obtain and react, that is, it is easy to carry out thermal hardening or photohardening and rapid reaction.

As described above, Y represents a divalent hydrocarbon group having 2 to 10 carbon atoms.

Examples thereof include: -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ -, -(CH ₂ ) ₆ -, -(CH _{2 8} -, -(CH ₂ ) ₁₀ -, -CH(CH ₃ )CH ₂ -, -C(CH ₃ ) ₂ -, etc., especially from -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ - The material of -(CH ₂ ) ₆ - is preferred because it is easy to obtain and react, that is, it is easy to carry out thermal hardening or photohardening and rapid reaction.

As described above, the organopolysiloxane of the present embodiment has the constitution of any combination of (i) F1 and M1, (ii) F1 and T, (iii) F1, M1 and T. unit.

The organopolysiloxane of the present embodiment preferably satisfies the following general formula (1) in a, b, and c of the above formulas (1) to (3).

0.1≦a/(b+c)≦5.........(I)

The value of a/(b+c) of the above formula (1) is preferably 0.1 or more from the viewpoint of the hardness of the cured product of the curable resin composition of the organopolysiloxane described later. From the viewpoint of heat-resistant yellowing and light resistance, it is preferably 5 or less.

In this case, the preferred range is 0.12 or more and 4 or less, and more preferably 0.15 or more and 3 or less. Specific examples of the organopolysiloxane of the present embodiment include the following compounds.

In the above formulae (13) to (31), m represents an integer of 0 to 2000; n represents an integer of 0 to 20; and r represents an integer of 0 to 20.

The organopolysiloxane of the present embodiment is preferably ^one in which R ¹ is a methyl group from the viewpoint of light resistance, and the above R ² is an acryloxy group or a methacrylic group from the viewpoint of reactivity. The oxime is preferred; from the viewpoint of easy availability of the starting material, it is preferred that Y is -(CH ₂ ) ₃ - or -(CH ₂ ) ₄ - or -(CH ₂ ) ₆ -.

In the organopolysiloxane of the present embodiment, the R ² in the constituent unit F1 represented by the above formula (1) contains an acryloxy group or a methacryloxy group, and the organic polyfluorene in the embodiment. The functional group equivalent of the all-acryloxy group or the methacryloxy group contained in the oxyalkylene is derived from the viewpoint of heat-resistant yellowing and light resistance of the cured product of the curable resin composition of the organopolysiloxane described later. It is preferably 210 g/mol or more, and more preferably 2000 g/mol or less from the viewpoint of hardness. From this point of view, the functional group equivalent of the acryloxy group or the methacryloxy group is preferably 250 g/mol or more and 1500 g/mol or less, more preferably 300 g/mol or more and 1000 g/mol or less.

Further, the functional group equivalent of the acryloxy group or the methacryloxy group can be measured by the method described in the examples below.

The weight average molecular weight of the organopolysiloxane of the present embodiment is preferably 700 or more from the viewpoint of the thermal shock resistance of the cured product of the curable resin composition of the organopolysiloxane described later; From the viewpoint of hardness, it is preferably 5,000,000 or less, more preferably 1,000 or more and 3,000,000 or less, and still more preferably 1,500 or more and 1,000,000 or less.

Further, the organopolysiloxane of the present embodiment has a viscosity at 25 ° C from the organopolyoxane, and is 50 mPa from the viewpoint of dispersion stability of the phosphor and the color former. Above s is better; from the point of view of workability, it is 1000000mPa. The following is better. The viscosity is again 80mPa. s above 500000mPa. s below is better, 100mPa. s above 100000mPa. s is better below.

The weight average molecular weight and viscosity of the organopolyoxane can be measured by the methods described in the examples below.

[Method for Producing Organic Polyoxane]

The organopolyoxane of the present embodiment is a hydrogenated polyadenine (a1) represented by the following formula (11) and a hydrogenation of one or more hydrogen atoms directly bonded to a ruthenium atom as required. Polyoxane (a2), i) a vinyl group-containing organopolyoxane (b1) having two or more vinyl groups directly bonded to a ruthenium atom or a polyoxy siloxane (b2) having two or more hydroxyl groups directly bonded to a ruthenium atom, And ii) an addition reaction of the organic compound (c) having two or more unsaturated bonds in one molecule, and is produced by carrying out the reaction of the hydrazine hydrogenation catalyst (d).

R ¹ in the above formula (11) represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, and Any one selected from the group consisting of substituted or unsubstituted aralkyl groups; j represents an integer of 1 or more; k represents an integer of 0 or more; and j+k represents an integer of 3 to 20.

An example of the hydrogenated polyoxyalkylene (a1) having at least one SiH group in one molecule represented by the above formula (11) is as shown in the following formula (32), (33) or (34). Compound.

The above-mentioned hydrogenated polyoxyalkylene oxide (a1) may be used alone or in combination of two or more.

Examples of the hydrogenated polyoxyalkylene (a2) having one or more hydrogen atoms bonded directly to a halogen atom may be as shown in the following formula (35), (36), (37) or (38). Compound.

In the case of having one or more hydrogenated polyoxyalkylenes directly bonded to a hydrogen atom of a halogen atom, the above (a1) and the above (a2) may be combined in an arbitrary ratio to adjust the hardness and gas barrier properties of the cured product. The viscosity of the curable resin composition containing the organopolysiloxane of the present embodiment.

When the ratio of the above (a1) is increased, the hardness and gas barrier properties of the cured product can be increased. When the ratio of the above (a2) is increased, the curable resin composition containing the polysiloxane of the present embodiment can be reduced. Viscosity makes operation easy.

The vinyl group-containing organopolyoxane (b1) having two or more vinyl groups directly bonded to the above-mentioned ruthenium atom can be exemplified as follows. For example: CH ₂ =CHSi(Me) ₂ O-Si(Me) ₂ CH=CH ₂ , CH ₂ =CHSi(Me) ₂ O-Si(Me) ₂ O-Si(Me) ₂ CH=CH ₂ , CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₂ -Si(Me) ₂ CH=CH ₂ , CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₃ -Si (Me) ₂ CH=CH ₂ , CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₆ -Si(Me) ₂ CH=CH ₂ , CH ₂ =CHSi(Me) ₂ O-( Si(Me) ₂ O) ₈ -Si(Me) ₂ CH=CH ₂ , CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₁₁ -Si(Me) ₂ CH=CH ₂ ,CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₁₂ -Si(Me) ₂ CH=CH ₂ , CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₂₀ -Si (Me) ₂ CH=CH ₂ , CH ₂ =CHCH ₂ Si(Me) ₂ O-Si(Me) ₂ CH ₂ CH=CH ₂ and CH ₂ =CHCH ₂ Si(Me) ₂ O-Si(Me) ₂ O-Si(Me) ₂ CH ₂ CH=CH ₂ .

In the above formula, Me represents a methyl group.

The vinyl group-containing organopolyoxane (b1) having two or more vinyl groups bonded directly to a ruthenium atom may be used alone or in combination of two or more.

The polyoxane (b2) having two or more hydroxyl groups directly bonded to the above-mentioned ruthenium atom can be exemplified as follows. For example: HO-Si(Me) ₂ O-Si(Me) ₂ -OH, HO-Si(Me) ₂ O-Si(Me) ₂ O-Si(Me) ₂ -OH, HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₂ -Si(Me) ₂ -OH, HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₃ -Si(Me) ₂ -OH, HO- Si(Me) ₂ O-(Si(Me) ₂ O) ₆ -Si(Me) ₂ -OH, HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ - OH, HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₁₁ -Si(Me) ₂ -OH, HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₁₂ -Si( Me) ₂ -OH, HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₂₀ -Si(Me) ₂ -OH.

In the above formula, Me represents a methyl group.

The polyoxyalkylene (b2) having two or more hydroxyl groups directly bonded to the above-mentioned ruthenium atom may be used alone or in combination of two or more.

The organic compound (c) having two or more unsaturated bonds in the above one molecule is represented by the following formula (39).

CH ₂ =CH-R ³ -R ² .........(39)

R ² in the above formula (39) represents a group having 2 to 10 carbon atoms and an unsaturated bond; and R ³ represents a divalent hydrocarbon group having 1 to 8 carbon atoms.

The carbon number of R ³ is particularly preferably from 1 to 4. In this way, the hydrogenation reaction of hydrazine can be carried out reliably.

On the other hand, when R ³ is 4 or less, the boiling point thereof can be suppressed, so that the above (c) remaining from the reaction solution can be easily distilled off.

The organic compound (c) having two or more unsaturated bonds in the above-mentioned one molecule may be used alone or in combination of two or more.

In the production step of the organopolyoxane of the present embodiment, the amount of the organic compound (c) having two or more unsaturated bonds in one molecule (molar amount) can be reacted without leaving a SiH group. From the last point of view, the molar amount of the SiH group derived from the hydrogenated polyoxyalkylene (a1) represented by the above formula (11) is added as desired, and has one or more direct bonds. a molar amount of a molar amount of a SiH group derived from a hydrogenated polyoxyalkylene (a2) bonded to a hydrogen atom of the above-mentioned germanium atom, and a vinyl group-containing organic having two or more vinyl groups directly bonded to the above-mentioned germanium atom Polyoxyalkylene (b1) ethylene The molar amount of the base or the molar amount of the hydroxyl group of the polyoxyalkylene (b2) having two or more hydroxyl groups bonded directly to the halogen atom, that is, the molar amount of the SiH group relative to [(a1) The molar amount of the SiH group of the amount +(a2)]-[the molar amount of the vinyl group of (b1) or the molar amount of the hydroxyl group of (b2) is preferably added excessively.

Specifically, it is [the molar amount of the organic compound (c) having two or more unsaturated bonds in one molecule] / [(the molar amount of the SiH group derived from (a1), (a2)) - ( The molar amount of the vinyl group derived from (b1) or the molar amount of the hydroxyl group derived from (b2) is preferably 1.2 to 3.0.

The above-mentioned hydrazine hydrogenation catalyst (d) is not particularly limited, and any of the known species can be used.

For example, platinum black, platinum chloride, chloroplatinic acid, a product of reaction of chloroplatinic acid with a monohydric alcohol, a complex of chloroplatinic acid and an olefin, a platinum-based catalyst such as bis-acetonitrile platinum; A platinum group metal catalyst other than a platinum-based catalyst such as a catalyst or a ruthenium catalyst.

The hydrazine hydrogenation catalyst (d) may be used alone or in combination of two or more.

The amount of the hydrazine hydrogenation catalyst (d) is not particularly limited, and is further bonded to the ruthenium atom with respect to the hydrogenated polyoxy siloxane (a1) represented by the formula (11) and, if necessary, one or more. a hydrogenated polyoxyalkylene (a2) having a hydrogen atom, and i) a vinyl group-containing organopolyoxane (b1) having two or more vinyl groups bonded directly to a ruthenium atom, or having two or more direct bonds An organic compound (c) having two or more unsaturated bonds in one molecule of a polyoxyalkylene (b2) of a hydroxyl group of a halogen atom and ii), which is obtained by an addition reaction The weight of the organic polyoxane of the product is preferably from 0.01 to 100 ppm.

The amount of the above-mentioned hydrazine hydrogenation catalyst (d) is preferably 0.01 ppm or more from the viewpoint of sufficiently obtaining the effect of addition, and is preferably 100 ppm or less from the viewpoint of cost.

Meanwhile, the rhodium hydrogenation catalyst (d) may be removed by an adsorbent such as activated alumina or activated carbon after the addition reaction.

From the viewpoint of heat-resistant yellowing and light resistance, the amount of the hydrogenation-reactive catalyst (d) described later is based on 100 parts by mass of the hydrogenated polyoxane (a1) represented by the above formula (11). A vinyl-containing organic polyfluorene having one or more hydrogenated polyoxyalkylenes (a2) directly bonded to a hydrogen atom of a halogen atom, and i) having two or more vinyl groups directly bonded to a halogen atom of a halogen atom. Oxygenane (b1) or an organic compound (c) having two or more polyoxyalkylenes (b2) directly bonded to a hydroxyl group of a halogen atom and ii) having two or more unsaturated bonds in one molecule undergoing an addition reaction The product obtained, that is, the organopolysiloxane, is preferably 0.001 parts by mass or less.

The amount of the hydrazine hydrogenation catalyst (d) in the curable resin composition can be measured by analyzing a curable resin composition described later.

In the above-described addition reaction in the production step of the organopolysiloxane of the present embodiment, the reaction can be generally carried out at room temperature to 100 °C.

When the above R ² is a (meth) propylene fluorenyloxy group, the (meth) propylene fluorenyloxy group may be colloidalized by being easily reacted at a high temperature, and the reaction temperature is preferably 40 ° C to 70 ° C.

The above addition reaction can also be carried out in a solvent as required.

As an example of the solvent, an aromatic solution such as toluene or xylene can be used. An aliphatic solvent such as hexane or octane; a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone; an ester solvent such as ethyl acetate or isobutyl acetate; diisopropyl ether; An ether solvent such as dioxane, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or propylene glycol monomethyl ether acetate; and an alcohol solvent such as isopropyl alcohol; or a mixture thereof Solvent.

The environment in the addition reaction can be any of air or inert gas. In the case where the color of the obtained organic hydrogenated polyoxyalkylene is less colored, it is preferably an inert gas such as nitrogen, argon or helium, and when the above R ² is a (meth)acryloxy group, it is prevented ( For the purpose of the polymerization of methyl) propylene methoxy group, a small amount of oxygen can be introduced.

When R ² is a (meth) propylene oxime group, a phenothiazine, a hindered phenol compound, an amine compound, and the like are added to the reaction system in advance for the purpose of preventing polymerization of the (meth) propylene oxime group. A polymerization inhibitor such as a lanthanoid compound is preferred. The type and amount of the polymerization inhibitor are not hindered by the addition of such a hydrazine reaction, such as prevention of (meth) propylene oxime, that is, propylene oxime or methacryloxy group. The polymerization reactor is not particularly limited.

After the end of the addition reaction, the reaction mixture may be further subjected to removal of the addition reaction catalyst by a usual method such as water washing or activated carbon treatment. When the organic compound (c) and the solvent having two or more unsaturated bonds in the remaining one molecule are used, they can be distilled off under heating and/or reduced pressure to obtain the above formula (1) to (3). (i) F1 and M1, (ii) F1 and T in the constituent units F1, M1, T shown, (iii) an organic polyoxane of a constituent unit of any combination of F1, M1 and T.

In the production step of the organopolyoxane of the present embodiment, the following reaction liquid can be prepared in advance, and then the hydrazine hydrogenation reaction catalyst (d) is added to the reaction liquid to carry out the above-described addition reaction and synthesis, and the reaction is carried out. The liquid system contains the hydrogenated polyoxyalkylene oxide (a1) and, if necessary, two or more of the hydrogenated polyoxyalkylene oxide (a2) and the vinyl group-containing organic polyoxane (b1) and one molecule. An organic compound (c) having an unsaturated bond or an organic compound (c) having two or more polyoxyalkylenes (b2) directly bonded to a hydroxyl group of the above-mentioned ruthenium atom and one or more unsaturated bonds in one molecule; By

Further, in the above-described addition reaction in the production step of the organopolysiloxane of the present embodiment, the first step and the second step may be sequentially performed, and the first step is to preliminarily prepare the above-mentioned hydrogenated polyoxyalkylene ( A1) a reaction liquid of the above-mentioned hydrogenated polyoxyalkylene (a2) and an organic compound (c) having two or more unsaturated bonds in one molecule, and further adding a hydrogenation catalyst (d) to the reaction liquid The step of producing the above-mentioned hydrogenated polyoxyalkylene oxide (a1), the above-mentioned hydrogenated polyoxyalkylene oxide (a2), and an organic compound (c) having two or more unsaturated bonds in one molecule The second stage is a step of adding the vinyl group-containing organopolyoxane (b1) or the polyoxyalkylene (b2) having two or more hydroxyl groups directly bonded to the above ruthenium atom to the reaction liquid. .

[Cure resin composition] (thermal radical generator)

One form of the thermosetting resin composition of the present embodiment is exemplified For example, a so-called thermosetting resin composition containing the above organopolysiloxane and a thermal radical generator.

The above-mentioned thermal radical generating agent is not particularly limited as long as it can radically polymerize a (meth)acryloxy group by heat.

Examples thereof include an organic peroxide such as benzamidine peroxide, laurel peroxide, tributane peroxide, cumene hydroperoxide, or an azo compound such as azobisisobutyronitrile.

Specific examples thereof include 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Nippon Wako Pure Chemical Industries, Ltd.), 2, 2' -Azobis(2,4-dimethylvaleronitrile) (V-65, manufactured by Nippon Wako Pure Chemical Industries, Ltd.), 2,2'-azobisisobutyronitrile (V-60, manufactured by Nippon Wako Pure Chemical Industries, Ltd.) And an azonitrile compound such as 2,2'-azobis(2-methylbutyronitrile) (V-59, manufactured by Nippon Wako Pure Chemical Co., Ltd.); PEROYL O (manufactured by Nippon Oil & Fats Co., Ltd.) , Peroxidic Laurel (PEROYL L, manufactured by Nippon Oil & Fats Co., Ltd.), Peroxylated Rhenol (PEROYL S, manufactured by Nippon Oil & Fats Co., Ltd.), Peroxidic Succinic Acid (PEROYL SA, manufactured by Nippon Oil & Fats Co., Ltd.), Benzoyl peroxide ( NYPER BW, manufactured by Nippon Oil & Fats Co., Ltd., isobutyl oxime (PEROYL IB, manufactured by Nippon Oil & Fats Co., Ltd.), perylene-2,4-dichlorobenzamide (manufactured by Nippon Oil & Fats Co., Ltd.) and peroxidized-3 , 5,5-trimethylhexanide (PEROYL 355, manufactured by Nippon Oil & Fats Co., Ltd.), etc.; di-n-propyl peroxydicarboxylate (PEROYL NPP-50M, manufactured by Nippon Oil & Fats Co., Ltd.), peroxidation Diisopropyl dicarboxylate (PEROYL IPP-50, Oil & Fat Co., Ltd.), a dicarboxylic acid peroxide, bis (4-tert-butyl-cyclohexyl) ester (PEROYL TCP, manufactured by Nippon Oil Corporation) peroxide, di-dicarboxylic acid Ethoxyethyl ester (PEROYL EEP, manufactured by Nippon Oil & Fats Co., Ltd.), di-2-ethoxyhexyl peroxydicarboxylate (PEROYL OPP, manufactured by Nippon Oil & Fats Co., Ltd.), di-2-methoxybutyl peroxide dicarboxylate (PEROYL MBP, manufactured by Nippon Oil & Fats Co., Ltd.) and peroxydicarboxylates such as di(3-methyl-3-methoxybutyl)peroxydicarboxylate (PEROYL SOP, manufactured by Nippon Oil & Fats Co., Ltd.); Hydroperoxide, such as PERBUTYL H-69 (manufactured by Nippon Oil & Fats Co., Ltd.) and peroxidized-1,1,3,3-tetramethylbutane (PEROCTA H, manufactured by Nippon Oil & Fats Co., Ltd.) Benzene peroxide (PERBUTYL D, manufactured by Nippon Oil & Fats Co., Ltd.), 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane (PERHEXA 25B, manufactured by Nippon Oil & Fats Co., Ltd.) And other dioxanes; α,α'-bis(new bismuth peroxide) diisopropylbenzene (DYPER ND, manufactured by Nippon Oil & Fats Co., Ltd.), isopropenyl neodecanoate (PERCUMYL ND, Japan) Produced by Oils and Fats Co., Ltd., peroxy neodecanoic acid-1,1,3,3-tetramethylbutyl ester (PEROCTA ND, manufactured by Nippon Oil & Fats Co., Ltd.), peroxy neodecanoate-1-cyclohexyl-1-methylethyl ester (PERCYCLO ND, Japan Oil Company Manufactured, perhexyl neodecanoate (PERHEXYL ND, manufactured by Nippon Oil Co., Ltd.), perbutyl neodecanoate (PERBUTYL ND, manufactured by Nippon Oil Co., Ltd.), trimethylacetate peroxide Ester (PERHEXYL PV, manufactured by Nippon Oil & Fats Co., Ltd.), tributyl methacrylate (PERBUTYL PV, manufactured by Nippon Oil & Fats Co., Ltd.), peroxy-2-ethylhexanoic acid-1,1,3,3-tetra Methyl butyl ester (PEROCTA O, manufactured by Nippon Oil & Fats Co., Ltd.), 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane (PERHEXA 250, manufactured by Nippon Oil & Fats Co., Ltd.), Peroxy-2-ethylhexanoate-1-cyclohexyl-1-methylethyl ester (PERCYCLO O, manufactured by Nippon Oil & Fats Co., Ltd.), third hexyl peroxy-2-ethylhexanoate (PERHEXYL O, manufactured by Nippon Oil & Fats Co., Ltd.), tert-butyl peroxy-2-ethylhexanoate (PERBUTYL O, manufactured by Nippon Oil & Fats Co., Ltd.), and tert-butyl peroxyisobutyrate (PERBUTYL IB, manufactured by Nippon Oil & Fats Co., Ltd.) ), isopropyl peroxy monocarboxylic acid trihexyl ester (PERHEXYL I, manufactured by Nippon Oil & Fats Co., Ltd.) and perbutyl maleic acid tert-butyl ester (PERBUTYL MA, manufactured by Nippon Oil Co., Ltd.), peroxy-2- Tripentyl ethyl hexanoate (Trigonox 121, manufactured by Nippon Chemical Co., Ltd.), 3,5,5-trimethylhexanoic acid, triamyl ester (Kayaester AN, manufactured by Nippon Chemical Co., Ltd.), etc. The organic peroxide or the like such as a peroxyester is not particularly limited thereto.

The thermal radical generating agent may be used singly or in combination of two or more.

The content of the thermal radical generator is more than 100 parts by mass of the hydrogenated polyoxyalkylene (a1) represented by the above formula (11) and, if necessary, one or more hydrogen atoms directly bonded to the halogen atom. The hydrogenated polyoxyalkylene oxide (a2) and i) have two or more vinyl group-containing organopolyoxanes (b1) directly bonded to the above-mentioned fluorene atom, or have two or more direct bonds to The organopolyoxane of the present embodiment of the addition reaction product of the organic compound (c) having two or more unsaturated bonds in the above one molecule, wherein the polyoxyalkylene (b2) of the hydroxyl group of the halogen atom and the ii) It is preferably from 0.5 to 10 parts by mass.

When the content of the thermal radical generator is 0.5 parts by mass or more, the curable resin composition is excellent in curability; and when it is 10 parts by mass or less, a curable resin composition and a cured product excellent in heat yellow resistance are obtained. From this viewpoint, the content of the thermal radical generating agent is preferably 1 part by mass or more and 8 parts by mass or less, more preferably 2 parts by mass or more and 5 parts by mass or less.

(photoradical generator)

One of the embodiments of the curable resin composition of the present embodiment is a so-called photocurable resin composition containing the above-mentioned organopolysiloxane and a photoradical generator.

The photoradical generating agent is not particularly limited as long as it is a species capable of photopolymerizing a (meth)acryloxy group.

Specific examples thereof include a triazine derivative described in Japanese Patent Publication No. Sho 59-1281, Japanese Patent Publication No. Sho 61-9621, and Japanese Patent Laid-Open Publication No. Sho 60-60104, and the like. An organic peroxide described in, for example, Japanese Patent Publication No. Sho 43-243807, Japanese Patent Publication No. Sho 43-23684, Japanese Patent Publication No. Sho 44-6413, and Japanese The diazo compound described in the specification of U.S. Patent No. 3,567,453, and the specification of U.S. Patent No. 2,848,328, the specification of U.S. Patent No. 2,852,379, and the U.S. Patent No. Japanese Patent Publication No. Sho. The ortho-quinonediazide compounds described in the above, and each of the publications of Japanese Patent Publication No. Sho 55-39162 and JP-A-59-14023, and "Macromolecules, Vol. 10, p. 1307 ( 1977) It described the various onium compounds (onium compounds); azo compound in Japanese Unexamined Patent Publication No. 59-142205 described in the; Japanese Unexamined Patent Publication No. 1-54440, European Patent No. 109,851 No. specification, European Patent No. 126,712 and "J.Imag. Sci., Vol. 30, p. 174 (1986)", etc.; in Japanese Patent Laid-Open No. 6-213861 (a oxy) sulfonium organoboron compound described in Japanese Laid-Open Patent Publication No. Hei 6-255347; "Coordination Chemistry Review, Vol. 84, pp. 85‧ 277 (1988)" and a transition metal complex containing a transition metal such as ruthenium described in JP-A-2-182701; The 2,4,5-triarylimidazole dimer described in the publication No. 209 477, the carbon tetrachloride, and the organohalogen compound described in JP-A-59-107344.

These species may be used alone or in combination of two or more.

The content of the photoradical generator is more than one part by weight of the hydrogenated polyoxoxane (a1) represented by the above formula (11) and one or more hydrogen atoms directly bonded to the above ruthenium atom. a hydrogenated polyoxyalkylene (a2), and i) a vinyl group-containing organopolyoxane (b1) having two or more vinyl groups bonded directly to the above-mentioned germanium atom, or having two or more direct bonds The organopolyoxane of the present embodiment of the addition reaction product of the organic compound (c) having two or more unsaturated bonds in the above one molecule, wherein the polyoxyalkylene (b2) of the hydroxyl group of the halogen atom and the ii) It is preferably from 0.5 to 20 parts by mass.

When the content of the photoradical generator is 0.5 parts by mass or more, the curable resin composition is excellent in curability, and when it is 20 parts by mass or less, a curable resin composition and a cured product excellent in light resistance are obtained. From this point of view, the content of the photo radical generating agent is preferably 0.1 part by mass or more and 15 parts by mass or less. It is more preferably 10 parts by mass or less.

(other ingredients)

In the curable resin composition of the present embodiment, it is also possible to add (meth) acrylate monomers and low in order to promote the curability (enhance the sensitivity) of energy such as heat and ultraviolet rays. A radical polymerizable compound such as a polymer or a vinyl (meth)acrylate.

Others, anti-aging agents, mold release agents, diluents, antioxidants, thermal stabilizers, flame retardants, plasticizers, surfactants, etc. may be blended in the range of amounts and qualities without departing from the scope of the invention. Additives.

Further, the curable resin composition of the present embodiment may further contain an inorganic material such as glass, metal or vermiculite or an organic material such as synthetic resin. Further, when the inorganic material and the organic material are contained, the hydrogenated polyoxyalkylene (a1) and the compound represented by the above formula (11) are produced in the step of producing the organopolysiloxane having the curable resin composition. The above-mentioned hydrogenated polyoxyalkylene (a2) having one or more hydrogen atoms directly bonded to a halogen atom, and i) a vinyl group-containing organic having two or more vinyl groups directly bonded to a halogen atom a polyoxyalkylene (b1) or a polyoxyalkylene (b2) having two or more hydroxyl groups directly bonded to the above-mentioned ruthenium atom, and ii) an organic compound having two or more unsaturated bonds in the above one molecule (c) The decane coupling agent should be further formulated in the product obtained by the addition reaction.

The decane coupling agent has a reactive group capable of forming a chemical bond with an inorganic material such as glass, metal or vermiculite in one molecule, and a reactive group capable of forming a chemical bond with an organic material such as a synthetic resin or a miscible with an organic material. The compound of the substituent is not particularly limited.

The above-mentioned reactive group capable of forming a chemical bond with an inorganic material may, for example, be a methoxy group or an ethoxy group.

The above-mentioned reactive group capable of forming a chemical bond with an organic material may, for example, be a vinyl group, an epoxy group, an amine group, a methacryl group, an acryl group, a thiol group or an isocyanate group.

The substituent which is excellent in miscibility with the organic material may, for example, be an isomeric cyanate group. Specific examples thereof include vinyl trimethoxy decane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.), vinyl triethoxy decane (KBE-1003, manufactured by Shin-Etsu Chemical Co., Ltd.), and 2-(3,4-ring). Oxycyclohexyl)ethyltrimethoxydecane (KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldimethoxydecane (KBM-402, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-ring Oxypropoxypropyltrimethoxydecane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldiethoxydecane (KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-epoxy Propoxypropyl triethoxy decane (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.), p-styrene trimethoxy decane (KBM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methylpropenyl methoxypropylmethyl Methoxysilane (KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methylpropenyl methoxypropylmethyl Diethoxy decane (KBE-502, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryl oxime propyl triethoxy decane (KBE-503, Shin-Etsu Chemical Co., Ltd., Japan) Manufactured by the company, 3-propenyl methoxypropyltrimethoxy decane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), N-2-(aminoethyl)-3-aminopropylmethyldimethoxy decane (KBM- 602, manufactured by Shin-Etsu Chemical Co., Ltd., N-2-(Aminoethyl)-3- Aminopropyltrimethoxydecane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-aminopropyltrimethoxydecane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-aminopropyltriethoxydecane (KBE- 903, manufactured by Shin-Etsu Chemical Co., Ltd., 3-triethoxyindol-3-N-(1,3-dimethyl-butylene) propylamine (KBE-9103, manufactured by Shin-Etsu Chemical Co., Ltd.), N-phenyl 3-aminopropyltrimethoxy decane (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.), N-(vinylbenzyl)-2-amineethyl-3-aminopropyltrimethoxy decane hydrochloride ( KBM-575, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-ureidopropyltriethoxysilane (KBE-585, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-hydrothiopropylmethyldimethoxydecane (KBM-802, Japan) (manufactured by Shin-Etsu Chemical Co., Ltd.), 3-hydrothiopropyltrimethoxy decane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.), bis(triethoxyphosphoryl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-isocyanate propyl triethoxy decane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.), tris-(3-trimethoxydecylpropyl) isocyanurate (X-12-965, Japan Shin-Etsu Chemical Co., Ltd. Manufacturing), etc., but not limited Here.

Further, these decane coupling agents may be used singly or in combination of two or more.

The content of the decane coupling agent in the curable resin composition of the present embodiment is preferably 0.5 to 10 parts by mass based on 100 parts by mass of the organopolysiloxane.

When the content of the decane coupling agent is 0.5 parts by mass or more, the adhesion can be excellent, and when it is 10 parts by mass or less, the heat yellow resistance can be improved. From this point of view, the content of the decane coupling agent is 0.7 parts by mass or more and 8 masses. The following is preferred, and more preferably 1 part by mass or more and 5 parts by mass or less.

In the step of the addition reaction of the organopolyoxane in the step of the addition reaction of the organopolyoxane, the (d) hydrazine hydrogenation catalyst is used in an amount of 100 parts by mass of the organopolyoxane. d) The rhodium hydrogenation catalyst may be contained in an amount of 0.001 part by mass or less.

The rhodium hydrogenation catalyst (d) can be removed by an adsorbent such as activated alumina or activated carbon after the addition reaction of the organopolyoxane as described above.

The content of the (d) hydrazine hydrogenation catalyst is preferably 0.001 parts by mass or less, more preferably 0.0008 parts by mass or less, more preferably 0.0005 parts by mass or less, from the viewpoint of heat yellowing resistance and light resistance.

The curable resin composition of the present embodiment has improved heat yellowing resistance, light resistance, hardness, electrical conductivity, thermal conductivity, thixotropy, and low thermal expansion property in the organopolysiloxane of the present embodiment. The purpose is to contain a filler represented by an inorganic oxide as needed.

Examples of the filler include cerium oxide (fumed silica, colloidal silica, and precipitated silica), tantalum nitride, boron nitride, and oxidation. Inorganic oxides or inorganic nitrides such as aluminum, zirconia, titanium oxide and barium titanate, glass, ceramics, silver powder, gold powder and copper powder.

The filler can be used with or without surface treatment, and when subjected to surface treatment, the fluidity of the curable resin composition can be increased, and the filling rate can be increased, which is industrially preferable.

Examples of the surface-treated particulate inorganic filler may be, for example, those subjected to methoxylation, trimethylation, octopine or eucalyptus.

The content of the inorganic oxide in the curable resin composition of the present embodiment is preferably 0.1 to 500 parts by mass based on 100 parts by mass of the organopolysiloxane.

[hardened matter]

The curable resin composition of the present embodiment is liquid or solid before curing, and can be formed into a cured product by a predetermined treatment.

For example, when the above-mentioned thermal radical generating agent is contained in the curable resin composition, the cured product can be obtained by heat treatment. The hardening temperature therein is generally from 100 to 250 °C.

The curing method and molding method of the curable resin composition are not particularly limited. When the curable resin composition is in a liquid state, it can be molded by, for example, casting, low pressure transfer molding, potting, dipping, press molding, and injection molding.

When the curable resin composition is in a solid form, it can be molded by heating and hardening under pressure using, for example, an extruder or a low-pressure transfer molding machine.

The cured product of the curable resin composition of the present embodiment is also suitable for use as a sealing material for an optical semiconductor device.

Further, the curable resin composition of the present embodiment can also be used as a wafer bonding paste, and the cured product can be used as a wafer bonding material.

At the same time, the cured product of the curable resin composition of the present embodiment is also suitably used in the use of an optical semiconductor device such as a coating material or a lens material around the coated wafer.

In this case, the optical semiconductor may be, for example, an LED lamp, a wafer type LED, a semiconductor laser, an optical coupler, and a photodiode.

The optical semiconductor device using the cured product of the curable resin composition of the present embodiment as the sealing material for the optical semiconductor includes the following structure: an outer casing material, a tantalum wafer provided in the outer casing material, and the present embodiment. The cured product of the curable resin composition serves as a sealing material for sealing the above-mentioned tantalum wafer.

The material of the outer casing material is not particularly limited, and examples thereof include aromatic polyamines such as polyphthalamide; engineering plastics such as 66 nylon; ceramics, and the like, in the case of polyphthalamide. In particular, it can exhibit high adhesion.

When the glass material is further contained in the outer casing, the strength of the bonding can be improved and it is more preferable. The content of the above glass fiber is preferably from 5 to 40% by mass, more preferably from 10 to 30% by mass, particularly preferably from 15 to 25% by mass, based on the mass of the outer shell material. When the content of the glass fiber is within this numerical range, the adhesion can be more significantly exhibited.

As described above, the curable resin composition of the present embodiment is liquid or solid before being cured, and when it is prepared by a predetermined photoradical generator, it can be irradiated with an energy beam such as ultraviolet rays to produce a cured product.

When the photo-radical generator is formulated, the curable resin composition is also suitable for use as a coating material for a resin film, a substrate, or the like which is required to be rapidly cured without heating.

For example, it is a coating material for forming an antireflection film which can be used in a flat panel display (FPD) or the like.

In particular, when used as the coating material for forming an antireflection film, it is preferable to form a cured film having a refractive index of 1.4 or less, and the curable resin composition preferably contains porous fine particles which form voids.

The porous fine particles may be cerium oxide particles having an average particle diameter of 5 nm to 1 μm, and from the viewpoint of transparency of the cured film, cerium oxide particles having an average particle diameter of 5 to 100 nm are preferable. Specific examples are "Aerosil" (trade name, manufactured by Nippon Aerosil Co., Ltd.) which is hydrophilic or has a surface-hydrophobized gas phase oxidized ruthenium, and a pearl chain sputum sol which is linearly linked by cerium oxide particles. "SNOWTEX PS" (trade name, manufactured by Nissan Chemical Co., Ltd.). The porous fine particles are preferably used in an amount of from 10 to 70 parts by mass based on 100 parts by mass of the total of the porous fine particles, and are uniform in the curable resin composition by using a homogenizer or the like. Dispersion is better.

When the curable resin composition of the present embodiment is used as a coating material, the method for forming the cured film may be, for example, a transparent substrate (for example, polymethyl methacrylate, polycarbonate, polystyrene, and triacetone). The surface of the cellulose resin substrate or the inorganic material such as glass is coated with a coating material containing the curable resin composition of the present embodiment, and the coating film is further photocured to form an antireflection film and a protective film. A method of hardening a film having a thickness of 10 nm to 1 μm.

When coating on a substrate, it is necessary to form a thin film with high fineness. At this time, a micro gravure coating method, a roll coating method, a shower coating method, a spin coating method, a rigid mold coating method, and a flow extension can be used. Coating method and spraying method.

The curable resin composition may be diluted with a solvent or the like for adjusting the viscosity as needed, or may be in the form of a sol containing porous fine particles or the like. When it is used for dilution with a solvent or the like, and when it is used in the form of a sol containing porous fine particles or the like, the solvent component is volatilized in advance, and may be 50 to 50 before curing. Heating at about 150 ° C for about several minutes.

In the curable resin composition of the present embodiment, a coloring agent is further added to form a curable ink.

As the above coloring agent, various organic pigments and inorganic pigments can be used. For example: white pigments such as titanium oxide, zinc white, lead white, zinc antimony and antimony oxide; black pigments such as aniline black, iron black and carbon black; chrome yellow, yellow iron oxide, Hansa yellow (100, 50) , 30, etc., yellow pigments such as titanium yellow, petroleum ether yellow and permanent yellow; orange pigments such as Chrome Vermilion, permanent orange, Vulcan Fast Orange; iron oxide, permanent brown and Brown pigment such as brown; red iron oxide, cadmium red, strontium sand, permanent red, rose red lake, alizarin lake, thiored red, PV carmine red, Monolight permanent red and quinophthalone red Red pigments such as pigments; purple pigments such as cobalt violet, manganese violet, permanent violet, methyl violet lake, indanthrene brilliant violet, diazilium violet; ultramarine blue, Prussian blue, cobalt blue, alkaline blue lake, Blue pigments without metal phthalocyanine blue, copper sapphire blue, indanthrene blue, indigo, etc.; chrome green, chrome oxide, emerald green, naphthol green, golden green, acid green lake, peacock green lake, 酞Green pigments such as cyanine green and copper chlorobromide; other various fluorescent pigments, metallic pigments and physique Pigments, etc. The amount of these coloring agents is preferably from 1 to 50% by mass, more preferably from 5 to 25% by mass, based on the total amount of the curable resin composition.

In the curable ink, the colorant can also be used as needed.

Examples of the pigment dispersant include higher fatty acid salts, alkyl sulfates, alkyl ester sulfates, alkyl sulfonates, sulfosuccinates, and naphthalenesulfonic acids. Activator of salt, alkyl phosphate, polyoxyalkylene ether phosphate, polyoxyalkylene alkyl phenyl ether, glycerol ester, sorbitan ester and polyoxyethylene fatty decylamine; from styrene, benzene Ethylene derivative, vinyl naphthalene derivative, acrylic acid, acrylic acid derivative, maleic acid, maleic acid derivative, itaconic acid, itaconic acid derivative, fumaric acid and fumaric acid A block copolymer or a random copolymer composed of two or more kinds of monomers selected from the group consisting of salts of such species, and the like.

The method for dispersing the coloring agent in the curable ink can be used as follows: ball mill, sand mill, grinder, roll mill, mixer, Henschel mixer, rubber mill, ultrasonic homogenizer, bead mill A method of various dispersers such as a machine, a wet jet mill, and a paint shaker.

Further, for the purpose of removing coarse particles of the pigment dispersion in the curable ink, a predetermined treatment can be carried out using a centrifuge or a filter.

When the pigment ink is used as the coloring agent, the average particle diameter of the pigment particles in the pigment ink is selected in consideration of stability in the curable ink, image density, glossiness, light resistance, etc., and the gloss is increased. From the viewpoint of improving the texture, it is preferred to appropriately select the average particle diameter of the pigment particles.

The curable resin composition of the present embodiment exhibits heat-resistant yellowing and high transparency, and is suitable for use in spectacle lenses, optical device lenses, CD and DVD reading lenses, automotive headlight lenses, and projectors. The material of the lens such as a lens is used in various optical member materials such as an optical fiber, an optical waveguide, a filter, an optical adhesive, a disk substrate, a display substrate, and a curable resin for nanoimprint.

The curable resin composition of the present embodiment can be used as an optical semiconductor The sealing material is used, and the cured product is suitable as a transparent resin for a semiconductor package, and the above-mentioned optical semiconductor sealing material can be obtained by molding.

The sealing material for an optical semiconductor is applied to a workpiece subjected to a base film treatment after plasma treatment, and is directly applied by a coating device such as a dispenser or a rotary dispenser.

The coated optical semiconductor sealing material can be cured or cured by a molding machine or the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples.

In the examples and comparative examples, the measurement and evaluation were carried out in the following manner.

<(1) Calculation of reaction rate of SiH>

0.05 g of the sample reaction solution (that is, the reaction solution in the synthesis of the organopolyoxane in the examples and the comparative examples described later, the solution after 72 hours from the start of the reaction) was dissolved in 1 g of the deuterated chloroform solvent as a measurement. Sample.

Then, the measurement sample was subjected to ¹ H NMR measurement at a cumulative frequency of 100 times at 400 MHz (manufactured by JASCO Corporation, α-400), and the measurement results were analyzed.

The reaction rate of SiH was determined by calculating the area ratio of the peak of 0.2 ppm from Si-CH ₃ and the peak of 4.6 ppm from SiH before and after the reaction, and then calculated according to the following formula.

After that, when the reaction rate of SiH is 98% or more, it is ◎, 90% or more. When it is less than 98%, it is ○, and when it is less than 90%, it is ×.

Reaction rate of SiH (%) = [(X1-Y1) / X1] × 100

X1: peak area ratio before reaction

(peak area of SiH before reaction) / (peak area of Si-CH ₃ before reaction)

Y1: peak area ratio after reaction

(peak area of SiH after reaction) / (peak area of Si-CH ₃ after reaction)

<(2) Identification of molecular structure>

With respect to 20 mg of the samples of the organopolyoxanes (A1) to (A17) prepared in the examples and the comparative examples described later, a solution dissolved in a deuterated chloroform solvent at a ratio of 1 g was used as a measurement sample. Further, the measurement sample was subjected to ¹ H NMR measurement at a cumulative number of times of α-400 manufactured by JASCO Corporation, and the results of the measurement were analyzed.

Further, a solution which was dissolved in a deuterated chloroform solvent in a ratio of 1 g with respect to a sample of 0.3 g was used as a measurement sample. The measurement sample was subjected to ¹³ C NMR measurement at a cumulative number of 20,000 times by α-400 manufactured by JASCO Corporation, and the results of the measurement were analyzed.

Further, it was dissolved in a deuterated chloroform solvent in a ratio of 1 g with respect to 0.15 g of the sample, and a solution of 8 g% of Cr(acac) ₃ with respect to the decane was added as a measurement sample. Further, the measurement sample was subjected to ²⁹ Si NMR measurement at a cumulative number of times of α-400 manufactured by JASCO Corporation, and the results of the measurement were analyzed.

Then, the results obtained by the ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR were analyzed to determine the molecular structures of the organopolyoxanes (A1) to (A17).

<(3) Calculation of functional group equivalents of (meth)acryloxyloxy group>

A solution of the organopolyoxane (A1) to (A17) produced in the examples and the comparative examples described later in a ratio of 1 g was dissolved in a solvent of deuterated chloroform as a measurement sample. Then, the measurement sample was subjected to ¹ H NMR measurement at a cumulative number of times of α-400 manufactured by JASCO Corporation, and the average composition in the molecule of the organopolysiloxane was determined by the analysis.

Further, it was dissolved in a deuterated chloroform solvent at a ratio of 1 g with respect to 0.15 g of the sample, and a solution of 8 g% of Cr(acac) ₃ with respect to the decane was added as a measurement sample. Then, the measurement sample was subjected to ²⁹ Si NMR measurement at a cumulative number of 4,000 times by α-400 manufactured by JASCO Corporation, and the average composition in the molecule of the organopolysiloxane was determined by the analysis and measurement.

Thereafter, the results obtained by ¹ H NMR and ²⁹ Si NMR were analyzed, and the functional group equivalent (mass per 1 mol of the functional group) of the (meth)acryloxy group was calculated.

<(4) Calculation of weight average molecular weight>

The sample for measurement of the organopolyoxane (A1) to (A17) produced in the examples and the comparative examples described later was dissolved in a chloroform solvent at a ratio of 2 g, and filtered through a filter of 0.45 μm. As a sample solution.

Then, under the conditions of a column temperature of 40 ° C and a flow rate of the eluent (chloroform) of 1 mL/min, the column was constructed. The column was protected, and the Tskguard column H hour-H manufactured by Tosoh Corporation of Japan was used. Business Standard), Tskgel (registered trademark) G5000H hour manufactured by Tosoh Corporation of Japan and Tskgel (registered trademark) G3000H hour manufactured by Tosoh Corporation of Japan, Tskgel (registered trademark) G1000H hour manufactured by Tosoh Corporation of Japan Even configuration]. In addition, monodisperse polystyrene standards of known molecular weights of molecular weights of 7,500,000, 2,560,000, 841,700, 320,000, 148,000, 59,500, 28,500, 10,850, 2,930, 580 and styrene monomers (molecular weight) manufactured by Polymer Laboratories, Inc., were previously prepared. 104) A calibration curve for the extraction time is determined by RI detection.

Thereafter, the molecular weight was calculated from the above calibration curve by measuring the elution time and the detection intensity of the sample solution.

<(5) Determination of viscosity>

For the measurement samples of the organopolyoxane (A1) to (A17) produced in the examples and the comparative examples described later, the viscosity at a temperature of 25 ° C was measured using TVE-22H manufactured by Nippon Seiki Co., Ltd. .

<(6) Calculation of the ratio of the compound content [WB] represented by the formula (10) to the compound content [WA] represented by the formula (9) ([WB]/[WA]) >

The values of [WA] and [WB] are determined by the matrix-assisted free time-of-flight mass spectrometry (hereinafter referred to as MALDI-TOF/MS) using organopolysiloxane to satisfy the general formula (9) and the general formula. The mass of each structure of (10) and the intensity of the peak corresponding to the mass of the sodium mass 23 are shown.

In addition, the mass of each structure conforming to the general formula (9) and the general formula (10), when the constituent elements of the above structure have an isotope, means that the existence ratio is the highest within the mass of the isotope of each element. The value calculated for the mass of the isotope.

Meanwhile, when a plurality of peaks conforming to the general formula (9) and the general formula (10) are present, the content of the compound having the structure of the general formula (9) [WA] and the content of the compound represented by the general formula (10) [WB 〕, each line meets the total value of the peak intensity of its structure.

However, the maximum intensity of the peak corresponding to the mass of the respective structures conforming to the general formula (9) and the general formula (10) and the total mass of the sodium mass 23 has a peak intensity of 3% or less, and the peak is calculated. The total value of the strength is excluded.

The measurement method of MALDI-TOF/MS was carried out in the following manner.

<Method for measuring MALDI-TOF/MS>

A solution of 0.1 g of the organopolyoxane (A5), (A6), (A11), and (A12) prepared in the examples and the comparative examples described later in 100 mL of tetrahydrofuran at room temperature was used. A solution of 10 mg of stilbene (Dithranol) dissolved in 1 mL of tetrahydrofuran was uniformly mixed at room temperature in a ratio of 1:1 to prepare a solution a. Next, 1 μL of the solution a was added dropwise to a test disk containing 1 μL of a solution in which 10 mg of sodium iodide was dissolved in 1 mL of acetone, and then the solvent was evaporated at room temperature, and then MALDI was carried out under the following measurement conditions. - Determination of TOF/MS.

(measurement conditions)

Device: AXIMA CFR plus, Shimadzu Corporation, Japan

Laser light: nitrogen laser light (337nm)

Detector form: linear

Ion detection: positive ion (positive ion type)

Cumulative number: 500 times

<(7) Heat-resistant yellowing>

The cured product prepared in the examples and the comparative examples described later was a sample for measurement, and a cured product having a thickness of 3 mm was used, and the Y1 was measured by a spectrophotometer CM-3600d (trade name) manufactured by Konica-Minolta Co., Ltd., Japan. Yellow degree).

Next, the cured product was coated with aluminum foil, and heat-treated at 150 ° C for 150 hours in the air, and then measured by a spectrophotometer CM-3600d (trade name) manufactured by Konica-Minolta Co., Ltd., Japan. degree).

The change in Y1 before and after the heat treatment was ΔY1, and it was evaluated that ΔY1 was less than 1.0, ◎, 1.0 or more and less than 3.0 were ○, and 3.0 or more was ×.

<(8) Light resistance>

The cured product prepared in the examples and the comparative examples described later is a sample for measurement, and a cured product having a thickness of 3 mm is used, and the Y1 is measured by a spectrophotometer CM-3600d (trade name) manufactured by Konica-Minolta Co., Ltd., Japan. (yellowness).

Next, the cured product was placed in a constant temperature dryer set to 50 ° C, and then a UV irradiation apparatus (manufactured by Ushio Electric Co., Ltd., trade name: SP-7) equipped with a 365 nm band pass filter at 365 nm. The irradiation was performed at an illuminance of 4 W/cm ^{2 for} 100 hours.

Thereafter, the Y1 (yellowness) was measured again by a spectrophotometer CM-3600d (trade name) manufactured by Konica-Minolta Co., Ltd., Japan. The change in Y1 before and after UV irradiation was ΔY1, and it was evaluated that ΔY1 was less than 1.0, ◎, 1.0 or more and less than 3.0 were ○, and 3.0 or more was ×.

<(9) Resistance to thermal shock resistance>

10mm in the center of the 20mm × 20mm × 2mm flat plate A 5 mm × 5 mm × 0.2 mm tantalum wafer was placed in the outer shell of the molded body of the polyphenylene amide resin (AModel 4122 manufactured by Solvay Co., Ltd.) having a groove of 1 mm in depth.

Next, the curable resin compositions produced in Examples 1 to 17 and Comparative Examples 1 to 6 were injection-molded, and then heated or photo-cured to form a cured product (sealing material) for sealing the wafer, thereby obtaining an optical semiconductor device. Test piece.

The obtained test piece was further circulated at room temperature to -40 ° C (15 minutes) to 120 ° C (15 minutes) to room temperature for 1 cycle at a small thermal shock device TSE-11 manufactured by Espec Corporation of Japan. The number of times so far.

The peeling does not occur in 100 cycles or more, and the peeling occurs when the peeling is 50 or more and less than 100 times, and the peeling occurs when it is less than 50 times.

<(10) hardness>

The cured product prepared in the examples and the comparative examples described later was a sample for measurement, and a cured product having a length of 35 mm, a width of 8 mm, and a thickness of 2 mm was used, and then it was measured at -120 ° C to 150 ° C by MCR-301 manufactured by Anton Parr Co., Ltd., Japan ( Dynamic viscoelasticity at a heating rate of 2 ° C / min).

The hardness was evaluated as a value of G' (storage modulus) at 30 ° C, and was ◎ when it was 10 ⁷ or more, ○ when it was 10 ⁶ or more and less than 10 ⁷ , and × when it was less than 10 ⁶ .

<(11) Adhesion>

10mm in the center of the 20mm × 20mm × 2mm flat plate In the model of a polyphthalamide resin (AModel 4122 manufactured by Solvay Co., Ltd.) having a groove of 1 mm in depth, the curable resin composition prepared in Examples 1 to 17 and Comparative Examples 1 to 6 was injection molded, and then passed through. A test piece can be obtained by heating or photohardening.

The obtained test piece was further circulated at room temperature to -40 ° C (15 minutes) to 120 ° C (15 minutes) to room temperature for 1 cycle at a small thermal shock device TSE-11 manufactured by Japan Espec Co., Ltd., to visually observe that peeling occurred. The number of times so far.

The peeling does not occur in 100 cycles or more, and the peeling occurs when the peeling is 50 or more and less than 100 times, and the peeling occurs when it is less than 50 times.

<(12) Gas barrier property>

The cured product prepared in the examples and the comparative examples described later was a sample for measurement, and a cured product of 100 mm × 100 mm having a thickness of 0.2 mm was used, and the oxygen permeability measuring device Model 8001 was manufactured by Systech Illinois Japan Co., Ltd. at a temperature of 23 ° C. The oxygen transmission rate was measured under dry conditions. When the oxygen permeability is less than 500 cc/m ² /day, it is ◎, 500 cc/m ² /day or more and less than 1000 cc/m ² /day is ○, and when it is 1000 cc/m ² /day or more, it is ×.

[Example 1] <Manufacture of Organic Polyoxane (A1) Having a Group Containing an Unsaturated Bond>

In a 3.0-liter 3-neck retort equipped with a stirring device, a thermometer, and a reflux condenser, 53 g (0.2 mol) of 1,3,5,7-tetramethylcyclotetrazepine as the component (a1) was added. Alkyl, 27 g (0.1 mol) of methyltris(dimethyloxy)decane as component (a2), 242 g (0.3 m) The polydimethyl siloxane having a weight average molecular weight of 780, which is represented by the following average composition formula (B1-1), having a weight average molecular weight of 780, and 101 g (0.9 m) as the component (b1) (c) component of 6-vinylbicyclo[2.2.1]hept-2-ene, 1600 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor), stirred under nitrogen and simultaneously heated to 60 °C.

CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ CH=CH ₂ ... (B1-1)

In the above average composition formula (B1-1), Me represents a methyl group (the same is true for the average composition formula shown in the examples and the comparative examples in the present specification).

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polysiloxane of the addition reaction product 20 ppm.

After confirming the start of the rhodium hydrogenation reaction, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and it was found that the reaction rate of the SiH group was 98%.

Thereafter, the activated carbon treatment is carried out to distill off the volatile component, whereby 350 g of an organopolyoxane (A1) having an unsaturated bond-containing group represented by the following formula (40) can be obtained.

The obtained unsaturated poly bond-containing organopolyoxane (A1), which does not contain a (meth) propylene fluorenyl group, has a functional group equivalent of 694 g/mol of an unsaturated bond group, as determined by GPC The calculated weight average molecular weight is 37,500, and the viscosity at 25 ° C is 2800 mPa. s.

In the above formula (40), m represents an integer of 10 on average; n represents an integer of 8 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -17.2ppm

M1: +8.8ppm

T: -66.2 ppm

D2: -19.8ppm

D3: -21.2ppm

The value of a/(b+c) is 0.78.

However, no peak of S: -32.3 ppm was observed; the value of d/a was zero.

<Manufacture and Characterization of Hardened Materials>

100 parts by mass of an organopolyoxane (A1) having an unsaturated bond group 2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Nippon Chemical Co., Ltd., trade name: Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, and the mixture was stirred to make the whole uniform. Then, after defoaming, a hardenable composition is obtained.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 1 below.

[Example 2] <Manufacture of organopolyoxyalkylene (A2) containing methacryloxyloxy group>

In a 3.0-liter 3-neck retort equipped with a stirring device, a thermometer, and a reflux condenser, 53 g (0.2 mol) of 1,3,5,7-tetramethylcyclotetrazepine as the component (a1) was added. Alkane, 27 g (0.1 mol) of methyltris(dimethyloxy)decane as a component (a2), and 242 g (0.3 mol) of the component (b1) as the following average composition formula (B1-2) The weight average molecular weight shown is 780 of a vinyl dimethyloxy end-terminated polydimethyl siloxane, 118 g (0.9 mol) of 3-butenyl methacrylate as component (c), 1600 g Toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were stirred under a nitrogen atmosphere and simultaneously heated to 60 °C.

CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ CH=CH ₂ ... (B1-2)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polyoxyalkylene of the addition reaction product 20 ppm.

After determining that the hydrogenation reaction begins, the reaction system is kept warm and Water or air cooling was maintained at 55 to 65 ° C while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 99%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 370 g of the methacryloxy group-containing organopolyoxane (A2) represented by the following formula (41) can be obtained.

The obtained methacryloxy group-containing organopolyoxane (A2) has a functional group equivalent of 714 g/mol, a weight average molecular weight calculated by GPC of 38,200, and a viscosity at 25 ° C of 2600 mPa. s.

In the above formula (41), m represents an integer of 10 on average; n represents an integer of 8 on average.

The results of Si NMR measurement were observed to be equivalent to the constituent units as follows The peak shown.

F1: -18.2ppm

M1: +8.8ppm

T: -66.2 ppm

D2: -19.8ppm

D3: -21.2ppm

The value of a/(b+c) is 0.78.

However, no peak of S: -32.3 ppm was observed; the value of d/a was zero.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Akzo Co., Ltd., a trade name of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A2) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 1 below.

[Example 3] <Manufacture of organopolyoxyalkylene (A3) containing methacryloxyloxy group>

In a 3.0-liter 3-neck retort equipped with a stirring device, a thermometer, and a reflux condenser, 53 g (0.2 mol) of 1,3,5,7-tetramethylcyclotetrazepine as the component (a1) was added. Alkane, 16g (0.05m) of tetrakis(dimethyloxy)decane as component (a2), 203g (0.3m) as (b1) The component has a weight average molecular weight of 780 as shown in the following average composition formula (B1-3), a polydimethylsiloxane having a vinyl dimethyloxy group at the end of 780, and 118 g (0.9 mol) as a component (c). The -3-butenyl methacrylate, 1500 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were stirred under nitrogen and simultaneously heated to 60 °C.

CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ CH=CH ₂ ... (B1-3)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polysiloxane of the addition reaction product 20 ppm.

After confirming the start of the rhodium hydrogenation reaction, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and it was found that the reaction rate of the SiH group was 97%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 330 g of the methacryloxy group-containing organopolyoxane (A3) represented by the following formula (42) can be obtained.

The obtained methacryloxy group-containing organopolyoxane (A3) has a functional group equivalent of 626 g/mol, a weight average molecular weight calculated by GPC of 34,200, and a viscosity at 25 ° C of 3,500 mPa. s.

In the above formula (42), m represents an integer of 5 on average; n represents an integer of 8 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

M1: +8.8ppm

D2: -19.8ppm

D3: -21.2ppm

S: -32.3 ppm

The value of a/(b+c) is 1.08; the value of d/a is 0.08.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Akzo Co., Ltd., a trade name of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A3) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 1 below.

[Example 4] <Manufacture of organopolyoxyalkylene (A4) containing methacryloxyloxy group>

In a 3.0 L 3-port retort equipped with a stirring device, a thermometer, and a reflux condenser, 41 g (0.2 mol) of 1,3,5,7-tetramethylcyclotetrazepine as the component (a1) was added. Alkane, 125 g (0.2 mol) of polydimethyl methoxy oxane having a weight average molecular weight of 780 as shown in the following average composition formula (B1-4) as a component (b1) 76 g (0.6 mol) of 3-butenyl methacrylate as component (c), 864 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor), stirred under nitrogen atmosphere and simultaneously added Warm to 60 ° C.

CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ CH=CH ₂ ... (B1-4)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polysiloxane of the addition reaction product 20 ppm.

After confirming the start of the rhodium hydrogenation reaction, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 99%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 205 g of the methacryloxy group-containing organopolyoxane (A4) represented by the following formula (43) can be obtained.

The obtained methacryloxy-containing organopolyoxane (A4) has a functional group equivalent of 600 g/mol, a weight average molecular weight calculated by GPC of 19,800, and a viscosity at 25 ° C of 4,500 mPa. s.

In the above formula (43), m represents an integer of 15 on average; n represents an integer of 8 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

M1: +8.8ppm

D2: -19.8ppm

D3: -21.2ppm

The value of a/(b+c) is 1.13.

However, no peak of S: -32.3 ppm was observed; the value of d/a was zero.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Akzo Co., Ltd., a trade name of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A4) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 1 below.

[Example 5] <Manufacture of organopolysiloxane (A5) containing methacryloxyloxy group>

In a 3.0 L 3-port retort equipped with a stirring device, a thermometer, and a reflux condenser, 68 g (0.3 mol) of 1,3,5,7-tetramethylcyclotetrazepine as the component (a1) was added. 51 g (0.3 mol) of dimethyl dimethyl oxane having a molecular weight of 186 and having a molecular weight of 186 as the component (b1) below, 119 g (0.9 mol) of 3-butenyl methacrylate as component (c), 795 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor), stirred under a nitrogen atmosphere and At the same time, the reaction was heated to 60 ° C.

CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ CH=CH ₂ ... (B1-5)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polysiloxane of the addition reaction product 20 ppm.

After confirming the start of the rhodium hydrogenation reaction, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 99%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 188 g of the methacrylic oxime represented by the following formula (44), the following formula (45), and the following formula (46) can be obtained. Based on organopolyoxane (A5).

The obtained methacryloxy-containing organopolyoxane (A5) has a functional group equivalent of 350 g/mol, a weight average molecular weight of 16400 as determined by GPC, and a viscosity of 15000 mPa at 25 ° C. s.

The obtained methacryloxy group-containing organopolyoxane (A5) had a value of [WB]/[WA] of 1.7. Further, the formula (45) corresponds to the formula (9), and the formula (46) corresponds to the formula (10).

In the above formula (44), m represents an integer of 25 on average; n represents an integer of 0 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

M1: +8.8ppm

D2: -19.8ppm

The value of a/(b+c) is 1.04.

However, no peak of S: -32.3 ppm was observed; the value of d/a was zero.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (100 parts by mass) of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A5) The chemical company Akzo Co., Ltd., trade name: Trigonox 121-50E, 50% by mass solution) is mixed under nitrogen and oxygen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 1 below.

[Example 6] <Manufacture of organopolyoxyalkylene (A6) containing methacryloxyloxy group>

In a 3.0-liter 3-neck retort equipped with a stirring device, a thermometer, and a reflux condenser, 201 g (0.8 mol) of 1,3,5,7-tetramethylcyclotetrazepine as component (a1) was added. 269 g (1.4 mol) of a polydimethylsiloxane having a molecular weight of 186 as shown in the following average composition formula (B1-6) as a component (b1): 97 g of a vinyl dimethyloxy end group, 97 g (0.7 mol) of 3-butenyl methacrylate as component (c), 2138 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor), stirred under nitrogen and simultaneously heated to Reaction at 60 ° C.

CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ CH=CH ₂ ... (B1-6)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polysiloxane of the addition reaction product 20 ppm.

After confirming the start of the rhodium hydrogenation reaction, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 99%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 520 g of the methacrylic acid-containing oxime represented by the following formula (47), the following formula (48), and the following formula (49) can be obtained. Based on organopolyoxane (A6).

The obtained methacryloxy-containing organopolyoxane (A6) has a functional group equivalent of 1157 g/mol, a weight average molecular weight calculated by GPC of 98600, and a viscosity at 25 ° C of 26000 mPa. s.

The value of [WB]/[WA] of the obtained methacryloxy group-containing organopolyoxane (A6) was 10.1. Further, the formula (48) corresponds to the formula (9), and the formula (49) corresponds to the formula (10).

In the above formula (47), m represents an integer of 30 on average; n represents an integer of 0 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

M1: +8.8ppm

D2: -19.8ppm

The value of a/(b+c) is 0.16.

However, no peak of S: -32.3 ppm was observed; the value of d/a was zero.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Akzo Co., Ltd., a trade name of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A6) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 1 below.

[Example 7] <Manufacture of organopolyoxyalkylene (A7) containing methacryloxyloxy group>

In a 3.0-liter 3-neck retort equipped with a stirring device, a thermometer, and a reflux condenser, 24 g (0.1 mol) of 1,3,5,7-tetramethylcyclotetrazepine as the component (a1) was added. Alkyl, 13 g (0.05 mol) of methyltris(dimethyloxy)decane as component (a2) and 0.1 g (0.002 mol) of tetramethyl decane, 119 g (0.2 mol) as (b1) The component has a weight average molecular weight of 780 as shown in the following average composition formula (B1-7): a vinyl dimethyloxy end group of polydimethyl methoxy oxane, and 53 g (0.3 mol) of (c) component. The 3-butenyl methacrylate, 768 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were stirred under a nitrogen atmosphere while heating to 60 ° C for reaction.

CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ CH=CH ₂ ... (B1-7)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polysiloxane of the addition reaction product 20 ppm.

After confirming the start of the rhodium hydrogenation reaction, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 99%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 180 g of the methacryloxy group-containing organopolyoxane (A7) represented by the following formula (50) can be obtained.

The obtained methacryloxy-containing organopolyoxane (A7) has a functional group equivalent of 767 g/mol, a weight average molecular weight calculated by GPC of 189,800, and a viscosity at 25 ° C of 45,000 mPa. s.

In the above formula (50), m represents an integer of 50 on average; n represents an integer of 8 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

M1: +8.8ppm

T: -66.2 ppm

D2: -19.8ppm

D3: -21.2ppm

The value of a/(b+c) is 0.70.

However, no peak of S: -32.3 ppm was observed; the value of d/a was zero.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Akzo Co., Ltd., a trade name of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A7) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 1 below.

[Example 8] <Manufacture of organopolyoxyalkylene (A8) containing methacryloxyloxy group>

3.0L 3 equipped with a stirring device, thermometer, and reflux condenser In a retort, 53 g (0.2 mol) of 1,3,5,7-tetramethylcyclotetraoxane as component (a1) and 27 g (0.1 mol) of a component (a2) were added. A hydroxy dimethyl methoxy end group having a weight average molecular weight of 760 as shown in the following average composition formula (B1-8) as a component of the (b2) component of bis(xycyloxy)decane, 235 g (0.3 mol) Polydimethyloxane, 118 g (0.9 mol) of 3-butenyl methacrylate as component (c), 1600 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor), The mixture was stirred under a nitrogen atmosphere while heating to 60 ° C.

HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ -OH.........(B1-8)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polyoxyalkylene of the addition reaction product 40 ppm.

After the start of the dehydrogenation reaction was determined, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 96%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 370 g of the methacryloxy group-containing organopolyoxane (A8) represented by the following formula (51) can be obtained.

The obtained methacryloxy group-containing organopolyoxane (A8) has a functional group equivalent of 703 g/mol, a weight average molecular weight calculated by GPC of 34,500, and a viscosity at 25 ° C of 2,500 mPa. s.

In the above formula (51), m represents an integer of 10 on average; n represents an integer of 8 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

T: -66.2 ppm

D1 and D2: -19.8ppm

D3: -21.2ppm

S: -32.3 ppm

The value of a/(b+c) is 1.33; the value of d/a is 0.09.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (100 parts by mass) of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A8) The chemical product manufactured by Akzo Co., Ltd., trade name: Trigonox 121-50E, 50% by mass solution) is mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 1 below.

[Example 9] <Manufacture of organopolyoxyalkylene (A9) containing methacryloxyloxy group>

In a 3.0-liter 3-neck retort equipped with a stirring device, a thermometer, and a reflux condenser, 53 g (0.2 mol) of 1,3,5,7-tetramethylcyclotetraindole as the component (a1) was added. As the oxyalkylene, 16 g (0.05 mol) of tetrakis (dimethyl methoxy) decane as the component (a2) and 197 g (0.3 mol) as the component (b2), as shown in the following average composition formula (B1-9) The weight average molecular weight is 760 hydroxy dimethyl methoxy end polydimethyl methoxy oxane, 118 g (0.9 mol) of (c) component methacrylic acid 3-butenyl ester, 1500 g of toluene And 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor), stirred under a nitrogen atmosphere and simultaneously heated to 60 ° C to react.

HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ -OH.........(B1-9)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polyoxyalkylene of the addition reaction product 40 ppm.

After the start of the dehydrogenation reaction was determined, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

After analyzing the contents of the distillation bottle, the reaction rate of the SiH group is known. It is 97%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 325 g of the methacryloxy group-containing organopolyoxane (A9) represented by the following formula (52) can be obtained.

The obtained methacryloxy-containing organopolyoxane (A9) has a functional group equivalent of 617 g/mol, a weight average molecular weight calculated by GPC of 33,200, and a viscosity at 25 ° C of 3400 mPa. s.

In the above formula (52), m represents an integer of 5 on average; n represents an integer of 8 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

T: -66.2 ppm

D3: -21.2ppm

S: -32.3 ppm

The value of a/(b+c) is 1.75; the value of d/a is 0.08.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Akzo Co., Ltd., a trade name of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A9) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 2 below.

[Example 10] <Manufacture of organopolyoxyalkylene (A10) containing methacryloxyloxy group>

In a 3.0 L 3-port retort equipped with a stirring device, a thermometer, and a reflux condenser, 41 g (0.2 mol) of 1,3,5,7-tetramethylcyclotetrazepine as the component (a1) was added. 122 g (0.2 mol) of polydimethyl methoxyoxane having a weight average molecular weight of 760 as shown in the following average composition formula (B1-10) as a component (b2), 76g (0.6 Methyl 3-butenyl methacrylate as component (c), 864 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor), stirred under nitrogen atmosphere and simultaneously heated to 60 ° C reaction.

HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ -OH.........(B1-10)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polyoxyalkylene of the addition reaction product 40 ppm.

After the start of the dehydrogenation reaction was determined, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 96%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 201 g of the methacryloxy group-containing organopolyoxane (A10) represented by the following formula (53) can be obtained.

The obtained methacryloxy group-containing organopolyoxane (A10) has a functional group equivalent of 591 g/mol, a weight average molecular weight calculated by GPC of 19,500, and a viscosity at 25 ° C of 4,200 mPa. s.

In the above formula (53), m represents an integer of 15 on average; n represents an integer of 8 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

T: -66.2 ppm

D3: -21.2ppm

S: -32.3 ppm

The value of a/(b+c) is 1.13; the value of d/a is 0.08.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Akzo Co., Ltd., a trade name of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A10) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 2 below.

[Example 11] <Manufacture of organopolyoxyalkylene (A11) containing methacryloxyloxy group>

In a 3.0 L 3-port retort equipped with a stirring device, a thermometer, and a reflux condenser, 68 g (0.3 mol) of 1,3,5,7-tetramethylcyclotetrazepine as the component (a1) was added. Alkane, 45g (0.3m) as (b2) The dimethyl hydroxy methoxy end of dimethyl dioxane having a molecular weight of 166, and the 119 g (0.9 mol) of the methyl group as the component (c) represented by the following average composition formula (B1-11) 3-butenyl acrylate, 795 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were stirred under a nitrogen atmosphere while heating to 60 ° C for reaction.

HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ -OH.........(B1-11)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polyoxyalkylene of the addition reaction product 40 ppm.

After the start of the dehydrogenation reaction was determined, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 99%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 183 g of the methacrylic acid-containing oxime represented by the following formula (54), the following formula (55), and the following formula (56) can be obtained. Based on organopolyoxane (A11).

The obtained methacryloxy-containing organopolyoxane (A11) has a functional group equivalent of 340 g/mol, a weight average molecular weight calculated by GPC of 17600, and a viscosity at 25 ° C of 14500 mPa. s.

The value of [WB]/[WA] of the obtained methacryloxy group-containing organopolyoxane (A11) was 1.9. Further, the formula (55) corresponds to the formula (9), and the formula (56) corresponds to the formula (10).

In the above formula (54), m represents an integer of 25 on average; n represents an integer of 0 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

T: -66.2 ppm

The value of a/(b+c) is 1.00.

However, no peak of S: -32.3 ppm was observed; the value of d/a was zero.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Akzo Co., Ltd., a trade name of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A11) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 2 below.

[Example 12] <Manufacture of organopolyoxyalkylene (A12) containing methacryloxyloxy group>

In a 3.0-liter 3-neck retort equipped with a stirring device, a thermometer, and a reflux condenser, 201 g (0.8 mol) of 1,3,5,7-tetramethylcyclotetrazepine as component (a1) was added. An alkane, 240 g (1.4 mol) of dimethyl dimethyl oxane having a molecular weight of 166, which is represented by the following average composition formula (B1-12), having a molecular weight of 166, 97 g (1.4 mol). 0.7 moles of 3-butenyl methacrylate as component (c), 2138 g of toluene And 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor), stirred under a nitrogen atmosphere and simultaneously heated to 60 ° C to react.

HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ -OH.........(B1-12)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polyoxyalkylene of the addition reaction product 40 ppm.

After the start of the dehydrogenation reaction was determined, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 93%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 490 g of the methacrylic oxime represented by the following formula (57), the following formula (58), and the following formula (59) can be obtained. Based on organopolyoxane (A12).

The obtained methacryloxy group-containing organopolyoxane (A12) has a functional group equivalent of 1094 g/mol, a weight average molecular weight calculated by GPC of 99700, and a viscosity at 25 ° C of 25500 mPa. s.

The value of [WB]/[WA] of the obtained methacryloxy group-containing organopolyoxane (A12) was 9.6. Further, the formula (58) corresponds to the formula (9), and the formula (59) corresponds to the formula (10).

In the above formula (57), m represents an integer of 30 on average; n represents an integer of 0 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

T: -66.2 ppm

The value of a/(b+c) is 0.15.

However, no peak of S: -32.3 ppm was observed; the value of d/a was zero.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Akzo Co., Ltd., a trade name of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A12) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 2 below.

[Example 13] <Manufacture of organopolyoxyalkylene (A13) containing methacryloxyloxy group>

In a 3.0-liter 3-neck retort equipped with a stirring device, a thermometer, and a reflux condenser, 24 g (0.1 mol) of 1,3,5,7-tetramethylcyclotetrazepine as the component (a1) was added. Alkane, 13 g (0.05 mol) of methyltris(dimethyloxy)decane as component (a2) and 0.1 g (0.002 mol) of tetramethyl decane, 116 g (0.2 mol) as (b2) The component has a weight average molecular weight of 760 as shown in the following average composition formula (B1-13): hydroxy dimethyl methoxy end of polydimethyl siloxane, 53 g (0.3 mol) as component (c) 3-butenyl methacrylate, 768 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were stirred under a nitrogen atmosphere while heating to 60 ° C for reaction.

HO-Si(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ -OH.........(B1-13)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polyoxyalkylene of the addition reaction product 40 ppm.

After the start of the dehydrogenation reaction was determined, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and it was found that the reaction rate of the SiH group was 97%.

Thereafter, the activated carbon treatment is carried out to distill off the volatile component, whereby 170 g of the methacryloxy group-containing organopolyoxane (A13) represented by the following formula (60) can be obtained.

The obtained methacryloxy-containing organopolyoxane (A13) The functional group equivalent weight is 756g/mol, the weight average molecular weight calculated by GPC is 182100, and the viscosity at 25 ° C is 42300mPa. s.

In the above formula (60), m represents an integer of 50 on average; n represents an integer of 8 on average.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

T: -66.2 ppm

D3: -21.2ppm

S: -32.3 ppm

The value of a/(b+c) is 1.25; the value of d/a is 0.10.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by the Japanese chemical company Akzo) in 100 parts by mass of the methacryloxy group-containing organopolyoxane (A13) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 2 below.

[Example 14] <Manufacture of organopolyoxyalkylene (A14) containing methacryloxyloxy group>

In a 3.0-liter 3-neck retort equipped with a stirring device, a thermometer, and a reflux condenser, 96 g (0.4 mol) of 1,3,5,7-tetramethylcyclotetrazepine as the component (a1) was added. As an alkane, 107 g (0.8 mol) of methyl-1,1,3,3-tetramethyldioxane as component (a2) and 269 g (1.4 mol) of the component (b1) as follows a dimethyl dimethyl oxane having a molecular weight of 186 and a vinyl dimethyloxy end group represented by the formula (B1-14), 97 g (0.7 mol) of methacrylic acid-3- as a component (c) Butenyl ester, 2138 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were stirred under a nitrogen atmosphere while heating to 60 ° C for reaction.

CH ₂ =CHSi(Me) ₂ O-(Si(Me) ₂ O) ₈ -Si(Me) ₂ CH=CH ₂ ... (B1-14)

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polysiloxane of the addition reaction product 20 ppm.

After determining that the hydrogenation reaction begins, the reaction system is kept warm and Water or air cooling was maintained at 55 to 65 ° C while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 99%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 520 g of the organopolyoxane having the methacryloxy group represented by the following formula (61) and the following formula (62) can be obtained ( A14).

The obtained methacryloxy group-containing organopolyoxane (A14) has a functional group equivalent of 1300 g/mol, a weight average molecular weight of 11,000 calculated by GPC, and a viscosity of 600 mPa at 25 ° C. s.

The obtained methacryloxy group-containing organopolyoxane (A14), which contains at least one SiH group-containing hydrogenated polyoxane component in one molecule of the raw material, is used in combination (a1) and (a2). . Therefore, the crosslinked structure of the obtained methacryloxy group-containing organopolyoxane (A14) is lowered to lower the viscosity.

In the above formula (61), m represents an integer of averaging 30; n represents an integer of 0; and r represents an integer of 0.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

M1: +8.8ppm

D2: -19.8ppm

F2: +7.0ppm

The value of a/(b+c) is 0.16.

However, no peak of S: -32.3 ppm was observed; the value of d/a was zero.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by the Japanese chemical company Akzo) in 100 parts by mass of the methacryloxy group-containing organopolyoxane (A14) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Thereafter, the curable composition was poured into a frame model made of SUS316, and the hardening reaction was carried out at 100 ° C for 4 hours and at 150 ° C for 1 hour. The hardened material can be obtained.

The evaluation results of the obtained cured product characteristics are shown in Table 2 below.

[Example 15] <Manufacture of organopolyoxyalkylene (A2) containing methacryloxyloxy group>

In the first stage of the reaction, a 3.0-liter 3-neck retort equipped with a stirring device, a thermometer, and a reflux condenser was charged with 53 g (0.2 mol) of 1,3,5,7- as the component (a1). Tetramethylcyclotetraoxane, 27 g (0.1 mol) of methyltris(dimethyloxy)decane as component (a2), 40 g (0.3 mol) of methacrylic acid as component (c) 3-butenyl ester, 1600 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were stirred under a nitrogen atmosphere while heating to 60 ° C for reaction.

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polysiloxane of the addition reaction product 20 ppm.

After confirming the start of the rhodium hydrogenation reaction, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

In the second-stage reaction, 242 g (0.3 mol) of the component (b1) having a weight average molecular weight of 780 as shown in the following average composition formula (B1-1) is added to the reaction liquid of the first stage. The vinyl dimethyl oxy-terminated polydimethyl siloxane was incubated, and the reaction was incubated and kept at 55 to 65 ° C with water or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 99%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 360 g of the organopoly(meth) group having the methacryloxy group represented by the following formula (41) can be obtained. Oxane (A2).

The obtained methacryloxy group-containing organopolyoxane (A2) has a functional group equivalent of 714 g/mol, a weight average molecular weight calculated by GPC of 38,200, and a viscosity at 25 ° C of 2600 mPa. s.

As a result of Si NMR measurement, a peak as shown below corresponding to the constituent unit was observed.

F1: -18.2ppm

M1: +8.8ppm

T: -66.2 ppm

D2: -19.8ppm

D3: -21.2ppm

The value of a/(b+c) is 0.78.

However, no peak of S: -32.3 ppm was observed; the value of d/a was zero.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Akzo Co., Ltd., a trade name of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A2) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 2 below.

[Example 16] <Manufacture of organopolyoxyalkylene (A2) containing methacryloxyloxy group>

The organopolyoxyalkylene (A2) containing a methacryloxy group was produced in the same manner as in Example 2.

<Manufacture and Characterization of Hardened Materials>

3 parts by mass of 1-hydroxy-cyclohexyl-benzophenone (manufactured by BASF Japan, trade name: IRGACURE 184), in 100 parts by mass of the organopolysiloxane (A2) containing methacryloxyloxy group, 3 parts by mass of 2-methyl-1-[4-methylthio-phenyl]-2-N-norpoline propan-1-one (manufactured by BASF Japan, trade name: RGACURE 907) was mixed and stirred. After the whole is uniform, the foaming composition is obtained by defoaming.

Then, the curable composition was placed on a glass plate (50 mm in length × 50 mm in width × 3 mm in thickness) to form a mold having a spacing (50 mm in length × 50 mm in width × 3 mm in thickness), and the hardening property was further inside the space. The composition was injected and clamped with a glass plate.

Thereafter, the glass plate side was exposed to a cumulative irradiation amount of 2000 mJ/cm ² by an ultraviolet irradiation apparatus (manufactured by Japan SENENGINEERING Co., Ltd.) containing a high pressure mercury lamp.

The hardening is carried out in an environment of temperature: 23 ° C and humidity: 60% RH.

The mold is then removed to obtain a cured product.

The evaluation results of the obtained cured product characteristics are shown in Table 2 below.

[Example 17] <Manufacture of organopolyoxyalkylene (A2) containing methacryloxyloxy group>

Organopolyoxyalkylene (A2) containing methacryloxyloxy group Example 2 was produced in the same manner.

<Manufacture and Characterization of Hardened Materials>

3 parts by mass of 3-methylpropenyloxypropylmethyldimethoxydecane (KBM-502, Shin-Etsu Chemical Co., Ltd.) in 100 parts by mass of the methacryloxy-containing organopolyoxane (A2) (manufactured by the company) and 2.5 parts by mass of triamyl peroxy-2-ethylhexanoate (manufactured by Nippon Chemical Co., Ltd., trade name: Trigonox 121-50E, 50% by mass solution), mixed under nitrogen, and stirred After the whole is uniform, the hardening composition can be obtained by defoaming.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 2 below.

[Comparative Example 1] <Manufacture of organopolyoxyalkylene (A15) containing methacryloxyloxy group>

In a 3.0 L 3-port retort equipped with a stirring device, a thermometer, and a reflux condenser, 134 g (1.0 mol) of 1,1,3,3-tetramethyldioxane, 420 g (3.0 m) was charged. Benzyl methacrylate, 1600 g of toluene and 0.05 g of hydroquinone monomethyl ether (polymerization inhibitor) were stirred under a nitrogen atmosphere while heating to 60 ° C for reaction.

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polysiloxane of the addition reaction product 20 ppm.

After confirming the start of the rhodium hydrogenation reaction, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 99%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 405 g of the methacryloxy group-containing organopolyoxane (A15) represented by the following formula (63) can be obtained.

The obtained methacryloxy group-containing organopolyoxane (A15) has a functional group equivalent of 415 g/mol, a weight average molecular weight of 400 by GPC measurement, and a viscosity of 150 mPa at 25 ° C. s.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by Akzo Co., Ltd., a trade name of 100 parts by mass of the methacryloxy group-containing organopolyoxane (A15) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 3 below.

[Comparative Example 2] <Manufacture of organopolyoxyalkylene (A16) containing methacryloxyloxy group>

A methacryloxy-containing organic polyfluorene represented by the following formula (64) Oxane (A16) was X22-164C manufactured by Shin-Etsu Chemical Co., Ltd., Japan.

The functional group equivalent of the methacryloxy group-containing organopolyoxane (A16) is 2300 g/mol, and the weight average molecular weight calculated by GPC is 4500, and the viscosity at 25 ° C is 3600 mPa. sS.

<Manufacture and Characterization of Hardened Materials>

2.5 parts by mass of a third amyl peroxy-2-ethylhexanoate (manufactured by the Japanese chemical company Akzo) in 100 parts by mass of the methacryloxy group-containing organopolyoxane (A16) : Trigonox 121-50E, 50% by mass solution) was mixed under nitrogen, stirred to make the whole uniform, and then defoamed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened material was obtained by performing a hardening reaction at 100 ° C for 4 hours and at 150 ° C for 1 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 3 below.

[Comparative Example 3] <Manufacture of epoxy-containing organopolyoxane (A17)>

In a 3.0-liter 3-neck retort equipped with a stirring device, a thermometer, and a reflux condenser, 53 g (0.2 mol) of 1,3,5,7-tetramethylcyclotetrazepine as the component (a1) was added. Alkyl, 27 g (0.1 mol) of methyltris(dimethyloxy)decane as component (a2), and 242 g (0.3 mol) of the component (b1) as the following average composition formula (B1-1) Weight shown a polydimethylsiloxane having a vinyl dimethyloxy group at a molecular weight of 780, 104 g (0.9 mol) of a vinylcyclohexene oxide as a component (c), and 1300 g of toluene in a nitrogen atmosphere The mixture was stirred while heating to 60 ° C.

Thereafter, a solution of chloroplatinic acid in isopropyl alcohol was added to make the weight of the platinum metal relative to the organic polysiloxane of the addition reaction product 20 ppm.

After confirming the start of the rhodium hydrogenation reaction, the reaction system was kept warm and kept at 55 to 65 ° C with water cooling or air cooling while stirring for 72 hours.

Thereafter, the contents of the distillation flask were analyzed, and the reaction rate of the SiH group was found to be 99%.

Thereafter, after the activated carbon treatment and distillation of the volatile component, 310 g of the epoxy group-containing organopolyoxane (A17) represented by the following formula (65) can be obtained.

The epoxy group-containing organopolyoxane (A17) has no group containing an unsaturated bond.

The obtained epoxy group-containing organopolyoxane (A17) has a weight average molecular weight of 30,500 as determined by GPC and a viscosity of 5,600 mPa at 25 ° C. s.

In the above formula (65), m represents an integer of 10 on average, and n represents an integer of 8 on average.

<Manufacture and Characterization of Hardened Materials>

6 parts by mass of methyl hexahydrophthalic anhydride and 1 part by mass of diazabicycloundecene octoate, in 100 parts by mass of the epoxy group-containing organopolyoxane (A17), After stirring, the whole is uniform, and then defoaming is performed to obtain a curable composition.

Thereafter, the curable composition was injected into the mold, and the hardened product was obtained by performing a hardening reaction at 120 ° C for 1 hour and then at 150 ° C for 2 hours.

The evaluation results of the obtained cured product characteristics are shown in Table 3 below.

[Comparative Example 4] <Curable resin composition (A18)>

In the curable resin composition (A18), the KER-2500 manufactured by Shin-Etsu Chemical Co., Ltd., which is commercially available, is used as the curable resin composition for the optical semiconductor sealing material.

<Manufacture and Characterization of Hardened Materials>

The KER-2500A and KER-2500B which have been sold are mixed in 100 parts by mass, and after stirring, the whole is uniform, and then defoaming is performed to obtain a curable composition.

Then, the curable composition was poured into a frame model made of SUS316, and the hardened product was obtained by performing a hardening reaction at 100 ° C for 1 hour and at 150 ° C for 5 hours.

The evaluation results of the obtained cured product characteristics are shown in Table 3 below.

[Comparative Example 5] <Curable resin composition (A19)>

The curable resin composition (A19), which is a curable resin composition for an optical semiconductor sealing material, is ASP-1010 manufactured by Shin-Etsu Chemical Co., Ltd., which is already sold.

<Manufacture and Characterization of Hardened Materials>

Each of the sold ASP-1010A (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and ASP-1010B (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed in an amount of 100 parts by mass, stirred to make the whole uniform, and then defoamed. A hardenable composition can be obtained.

Thereafter, the curable composition was poured into a frame model made of SUS316, and the hardening reaction was carried out at 100 ° C for 1 hour and then at 150 ° C for 5 hours. The hardened material can be obtained.

The evaluation results of the obtained cured product characteristics are shown in Table 3 below.

[Comparative Example 6] <Curable resin composition (A20)>

The curable resin composition (A20), which is a curable resin composition for an optical semiconductor sealing material, is commercially available as FX-001 manufactured by Kaneka Co., Ltd., Japan.

<Manufacture and Characterization of Hardened Materials>

FX-001A (trade name, manufactured by Kaneka Co., Ltd., Japan): 40 parts by mass and FX-001B (trade name, manufactured by Kaneka Co., Ltd., Japan): 60 parts by mass, stirred, homogenized, and then defoamed A hardenable composition can be obtained.

Then, the curable composition was poured into a frame model made of SUS316, and the cured product was obtained by curing at 100 ° C for 1 hour, at 150 ° C for 1 hour, and at 180 ° C for 0.5 hour.

The evaluation results of the obtained cured product characteristics are shown in Table 3 below.

The organopolyoxane of the present embodiment has (i) F1 and M1, (ii) F1 and T among the constituent units F1, M1 and T represented by the above formulas (1) to (3) in the molecular structure. And (iii) the constituent unit of any combination of F1, M1 and T.

By containing the constituent units F1, M1, and T, an organic polyoxane excellent in heat yellowing resistance and light resistance can be obtained.

At the same time, the portion of the crosslinked structure formed by the constituent unit F1 and the portion of the buffer containing the constituent unit M1 or T which can alleviate the stress are included in the partial molecular structure, thereby making it possible With hardness, cold and thermal shock resistance, gas barrier.

It can be seen from Examples 1 to 17 that in terms of heat-resistant yellowing, light resistance, thermal shock resistance, hardness, adhesion, and gas barrier properties, it is possible to obtain a sufficient degree of formation, particularly in the use of optical semiconductors. An organic polysiloxane having a transparent cured product and a curable resin composition using the same.

As is clear from Comparative Examples 1 to 6, since the above-described configuration of the present embodiment is not provided, the desired characteristics among the heat-resistant yellowing, light resistance, thermal shock resistance, hardness, adhesion, and gas barrier properties are as follows. From the point of view of the balance of characteristics, the actual characteristics cannot be obtained in full.

This patent application is also filed with the European Patent Application (PCT/JP2011/058115) filed with the Japanese Patent Office on March 30, 2011, and the Intellectual Property Office of the Ministry of Economic Affairs of the Republic of China on March 31, 2011. Patent application (No. 100111196), the contents of which are also incorporated herein by reference.

[Industrial availability]

The organopolysiloxane of the present invention and the curable resin composition using the same can be used as a wafer bonding material for an optical semiconductor, a coating material, a curable resin composition for nano-imprinting, and a material for ink printing. Available on the top.

Claims (28)

An organopolyoxane having one or more unsaturated bond-containing groups in one molecule and having the constituent units F1, M1, and T represented by the following general formulae (1) to (3) (i) a constituent unit of any combination of F1 and M1, (ii) F1 and T, (iii) F1, and M1 and T, and any one of the following general formulae (14) to (25), (28) to (31) As shown by the person; F1: M1: T: (In the general formulae (1) to (3), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted group. Any one selected from the group consisting of an aryl group and a substituted or unsubstituted aralkyl group; R ² represents a group having 2 to 10 carbon atoms and an unsaturated bond; and X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; a divalent hydrocarbon group having 2 to 10 carbon atoms; a, b, and c each independently represent an integer of 1 or more; wherein F1 represents a constituent unit of the cyclic organopolyoxane) (In the above general formulae (14) to (25), (28) to (31), m represents an integer of 0 to 2000, n represents an integer of 0 to 20, and r represents an integer of 0 to 20). In the above-mentioned general formulae (1) to (3), a, b, and c satisfy the following formula (I), 0.1≦a/(b+c), in the above-described general formula (1) to (3). ≦5. . . (I). The organopolysiloxane according to claim 1 or 2, wherein R ² in the constituent unit F1 represented by the above formula (1) is an acryloxy group or a methacryloxy group. The organopolyoxane according to claim 1 or 2, which comprises any of the constituent units represented by the following general formulae (4) to (6): D1, D2, and D3, D1: R ¹ ₂ SiO ₂ / ₂ ). . . (4) D2: D3: (R ¹ ₂ SiO ₂ / ₂ ). . . (6) (In the general formulae (4) to (6), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a substitution. Or any one selected from the group consisting of an unsubstituted aryl group and a substituted or unsubstituted aralkyl group; X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; wherein D1 and D2 represent a cyclic organopolyoxane The constituent unit, D3 represents the constituent unit of the chain organopolysiloxane. The organopolyoxane according to claim 1 or 2, which contains the constituent unit S represented by the following formula (7), and the content of the constituent unit represented by the formula (7), With respect to the content of the constituent unit F1 represented by the above formula (1), the following formula (II) is satisfied: d/a ≦ 0.1. . . (II) S: (In the formula (7), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, and Any one selected from the group consisting of a substituted or unsubstituted aralkyl group; wherein the constituent unit S represents a constituent unit of a cyclic or chain organopolysiloxane. The organopolyoxyalkylene as described in claim 1 or 2, wherein only the constituent unit F1 represented by the above formula (1) is contained, and the constituent unit of the above R ² is contained. The organic polyoxosiloxane according to the first or second aspect of the invention, wherein the constituent unit F1 represented by the above formula (1) and the constituent unit F2 represented by the following formula (8) are contained as The constituent unit of the above R ² (and, in the following formula (8), R ²¹ is contained in the above R ² ) F2: (In the above formula (8), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. And any one selected from the group consisting of substituted or unsubstituted aralkyl groups; R ²¹ represents an acryloxy group or a methacryloxy group; Y represents a divalent hydrocarbon group having 2 to 10 carbon atoms; wherein F2 represents The constituent unit of the chain organopolyoxane). An organopolyoxane, which further contains 0.1 to 100 parts by mass of the following formula with respect to 100 parts by mass of the organopolyoxane as described in any one of claims 1 to 7. 9) a cyclic organopolyoxane, (In the above formula (9), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. And any one selected from the group consisting of substituted or unsubstituted aralkyl groups; R ²¹ represents an acryloxy group or a methacryloxy group; X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and e represents 1 or more An integer; f represents an integer greater than 0; e+f represents an integer from 3 to 20. An organic polyoxoxane, which further contains 0.01 to 1000 parts by mass of the following formula with respect to 100 parts by mass of the organopolyoxane shown in any one of claims 1 to 8. 10) the compound shown, (In the above formula (10), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. And any one selected from the group consisting of a substituted or unsubstituted aralkyl group; R ²¹ represents an acryloxy group or a methacryloxy group; X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and g represents 1 or more An integer; h represents an integer greater than 0; i represents an integer from 0 to 20. The organopolyoxane according to any one of the preceding claims, wherein the cyclic polyorganosiloxane represented by the following formula (9) and the following a compound of the formula (10), (In the above formula (9), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group. And any one selected from the group consisting of substituted or unsubstituted aralkyl groups; R ²¹ represents an acryloxy group or a methacryloxy group; X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and e represents 1 or more An integer; f represents an integer greater than 0; e+f represents an integer from 3 to 20) . . . (10) (In the formula (10), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, substituted or unsubstituted. Any one selected from the group consisting of an aryl group and a substituted or unsubstituted aralkyl group; R ²¹ represents an acryloxy group or a methacryloxy group; X represents a divalent hydrocarbon group having 2 to 10 carbon atoms; An integer of 1 or more; h represents an integer of 0 or more; i represents an integer of 0 to 20) which is calculated by the following formula (III) by the intensity of a peak obtained by matrix-assisted free time-of-flight mass spectrometry. The ratio of the content of the compound represented by the above formula (10) [WB] to the content of the compound represented by the above formula (9) [WA]: the value of [WB] / [WA] is 0.1 or more and 20.0 or less, [WB ] / [WA] = the intensity of the peak corresponding to the mass of the structure of the general formula (10) and the total mass of the sodium mass 23 / the quality of the structure conforming to the general formula (9) and the total mass of the sodium mass 23 The intensity of the peak. . . . (III). The organopolyoxane according to any one of claims 1, 2, 8 and 9, wherein the above R ¹ is an alkyl group having 1 to 10 carbon atoms. The organopolyoxane according to any one of claims 1, 2, 8 and 9, wherein the above R ¹ is a methyl group. The organopolyoxane according to any one of claims 1, 2, 8 and 9, wherein the above R ² contains an acryloxy group or a methacryloxy group, and the propylene oxime group or The functional equivalent of the methacryloxy group is from 210 to 2100 g/mole. The organopolyoxane according to any one of claims 1, 2, 8 and 9 which has a weight average molecular weight of 700 to 5,000,000 and a viscosity at 25 ° C of 50 to 1,000,000 mPa. s. A method for producing an organopolyoxane, which is a method for producing an organopolyoxane according to any one of claims 1 to 14, which has the following step: (11) The hydrogenated polyoxyalkylene (a1) shown, and the hydrogenated polyoxyalkylene (a2) and i) having one or more hydrogen atoms directly bonded to a halogen atom, have two or more direct bonds to the hydrazine. a vinyl group-containing vinyl polyorganosiloxane (b1) of an atom or a polyoxyalkylene (b2) having two or more hydroxyl groups directly bonded to a ruthenium atom, and ii) having two or more in one molecule a step of performing an addition reaction of a saturated bond organic compound (c) in the presence of a rhodium hydrogenation catalyst (d), (In the formula (11), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group, and Any one selected from the group consisting of substituted or unsubstituted aralkyl groups; j represents an integer of 1 or more; k represents an integer of 0 or more; j+k represents an integer of 3 to 20). The method for producing an organopolyoxane according to claim 15, wherein the step of performing the addition reaction comprises the steps of: preparing a reaction liquid, and adding a hydrogenation catalyst (d) to the reaction liquid. And the reaction liquid contains the hydrogenated polyoxyalkylene (a1) represented by the above formula (11), and the above-mentioned hydrogenated polyfluorene having one or more hydrogen atoms directly bonded to a halogen atom. An alkane (a2), the above-mentioned vinyl group-containing organopolyoxane (b1) having two or more vinyl groups bonded directly to a ruthenium atom, and an organic compound having two or more unsaturated bonds in one molecule (c) Or an organic compound (c) having two or more polyoxyalkylenes (b2) directly bonded to a hydroxyl group of a halogen atom and two or more unsaturated bonds in one molecule. The method for producing an organopolyoxane according to claim 15, wherein the step of performing the addition reaction is carried out in the following steps: a step of preparing a reaction liquid, the reaction liquid containing the above The hydrogenated polyoxyalkylene (a1) represented by the formula (11) and the above-mentioned hydrogenated polyoxyalkylene (a2) having one or more hydrogen atoms bonded directly to a halogen atom, and having 2 molecules in one molecule The organic compound (c) having one or more unsaturated bonds; and the step of forming an adduct by adding a hydrogenation catalyst (d) to the reaction liquid to form a hydrogenated polyoxyalkylene represented by the above formula (11) ( A1), as described above, having more than one hydrogenated polyoxane (a2) and one molecule directly bonded to a hydrogen atom of a halogen atom An adduct of an organic compound (c) having two or more unsaturated bonds; and an addition step of adding a vinyl group-containing organic polymer having two or more vinyl groups directly bonded to a ruthenium atom to the above reaction liquid A decane (b1) or a polyoxyalkylene (b2) having two or more hydroxyl groups bonded directly to a ruthenium atom. A curable resin composition comprising 100 parts by mass of the organopolysiloxane according to any one of claims 1 to 14 and 0.5 to 10 parts by mass of a thermal radical generator. A curable resin composition containing 100 parts by mass of the organic polysiloxane of any one of claims 1 to 14 and 0.5 to 20 parts by mass of a photo radical generator. The sclerosing resin composition according to claim 18, wherein the organic polyoxane according to any one of claims 1 to 14 is further contained in an amount of 100 parts by mass. 0.1 to 10 parts by mass of a decane coupling agent. The sclerosing resin composition according to claim 18, wherein the organic polyoxane according to any one of claims 1 to 14 is further contained in an amount of 100 parts by mass. 0.001 parts by mass or less of (d) hydrazine hydrogenation catalyst. The sclerosing resin composition according to claim 18, wherein the organic polyoxane according to any one of claims 1 to 14 is further contained in an amount of 100 parts by mass. 0.1 to 500 parts by mass of the inorganic oxide. A sealing material for an optical semiconductor, comprising the curable resin composition according to any one of claims 18 to 22. A die bonding material for an optical semiconductor, comprising the curable resin composition according to any one of claims 18 to 22. A coating material comprising the curable resin composition according to any one of claims 18 to 22. A curable resin composition for a nano-imprint, which comprises the curable resin composition according to any one of claims 18 to 22. An ink comprising the curable resin composition according to any one of claims 18 to 22, and a coloring agent. An optical semiconductor package formed by using a sealing material for an optical semiconductor according to claim 23 of the patent application.