TW201609977A - Curable silicone resin composition, cured object obtained therefrom, and optical semiconductor device formed using same - Google Patents

Abstract

This curable silicone resin composition is characterized by comprising component (A), which is a silicone resin containing hydrogen atoms each bonded to a silicon atom (SiH groups), component (B), which is a silicone resin containing vinyl groups each bonded to a silicon atom (Si-CH=CH2 groups), and component (C), which is a platinum catalyst. The composition is further characterized in that the total content of silanol groups (Si-OH groups) in components (A) and (B) is 0.5-5.0 mmol/g and the content of platinum atoms in component (C) is 0.003-3.0 mass ppm of the sum of components (A), (B), and (C). A cured object obtained by heating the composition is suitable for use as the encapsulating material of an optical semiconductor device.

Description

Curable polyoxynoxy resin composition and cured product thereof, and optical semiconductor device using same

The present invention relates to a curable polyoxyxene resin composition which can be preferably used as a raw material of a sealing material for an optical semiconductor element such as a light-emitting diode, and a cured material thereof, and a cured product thereof, and an optical semiconductor using the same Device.

A cured product such as an epoxy resin composition or a polyoxyxylene resin composition is used for a sealing material of a light-emitting device using an optical semiconductor element such as a light-emitting diode (abbreviation: LED). For their sealing materials, it is required to maintain transparency even when exposed to high temperatures for a long period of time, that is, it is required to have excellent "heat-resistant transparency".

In general, the cured product of the epoxy resin composition has a high hardness, and therefore has excellent handleability. For example, in a low-output white LED sealing application, the desired durability can be obtained, and therefore it is often used for low-output applications.

However, it is known that, in recent years, LEDs have been gradually increased in brightness and output, and have been used for power semiconductors, high-intensity light-emitting elements (such as automobile headlights or liquid crystals) for cured products of the prior transparent epoxy resin composition. When a short-wavelength semiconductor laser such as a high-brightness LED for a television backlight or a blue laser is used, the heat resistance is insufficient, and current leakage or yellowing due to high-temperature deterioration may occur.

Recently, in order to solve the problems, a cured product of a resin composition based on an epoxy resin having excellent heat resistance instead of an epoxy resin has been used for a sealing material for LEDs. For example, in Patent Document 1, as a material for protecting a sealing optical device or a semiconductor device, An addition-curable polydecane resin composition using an addition reaction (hydrogenation reaction) of a SiH group and an alkenyl group has been reported.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-198930

Most of the addition-hardening polyoxynoxy resin compositions contain a platinum-based metal catalyst, particularly a platinum catalyst, as a hardening catalyst. However, the polyoxynoxy resin composition containing a platinum catalyst may be yellowed if exposed to a high temperature for a long period of time. As a result, in the cured product of the platinum-containing catalyst-containing polyoxyxene resin composition, there is a problem that transparency is impaired when exposed to a high temperature for a long period of time. With the development of high-luminance LEDs in recent years, it has been desired to develop a polyoxyxylene resin composition which can provide such a cured product which has sufficient transparency, that is, a heat-resistant transparency, which is excellent in heat resistance even when exposed to a high temperature for a long period of time. .

The present invention has been made in view of the above circumstances, and an object of the invention is to provide an addition-curable curable polyoxynoxy resin composition capable of providing a cured product excellent in heat-resistant transparency, a cured product thereof, and an optical semiconductor using the same. Device.

The present inventors have conducted intensive studies to achieve the above object, and as a result, it has been found that by using a polyfluorene containing at least the component (A): a hydrogen atom (SiH group) bonded to a ruthenium atom, which is represented by the following formula [1] Oxygen resin and component (B): a polyfluorene oxide resin having a vinyl group (Si-CH=CH ₂ group) bonded to a ruthenium atom and a component (C): a platinum catalyst And the total content of the stanol group (Si-OH group) in the component (A) and the component (B) is 0.5 to 5.0 mmol/g, and the content of the platinum atom in the component (C) is relative to the component (A) (C) The total mass of the component (C) and the curable polyoxynene resin composition of 0.003 to 3.0 ppm by mass, which achieves the above-mentioned problems, and achieves hardening and hardening of the heat-resistant transparency. Polyoxygenated resin composition.

(H-SiR ¹ ₂ O _1/2 ) _a (SiR ² ₂ O _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d [1]

(wherein R ¹ is an alkyl group having 1 to 3 carbon atoms, 2 R ¹ may be the same or different from each other, and R ² is an alkyl group having 1 to 3 carbon atoms, and 2 R ² may be the same or mutually In different types, R ³ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a, b, and c are each more than 0 and not up to 1, and d is 0 or more and less than 1 The number of oxygen atoms in the structural unit represented by a+b+c+d=1, (SiR ² ₂ O _2/2 ), (R ³ SiO _3/2 ), and (SiO _4/2 ) respectively Forming an oxygen atom of a siloxane chain or forming an oxygen atom of a stanol group)

(CH ₂ =CH-SiR ⁴ ₂ O _1/2 ) _e (SiR ⁵ ₂ O _2/2 ) _f (R ⁶ SiO _3/2 ) _g (SiO _4/2 ) _h [2]

(wherein R ⁴ is an alkyl group having 1 to 3 carbon atoms, 2 R ⁴ may be the same or different from each other, and R ⁵ is an alkyl group having 1 to 3 carbon atoms, and 2 R ⁵ may be the same or mutually In different types, R ⁶ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and e, f, and g are each more than 0 and less than 1, and h is 0 or more and less than 1 The number of oxygen atoms in the structural unit represented by e+f+g+h=1, (SiR ⁵ ₂ O _2/2 ), (R ⁶ SiO _3/2 ), and (SiO _4/2 ) Forming an oxygen atom of a siloxane chain or forming an oxygen atom of a stanol group)

That is, the present invention includes the following Inventions 1 to 15.

[Invention 1]

A curable polyoxyxene resin composition containing at least (A) a component: a polyoxyxylene resin having a hydrogen atom (SiH group) bonded to a ruthenium atom and a component (B) represented by the following formula [1] a polyfluorene oxy-resin represented by the following formula [2] and having a vinyl group (Si-CH=CH ₂ group) bonded to a ruthenium atom, and a component (C): a platinum catalyst, and the component (A) The total content of the stanol group (Si-OH group) in the component (B) is 0.5 to 5.0 mmol/g, and the content of the platinum atom in the component (C) is relative to the component (A) and the component (B) and (C). The total mass of the components, in terms of mass units, is 0.003 to 3.0 ppm, [Chemical 3] (H-SiR ¹ ₂ O _1/2 ) _a (SiR ² ₂ O _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d [1]

(wherein R ¹ is an alkyl group having 1 to 3 carbon atoms, 2 R ¹ may be the same or different from each other, and R ² is an alkyl group having 1 to 3 carbon atoms, and 2 R ² may be the same or mutually In different types, R ³ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a, b, and c are each more than 0 and not up to 1, and d is 0 or more and less than 1 The number of oxygen atoms in the structural unit represented by a+b+c+d=1, (SiR ² ₂ O _2/2 ), (R ³ SiO _3/2 ), and (SiO _4/2 ) respectively Forming an oxygen atom of a siloxane chain or forming an oxygen atom of a stanol group)

(CH ₂ =CH-SiR ⁴ ₂ O _1/2 ) _e (SiR ⁵ ₂ O _2/2 ) _f (R ⁶ SiO _3/2 ) _g (SiO _4/2 ) _h [2]

(wherein R ⁴ is an alkyl group having 1 to 3 carbon atoms, 2 R ⁴ may be the same or different from each other, and R ⁵ is an alkyl group having 1 to 3 carbon atoms, and 2 R ⁵ may be the same or mutually In different types, R ⁶ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and e, f, and g are each more than 0 and less than 1, and h is 0 or more and less than 1 The number of oxygen atoms in the structural unit represented by e+f+g+h=1, (SiR ⁵ ₂ O _2/2 ), (R ⁶ SiO _3/2 ), and (SiO _4/2 ) An oxygen atom forming a siloxane chain or an oxygen atom forming a stanol group).

[Invention 2]

The curable polyoxyxene resin composition according to Invention 1, wherein the number of moles of the hydrogen atom bonded to the ruthenium atom in the component (A): the mole of the vinyl group bonded to the ruthenium atom in the component (B) The number is 0.8:0.2~0.5:0.5.

[Invention 3]

The curable polyoxyxene resin composition according to Invention 1 or 2, wherein, in the component (A), a, b, c and d are a: b: c: d = 0.10 to 0.40: 0.10 to 0.80: 0.10 to 0.80. :0~0.70, in the component (B), e, f, g, and h are e:f:g:h=0.10~0.40:0.10~0.80:0.10~0.80:0~0.70.

[Invention 4]

The curable polyoxyxene resin composition according to any one of Inventions 1 to 3, wherein, in the component (A), a, b, c and d are a: b: c: d = 0.20 to 0.40: 0.10 to 0.40. : 0.30~0.60: 0.10~0.30. In the component (B), e, f, g, and h are e:f:g:h=0.20~0.40:0.10~0.40:0.30~0.60:0.10~0.30.

[Invention 5]

The curable polyoxyxene resin composition according to Invention 1 or 2, wherein in the component (A), d = 0, a, b and c are a: b: c = 0.05 to 0.40: 0.10 to 0.80: 0.10 to 0.80. In the component (B), h=0, e, f, and g are e:f:g=0.05~0.40:0.10~0.80:0.10~0.80.

[Invention 6]

The curable polydecane resin composition according to any one of Inventions 1 to 5, which further contains a hardening retarder.

[Invention 7]

The curable polyoxyxene resin composition according to any one of Inventions 1 to 6, which further contains an antioxidant or a light stabilizer.

[Invention 8]

The curable polyoxyxene resin composition according to any one of the first to seventh aspects of the present invention, further comprising one or more selected from the group consisting of a subsequent imparting agent, a phosphor, and inorganic particles.

[Invention 9]

The curable polyoxyxene resin composition according to any one of Inventions 1 to 8, which further comprises a release agent, a resin modifier, a colorant, a diluent, an antibacterial agent, an antifungal agent, One or more of the group consisting of a leveling agent and an anti-sagging agent.

[Invention 10]

A cured product obtained by hardening the curable polyoxyxene resin composition according to any one of Inventions 1 to 9.

[Invention 11]

A sealing material comprising the cured product of the curable polyoxynoxy resin composition according to any one of Inventions 1 to 9.

[Invention 12]

A method for producing a cured product of a curable polyanthracene resin composition, which comprises heating the curable polyanthracene resin composition according to any one of Inventions 1 to 9 at 45 ° C or higher and 300 ° C or lower. hardening.

[Invention 13]

An optical semiconductor device obtained by sealing at least an optical semiconductor element with a cured product of the curable polyoxyxene resin composition according to any one of Inventions 1 to 9.

[Invention 14]

An adhesive for a semiconductor comprising the cured product of the curable polyoxyxene resin composition according to any one of Inventions 1 to 9.

[Invention 15]

An optical semiconductor device using the semiconductor adhesive of Invention 14.

In the present specification, specific examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The aromatic hydrocarbon group having 6 to 10 carbon atoms may be a substituted or unsubstituted aromatic hydrocarbon group, and part or all of the hydrogen atom may be substituted with a fluorine atom. Specific examples include phenyl, naphthyl, tolyl, xylyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, and 3,5-di(trifluoromethylphenyl). ) base.

According to the present invention, it is possible to provide a hardened material which can provide excellent heat resistance and transparency. A chemical polyoxymethylene resin composition and a cured product thereof, and an optical semiconductor device using the same.

1‧‧‧ sealing material

2‧‧‧Optical semiconductor components

3‧‧‧bonding line

4‧‧‧Reflecting material

5‧‧‧ lead frame

6‧‧‧Optical semiconductor substrate

10‧‧‧Optical semiconductor devices

Fig. 1 is a schematic cross-sectional view showing an example of an optical semiconductor device of the present invention.

Fig. 2 is a graph showing the relationship between the shear viscosity and the temperature of the compositions (composition 1-1 to composition 1-5, comparative composition 1-1) prepared in the examples and the comparative examples.

Fig. 3 is a graph showing the relationship between the shear viscosity and the temperature of the compositions (composition 4-1 to composition 4-3, comparative composition 4-1) prepared in the examples and the comparative examples.

Fig. 4 is a graph showing the relationship between shear viscosity and time of the compositions (composition 1-1, composition 1-6 to composition 1-9) prepared in the examples.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[Sclerosing Polyoxymethylene Resin Composition]

The curable polyanthracene resin composition of the present invention (hereinafter sometimes referred to simply as "the composition of the present invention") contains at least a specific amount of the components (A) to (C), and the cured product obtained by heating the composition is obtained. It can be preferably used as a sealing material for an optical semiconductor device. Hereinafter, each component contained in the composition of the present invention will be described.

<(A) component>

The component (A) is a polyfluorene oxide resin represented by the following formula [1] and containing a hydrogen atom (SiH group) bonded to a ruthenium atom. The component (A) may be used alone or in combination of two or more.

(H-SiR ¹ ₂ O _1/2 ) _a (SiR ² ₂ O _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d [1]

The above formula [1] represents an average composition formula. In the formula [1], R ¹ is an alkyl group having 1 to 3 carbon atoms, and two R ^{1 's} may be the same or different from each other. R ² is an alkyl group having 1 to 3 carbon atoms, and two R ^{2 's} may be the same or different from each other. R ³ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. a, b, and c are respectively in the range of more than 0 and not up to 1, and d is a number in the range of 0 or more and less than 1, satisfying a+b+c+d=1. The oxygen atoms in the structural unit represented by (SiR ² ₂ O _2/2 ), (R ³ SiO _3/2 ), and (SiO _4/2 ) respectively represent an oxygen atom forming a siloxane chain or forming a stanol group. Oxygen atom.

The alkyl group having 1 to 3 carbon atoms of R ¹ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The alkyl group having 1 to 3 carbon atoms of R ² is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The alkyl group having 1 to 3 carbon atoms of R ³ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The aromatic hydrocarbon group having 6 to 10 carbon atoms of R ³ is preferably a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group or a 3,5-di(trifluoromethylphenyl group). Base, especially phenyl.

The combination of R ¹ , R ² and R ³ is not particularly limited. Wherein R ¹ is methyl or ethyl, R ² is methyl or ethyl, and R ³ is methyl, ethyl, phenyl, 3-trifluoromethylphenyl, 4-trifluoromethyl Any of a phenyl group or a 3,5-bis(trifluoromethylphenyl) group, particularly preferably R ¹ is a methyl group, R ² is a methyl group, and R ³ is a phenyl group.

The value of a is not particularly limited as long as it exceeds 0 and does not reach the range of 1 and satisfies a+b+c+d=1. The value of a is preferably 0.05 to 0.40, and particularly preferably 0.20 to 0.40. When the value of a is 0.05 or more, the composition of the present invention has good moldability, and if it is 0.40 or less, the cured product of the present invention has good mechanical strength.

The value of b is not particularly limited as long as it exceeds 0 and does not reach the range of 1 and satisfies a+b+c+d=1. The value of b is preferably 0.10 to 0.80, and particularly preferably 0.10 to 0.40. When the value of b is 0.10 or more, the composition of the present invention has good formability, and if it is 0.80 or less, the cured product of the present invention has good mechanical strength.

The value of c is not particularly limited as long as it exceeds 0 and does not reach the range of 1 and satisfies a+b+c+d=1. The value of c is preferably from 0.10 to 0.80, and more preferably from 0.30 to 0.60. When the value of c is 0.10 or more, the cured product of the present invention has good mechanical strength, and if it is 0.80 or less, the composition of the present invention has good formability.

The value of d is not particularly limited as long as it is 0 or more and does not reach the range of 1 and satisfies a+b+c+d=1. The value of d is preferably from 0 to 0.70. Among them, in the case where the cured product of the present invention exhibits a good bonding strength and a good hardness, the value of d is particularly preferably from 0.10 to 0.30. Further, in the case where the value of d is 0, the structural unit of (SiO _4/2 ) in the above formula [1] does not exist.

The values of a, b, c and d are preferably a: b: c: d = 0.05 to 0.40: 0.10 to 0.80: 0.10 to 0.80: 0 to 0.70, and more preferably a: b: c: d = 0.20 to 0.40. : 0.10~0.40: 0.30~0.60: 0.10~0.30.

When the value of d is 0, the values of a, b, and c are preferably a: b: c = 0.05 to 0.40: 0.10 to 0.80: 0.10 to 0.80.

The values of a, b, c, and d can be calculated by using a nuclear magnetic resonance apparatus to measure the ²⁹ Si-NMR spectrum of the component (A) and the ¹ H-NMR spectrum, and using them in a complementary combination.

In the above formula [1], the structural unit represented by (SiR ² ₂ O _2/2 ) may include a structure represented by the following formula [1-2], that is, a structure represented by (SiR ² ₂ O _2/2 ) One of the oxygen atoms bonded to the germanium atom in the unit forms a structure of a stanol group.

[6] (R ² SiXO _1/2 ) [1-2]

The above formula [1-2], R ² is the above formula [1] in the same meaning as R ^2, X represents a hydroxyl group.

The structural unit represented by (SiR ² ₂ O _2/2 ) includes a portion surrounded by a broken line in the structural unit represented by the following formula [1-b], and may further include a formula represented by the following formula [1-2-b] The portion of the structural unit that is surrounded by a dotted line. That is, a structural unit having a group represented by R ² and having a hydroxyl group remaining at the terminal to form a stanol group is also included in the structural unit represented by (SiR ² ₂ O _2/2 ). Further, in the structural unit represented by the following formulas [1-b] and [1-2-b], the oxygen atom in the Si-O-Si bond forms a decane bond with the adjacent ruthenium atom, and the adjacent structure The unit shares an oxygen atom. Therefore, one of the Si-O-Si bonds is "O _1/2 ".

[Chemistry 7]

The above formula [1-b] and [1-2-b], R ² is the above formula [1] in the same meaning as R ^2. In the above formula [1-2-b], X represents a hydroxyl group.

The structural unit represented by (R ³ SiO _3/2 ) may include a structure represented by the following formula [1-3] or [1-4], that is, a structural unit represented by (R ³ SiO _3/2 ) The two oxygen atoms bonded to the atom respectively form a structure of a stanol group or one of the oxygen atoms bonded to the ruthenium atom in the structural unit represented by (R ³ SiO _3/2 ) to form a decyl alcohol group. The structure.

(R ³ SiX ₂ O _1/2 ) [1-3] (R ³ SiXO _2/2 ) [1-4]

The above formula [1-3] and the formula [1-4], R ³ of the above formula [1] in the same meaning as R ^3, X represents a hydroxyl group.

The structural unit represented by (R ³ SiO _3/2 ) includes a portion surrounded by a broken line in the structural unit represented by the following formula [1-c], and may further include the following formula [1-3-c] or [1] -4-c] The portion of the structural unit represented by a dotted line. That is, a structural unit having a group represented by R ³ and having a hydroxyl group remaining at the terminal to form a stanol group is also included in the structural unit represented by (R ³ SiO _3/2 ).

[Chemistry 9]

The above formula [1-c], [1-3 -c] and [1-4-c] R ³ in the above formula [1] in the same meaning as R ^3. In the above formulas [1-3-c] and [1-4-c], X represents a hydroxyl group.

In the above formula [1], the structural unit represented by (SiO _4/2 ) may include a structure represented by the following formula [1-5], [1-5] or [1-7], that is, (SiO _{4 /2} ) three or two oxygen atoms bonded to a ruthenium atom in the structural unit represented by the structure, or a bond of a ruthenium atom in a structural unit represented by (SiO _4/2 ) One of the oxygen atoms forms a structure of a stanol group.

(SiX ₃ O _1/2 ) [1-5] (SiX ₂ O _2/2 ) [1-6] (SiXO _3/2 ) [1-7]

In the above formulas [1-5], [1-6] and [1-7], X represents a hydroxyl group.

The structural unit represented by (SiO _4/2 ) includes a portion surrounded by a broken line in the structural unit represented by the following formula [1-d], and may further include the following formula [1-5-d], [1-6 -d] or a portion surrounded by a broken line in the structural unit represented by [1-7-d]. That is, a structural unit in which a hydroxyl group remains at the terminal to form a stanol group is also included in the structural unit represented by (SiO _4/2 ).

[11]

In the above formulas [1-5-d], [1-6-d] and [1-7-d], X represents a hydroxyl group.

The component (A) contains at least a hydrogen atom (SiH group) bonded to a ruthenium atom, and the number thereof is not particularly limited. It is preferable to contain two or more in one molecule. In the case of obtaining a good hardened body, the content of the hydrogen atom (SiH group) bonded to the ruthenium atom in the component (A) is preferably from 1.0 mmol/g to 4.0 mmol/g.

The mass average molecular weight of the component (A) is not particularly limited. It is preferably 500 to 10,000, and more preferably 800 to 7,000. When the mass average molecular weight is 500 or more, the cured product of the present invention has good resin strength, and if it is 10,000 or less, the composition of the present invention has good formability. Among them, when d = 0, the cured product of the present invention has excellent mechanical strength, and therefore it is particularly preferably from 3,500 to 7,000. Here, the mass average molecular weight is measured by a gel permeation chromatography (abbreviation: GPC) method, and the value obtained by a standard polystyrene calibration curve is converted (in the present specification, the same applies hereinafter).

The viscosity of the component (A) is not particularly limited. From the viewpoint of handling workability, the viscosity at 25 ° C is preferably 0.001 to 10,000,000 cP (centipoise), and more preferably 0.01 to 500,000 cP. If the viscosity exceeds 10,000,000 cP, the formability may be deteriorated, but the treatment may be performed by heating to lower the viscosity. Here, the viscosity of the component (A) can be measured by a rotary viscometer or the like.

The amount of the Si-OH group contained in the component (A) is not particularly limited. It is preferably 0.5 to 4.5 mmol/g, and more preferably 1.0 to 3.5 mmol/g. When the content of the Si-OH group exceeds 4.5 mmol/g, bubbles are observed in the cured product.

<(B) component>

The component (B) is a polyfluorene oxide resin represented by the following formula [2] and containing a vinyl group (Si-CH=CH ₂ group) bonded to a ruthenium atom. The component (B) may be used alone or in combination of two or more.

(CH ₂ =CH-SiR ⁴ ₂ O _1/2 ) _e (SiR ⁵ ₂ O _2/2 ) _f (R ⁶ SiO _3/2 ) _g (SiO _4/2 ) _h [2]

The above formula [2] represents an average composition formula. In the formula [2], R ⁴ is an alkyl group having 1 to 3 carbon atoms, and two R ^{4 's} may be the same or different from each other. R ⁵ is an alkyl group having 1 to 3 carbon atoms, and two R ^{5 's} may be the same or different from each other. R ⁶ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. e, f, and g are respectively in the range of more than 0 and not up to 1, and h is a number in the range of 0 or more and less than 1, and satisfies e+f+g+h=1. The oxygen atoms in the structural unit represented by (SiR ⁵ ₂ O _2/2 ), (R ⁶ SiO _3/2 ), and (SiO _4/2 ) respectively represent an oxygen atom forming a siloxane chain or forming a stanol group. Oxygen atom.

The alkyl group having 1 to 3 carbon atoms of R ⁴ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The alkyl group having 1 to 3 carbon atoms of R ⁵ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The alkyl group having 1 to 3 carbon atoms of R ⁶ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The aromatic hydrocarbon group having 6 to 10 carbon atoms of R ⁶ is preferably a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group or a 3,5-di(trifluoromethylphenyl group). Base, especially phenyl.

The combination of R ⁴ , R ⁵ and R ⁶ is not particularly limited. Wherein R ⁴ is preferably methyl or ethyl, R ⁵ is methyl or ethyl, and R ⁶ is methyl, ethyl, phenyl, 3-trifluoromethylphenyl, 4-trifluoromethyl Any of a phenyl group or a 3,5-bis(trifluoromethylphenyl) group, particularly preferably R ⁴ is a methyl group, R ⁵ is a methyl group, and R ⁶ is a methyl group or a phenyl group.

The value of e is not particularly limited as long as it exceeds 0 and does not reach the range of 1 and satisfies e+f+g+h=1. The value of e is preferably 0.05 to 0.40, and particularly preferably 0.15 to 0.30. When the value of e is 0.05 or more, the composition of the present invention has good formability, and if it is 0.40 or less, the cured product of the present invention has good mechanical strength.

The value of f is not particularly limited as long as it exceeds 0 and does not reach the range of 1 and satisfies e+f+g+h=1. The value of f is preferably 0.10 to 0.80, and particularly preferably 0.20 to 0.70. When the value of f is 0.10 or more, the composition of the present invention has good formability, and if it is not more than 0.80, the cured product of the present invention has good mechanical strength.

The value of g is not particularly limited as long as it exceeds 0 and does not reach the range of 1 and satisfies e+f+g+h=1. The value of g is preferably from 0.10 to 0.80, and particularly preferably from 0.20 to 0.70. When the value of g is 0.10 or more, the cured product of the present invention has good mechanical strength, and if it is 0.80 or less, the composition of the present invention has good formability.

The value of h is not particularly limited as long as it exceeds 0 and does not reach the range of 1 and satisfies e+f+g+h=1. The value of h is preferably from 0 to 0.70. Among them, the value of h is particularly preferably 0.10 to 0.30 in terms of the hardness of the cured product of the present invention which exhibits good adhesion strength and good performance. Further, when the value of h is 0, the structural unit of (SiO _4/2 ) in the above formula [2] does not exist.

The values of e, f, g, and h are preferably e:f:g:h=0.05~0.40:0.10~0.80:0.10~0.80:0~0.70, especially preferably e:f:g:h=0.20~0.40 : 0.10~0.40: 0.30~0.60: 0.10~0.30.

When the value of h is 0, the values of e, f, and g are preferably e:f:g=0.05~0.40:0.10~0.80:0.10~0.80.

The values of e, f, g, and h can be calculated by using a nuclear magnetic resonance apparatus to measure the ²⁹ Si-NMR spectrum and the ¹ H-NMR spectrum of the component (B), and using them in a complementary combination.

In the above formula [2], the structural unit represented by (SiR ⁵ ₂ O _2/2 ) may include a structure represented by the following formula [2-2], that is, a structure represented by (SiR ⁵ ₂ O _2/2 ) One of the oxygen atoms bonded to the germanium atom in the unit forms a structure of a stanol group.

[13] (R ⁵ SiXO _1/2 ) [2-2]

The above formula [2-2], R ⁵ is of the formula [2] in the same meaning as R ^5, X represents a hydroxyl group.

The structural unit represented by (SiR ⁵ ₂ O _2/2 ) includes a portion surrounded by a broken line in the structural unit represented by the following formula [2-b], and may further include a formula represented by the following formula [2-2-b] The portion of the structural unit that is surrounded by a dotted line. That is, a structural unit having a group represented by R ⁵ and having a hydroxyl group remaining at the terminal to form a stanol group is also included in the structural unit represented by (SiR ⁵ ₂ O _2/2 ). Further, in the structural unit represented by the following formulas [2-b] and [2-2-b], the oxygen atom in the Si-O-Si bond forms a decane bond with the adjacent ruthenium atom, and the adjacent structure The unit shares an oxygen atom. Therefore, one of the Si-O-Si bonds is "O _1/2 ".

Formula [2-b] and [2-2-b], R ⁵ is of the formula [2] R ⁵ containing the same. In the above formula [2-2-b], X represents a hydroxyl group.

In the above formula [2], the structural unit represented by (R ⁶ SiO _3/2 ) may include a structure represented by the following formula [2-3] or [2-4], that is, (R ⁶ SiO _3/2 ) Two of the oxygen atoms bonded to the argon atoms in the structural unit to be formed form a stanol group structure, or an oxygen atom bonded to a ruthenium atom in the structural unit represented by (R ⁶ SiO _3/2 ) One of the structures forming a stanol group.

(R ⁶ SiX ₂ O _1/2 ) [2-3] (R ⁵ SiXO _2/2 ) [2-4]

The above formula [2-3] and [2-4], R ^{6 is} and [2] of the formula R ⁶ containing the same, X represents a hydroxyl group.

The structural unit represented by (R ⁶ SiO _3/2 ) includes a portion surrounded by a broken line in the structural unit represented by the following formula [2- _c ], and may further include the following formula [2-3-c] or [2] -4-c] The portion of the structural unit represented by a dotted line. That is, a structural unit having a group represented by R ⁶ and having a hydroxyl group remaining at the terminal to form a stanol group is also included in the structural unit represented by (R ⁶ SiO _3/2 ).

Formula [2-c], [2-3 -c] and [2-4-c], R ^{6 is} of the formula [2] in the same meaning as R ^6. In the above formulas [2-3-c] and [2-4-c], X represents a hydroxyl group.

The structural unit represented by (SiO _4/2 ) may include a structure represented by the following formula [2-5], [2-6] or [2-7], that is, a structural unit represented by (SiO _4/2 ) One or two oxygen atoms bonded to a ruthenium atom are formed into a structure of a decyl alcohol group, or one of oxygen atoms bonded to a ruthenium atom in a structural unit represented by (SiO _4/2 ) The structure of the stanol group.

(SiX ₃ O _1/2 ) [2-5] (SiX ₂ O _2/2 ) [2-6] (SiXO _3/2 ) [2-7]

In the above formulas [2-5], [2-6] and [2-7], X represents a hydroxyl group.

The structural unit represented by (SiO _4/2 ) includes a portion surrounded by a broken line in the structural unit represented by the following formula [2-d], and further may include the following formula [2-5-d], [2-6] -d] or a portion surrounded by a broken line in the structural unit represented by [2-7-d]. That is, a structural unit in which a hydroxyl group remains at the terminal to form a stanol group is also included in the structural unit represented by (SiO _4/2 ).

In the above formulas [2-5-d], [2-6-d] and [2-7-d], X represents a hydroxyl group.

The component (B) contains at least a vinyl group (Si-CH=CH ₂ group) bonded to a ruthenium atom, and the number thereof is not particularly limited. It is preferable to contain two or more in one molecule. In the case of obtaining a good hardened body, the content of the vinyl group (Si-CH=CH ₂ group) bonded to the ruthenium atom in the component (B) is preferably from 0.5 mmol/g to 4.0 mmol/g.

The mass average molecular weight of the component (B) is not particularly limited. It is preferably 500 to 10,000, and more preferably 800 to 7,000. When the mass average molecular weight is 500 or more, the cured product of the present invention has good resin strength, and if it is 10,000 or less, the composition of the present invention has good formability. Among them, when h = 0, the cured product of the present invention has excellent mechanical strength, and therefore it is particularly preferably from 3,500 to 7,000.

The viscosity of the component (B) is not particularly limited. The viscosity at 25 ° C is preferably 0.001 to 10,000,000 cP, and more preferably 0.001 to 500,000 cP from the viewpoint of handling workability. If the viscosity exceeds 10,000,000 cP, the formability may be deteriorated, but the treatment may be performed by heating to lower the viscosity. Here, the viscosity of the component (B) can be measured by a rotary viscometer or the like.

The amount of the Si-OH group contained in the component (B) is not particularly limited. The content of the Si-OH group is preferably from 0.5 to 6.0 mmol/g, particularly preferably from 1.0 to 3.5 mmol/g. If the content of the Si-OH group exceeds 6.0 mmol/g, there is a possibility that bubbles are observed in the cured product.

<(C) component>

The component (C) is prepared in order to promote the addition hardening reaction of the SiH-CH=CH ₂ group in the component (B) and the component (B). The component (C) may be used alone or in combination of two or more. The type of the component (C) is not particularly limited. Specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum-carbonylvinylmethyl complex, and platinum-divinyltetramethyldioxane complex (Castel catalyst) can be exemplified. (Karstedt's catalyst)), a platinum-cyclovinylmethyl oxime complex, or a platinum-octanal complex. Among them, a platinum-divinyltetramethyldioxane complex (caster catalyst) and a platinum-cyclovinylmethyloxane complex are preferable.

<Other Additives>

In the composition of the present invention, in addition to the above components (A) to (C), it is also possible to improve the storage stability and handling workability of the composition, and to adjust the hardening retardant for the purpose of adjusting the hydrogenation reactivity during the hardening process. . The composition of the present invention can be used as a cured product at a relatively low temperature, so that it can be preferably used for coating and sealing of a relatively weak thermal semiconductor member. On the other hand, from the viewpoint of the storage stability and handling workability of the composition of the present invention from the viewpoint of the coating and sealing work environment, it is also preferred to adjust the hardening retarder in order to adjust the curing rate. The type of the hardening retarder is not particularly limited as long as it has a curing retarding effect on the component (C), and a conventionally known one can also be used. For example, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, a nitrogen-containing compound, an organic sulfur compound, an organic peroxide, or the like can be given. These compounds may be used in a single species or in combination.

Specific examples of the compound containing an aliphatic unsaturated bond include 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, and 3,5-dimethyl- Propargyl alcohols such as 1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic anhydride, dimethyl maleate, etc. Acid esters, etc.

Specific examples of the organophosphorus compound include triorganophosphines, diorganophosphines, organophosphines, and triorganophosphites.

Specific examples of the nitrogen-containing compound include N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetraethylethylenediamine, and the like, N, N, N', N'-tetrasubstituted alkylenediamines, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, N,N-di N,N-disubstituted extensions such as butyl-1,3-propanediamine, N,N-dimethyl-1,3-propanediamine, N,N-dibutyl-1,4-butanediamine Alkyldiamines, trisubstituted amines such as tributylamine, benzotriazole, 2,2'-bipyridine, and the like.

Specific examples of the organic sulfur compound include organic mercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, and benzothiazole disulfide.

Specific examples of the organic peroxide include ditributyl peroxide, dicumyl peroxide, benzammonium peroxide, and tert-butyl perbenzoate. Among the oxidative retarders, preferred are compounds containing an aliphatic unsaturated bond, nitrogen-containing compounds, preferably maleic esters, propynols, N, N, N', N'-four. Substituted alkylenediamines, especially dimethyl maleate, 2-methyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, N, N, N ', N'-tetramethylethylenediamine.

The content of the hardening retarder in the composition of the present invention is not particularly limited. Usually, the hardening retarder may be added in an amount of 20 to 200 equivalents per equivalent of the platinum atom in the component (C) contained in the composition, but is not limited thereto. The degree of hardening retardation effect obtained by hardening the retarder varies depending on the chemical structure of the hardening retarder. Therefore, it is preferred to adjust the blending amount to an optimum amount depending on the type of the hardening retarder to be used. By adding an optimum amount of the hardening retarder, the composition of the present invention is excellent in long-term storage stability and heat hardenability at room temperature (especially at an ambient temperature of unheated or cooled, usually 15 to 30 ° C; the same below) By.

In the composition of the present invention, in addition to the above components (A) to (C), a subsequent addition agent may be added for the purpose of improving the adhesion. Examples of the adhesion-imparting agent include a decane coupling agent or a hydrolysis-condensation product thereof. Examples of the decane coupling agent include an epoxy group-containing decane coupling agent such as γ-glycidoxypropyltrimethoxy decane, a (meth)acryl fluorenyl group-containing decane coupling agent, and an isocyanate group-containing decane coupling agent. Isocyanurate-containing decane A known coupling agent, an amine group-containing decane coupling agent, and a mercapto group-containing decane coupling agent are known. The content of the adhesion-imparting agent in the composition of the present invention is not particularly limited. The composition of the present invention is preferably in the range of 1 to 20% by mass, particularly preferably in the range of 5 to 15% by mass.

In order to suppress the occurrence of coloration, oxidative degradation, and the like of the cured product, a previously known antioxidant may be added to the composition of the present invention. Examples of such an antioxidant include a phenolic antioxidant, a thioether antioxidant, and a phosphorus antioxidant. Among them, a phenol-based antioxidant or a thioether-based antioxidant is preferred, and a thioether-based antioxidant is particularly preferred. These antioxidants may be used alone or in combination of two or more.

As the phenolic antioxidant, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-three can be mentioned. -2,4,6-(1H,3H,5H)-Trione, 4,4',4'-(1-methylpropyl-3-ylidene)tris(6-tert-butyl-intermediate Phenol, 6,6'-di-tert-butyl-4,4'-butylidene-di-m-cresol, octadecyl-3-(3,5-di-t-butyl-4-hydroxyl Phenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-double {2-[3-(3- Tributyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecene 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, and the like.

Examples of the thioether-based antioxidant include 2,2-bis({[3-(dodecylthio)propenyl)oxy}methyl)-1,3-propanediyl=bis[3] -(dodecylthio)propionate], di(tridecyl)3,3'-thiodipropionate, and the like. Examples of the phosphorus-based antioxidant include 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxy-3,9-diphosphorylcyclo[5,5]undecene. 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphine spiro[5,5] Undecene, 2,2'-methylenebis(4,6-di-t-butylphenyl)-2-ethylhexylphosphite, tris(2,4-di-t-butyl) Phenyl) ester, tris(nonylphenyl) phosphite, tetra-C _12-15 -alkyl (propane-2,2-diylbis(4,1-phenylene)) bis(phosphite) ), 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, and the like.

Commercially available products can be used as the antioxidant, and a synthesizer can also be used. As a commercial item, Example: Adekastab (made by ADEKA): AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330, AO-412S, AO -503, PEP-8, PEP-8W, PEP-36, PEP-36A, HP-10, 2112, 2112 RG, 1178, 1500, C, 135A, 3010, TPP, and the like.

The blending amount in the case of using the antioxidant is not particularly limited as long as it does not impair the range of characteristics such as transparency of the cured product of the present invention and is an effective amount as an antioxidant. The total mass of the composition of the present invention can be adjusted to 0.001 to 2% by mass, preferably 0.01 to 1% by mass. When the amount is within the above range, the antioxidant ability can be sufficiently exhibited, so that occurrence of coloring, white turbidity, oxidative degradation, and the like can be suppressed, and a cured product excellent in workability can be obtained.

In order to impart resistance to photodegradation caused by light energy such as sunlight or fluorescent lamps, a previously known light stabilizer may be added to the composition of the present invention. As the light stabilizer, a hindered amine-based stabilizer capable of capturing a radical generated by photooxidation (photodegradation) can be preferably used, and the antioxidant effect can be further enhanced by using it together with the above-mentioned antioxidant. Specific examples of the light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and 4-benzylidene-2,2,6. 6-Tetramethylpiperidine, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)butane-1,2,3,4-tetracarboxylate, carbonic acid double (1 - undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl)ester and the like. Among them, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate is preferred.

Commercially available products can be used as the light stabilizer, and a synthesizer can also be used. As a commercial item, Adekastab (made by Adeka Corporation): LA-77Y, LA-77G, LA-82, etc. are illustrated.

The blending amount in the case of using the light stabilizer is not particularly limited as long as it does not impair the range of characteristics such as transparency of the cured product of the present invention and is an effective amount as a light stabilizer. The total mass of the curable polyoxyxene resin composition of the present invention can be adjusted to 0.01 to 5% by mass, preferably 0.05 to 0.5% by mass.

A phosphor as an optional component can be formulated in the composition of the present invention. The type of the phosphor is not particularly limited. For example, it can be cited that it is widely used in light-emitting diodes (LEDs). Yellow, red, green, and blue luminescent fluorescent light including an oxide-based phosphor, an oxynitride-based phosphor, a nitride-based phosphor, a sulfide-based phosphor, and an oxysulfide-based phosphor body.

Examples of the oxide-based phosphor include a YAG (Yttrium Aluminum Garnet)-based green-yellow luminescent phosphor containing cerium ions, aluminum, and garnet, and a cerium-containing cerium, aluminum, or garnet system. TAG (terbium aluminum garnet) is a yellow-emitting phosphor, and includes a bismuth or strontium ion citrate-based green-yellow luminescent phosphor. Examples of the oxynitride phosphor include cerium ions containing cerium ions, aluminum, oxygen, and nitrogen-based sialon-based red-green luminescent phosphors. Examples of the nitride-based phosphor include a calcium-containing cerium ion, a total of aluminum, cerium, and a nitrogen-based CASN (AlSiN ₃ :Eu)-based red luminescent phosphor. Examples of the sulfide system include a ZnS-based green color-emitting phosphor containing copper ions or aluminum ions. Examples of the oxysulfide-based phosphor include a Y ₂ O ₂ S-based red light-emitting phosphor containing cerium ions. These phosphors may be used singly or in combination of two or more.

The blending amount of the phosphor is not particularly limited. The composition of the present invention is preferably in the range of 10 to 70% by mass, particularly preferably in the range of 20 to 50% by mass.

In the composition of the present invention, inorganic particles may be blended in order to improve the optical properties, workability, mechanical properties, and physicochemical properties of the cured product.

The type of the above inorganic particles may be selected according to the purpose, and a single type may be added, or a plurality of types may be combined and formulated. Further, in order to improve the dispersibility, the inorganic particles may be surface-treated with a surface treatment agent such as a decane coupling agent.

Examples of the type of the inorganic particles include inorganic oxide particles such as cerium oxide, barium titanate, titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, cerium oxide, and cerium oxide, or cerium nitride, boron nitride, and carbonization. Nitride particles such as ruthenium or aluminum nitride, carbon compound particles, diamond particles, and the like may be selected depending on the purpose, and are not limited thereto.

The form of the inorganic particles may be determined according to the purpose such as a powder form or a slurry form. Any form. It is preferably formulated in the composition of the present invention in accordance with the desired transparency, the refractive index of the cured product of the present invention, or as a water-based or solvent-based transparent sol.

The average particle diameter of the inorganic particles to be blended is not particularly limited, and those having an average particle diameter determined according to the purpose can be used. Usually, it is about 1/10 or less of the particles of the following phosphor. In addition, the average particle diameter of the inorganic particles means an arithmetic mean value when a long diameter is measured by selecting any 20 particles from 50 or more particles as observed by a scanning electron microscope (abbreviation: SEM).

The amount of the inorganic particles to be blended is arbitrary unless the heat-resistant transparency of the cured product of the present invention is not impaired. When the amount of the inorganic particles is too small, the desired effect may not be obtained, and if it is too large, the properties such as heat-resistant transparency, adhesion, transparency, moldability, and hardness of the cured product may be adversely affected. It can be adjusted to about 1~50% by mass, preferably about 5~35质量%.

In addition to these, the composition of the present invention may contain a release agent, a resin modifier, a colorant, a diluent, an antibacterial agent, an antifungal agent, and a tune within a range that does not impair the transparency of the cured product. Flat agent, anti-sagging agent, etc.

<Formation amount of (A) component, (B) component, and (C) component>

The compounding ratio of the component (A) to the component (B) in the composition of the present invention is not particularly limited. The preparation is carried out based on the molar ratio of the Si—CH=CH 2 group contained in the molecule of the (H) component and the Si—CH=CH 2 group. Specifically, the number of moles of the SiH group contained in the molecule of the component (A) is preferably: the number of moles of the Si—CH=CH ₂ group contained in the molecule of the component (B) is 0.8: 0.2 to 0.5: The range of 0.5. When the ratio of the number of moles of the SiH group to the number of moles of the Si—CH=CH ₂ group is 0.8 or less, the composition of the present invention has good formability, and if it is 0.5 or more, the cured product of the present invention has Good heat and transparency.

The compounding amount of the component (C) in the composition of the present invention is based on the total mass of the component (A) and the component (B) and the component (C), and the platinum atom in the component (C) is preferably 0.003 in mass units. The amount in the range of 3.0 ppm is more preferably 0.003 to 2.0 ppm. If the (C) component is blended When the amount is 0.003 ppm or more, the addition hardening reaction of the component (A) and the component (B) proceeds smoothly. When the amount is 3.0 ppm or less, the obtained cured product has excellent heat-resistant transparency, so that heating due to prolonged heating can be suppressed. The discoloration of the hardened material. When the amount of the component (C) is less than the above, the cured product of the present invention tends to have excellent heat-resistant transparency. Therefore, the amount of the component (C) is preferably as small as possible.

The total content of the stanol group (Si-OH group) in the component (A) and the component (B) in the composition of the present invention may be 0.5 to 5.0 mmol/g, preferably 1.0 to 3.0 mmol/g, particularly Good is 1.5~3.0mmol/g. When it exceeds 5.0 mmol/g, bubbles may be generated from the hardened material produced by the composition. The generation of the bubble is one of the causes of the decrease in transparency or heat-resistant transparency of the cured product. Further, when it exceeds 5.0 mmol/g, the curing of the composition is not sufficiently performed, and the desired cured product cannot be obtained.

Among them, in the component (A), d=0, the mass average molecular weight is 3,500 to 7,000, the component (B) has h=0, and the mass average molecular weight is 3,500 to 7,000, in the components (A) and (B). The total content of the stanol group (Si-OH group) may be from 1.5 to 5.0 mmol/g, preferably from 1.7 to 3.0 mmol/g, since a hardened body exhibiting excellent adhesion to a package of various sizes can be obtained. Therefore, it is especially preferred to be 1.9~2.7mmol/g.

The content of the stanol group (Si-OH group) in the component (A) and the component (B) can be measured by using a nuclear magnetic resonance apparatus for ²⁹ Si-NMR spectrum and ¹ H-NMR spectrum, and the complementary combination is used to calculate the content of each component. .

The viscosity of the composition of the present invention is not particularly limited. The viscosity at 25 ° C is preferably 0.001 to 10,000,000 cP, and more preferably 0.001 to 500,000 cP from the viewpoint of handling workability. If the viscosity exceeds 10,000,000 cP, the formability may be deteriorated, but the treatment may be performed by heating to lower the viscosity. The viscosity of the composition of the present invention can be measured by a rotary viscometer or the like.

<Preparation of Curable Polyoxynoxy Resin Composition>

The composition of the present invention can be formulated by (A) component and (B) component and (C) component and as needed Prepared with other additives. It is preferred that the component (A), the component (B), the component (C), and the additive to be added as needed are substantially uniformly dispersed by mixing. The mixing method is not particularly limited. For example, a mixing method such as a universal kneader or a kneader can be employed. Further, the component (C) may be mixed with the component (A) and/or the component (B) in advance. Further, in order to stably store for a long period of time, the component (B) and the component (C) are held in another container, and for example, the first composition containing the component (A) and the component (C) may be contained in advance (for example). The residue of the component A and the second component of the component (B) are separately stored in different containers, and are mixed into the composition of the present invention before use, and are defoamed under reduced pressure to be used.

(Method of manufacturing component (A))

The method for producing the component (A) is not particularly limited. For example, a dialkoxy decane compound represented by the following general formula [3], a trialkoxy decane compound represented by the general formula [4], and a tetraalkoxy group represented by the general formula [5] can be used. A condensate obtained by hydrolyzing polycondensation of a decane compound (hereinafter sometimes referred to as "hydrolysis polycondensate [I]") and the following general formula [9-1], [9-2], [9-3] or [9- 4] The decane compound represented by the reaction is produced.

R ² ₂ Si(OR ⁷ ) ₂ [3] R ³ Si(OR ⁸ ) ₃ [4] Si(OR ⁹ ) ₄ [5]

General formula [3] is the same as R ² in the formula [1] The meaning of R ^2, R ⁷ represents an alkyl group having 1 to 3 carbon atoms, the two R ⁷ may be the same or different from each other species. Of the general formula [4] R ³ in the above formula [1] of the same meaning as R ^3, R ⁸ represents an alkyl group having 1 to 3 carbon atoms, the three R ⁸ may be the same or different from each other species. R ⁹ in the general formula [5] represents an alkyl group having 1 to 3 carbon atoms, and the four R ⁹ groups may be the same or different from each other.

H-SiR ¹ ₂ Cl [9-1] H-SiR ¹ ₂ (OH) [9-2] H-SiR ¹ ₂ (OR ¹³ ) [9-3] (H-SiR ¹ ₂ ) ₂ O [9-4]

Formula [9-1], [9-2], the same [9-3] and [9-4] in the R ¹ is of formula [1] The R & lt ^one meaning. R ¹³ in the formula [9-3] represents an alkyl group having 1 to 3 carbon atoms.

In the following, the dialkoxy decane compound represented by the general formula [3], the trialkoxy decane compound represented by the general formula [4], and the tetraalkoxy decane compound represented by the general formula [5] may be respectively It is represented by "dialkoxydecane [3]", "trialkoxydecane [4]", and "tetraalkoxydecane [5]". Further, the decane compounds represented by the general formulae [9-1], [9-2], [9-3], and [9-4] are respectively referred to as "chloromethane compounds [9-1]" and " The stanol compound [9-2]", the "monoalkoxy decane compound [9-3]", and the "dioxane compound [9-4]" are sometimes referred to as "when they are not distinguished from each other". Decane compound [9]".

Specific examples of the dialkoxydecane [3] include the following compounds, but are not limited to them:

Dimethyldimethoxydecane, dimethyldiethoxydecane, diethyldimethoxydecane, diethyldiethoxydecane.

Among them, preferred examples of the compound include dimethyldimethoxydecane and dimethyldiethoxydecane.

Specific examples of the trialkoxydecane [4] include, but are not limited to, the following compounds:

Methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, phenyl trimethoxy Decane, phenyltriethoxydecane, 3-(trifluoromethyl)phenyltrimethoxydecane, 3-(trifluoromethyl)phenyltriethoxydecane, 4-(trifluoromethyl)benzene Trimethoxy decane, 4-(trifluoromethyl)phenyltriethoxy decane, 3,5-(di-trifluoromethyl)phenyltrimethoxydecane, 3,5-(di-trifluoro Methyl)phenyltriethoxydecane, naphthyltrimethoxydecane, naphthyltriethoxydecane.

Preferred examples of such compounds include methyltrimethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, and 3-(trifluoromethyl). Phenyltrimethoxydecane, 3-(trifluoromethyl)phenyltriethoxydecane, 4-(trifluoromethyl)phenyltrimethoxydecane, 4-(trifluoromethyl)phenyltriethyl Oxydecane, 3,5-(di-trifluoromethyl)phenyltrimethoxydecane, 3,5-(di-trifluoromethyl)phenyltriethoxydecane, as a preferred compound, Methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane.

Specific examples of the tetraalkoxydecane [5] include the following compounds, but are not limited to them:

Tetramethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane.

Among them, preferred examples thereof include tetramethoxynonane and tetraethoxydecane.

The combination of the dialkoxy decane [3], the trialkoxy decane [4], and the tetraalkoxy decane [5] used in the production of the component (A) is not particularly limited. The dialkoxy decane [3], the trialkoxy decane [4], and the tetraalkoxy decane [5] may be used alone or in combination of plural kinds. As a preferred combination, the dialkoxy decane [3] is free from dimethyl dimethoxy decane, dimethyl diethoxy decane, diethyl dimethoxy decane and diethyl diethoxy decane. One or more selected from the group consisting of, the trialkoxydecane [4] is free of methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, ethylene. Trimethoxy decane, vinyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, 3-(trifluoromethyl)phenyl trimethoxy decane, 3-(trifluoromethyl) Phenyltriethoxydecane, 4-(trifluoromethyl)phenyltrimethoxydecane, 4-(trifluoromethyl)phenyltriethoxydecane, 3,5-(di-trifluoro One or more selected from the group consisting of methyl)phenyltrimethoxydecane and 3,5-(di-trifluoromethyl)phenyltriethoxynonane, tetraalkoxydecane [5] is free One or more selected from the group consisting of oxydecane, tetraethoxysilane, and tetraisopropoxy decane. Among them, as a preferred combination, the dialkoxy decane [4] may be selected from the group consisting of dimethyl dimethoxy decane and dimethyl diethoxy decane, and a trialkoxy decane [ 5] Free methyltrimethoxydecane, methyltriethoxysulfonium One or more selected from the group consisting of an alkane, a phenyltrimethoxydecane and a phenyltriethoxynonane, and the tetraalkoxydecane [6] is a group of free tetramethoxynonane and tetraethoxynonane. Choose more than one.

Specific examples of the chlorosilane compound [9-1] include the following compounds, but are not limited thereto: chlorodimethyl decane and chlorodiethyl decane.

Among them, preferred examples of the compound include chlorodimethyl decane.

Specific examples of the stanol compound [9-2] include the following compounds, but are not limited thereto: dimethyl stanol or diethyl stanol.

Among them, preferred examples thereof include dimethyl stanol.

Specific examples of the monoalkoxydecane compound [9-3] include, but are not limited to, dimethyl methoxy decane, dimethyl ethoxy decane, diethyl methoxy decane, and the like. Ethyl ethoxy decane.

Among them, preferred examples thereof include dimethylmethoxydecane and dimethylethoxydecane.

Specific examples of the dioxantane compound [9-4] include, but are not limited to, 1,1,3,3-tetramethyldioxane, 1,1,3,3-tetraethyl Dioxane.

Among them, preferred examples thereof include 1,1,3,3-tetramethyldioxane.

The production method of the hydrolysis polycondensate [I] is exemplified below.

First, a specific amount of a dialkoxy decane [3] and a trialkoxy decane [4] are added to the reaction vessel at room temperature according to the desired amount, and then added to make Each alkoxydecane compound hydrolyzes the polycondensed water and, if necessary, a reaction solvent, and a catalyst for carrying out a condensation reaction is added as needed to prepare a reaction solution. The order of input at this time is not In this case, it can be prepared as a reaction solution in any order. Then, the reaction solution is stirred at a specific temperature and a specific temperature while stirring, whereby a hydrolysis condensate [I] can be obtained. In this case, in order to prevent the alkoxydecane compound, water, reaction solvent and/or catalyst which are unreacted raw materials in the reaction system from being distilled out of the reaction system, it is preferred to provide a reflux device in the reaction vessel.

In the production of the hydrolysis polycondensate [I], the amount of the dialkoxydecane [3], the trialkoxydecane [4], and the tetraalkoxydecane [5] is not particularly limited. From the viewpoint of the physical properties of the component (A), it is preferred to formulate the dialkoxy decane [3]: trialkoxy decane [4] in a molar ratio of 85: 15 to 15:85, in particular Jia is equipped with 85:15~30:70. If the molar ratio of the dialkoxysilane [3] is less than 15, there is a case where the molecular weight is higher than the desired molecular weight. If it exceeds 85, the hydrolysis polycondensation reaction is difficult to proceed and is lower than the desired molecular weight. Further, as the amount in the case of using the tetraalkoxydecane [5], the total amount is 100 mol with respect to the dialkoxydecane [3], the trialkoxydecane [4], and the tetraalkoxydecane [5]. The ear is preferably 1 to 80 moles, and more preferably 1 to 60 moles.

In the production of the hydrolysis polycondensate [I], the amount of water used is not particularly limited. From the viewpoint of reaction efficiency, the molar equivalent of the alkoxy group contained in the alkoxydecane compound of the starting compound, that is, dialkoxydecane [3], trialkoxydecane [4] and The molar equivalent of the alkoxy group contained in the tetraalkoxydecane [5] is preferably 1.5 times or more and 5 times or less. If it is 1.5 times the molar equivalent or more, the hydrolysis of the alkoxydecane compound proceeds efficiently, and it is not necessary to add more than 5 times the molar equivalent.

In the production of the hydrolysis polycondensate [I], the reaction can also be carried out without a solvent, but a reaction solvent can also be used. The type of the reaction solvent is not particularly limited as long as it does not inhibit the reaction for producing the water-reactioned polycondensate [I]. Among them, a hydrophilic organic solvent such as an alcohol is preferred. Specific examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, butanol, and the like, but are not limited thereto. The amount of the reaction solvent used is preferably from 0.1 to 1,000% by mass, particularly preferably from 1 to 300% by mass based on the total amount of the alkoxydecane compound to be used. %. Further, the alcohol formed from the alkoxysilane compound of the reaction raw material during the reaction can function as a reaction solvent, and thus it is not necessary to add it.

As the kind of the catalyst used in the production of the hydrolysis polycondensate [I], an acidic catalyst or an alkaline catalyst can be used. Since it is easy to control the molecular weight of the hydrolyzed polycondensate [I], it is preferred to use an acidic catalyst. The type of the acidic catalyst is not particularly limited. For example, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc. are mentioned. Among them, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and more preferably acetic acid are preferred because the removal of the acid catalyst after the completion of the reaction is relatively easy. Further, the type of the alkaline catalyst is not particularly limited. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, pyridine, etc. are mentioned.

The amount of the catalyst used in the production of the hydrolyzed polycondensate [I] is preferably 0.001 to 5% by mass, particularly preferably 0.005 to 1% by mass, based on the total amount of the alkoxydecane compound, solvent and water to be used. .

The reaction time for the production of the hydrolysis polycondensate [I] is not particularly limited, and may be 3 hours or longer and 15 hours or shorter. The reaction temperature is not particularly limited, and may be 60 ° C or higher and 120 ° C or lower, preferably 80 ° C or higher and 100 ° C or lower.

After the reaction, from the viewpoint of the rationality of the hydrolysis of the polycondensate [I], it is preferred to separate the hydrolyzed polycondensate [I] from the reaction system for purification. This separation method is not particularly limited. As a separation method, the extraction method is mentioned, for example. Specifically, after the reaction solution after the above reaction is cooled to room temperature, it is brought into contact with a non-aqueous organic solvent as an extraction solvent, whereby the hydrolyzed polycondensate [I] present in the reaction system is extracted. Then, the catalyst contained in the extracted solution is removed. The method of removing the catalyst is not particularly limited. For example, if the catalyst (e.g., acetic acid) used is water soluble, the catalyst can be removed by washing the extracted solution with water. Then, a desiccant is added to the solution after removing the catalyst to remove dissolved water in the system. Further, the high-purity hydrolysis polycondensate [I] can be separated by undergoing removal of a desiccant and removal of the extraction solvent under reduced pressure. At this time, the desiccant may not be used, but after the catalyst is removed. The solution is simultaneously removed under reduced pressure during the removal of the extraction solvent under reduced pressure.

As the above extraction solvent, a non-aqueous organic solvent can be used. The type of the nonaqueous organic solvent is not particularly limited. For example, an aromatic hydrocarbon, an ether, etc. are mentioned. Specific examples thereof include toluene, diethyl ether, isopropyl ether, and dibutyl ether, but are not limited thereto.

The desiccant is not particularly limited as long as it can remove water from the system and is separated from the hydrolyzed polycondensate [I]. As such a desiccant, a solid desiccant is preferably used. Specific examples thereof include magnesium sulfate and the like, but are not limited thereto.

The separated and purified hydrolyzed polycondensate [I] can be further subjected to a condensation reaction by heating under reflux in a solvent or heating and stirring without a solvent. Thereby, the molecular weight of the hydrolyzed polycondensate [I] can be increased. When a solvent is used, the hydrolyzed polycondensate [I] and a solvent are introduced into a reaction vessel which can be heated and refluxed to prepare a solution. The solution is heated to reflux and azeotroped with the water formed in the system while being condensed. In this case, p-toluenesulfonic acid or the like may be added to the solution to be heated and refluxed. The type of the solvent to be used is not particularly limited as long as it can dissolve the hydrolysis-condensation product [I] and is a solvent that can be heated to reflux. Specific examples thereof include aromatic hydrocarbons such as toluene, xylene, and benzene; ethers such as diethyl ether and diisopropyl ether; and esters such as ethyl acetate.

Further, in the case of no solvent, the hydrolyzed polycondensate [I] is introduced into a reaction vessel which can be heated and stirred, and heated at 100 ° C or higher and 150 ° C or lower for 6 to 18 hours. In this case, in order to suppress the change in the composition ratio of the hydrolysis polycondensate [I], it is preferred to provide a reflux device (for example, a condenser) in the reaction container. After heating and stirring, the content liquid was cooled to room temperature. A series of operations can be repeated, and the number of repetitions is not particularly limited. It is preferably carried out 1 to 4 times.

Next, a method of producing the component (A) by reacting the hydrolyzed polycondensate [I] with a decane compound [9] will be described. This method is not particularly limited as long as the component (A) can be produced. For example, two methods of the first method and the second method described below can be cited. The first method is a method in which a hydrolyzed polycondensate (I) and a chlorodecane compound [9-1] which is one of the decane compounds [9] are reacted in a water-insoluble organic solvent to produce the component (A). The second method refers to the hydrolysis of the polycondensate (I) with a stanol compound which is one of the decane compounds [9] [9- 2] a monoalkoxydecane compound [9-3] or a dioxoxane compound [9-4], which is produced by reacting a solvent in a solvent mixture of a water-insoluble organic solvent and an alcohol solvent in the presence of an acid ( A) Method of ingredients. The two methods are specifically described below.

(first method)

In the first method, first, a specific amount of the hydrolyzed polycondensate (I) and a non-aqueous organic solvent are introduced into a reaction vessel to dissolve the hydrolyzed polycondensate (I). Then, the solution is stirred at about 0 to about 10 ° C while adding a specific amount of the chlorodecane compound [9-1]. The addition method is not particularly limited, and is preferably dropwise. After the completion of the addition, the mixture was stirred at 0 ° C to room temperature for 0.5 to 18 hours to cause a reaction. Thereafter, the reaction is terminated, whereby the component (A) can be obtained.

In the first method, the amount of the hydrolysis polycondensate (I) and the chlorodecane compound [9-1] used is not particularly limited. From the viewpoint of the physical properties of the component (A), it is preferred to use 0.2 to 10 mmol of the chlorodecane compound [9-1] with respect to 1 g of the hydrolysis polycondensate (I).

In the first method, the type of the water-insoluble organic solvent to be used is not particularly limited as long as it is water-insoluble and does not inhibit the reaction for producing the component (A). Among them, aromatic hydrocarbons, ethers and the like are preferred. Specific examples thereof include toluene, diethyl ether, tetrahydrofuran, diisopropyl ether, and the like, but are not limited thereto. The amount of the water-insoluble organic solvent to be used is preferably from 50 to 1,000% by mass, particularly preferably from 300 to 700% by mass, based on 1 g of the hydrolyzed polycondensate (I).

In the first method, the method of terminating the reaction is not particularly limited. The reaction is usually terminated by the dropwise addition of water (preferably ion-exchanged water) to the reaction system. After the reaction, from the viewpoint of the rationality of the component (A), it is preferred to separate the component (A) from the reaction system for purification. The separation and purification method is not particularly limited. For example, an extraction method can be cited. Specifically, the organic layer is separated from the reaction solution after the above reaction, and then the organic layer is washed with an acid and further washed with water. Then, a desiccant is added to the washed organic layer to remove dissolved water from the system. Furthermore, by undergoing removal of the desiccant, there is The solvent of the machine is removed under reduced pressure, and the component (A) can be separated in high purity. At this time, it is also possible to simultaneously remove the water under reduced pressure while removing the non-aqueous organic solvent under reduced pressure without using a desiccant. It is preferable that the component (A) after separation is heated and stirred under reduced pressure to remove water contained in the component (A). The heating temperature at this time is not particularly limited, but is usually 100 to 130 °C.

(second method)

In the second method, first, a specific amount of the hydrolyzed polycondensate (I) and a non-aqueous organic solvent are introduced into a reaction vessel according to a desired alcoholic solvent to dissolve the hydrolyzed polycondensate (I). Then, a specific amount of the stanol compound [9-2], the monoalkoxydecane compound [9-3] or the dioxantane compound [9-4] is added to the solution. Further, a catalyst for performing hydrolysis and dehydration condensation reaction is added to the reaction system, and the reaction is carried out by stirring the reaction system at room temperature for 1 to 48 hours. Thereafter, the reaction is terminated, whereby the component (A) can be obtained.

In the second method, the amount of the hydrolysis polycondensate (I) and the stanol compound [9-2], the monoalkoxydecane compound [9-3] or the dioxane compound [9-4] is not particularly limited. limited. From the viewpoint of the physical properties of the component (A), it is preferably a stanol compound [9-2], a monoalkoxydecane compound [9-3] or a dioxane relative to 1 g of the hydrolyzed polycondensate (I). The SiH group in the alkane compound [9-4] is used in the range of 0.2 mmol to 10 mmol.

In the second method, the type of the water-insoluble organic solvent to be used is not particularly limited as long as it does not inhibit the reaction for producing the component (A). Among them, aromatic hydrocarbons, ethers and the like are preferred. Specific examples thereof include toluene, diethyl ether, tetrahydrofuran, diisopropyl ether, and the like, but are not limited thereto. The amount of the water-insoluble organic solvent to be used is preferably from 50 to 1,000% by mass, particularly preferably from 100 to 500% by mass, based on 1 g of the hydrolyzed polycondensate (I).

In the second method, the type of the alcohol-based solvent to be used is not particularly limited as long as it does not inhibit the reaction for producing the component (A). Among them, an alcohol having 1 to 4 carbon atoms is preferred. Specific examples thereof include methanol, ethanol, 1-propanol, 2-propanol, butanol, and the like, but are not limited thereto. The amount of the alcohol-based solvent used is preferably 10% based on 1 g of the hydrolyzed polycondensate (I). 500% by mass, particularly preferably 50 to 300% by mass.

In the second method, it is preferred to use a mixed solvent of a water-insoluble organic solvent and an alcohol-based solvent depending on the kind of the catalyst to be used. In the case of using a protic acid catalyst, the reactivity can be improved by using the mixed solvent.

In the second method, the type of the catalyst to be used is not particularly limited as long as it has an action of promoting the reaction for producing the component (A). Among them, a mineral acid is preferred. Specific examples thereof include nitric acid, hydrochloric acid, sulfuric acid, and the like, but are not limited thereto. The amount of the catalyst used is preferably 0.0001 to 10 mmol%, particularly preferably 0.005 to 5 mmol%, based on 1 g of the hydrolysis polycondensate (I).

In the second method, the method of terminating the reaction is not particularly limited. The reaction is usually terminated by stirring with the addition of water (preferably ion-exchanged water) to the reaction system. After the reaction, from the viewpoint of the rationality of the component (A), it is preferred to separate the component (A) from the reaction system for purification. The separation and purification method is not particularly limited. For example, an extraction method can be cited. Specifically, the organic layer is separated from the solution after the above reaction, and then the organic layer is washed with water (preferably ion-exchanged water), and a desiccant is further added to remove the dissolved water in the system. Thereafter, the component (A) can be separated in high purity by undergoing pressure-removal removal from the organic layer to remove the desiccant and the non-aqueous organic solvent. At this time, it is also possible to simultaneously remove the water under reduced pressure while removing the non-aqueous organic solvent under reduced pressure without using a desiccant. It is preferable that the component (A) after separation is heated and stirred under reduced pressure to remove water contained in the component (A). The heating temperature at this time is not particularly limited, but is usually 100 to 130 °C.

(Method of manufacturing component (B))

The method for producing the component (B) is not particularly limited. For example, a dialkoxy decane compound represented by the following formula [6], a trialkoxy decane compound represented by the general formula [7], and a tetraalkoxy decane compound represented by the general formula [8] can be subjected to a reaction. The condensate obtained by hydrolysis polycondensation (hereinafter sometimes referred to as "hydrolysis polycondensate [II]") and represented by the general formula [10-1], [10-2], [10-3] or [10-4] The vinyl decane compound is produced by reacting.

[Formula _{^{21] R 5 2 Si (OR}} 10) 2 [6] R 6 Si (OR 11) 3 [7] Si (OR 12) 4 [8]

R ⁵ is the same as Formula Formula [2] of [6] The meaning of R ^5, R ¹⁰ represents an alkyl group having 1 to 3 carbon atoms, the two R ¹⁰ may be the same or different from each other species. General formula [7] is the same as R ⁶ in the formula [2] the meaning of R ^6, R ¹¹ represents an alkyl group having 1 to 3 carbon atoms, the three R ¹¹ may be the same or different from each other species. R ¹² in the general formula [8] represents an alkyl group having 1 to 3 carbon atoms, and the four R ¹² groups may be the same or different from each other.

CH ₂ =CH-SiR ⁴ ₂ Cl [10-1] CH ₂ =CH-SiR ⁴ ₂ (OH) [10-2] CH ₂ =CH-SiR ⁴ ₂ (OR ¹⁴ ) [10-3 ] (CH ₂ -CH=SiR ⁴ ₂ ) ₂ O [10-4]

Of the general formula [10-1], [10-2], [10-3] and [10-4] are the same as R ⁴ in the formula [2] the meaning of R ^4. R ¹⁴ in the formula [10-3] represents an alkyl group having 1 to 3 carbon atoms.

In the following, the dialkoxy decane compound represented by the general formula [6], the trialkoxy decane compound represented by the general formula [7], and the tetraalkoxy decane compound represented by the general formula [8] may be respectively used. It is represented by "dialkoxydecane [6], "trialkoxydecane [7]", "tetraalkoxydecane [8]". Further, the vinyl decane compounds represented by the general formulas [10-1], [10-2], [10-3], and [10-4] are sometimes referred to as "chlorovinyl decane compounds [10-1] ]", "vinyl stanol compound [10-2]", "monoalkoxy vinyl decane compound [10-3]", "divinyl dioxane compound [10-4]", When it is distinguished from each other, it is sometimes expressed as "vinyl decane compound [10]".

Specific examples of the dialkoxydecane [6] include, but are not limited to, dimethyldimethoxydecane, dimethyldiethoxydecane, and ethyldiethoxyanthracene. Alkyl, diethyldimethoxydecane, diethyldiethoxydecane.

Among them, preferred examples of the compound include dimethyldimethoxydecane and dimethyldiethoxydecane.

Specific examples of the trialkoxydecane [7] include, but are not limited to, methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, and ethyltriethoxylate. Decane, vinyltrimethoxydecane, vinyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, 3-(trifluoromethyl)phenyltrimethoxydecane, 3-( Trifluoromethyl)phenyltriethoxydecane, 4-(trifluoromethyl)phenyltrimethoxydecane, 4-(trifluoromethyl)phenyltriethoxydecane, 3,5-(two -Trifluoromethyl)phenyltrimethoxydecane, 3,5-(di-trifluoromethyl)phenyltriethoxydecane, naphthyltrimethoxydecane, naphthyltriethoxydecane.

Preferred examples of these compounds include methyltrimethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, and 3-(trifluoromethyl)benzene. Trimethoxy decane, 3-(trifluoromethyl)phenyltriethoxydecane, 4-(trifluoromethyl)phenyltrimethoxydecane, 4-(trifluoromethyl)phenyltriethoxy Pyridin, 3,5-(di-trifluoromethyl)phenyltrimethoxydecane, 3,5-(di-trifluoromethyl)phenyltriethoxydecane, as a preferred compound, Methyltrimethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane.

Specific examples of the tetraalkoxydecane [8] include, but are not limited to, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, and tetraisopropoxy decane.

Among them, preferred examples thereof include tetramethoxynonane and tetraethoxydecane.

The combination of the dialkoxy decane [6], the trialkoxy decane [7], and the tetraalkoxy decane [8] used in the production of the component (B) is not particularly limited. The dialkoxy decane [6], the trialkoxy decane [7], and the tetraalkoxy decane [8] may be used singly or in combination of plural kinds. As a preferred combination, the dialkoxy decane [6] is free from dimethyl dimethoxy decane, dimethyl diethoxy decane, diethyl dimethoxy decane and diethyl diethoxy decane. One or more selected from the group consisting of, the trialkoxydecane [7] is free of methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, benzene. Trimethoxy decane, phenyl triethoxy decane, 3-(trifluoromethyl)phenyltrimethoxy decane, 3-(trifluoromethyl)phenyltriethoxy decane, 4-(trifluoro Methyl)phenyltrimethoxydecane, 4-(trifluoromethyl)phenyltriethoxydecane, 3,5-(di-trifluoromethyl)phenyltrimethoxynonane and 3,5-( More than one selected from the group consisting of di-trifluoromethyl)phenyltriethoxydecane, tetraalkoxydecane [8] free tetramethoxynonane, tetraethoxydecane and tetraisopropoxy One or more of the groups consisting of decane are selected. Among them, as a preferred combination, the dialkoxy decane [6] may be selected from the group consisting of dimethyl dimethoxy decane and dimethyl diethoxy decane, and a trialkoxy decane [ 7] one or more selected from the group consisting of free methyltrimethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane and phenyltriethoxydecane, tetraalkoxydecane [8] One or more selected from the group consisting of tetramethoxy decane and tetraethoxy decane.

Specific examples of the chlorovinyl decane compound [10-1] include the following compounds, but are not limited thereto: chlorodimethyl vinyl decane and chlorodiethyl vinyl decane.

Among them, preferred examples of the compound include chlorodimethylvinyl decane.

Specific examples of the vinyl stanol compound [10-2] include the following compounds, but are not limited thereto: dimethylvinyl stanol or diethyl vinyl stanol.

Among them, preferred examples thereof include dimethylvinylstanol.

Specific examples of the monoalkoxyvinyl decane compound [10-3] include, but are not limited to, dimethyl methoxy vinyl decane, dimethyl ethoxy vinyl decane, diethyl Methoxyvinyl decane, diethyl ethoxy vinyl decane.

Preferred examples of these include dimethylmethoxyvinyl decane and dimethyl ethoxy vinyl decane.

Specific examples of the divinyldioxanane compound [10-4] include, but are not limited to, 1,1,3,3-tetramethyl-1,3-divinyldioxane. 1,1,3,3-tetraethyl-1,3-divinyldioxane.

Among them, preferred examples thereof include 1,1,3,3-tetramethyl-1,3-divinyldioxane.

The hydrolysis polycondensate [II] can be produced by applying the above-described method for producing the hydrolysis polycondensate [I]. That is, the dialkoxy decane [3], the trialkoxy decane [4], the tetraalkoxy decane [5] in the production method of the above-mentioned hydrolysis polycondensate [I] is replaced with a dialkoxy group, respectively. Hydrane [6], trialkoxydecane [7], tetraalkoxydecane [8], hydrolyzed polycondensate [I] substituted with hydrolyzed polycondensate [II], method for producing hydrolyzed polycondensate [II] .

Next, a method of producing the component (B) by reacting the hydrolyzed polycondensate [II] with a vinyl decane compound [10] will be described. The component (B) can be produced by a method in which the component (A) is produced by hydrolyzing the polycondensate [I]. That is, the decane compound [9], the chlorodecane compound [9-1], the stanol compound [9-2], the monoalkoxydecane compound [9- in the production method of the above hydrolysis polycondensate [II]. 3], the dioxantane compound [9-4] is substituted with a vinyl decane compound [10], a chlorovinyl decane compound [10-1], a vinyl stanol compound [10-2], a monoalkoxy group, respectively. a vinyl decane compound [10-3], a divinyl dioxane compound [10-4], and a SiH group, a hydrolyzed polycondensate [I], and (A) component are respectively substituted with a Si-CH=CH ₂ group, The method of producing the component (B) from the hydrolyzed polycondensate [II] can be explained by hydrolyzing the polycondensate [II] and (B) components.

(Method of obtaining (C) component)

A commercially available product can be used as the component (C), and a synthesizer can also be used. (C) component can be previously Synthesize by knowing the method.

[The cured product of the curable polyoxynoxy resin composition]

The cured product of the present invention can be obtained by heating the composition of the present invention.

The cured product of the present invention can be used as a sealing material for a semiconductor device, and is preferably used as a sealing material for an optical semiconductor device or a power semiconductor device. The sealing material for an optical semiconductor device can be preferably used as a sealing material for an optical member for an LED or a sealing member for an optical member for a semiconductor laser. Among them, a sealing material for an optical member for an LED is particularly preferable.

In general, the optical semiconductor device can improve its light extraction efficiency by various techniques. However, if the transparency of the sealing material of the optical semiconductor element is low, the sealing material absorbs light, and the light extraction efficiency of the optical semiconductor device using the same is lowered. As a result, there is a tendency that it is difficult to obtain a high-intensity optical semiconductor device product. Further, the energy corresponding to the decrease in the light extraction efficiency is converted into heat, which is a cause of thermal deterioration of the optical semiconductor device, which is not preferable.

The cured product of the present invention is excellent in transparency. Specifically, the cured product of the present invention has a good light transmittance in a wavelength of usually 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm or less. Therefore, if the cured product of the present invention is used as the sealing material on the optical semiconductor device having the emission wavelength in the region, an optical semiconductor device having high luminance can be obtained, which is preferable. Further, it is not hindered from using the cured product of the present invention as a sealing material on an optical semiconductor device having an emission wavelength outside the above region. Furthermore, the above light transmittance can be measured by transmittance measurement using an ultraviolet/visible spectrophotometer.

Further, the cured product of the present invention is excellent in heat-resistant transparency. That is, the cured product of the present invention has a property that the transmittance of light having a specific wavelength hardly changes even when it is left for a long period of time under high temperature conditions. Specifically, the cured product of the present invention has a transmittance of light having a wavelength of usually 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm or less, after being left at 200 ° C for 100 hours. Good maintenance rate. Therefore, if it is used in an optical semiconductor device having an emission wavelength in the region The cured product of the present invention is preferably used as a sealing material to obtain a high-intensity optical semiconductor device and is difficult to thermally deteriorate. Further, it is not hindered from using the cured product of the present invention as a sealing material on an optical semiconductor device having an emission wavelength outside the above region. Furthermore, the variation ratio of the transmittance can be measured by the transmittance measurement using an ultraviolet/visible spectrophotometer.

The method of hardening the composition of the present invention is not particularly limited. For example, by injecting, dropping, casting, casting, extruding from a container, etc., or by a transfer molding or injection molding, the composition of the present invention may be formed by, for example, transfer molding or injection molding. The LED sealing object combination is usually heated at 45 to 300 ° C, preferably 60 to 200 ° C, to cure the composition to a cured product, thereby sealing the sealing object. When the heating temperature is 45° C. or more, adhesion is hard to be observed in the obtained cured product, and when it is 300° C. or less, foaming is hardly observed in the obtained cured product, and it is practical. The heating time is not particularly limited and may be from about 0.5 hours to about 12 hours, preferably from about 1 hour to about 10 hours. When the heating time is 0.5 hours or more, the hardening is sufficiently performed. However, in the case where the precision for LED sealing or the like is required, the curing time is preferably extended.

[sealing material]

The cured product of the present invention can be used as a sealing material for a semiconductor device, and is particularly suitably used as a sealing material for an optical semiconductor device or a power semiconductor device. The sealing material containing the cured product of the present invention is excellent in heat-resistant transparency as described above. Moreover, it is generally excellent in heat resistance, cold resistance, and electrical insulation properties similarly to the cured product of the prior addition-hardening polyoxyxene resin composition.

[Optical semiconductor device]

The optical semiconductor device of the present invention is an optical semiconductor device including at least an optical semiconductor element, and at least the optical semiconductor element is sealed by the cured product of the present invention. The other configuration of the optical semiconductor device of the present invention is not particularly limited, and other members may be provided in addition to the optical semiconductor element. Examples of such a member include a base substrate, lead wires, wire harnesses, control elements, insulating substrates, reflective materials, heat sinks, conductive members, and die-bonding crystals. Materials, bonding pads, etc. Further, in addition to the optical semiconductor element, part or all of the member may be sealed by the cured product of the present invention.

Specific examples of the optical semiconductor device of the present invention include a light-emitting diode (LED) device, a semiconductor laser device, and a photocoupler, but are not limited thereto. The optical semiconductor device of the present invention can be preferably used, for example, for a backlight device such as a liquid crystal display, illumination, a light source for various sensors, printers, and photocopiers, a vehicle light source, a signal lamp, a display lamp, and a display device. Light source for a planar illuminator, display, decoration, various lamps, and switching elements.

An example of the optical semiconductor device of the present invention is shown in Fig. 1. As illustrated in FIG. 1 , the optical semiconductor device 10 includes at least the sealing material 1 , the optical semiconductor element 2 , and the bonding wires 3 on the optical semiconductor substrate 6 . The optical semiconductor substrate 6 has a concave portion including a bottom surface of the lead frame 5 and an inner peripheral side surface including the reflective material 4.

The optical semiconductor element 2 is connected to the lead frame 5 by using a die bond (not shown). A bonding pad (not shown) provided in the optical semiconductor element 2 and the lead frame 5 are electrically connected by a bonding wire 3 . The reflective material 4 has a function of reflecting light from the optical semiconductor element 2 in a specific direction. The sealing material 1 is filled in the region of the concave portion of the optical semiconductor substrate 6 so as to at least seal the optical semiconductor element 2. At this time, the sealing material 1 can be filled in such a manner that the bonding wire 3 is also sealed. The sealing material 1 contains the cured product of the present invention. The inside of the sealing material 1 may contain the above-mentioned phosphor (not shown). By the sealing material 1, the optical semiconductor element 2 can be protected from moisture, dust, and the like, and reliability can be maintained for a long period of time. Further, by sealing the bonding wire 3 also with the sealing material 1, it is possible to prevent electrical defects caused by the wire, the cutting, and the short circuit of the bonding wire 3 at the same time.

The cured product of the present invention can be used as an adhesive for a semiconductor as described below. Therefore, it can also be used as the above-mentioned cement crystal material or the like.

In the optical semiconductor device 10, the optical semiconductor element 2 sealed by the sealing material 1 including the cured product of the present invention includes, for example, an LED, a semiconductor laser, and a photodiode. Body, photoelectric crystal, solar cell, CCD (charge matching element), etc. Further, the structure shown in Fig. 1 is only an example of the optical semiconductor device of the present invention, and the structure of the reflective material, the structure of the lead frame, the mounting structure of the optical semiconductor element, and the like can be suitably modified.

The method of manufacturing the optical semiconductor device 10 shown in FIG. 1 is not particularly limited. For example, a method in which the optical semiconductor element 2 is bonded to the lead frame 5 including the reflective material 4, and the optical semiconductor element 2 and the lead frame 5 are bonded by a bonding wire 3, and then around the optical semiconductor element The inside of the reflective material (including the lead frame and the concave portion of the reflective material) is filled with the composition of the present invention, and then heated at 50 to 250 ° C to be hardened to obtain a sealing material 1.

[Binder for Semiconductor Device]

The composition of the present invention has good adhesion and can be used as an adhesive for semiconductor devices. Specifically, for example, in the case of the semiconductor element and the package, in the case of the semiconductor element and the sub-mount substrate, and then in the case where the package constitutes the elements, in the case of the semiconductor device and the external optical member Alternatively, the composition of the present invention can be used by coating, printing, potting, or the like. Since the composition of the present invention is excellent in heat resistance, it can provide high reliability which can withstand long-term use when it is used as an adhesive for an optical semiconductor device having a high output exposed to high temperature or ultraviolet light for a long period of time. Optical semiconductor device.

[Examples]

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

The physical properties of the polyanthracene resin synthesized in the following synthesis examples and comparative synthesis examples can be measured and evaluated according to the following methods.

[Quantification of SiH-based and Si-CH=CH ₂ groups]

20 to 30 mg of polyfluorene oxide resin was weighed in a 6 mL sample tube, and 0.8 mL of deuterated dichloromethane was added to dissolve the polyoxynoxy resin. 2.0 μL of dimethyl hydrazine (0.0282 mmol) was added to the solution with a micro syringe, the sample tube was closed, and the solution was stirred to make it uniform and became a measurement sample. The sample was measured in ¹ H-NMR, dimethyl sulfoxide calculating the ratio of the proton and the proton H-Si group or CH ₂ = CH-Si group ratio, measured in a sample determines the H-Si group or CH ₂ = The number of moles of CH-Si. Then, the content of each functional group in the measurement sample 1 g was calculated according to the following formula: the number of moles of the functional group in the polyoxynoxy resin (mmol) / the amount of the measurement sample (mg) × 1000 = the functional group in the measurement sample 1 g Amount (mmol/g).

Further, in the ¹ H-NMR measurement of the polyoxyxylene resin, a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model: ECA-400) having a resonance frequency of 400 MHz was used. The chemical shift of each functional group in the polyoxyxene resin is shown below: Me-Si: 0.0 to 0.5 ppm (3 H), H-Si: 4.0 to 5.0 ppm (1 H), CH ₂ = CH-Si: 5.5 ~6.5 ppm (3 H), Ph-Si: 7.0 to 8.0 ppm (5 H).

[Quantification of toluene]

20 to 30 mg of polyfluorene oxide resin was weighed in a 6 mL sample tube, and 0.8 mL of deuterated dichloromethane was added to dissolve the polyoxynoxy resin. The sample tube was closed, and the solution was stirred to make it uniform and became a measurement sample. The sample was measured by ¹ H-NMR, and the proton ratio of the Me group and the Ph group in the polyoxynoxy resin to the Me group of toluene was calculated, and the amount of toluene in the measurement sample was determined. Then, the content of toluene in the polyfluorene oxide resin was calculated according to the following formula: (molecular weight of toluene (mol/g) × area of Me (toluene) / 3) / ((( molecular weight (mol/g) of (PhSiO _1.5 )) ×((the area of Ph - (area of Me (toluene) × 5 / 3)) / 5)) + ((molecular weight of Me ₂ SiO (mol / g)) × area of Me × 6) + (molecular weight of toluene (mol/g) × area of Me (toluene) / 3)) = amount of toluene (wt%)

Further, in the ¹ H-NMR measurement of the polyoxyxylene resin, a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model: ECA-400) having a resonance frequency of 400 MHz was used. The chemical shift of each functional group in the polyoxyxene resin is shown below: Me: 0.0 to 0.5 ppm (3 H), Me (toluene): 2.2 to 2.4 ppm (3 H), and Ph: 7.0 to 8.0 ppm (5 H) ).

[Quantification of HO-Si based]

To 200 mg of the polyoxyxylene resin, 0.5 mL of chloroform was added to dissolve it, and 10 mg of an acetaminoacetate chromium (III) complex as a moderator was added. The solution thus prepared was measured by ²⁹ Si-NMR. The detected signals are classified into peaks (a) to (p) as shown in Table 1, and the sum of the respective peaks from the total integrated value is calculated as a percentage (integral ratio). Further, in the ²⁹ Si-NMR measurement of the polyoxyxylene resin, a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model: JNM-AL400) having a resonance frequency of 400 MHz was used.

(H-SiR ¹ ₂ O _1/2 ) _a (SiR ² ₂ O _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d [1]

The values of a, b, c, and d in the above formula [1] can be determined by the following equation: a = peak (i) area / total peak area sum, b = (peak (a) area + peak (b) area) / total peak area sum, c = (peak (c) area + peak (d) area + peak (e) area) / total peak area sum, d = (peak (f) area + peak (g) area + peak (h) area) / total peak area sum.

(CH ₂ =CH-SiR ⁴ ₂ O _1/2 ) _e (SiR ⁵ ₂ O _2/2 ) _f (R ⁶ SiO _3/2 ) _g (SiO _4/2 ) _h [2]

The values of e, f, g, and h in the above formula [2] can be determined by calculating from the following equation: e = sum of peak (j) area / total peak area, f = (peak (a) area + peak (b) area) / total peak area sum, g = (peak (c) area + peak (d) area + peak (e) area) / total peak area sum, h = (peak (f) area + peak (g) area + peak (h) area) / total peak area sum.

^{In the case of 29} Si-NMR, when the peaks of Me-Si group, Ph-Si group, H-Si group, CH ₂ =CH-Si group or other groups overlap, the Me-Si group based on ¹ H-NMR The integrated area of the peaks of the Ph-Si group, the H-Si group, the CH ₂ =CH-Si group or other groups is calculated.

Comparing the polyfluorene oxide resins (DA1) and (DB1) synthesized in the synthesis examples, the composition ratio was determined based on the following formula: composition ratio of (H-SiO _3/2 ) = (peak (k) area + peak ( l) area + peak (m) area) / total peak area sum, composition ratio of (CH ₂ =CHSiO _3/2 ) = (peak (n) area + peak (o) area + peak (p) area) / The sum of the total peak areas.

The content of HO-Si group (mmol/g) is determined by the above method and is determined according to the following formula: [A] = peak (a) integral ratio + 2 × peak (c) integral ratio + peak (d) integral Than +2× wave Peak (f) integral ratio + peak (g) integral ratio + 2 × peak (k) integral ratio + peak (l) integral ratio + 2 × peak (n) integral ratio + peak (o) integral ratio, [B] = Peak (a) integral ratio × 83.16 + peak (b) integral ratio × 74.15 + peak (c) integral ratio × 147. 2 peak (d) integral ratio × 138. 2 peak (e) integral ratio × 129. 2 + peak (f) integral Ratio × 78.10 + peak (g) integral ratio × 69.09 + peak (h) integral ratio × 60.08 + peak (i) integral ratio × 67.16 + peak (j) integral ratio × 93.20 + peak (k) integral ratio × 71.11 + peak (l) integral ratio × 62.10 + peak (m) integral ratio × 53.09 + peak (n) integral ratio × 97.15 + peak (o) integral ratio × 88.14 + peak (p) integral ratio × 79.13, content of HO-Si base (mmol/g) = ([A] / [B]) × 1000.

^In the measurement of ²⁹ Si-NMR, when the peak (i) and the peak (j) overlap with the peak (a), the integral ratio of Ph-Si to H-Si and Ph-Si were determined by ¹ H-NMR measurement. And CH=CH ₂ -Si, if there are other peaks, the percentage of the integral ratio of the other peaks, calculate the ²⁹ Si-NMR peak (c) integral ratio + peak (d) integral ratio + peak (e) integral ratio, since The integral ratio of ¹ H-NMR is calculated as the integral ratio of the ²⁹ Si-NMR of the peak (i) and the peak (j), and the integral value of the overlap between the peak (a) and the peak (i) and the peak (j) is subtracted. The integral ratio of the peak (i) and the peak (j) is calculated as the integral value of the peak (a). In the case where the peaks of ²⁹ Si-NMR overlap in other cases, the calculation is based on the integral ratio of ¹ H-NMR in the same manner as the above method.

[Measurement of mass average molecular weight (Mw)]

The mass average molecular weight (Mw) of the polyoxyxene resin is calculated by a gel permeation chromatography (abbreviation: GPC) method using the following conditions, and a calibration curve is prepared using polystyrene as a reference material: Device: Tosoh Co., Ltd. Manufactured, product name: HLC-8320GPC, pipe column: manufactured by Tosoh Co., Ltd., product name: TSK gel Super HZ 2000×4, 3000×2, eluent: tetrahydrofuran.

Further, regarding the mass average molecular weight (Mw) exceeding 1,500, the following conditions are employed. Gel permeation chromatography (abbreviation: GPC) method, using a polystyrene as a reference material to prepare a calibration curve and calculating the value: device: manufactured by Tosoh Co., Ltd., product name: HLC-8320GPC, column: manufactured by Tosoh Co., Ltd. Product name: TSK gel Super HZM-H×2 eluent: tetrahydrofuran.

[refractive index]

The refractive index of the polyoxyxene resin was measured using a refractometer (manufactured by Kyoto Electronics Manufacturing Co., Ltd., model: RA-600).

[Viscosity measurement]

Regarding the viscosity of the polyoxyxene resin, a rotary viscometer (manufactured by Brookfield. Engineering. Laboratories. Inc., product name: DV-II+PRO) and a temperature control unit (manufactured by Brookfield. Engineering. Laboratories. Inc., product name: THERMOSEL) are used. The value at 25 ° C was measured.

[Synthesis Example 1-1]

<Synthesis of polyoxyl resin (I-1)>

120.2 g (1.0 mol) of Me ₂ Si(OMe) ₂ and 198.3 g (1.0 mol) of PhSi(OMe) ₃ were taken in a three-necked flask having a volume of 2 L of a fluororesin stirring blade and a Dairy reflux. Then, 239.6 g of 2-propanol, 185.0 g of water, and 0.12 g of acetic acid were added to the flask, and the flask was continuously heated at 100 ° C for 6 hours to carry out hydrolysis and condensation reaction. Thereafter, the reaction solution was returned to room temperature, transferred to a 2 L separatory funnel, and 400 mL of toluene and 400 mL of water were added to carry out a liquid separation operation, and then the aqueous layer was removed. Then, the organic layer was washed twice with 400 mL of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure by an evaporator to obtain a polyfluorene oxide resin (I-1) as a colorless viscous liquid.

The yield of the polyoxyxylene resin (I-1) was 160.8 g, the mass average molecular weight (Mw) was 1,000, and the composition ratio was (Me ₂ SiO _2/2 ) _0.43 (PhSiO _3/2 ) _0.57 , and the content of the HO-Si group was It was 7.8 mmol/g (13 mass%).

[Synthesis Example 1-2]

<Synthesis of polyoxyl resin (A1)>

39.7 g of polyoxynoxy resin (I-1), 119 g of toluene, 39.7 g of methanol, 8.3 g of 1,1,3,3-tetramethyldioxane and 0.20 mL of 70% concentrated nitric acid were added. The flask was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 119 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated four times to wash the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then distilled under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (A1) as a colorless transparent viscous liquid.

The yield of polyoxyxylene resin (A1) was 42.5 g, the mass average molecular weight (Mw) was 1,900, the viscosity was 200 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.31 (PhSiO _3/2 ) _0.42 (H(Me) ₂ SiO _1/2 ) _0.27 , the content of the H-Si group was 2.8 mmol/g, and the content of the HO-Si group was 2.0 mmol/g (3.4% by mass).

[Synthesis Example 1-3]

<Synthesis of polyoxyl resin (B1)>

19.9 g of polydecane resin (I-1), 59.7 g of toluene, 19.9 g of methanol, 5.76 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane And 1.98 mL of 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 59.7 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated four times to wash the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then subjected to distillation under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (B1) as a colorless transparent viscous liquid.

The yield of the polyoxyxylene resin (B1) was 20.6 g, the mass average molecular weight (Mw) was 1,800, the viscosity was 350 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.32 (PhSiO _3/2 ) _0.45 (CH ₂ =CH). (Me) ₂ SiO _1/2 ) _0.23 , a CH ₂ =CH-Si group content of 2.3 mmol/g, and a HO-Si group content of 2.1 mmol/g (3.6 mass%).

[Synthesis Example 2-1]

<Synthesis of polyoxyl resin (I-2)>

In addition to using 114.2 g (0.95 mol) of Me ₂ Si(OMe) ₂ , 188.4 g (0.95 mol) of PhSi(OMe) ₃ and 13.0 g (0.063 mol) of Si(OEt) ₄ instead of 120.2 g (1.0 mol) The same operation as in Synthesis Example 1-1 was carried out except for Me ₂ Si(OMe) ₂ and 198.3 g (1.0 mol) of PhSi(OMe) ₃ . As a result, a polyfluorene oxide resin (I-2) as a colorless viscous liquid was obtained.

The yield of the polyoxyxylene resin (I-2) was 163.0 g, the mass average molecular weight (Mw) was 900, and the composition ratio of the product was (Me ₂ SiO _2/2 ) _0.41 (PhSiO _3/2 ) _0.52 (SiO _{4/). 2} ) _0.06 , and the content of the HO-Si group was 8.5 mmol/g (14% by mass).

[Synthesis Example 2-2]

<Synthesis of polyoxyl resin (A2)>

55.8 g of polyoxynoxy resin (I-2), 167.4 g of toluene, 55.8 g of methanol, 12.7 g of 1,1,3,3-tetramethyldioxane and 0.30 mL of 70% concentrated nitric acid It was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 167.4 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated four times to wash the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then subjected to distillation under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (A2) as a colorless transparent viscous liquid.

The yield of polyoxyxylene resin (A2) was 55.1 g, the mass average molecular weight (Mw) was 1,000, the viscosity was 140 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.21 (PhSiO _3/2 ) _0.45 (SiO _{4/2). 0.06} (H(Me) ₂ SiO _1/2 ) _0.28 , the content of the H-Si group was 2.6 mmol/g, and the content of the HO-Si group was 2.9 mmol/g (4.9% by mass).

[Synthesis Example 2-3]

<Synthesis of polyoxyl resin (B2)>

27.9 g of polyoxynoxy resin (I-2), 83.7 g of toluene, 27.9 g of methanol, and 8.81 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane And 3.03 mL of 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 83.7 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated four times to wash the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then subjected to distillation under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (B2) as a colorless transparent viscous liquid.

The yield of the polyoxyxylene resin (B2) was 29.5 g, the mass average molecular weight (Mw) was 1,100, the viscosity was 200 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.26 (PhSiO _3/2 ) _0.42 (SiO _{4/2). 0.05} (CH ₂ =CH(Me) ₂ SiO _1/2 ) _0.27 , the content of CH ₂ =CH-Si group was 2.7 mmol/g, and the content of HO-Si group was 1.7 mmol/g (2.9% by mass).

[Synthesis Example 3-1]

<Synthesis of polyoxyl resin (I-3)>

In place of 100.2 g (0.90 mol) of Me ₂ Si(OMe) ₂ , 178.5 g (0.90 mol) of PhSi(OMe) ₃ and 26.0 g (0.125 mol) of Si(OEt) ₄ instead of 120.2 g (1.0 mol) The same operation as in Synthesis Example 1-1 was carried out except for Me ₂ Si(OMe) ₂ and 198.3 g (1.0 mol) of PhSi(OMe) ₃ . As a result, a polyfluorene oxide resin (I-3) which is a colorless transparent viscous liquid was obtained.

The yield of the polyoxyxylene resin (I-3) was 154.2 g, the mass average molecular weight (Mw) was 900, and the composition ratio was (Me ₂ SiO _2/2 ) _0.35 (PhSiO _3/2 ) _0.56 (SiO _4/2 ) _0.10. The content of the HO-Si group was 8.5 mmol/g (14% by mass).

[Synthesis Example 3-2]

<Synthesis of polyoxyl resin (A3)>

57.4 g of polyoxynoxy resin (I-3), 172.2 g of toluene, 57.4 g of methanol, 16.4 g of 1,1,3,3-tetramethyldioxane and 0.39 mL of 70% concentrated nitric acid Add to the flask, at Stir at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 172.2 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated four times to wash the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then subjected to distillation under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (A3) as a colorless transparent viscous liquid.

The yield of polyoxyxylene resin (A3) was 58.4 g, the mass average molecular weight (Mw) was 1,100, the viscosity was 180 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.15 (PhSiO _3/2 ) _0.46 (SiO _{4/2). 0.07} (H(Me) ₂ SiO _1/2 ) _0.33 , the content of the H-Si group was 3.2 mmol/g, and the content of the HO-Si group was 2.7 mmol/g (4.6% by mass).

[Synthesis Example 3-3]

<Synthesis of polyoxyl resin (B3)>

28.7 g of polyoxynoxy resin (I-3), 86.1 g of toluene, 28.7 g of methanol, and 11.4 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane And 3.92 mL of 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 86.1 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated four times to wash the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then subjected to distillation under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (B3) as a colorless transparent viscous liquid.

The yield of polyoxyxylene resin (B3) was 32.7 g, the mass average molecular weight (Mw) was 1,300, the viscosity was 230 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.20 (PhSiO _3/2 ) _0.43 (SiO _{4/2). 0.07} (CH ₂ =CH(Me) ₂ SiO _1/2 ) _0.30 , the content of CH ₂ =CH-Si group was 2.8 mmol/g, and the content of HO-Si group was 1.7 mmol/g (2.9% by mass).

[Synthesis Example 4-1]

<Synthesis of polyoxyl resin (I-4)>

In place of 90.2 g (0.80 mol) of Me ₂ Si(OMe) ₂ , 158.6 g (0.80 mol) of PhSi(OMe) ₃ and 52.1 g (0.25 mol) of Si(OEt) ₄ instead of 120.2 g (1.0 mol) The same operation as in Synthesis Example 1-1 was carried out except for Me ₂ Si(OMe) ₂ and 198.3 g (1.0 mol) of PhSi(OMe) ₃ . As a result, a polyfluorene oxide resin (I-4) which is a colorless transparent viscous liquid was obtained.

The yield of the polyoxyxylene resin (I-4) was 143.4 g, the mass average molecular weight (Mw) was 1,100, and the composition ratio was (Me ₂ SiO _2/2 ) _0.34 (PhSiO _3/2 ) _0.51 (SiO _4/2 ) _0.15. The content of the HO-Si group was 7.7 mmol/g (13% by mass).

[Synthesis Example 4-2]

<Synthesis of polyoxyl resin (A4)>

173.7 g of polyoxynoxy resin (I-4), 521.1 g of toluene, 173.7 g of methanol, 31.4 g of 1,1,3,3-tetramethyldioxane and 0.75 mL of 70% concentrated nitric acid It was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 521.1 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated four times to wash the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then subjected to distillation under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (A4) as a colorless transparent viscous liquid.

The yield of polyoxyxylene resin (A4) was 165.7 g, the mass average molecular weight (Mw) was 1,500, the viscosity was 4,000 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.16 (PhSiO _3/2 ) _0.45 (SiO _{4/ 2} ) _0.15 (H(Me) ₂ SiO _1/2 ) _0.24 , the content of the H-Si group was 2.2 mmol/g, and the content of the HO-Si group was 3.1 mmol/g (5.3 mass%).

[Synthesis Example 4-3]

<Synthesis of polyoxyl resin (B4)>

91.4 g of polyoxynoxy resin (I-4), 274.2 g of toluene, 91.4 g of methanol, 23.0 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane 7.90 mL of 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 274.2 g of water was added thereto, and after the extraction operation, the organic layer was recovered. Repeat the same four times The operation is performed thereby cleaning the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then subjected to distillation under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (B4) as a colorless transparent viscous liquid.

The yield of polyoxyxylene resin (B4) was 99.2 g, the mass average molecular weight (Mw) was 1,400, the viscosity was 2,500 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.23 (PhSiO _3/2 ) _0.41 (SiO _{4/ 2} ) _0.13 (CH ₂ =CH(Me) ₂ SiO _1/2 ) _0.23 , the content of CH ₂ =CH-Si group is 2.2 mmol/g, and the content of HO-Si group is 1.9 mmol/g (3.2% by mass) .

[Synthesis Example 5-1]

<Synthesis of polyoxyl resin (I-5)>

In place of 90.2 g (0.75 mol) of Me ₂ Si(OMe) ₂ , 148.7 g (0.75 mol) of PhSi(OMe) ₃ and 65.1 g (0.313 mol) of Si(OEt) ₄ instead of 120.2 g (1.0 mol) The same operation as in Synthesis Example 1-1 was carried out except for Me2Si(OMe) ₂ and 198.3 g (1.0 mol) of PhSi(OMe) ₃ . As a result, a polyfluorene oxide resin (I-5) which is a colorless transparent viscous liquid was obtained.

The yield of the polyoxyxylene resin (I-5) was 137.7 g, the mass average molecular weight (Mw) was 1,300, and the composition ratio was (Me ₂ SiO _2/2 ) _0.28 (PhSiO _3/2 ) _0.53 (SiO _4/2 ) _0.19 The content of the HO-Si group was 7.4 mmol/g (13% by mass).

<Synthesis of polyoxyl resin (A5)>

28.6 g of polyoxynoxy resin (I-5), 85.8 g of toluene, 28.6 g of methanol, 5.69 g of 1,1,3,3-tetramethyldioxane and 0.14 mL of 70% concentrated nitric acid It was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 85.8 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated four times to wash the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then subjected to distillation under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (A5) as a colorless transparent viscous liquid.

The yield of polyoxyxylene resin (A5) was 27.5 g, the mass average molecular weight (Mw) was 1,600, the viscosity was 15,000 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.13 (PhSiO _3/2 ) _0.43 (SiO _{4/ 2} ) _0.21 (H(Me) ₂ SiO _1/2 ) _0.23 , the content of the H-Si group was 2.1 mmol/g, and the content of the HO-Si group was 2.7 mmol/g (4.6% by mass).

<Synthesis of polyoxyl resin (B5)>

14.3 g of polyoxynoxy resin (I-5), 42.9 g of toluene, 14.3 g of methanol, 3.95 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane And 1.36 mL of 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 42.9 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated four times to wash the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then subjected to distillation under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (B5) as a colorless transparent viscous liquid.

The yield of the polyoxyxylene resin (B5) was 15.2 g, the mass average molecular weight (Mw) was 1,500, the viscosity was 23,000 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.18 (PhSiO _3/2 ) _0.40 (SiO _{4/ 2} ) _0.19 (CH ₂ =CH(Me) ₂ SiO _1/2 ) _0.23 , the content of CH ₂ =CH-Si group is 2.3 mmol/g, and the content of Si-OH group is 1.7 mmol/g (2.9% by mass) .

[Synthesis Example 6-1]

<Synthesis of polyoxyl resin (I-6)>

In place of 80.2 g (0.70 mol) of Me ₂ Si(OMe) ₂ , 138.8 g (0.70 mol) of PhSi(OMe) ₃ and 78.1 g (0.375 mol) of Si(OEt) ₄ instead of 120.2 g (1.0 mol) The same operation as in Synthesis Example 1-1 was carried out except for Me ₂ Si(OMe) ₂ and 198.3 g (1.0 mol) of PhSi(OMe) ₃ . As a result, a polyfluorene oxide resin (I-6) which is a colorless transparent viscous liquid was obtained.

The yield of polyoxyxylene resin (I-6) was 140.8 g, the mass average molecular weight (Mw) was 1,500, and the composition ratio was (Me ₂ SiO _2/2 ) _0.29 (PhSiO _3/2 ) 0.44 (SiO _4/2 ) _0.27. The content of the HO-Si group was 6.8 mmol/g (12% by mass).

[Synthesis Example 6-2]

<Synthesis of polyoxyl resin (A6)>

47.9 g of polyoxynoxy resin (I-6), 143.7 g of toluene, 47.9 g of methanol, 10.9 g of 1,1,3,3-tetramethyldioxane and 0.26 mL of 70% concentrated nitric acid It was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 143.7 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated four times to wash the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then distilled under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (A6) as a colorless transparent viscous liquid.

The yield of polyoxyxylene resin (A6) was 59.3 g, the mass average molecular weight (Mw) was 1,900, the viscosity was 280,000 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.15 (PhSiO _3/2 ) _0.40 (SiO _{4/ 2} ) _0.22 (H(Me) ₂ SiO _1/2 ) _0.23 , the content of the H-Si group was 1.6 mmol/g, and the content of the HO-Si group was 2.5 mmol/g (4.3% by mass).

[Synthesis Example 6-3]

<Synthesis of polyoxyl resin (B6)>

23.9 g of polyoxynoxy resin (I-6), 71.7 g of toluene, 23.9 g of methanol, and 7.55 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane 2.60 mL of 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 71.7 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated four times to wash the organic layer. Toluene was removed by distillation from an organic layer by an evaporator, and then subjected to distillation under reduced pressure by heating (130 ° C, 2 hours) to obtain a polyoxyl resin (B6) as a colorless transparent viscous liquid.

The yield of polyoxyxylene resin (B6) was 32.0 g, the mass average molecular weight (Mw) was 1,900, the viscosity was 280,000 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.19 (PhSiO _3/2 ) _0.39 (SiO _{4/ 2} ) _0.21 (CH ₂ =CH(Me) ₂ SiO _1/2 ) _0.21 , the content of CH ₂ =CH-Si group is 1.9 mmol/g, and the content of HO-Si group is 1.6 mmol/g (2.7% by mass) .

[Comparative Synthesis Example]

<Synthesis of polyoxyl resin (DA1)>

In place of 92.57 g (0.77 mol) of Me ₂ Si(OMe) ₂ , 152.68 g (0.77 mol) of PhSi(OMe) ₃ and 47.05 g (0.385 mol) of HSi(OMe) ₃ instead of 120.2 g (1.0 mol) The same operation as in Synthesis Example 1-1 was carried out except for Me ₂ Si(OMe) ₂ and 198.3 g (1.0 mol) of PhSi(OMe) ₃ . As a result, a polyfluorene oxide resin (DA1) which is a colorless transparent viscous liquid was obtained.

The yield of polyoxyxylene resin (DA1) was 144.2 g, the mass average molecular weight (Mw) was 1,400, the viscosity was 34,000 cP, and the composition ratio was (Me ₂ SiO _2/2 ) 0.34 (PhSiO _3/2 ) _0.42 (HSiO _{3/ 2} ) _0.24 , the content of the H-Si group was 1.5 mmol/g, and the content of the HO-Si group was 7.2 mmol/g (12% by mass).

<Synthesis of polyoxyl resin (DA2)>

48.1 g (0.40 mol) of Me ₂ Si(OMe) ₂ , 79.3 g (0.40 mol) of PhSi(OMe) ₃ and 13.4 were taken in a three-necked flask having a volume of 2 L of a fluororesin stirring blade and a Dy's reflux vessel. g (0.10 mol) of 1,1,3,3-tetramethyldioxane. Then, 106 g of 2-propanol, 79.3 g of water, and 0.06 g of acetic acid were added to the flask, and the flask was continuously heated at 100 ° C for 6 hours to carry out hydrolysis and condensation reaction. Thereafter, the reaction liquid was returned to room temperature, transferred to a 1 L separatory funnel, and 200 mL of toluene and 200 mL of water were added to carry out a liquid separation operation, and then the aqueous layer was removed. The organic layer was then washed twice with 200 mL of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure by an evaporator to obtain a polyfluorene oxide resin (DA2) as a colorless viscous liquid.

The yield of polyoxyxylene resin (DA2) was 81.6 g, the mass average molecular weight (Mw) was 650, the viscosity was 300 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.38 (PhSiO _3/2 ) _0.40 (H(Me) ₂ SiO _1/2 ) _0.22 , the content of the H-Si group was 1.55 mmol/g, and the content of the HO-Si group was 4.7 mmol/g (8.0% by mass).

<Synthesis of polyoxyl resin (DB1)>

In place of 92.57 g (0.77 mol) of Me ₂ Si(OMe) ₂ , 152.68 g (0.77 mol) of PhSi(OMe) ₃ and 57.07 g (0.385 mol) of CH ₂ =CH-Si(OMe) ₃ instead of 120.2 g The same operation as in Synthesis Example 1-1 was carried out except for (1.0 mol) of Me ₂ Si(OMe) ₂ and 198.3 g (1.0 mol) of PhSi(OMe) ₃ . As a result, a polyfluorene oxide resin (DB1) which is a colorless transparent viscous liquid was obtained.

The yield of polyoxyxylene resin (DB1) was 122.3 g, the mass average molecular weight (Mw) was 1,200, the viscosity was 3,700 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.33 (PhSiO _3/2 ) _0.47 (CH ₂ = The content of CHSiO _3/2 ) _0.20 , CH ₂ =CH-Si group was 1.7 mmol/g, and the content of HO-Si group was 10.7 mmol/g (18% by mass).

<Synthesis of polyoxyl resin (DB2)>

30.1 g (0.25 mol) of Me ₂ Si(OMe) ₂ , 49.6 g (0.25 mol) of PhSi(OMe) ₃ and 11.7 were taken in a three-necked flask having a volume of 2 L of a fluororesin stirring blade and a Dy's reflux vessel. g (0.063 mol) of 1,3-divinyl-1,1,3,3-tetramethyldioxane. Then, 59.9 g of 2-propanol, 46.3 g of water, and 0.03 g of acetic acid were added to the flask, and the flask was continuously heated at 100 ° C for 6 hours to carry out hydrolysis and condensation reaction. Thereafter, the reaction solution was returned to room temperature, transferred to a 1 L separatory funnel, and 100 mL of toluene and 100 mL of water were added to carry out a liquid separation operation, and then the aqueous layer was removed. Then, the organic layer was washed twice by 100 mL of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure by an evaporator to obtain a polyoxyl resin (DB2) as a colorless viscous liquid.

The yield of polyoxyxylene resin (DB2) was 39.8 g, the mass average molecular weight (Mw) was 1,000, the viscosity was 12,000 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.42 (PhSiO _3/2 ) _0.54 (CH ₂ = CH(Me) ₂ ) _0.03 , CH ₂ =CH-Si group content was 0.05 mmol/g, and HO-Si group content was 8.6 mmol/g (15 mass%).

<Synthesis of polyoxyl resin (DB3)>

In place of 48.1 g (48.1 g (0.40 mol) of Me ₂ Si(OMe) ₂ , 79.3 g (0.40 mol) of PhSi(OMe) ₃ and 23.2 g (0.20 mol) of dimethylvinylmethoxy decane) 0.40 mol) of Me ₂ Si(OMe) ₂ , 79.3 g (0.40 mol) of PhSi(OMe) ₃ and 13.4 g (0.10 mol) of 1,1,3,3-tetramethyldioxane, and The same operation as the above <synthesis of poly(oxygen oxide resin (DA2)> was carried out except that the heating was continued for 15 hours at 100 ° C instead of continuously heating at 100 ° C for 6 hours. As a result, a polyfluorene oxide resin (DB3) as a colorless viscous liquid was obtained.

The yield of polyoxyxylene resin (DB3) was 89.3 g, the mass average molecular weight (Mw) was 630, the viscosity was 300 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.37 (PhSiO _3/2 ) _0.47 (CH ₂ =CH). (Me) ₂ SiO _1/2 ) _0.16 , a CH ₂ =CH-Si group content of 1.30 mmol/g, and a HO-Si group content of 6.8 mmol/g (12 mass%).

The composition ratios of the synthesized polyoxynoxy resins (A1) to (A6), polyoxyxylene resins (B1) to (B6), and polyoxyxylene resins (DA1) to (DA2) and (DB1) to (DB3) The physical property values (the content of the HO-Si group, the content of the SiH group or the Si-CH=CH ₂ group, the mass average molecular weight, the viscosity, the refractive index, and the transparency) are shown in Table 2. In Table 2, Vi represents a vinyl group (CH ₂ =CH- group).

<Curable polyoxyn resin composition and cured product thereof>

The viscosity of the prepared composition, the physical properties of the cured product obtained from the composition (hardness, adhesion, heat resistance, transparency, heat-resistant transparency, linear thermal expansion coefficient, 5% weight reduction temperature, adhesion strength), hardening The initial temperature and the appearance at the time of hardening were measured as follows. Further, the composition used in the measurement is a polyfluorene resin of the component (A) [polyoxygen resin (A1) to (A6), (DA1) to (DA2)] and (B). Oxygen resins [polyoxynoxy resins (B1) to (B6), (DB1) to (DB3)] are prepared in a mass ratio of 2:1, and are mixed with a platinum catalyst of the component (C) to prepare Examples 1 to 6 and The compositions of Comparative Examples 1 to 3 were used. Here, as the platinum catalyst, a platinum-divinyltetramethyldioxane complex is used in such a manner that the content of platinum atoms is 0.03 ppm by mass based on the total amount of the composition.

[Viscosity of composition]

Regarding the viscosity of the prepared composition, a rotational viscometer (manufactured by Brookfield. Engineering. Laboratories. Inc., product name: DV-II+PRO) and a temperature control unit (manufactured by Brookfield. Engineering. Laboratories. Inc., product name: THERMOSEL) were used. The value at 25 ° C was measured at a shear rate of 30 [1/s].

[hardness of hardened material]

The prepared mixture is transferred into the mold (25mm In the air, it was heated at 90 ° C for 1 hour in the air, and further heated at 150 ° C for 4 hours to prepare a cured product having a thickness of 4 to 5 mm. The hardness of the cured product was measured using a durometer (manufactured by Teclock Co., Ltd., model: GS-719R, GS-720R) in accordance with the method specified in JIS K 7215 "Testing methods for hardness of plastics". Or the hardness of Xiao's D. Further, in Comparative Example 2 and Comparative Example 3, the composition was not cured, and thus the measurement was not performed.

[Adhesiveness of hardened material]

The prepared composition was transferred into a 3528 SMD type PPA resin package (3528 surface mount type polyphthalamide resin package) (3.5 mm × 2.8 mm × 0.9 mm), and heated at 90 ° C for 1 hour in the air. Further, the sample was heated at 150 ° C for 4 hours to prepare 16 samples as a cured product. The specimens were confirmed by an optical microscope, and the cured product was evaluated as "peeling" from the package, and the unpeeled was evaluated as "close contact". The number of samples evaluated as "closed" among the 16 samples was listed as "qualified number". Further, in Comparative Example 2 and Comparative Example 3, the composition was not cured, and thus the measurement was not performed.

[Transparency of hardened material]

The prepared mixture is transferred into the mold (22mm In the air, it is heated at 90 ° C for 1 hour in the air, and further heated at 150 ° C for 4 hours to make 22 mm. , 2mm thick hardened material. The transmittance of the cured product in the wavelength region of 405 nm and 365 nm was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV-3150). Further, in Comparative Example 2 and Comparative Example 3, the composition was not cured, and thus the measurement was not performed.

[heat-resistant transparency of hardened materials]

The prepared mixture is transferred into the mold (22mm In the air, it is heated at 90 ° C for 1 hour in the air, and further heated at 150 ° C for 4 hours to make 22 mm. , 2mm thick hardened material. After the cured product was heated at 200 ° C for 100 hours, the transmittance in the wavelength region of 405 nm and 365 nm was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV-3150). Further, in Comparative Example 2 and Comparative Example 3, the composition was not cured, and thus the measurement was not performed.

[Linear thermal expansion coefficient of hardened material]

0.7 g of the prepared composition was added to a tube made of fluororesin (inner diameter: 5.8 mm) The height: 1.8 mm) was heated in air at 90 ° C for 1 hour, and further heated at 150 ° C for 4 hours to produce a cured product. Using a ThermoPlusTM A8310 (manufactured by RIGAKU Co., Ltd.), the cured product was heated in air at a heating rate of 5 ° C / min from 25 ° C to 200 ° C to measure the linear thermal expansion coefficient of the cured product. The measurement was carried out twice, and the measured value was the second value. Further, in Comparative Example 2 and Comparative Example 3, the composition was not cured, and thus the measurement was not performed.

[5% weight loss temperature (T _d5 )]

The prepared composition was heated in air at 90 ° C for 1 hour, and further heated at 150 ° C for 4 hours to prepare a cured product. Using ThermoPlus TG8120 (manufactured by RIGAKU Co., Ltd.) as a thermogravimetric/differential thermal analysis device (TG-DTA), the cured product was heated in air at a heating rate of 5 ° C / min. The mixture was heated to 500 ° C at 25 ° C, and the temperature (T _d5 ) at which 5% weight loss was measured was measured. Further, in Comparative Example 2 and Comparative Example 3, the composition was not cured, and thus the measurement was not performed.

[Continuity of hardened material]

The mixture of the prepared composition and the zirconia ball having a diameter of 50 μm was sandwiched between a glass wafer (5.0 mm × 5.0 mm × 1.1 mm) and a glass substrate (50 mm × 50 mm × 3.0 mm) or an alumina substrate (50 mm × 50 mm). In the state between ×2.0 mm), it was heated at 90 ° C for 1 hour in the air, and further heated at 150 ° C for 4 hours to be hardened. The adhesion (adequate strength) of the produced sample was measured by a bond strength tester (manufactured by Dage Japan Co., Ltd., model: Dage 4000 Plus). The case where the hardened material was destroyed at the time of measurement and the value of the subsequent strength was not obtained was referred to as "agglomeration destruction". Further, in Comparative Example 2 and Comparative Example 3, the composition was not cured, and thus the measurement was not performed.

[hardening initiation temperature]

The composition which was allowed to stand for 10 minutes after preparation was subjected to a rotational viscometer (manufactured by Brookfield. Engineering. Laboratories. Inc., product name: DV-II+PRO) and a temperature control unit (manufactured by Brookfield. Engineering. Laboratories. Inc., product name: THERMOSEL The change in viscosity at a temperature of 2.09 ° C / min from 25 ° C to 150 ° C was measured at a shear rate of 30 [1/s]. The temperature at which the viscosity exceeded 30,000 cP was evaluated as the hardening onset temperature.

[Appearance when hardened]

1 g of the prepared composition was thinly spread on a glass mold (22 mm) )in. Thereafter, the mixture was heated in air at 90 ° C for 1 hour, and further heated at 150 ° C for 4 hours to prepare a cured product. The hardened material produced was naturally cooled to 25 °C. Three test bodies were produced in the same manner. The state of the test body was visually confirmed, and the state in which the foaming and cracking were not observed was evaluated as "good" in all the test bodies, and the state of the bubble observed in the hardened body in any test body was evaluated as "Foaming" was evaluated as "unhardened" in the state in which the composition was not cured and remained in a viscous liquid in any of the test bodies.

The evaluation results of the compositions and cured products of Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 3.

In Examples 4 to 6 in which the composition ratio of (SiO) _{4/2 in} the (A) component or the (B) component polyoxyxylene resin was 0.1 or more, the Shore A hardness exceeded 70, and the Shore D hardness exceeded 10.

In the examples 4 to 6 in which the composition ratio of (SiO) _{4/2 in} the (A) component or the (B) component polyoxyxylene resin was 0.1 or more, the strength exceeded 100 N. In Examples 1 to 3, destruction of the resin (aggregation failure) was observed, and the measured value could not be detected. On the other hand, in Comparative Example 1, the subsequent strength was less than 50N.

Further, in the adhesion test, in Comparative Example 1, the cured product was "foamed", and the sample in which the package was well sealed was not observed, and the adhered samples were observed in the above Examples 1 to 6. In particular, in Examples 1 to 5, "close contact" was observed in more than half of the samples, and "close contact" was observed in all of the 16 samples in Example 1 and Examples 3 to 5.

In the transparency test of the cured product, the cured products of Examples 1 to 6 showed 88% or more at a wavelength of 365 nm and a high transparency of 90% or more at a wavelength of 405 nm. On the other hand, in the cured product of Comparative Example 1, the transmittance was 45% or less. The reason for this is considered to be caused by foaming of the cured product. Further, regarding the transparency (heat-resistant transparency) after continuously heating the cured product at 200 ° C for 100 hours, the cured products of Examples 1 to 6 were maintained at a wavelength of 405 nm of 88% or more, and maintained at a wavelength of 365 nm of 79% or more. High transmittance.

Regarding the heat resistance of the cured product, the cured products of Examples 1 to 6 showed T _{d5 of} 285 ° C or higher, and particularly the cured products of Examples 3 to 6, showing a high T _{d5 of} 395 ° C or higher.

Regarding the linear thermal expansion coefficient, the cured products of Examples 1 to 6 showed less than 300 ppm by volume, and in particular, the cured products of Examples 1 and 3 to 6 showed less than 250 ppm by volume, and the cured products of Examples 4 to 6 were not shown. A good linear thermal expansion coefficient of 215 vol. If the linear thermal expansion coefficient is low, the volume expansion and shrinkage under thermal cycling are small, and it is difficult to peel off from the mold. Therefore, it is preferred that the linear thermal expansion coefficient is low.

The compositions of Examples 1 to 6 had a hardening onset temperature of 58 to 79 ° C and had good hardenability. On the other hand, in Comparative Examples 1 to 3, curing did not start even if the temperature was raised to 150 °C.

According to the above content, the embodiments 1 to 6 in the scope of the present invention The composition has good hardenability and the cured product has high heat-resistant transparency. Moreover, the adhesion is also good. In particular, in the cured products of Examples 3 to 6, heat resistance and Shore hardness were also excellent. Further, in the cured products of Examples 4 to 6, it was shown to have a high bonding strength.

<Evaluation of Platinum Amount and Heat Resistance Transparency>

Next, the polyoxynoxy resin (A1) as the component (A) and the polyoxynoxy resin (B1) as the component (B) are blended in a mass ratio of 2:1, and are mixed with the platinum catalyst of the component (C). Compositions 1-1 to 1-5 were prepared. Further, a platinum catalyst having a component (C) was not prepared, and a comparative composition 1-1 in which only the polyfluorene oxide resin (A1) and the polyoxyxylene resin (B1) were blended in a mass ratio of 2:1 was prepared. Here, as the platinum catalyst, platinum-divinyltetramethyldioxane is used in such a manner that the content of platinum atoms is a specific amount in terms of mass units with respect to the total amount of the curable polyoxyxene resin composition. Compound.

Further, a composition of the composition 4-1 to the composition 4 was prepared in the same manner by using a polyoxyxylene resin (A4) instead of the polyoxynoxy resin (A1) and a polyoxyxylene resin (B4) instead of the polyoxynoxy resin (B1). -3 and comparative composition 4-1. According to the methods described in the above [Transparency of cured product], [heat-resistant transparency of cured product], [hardening initiation temperature], and [appearance at the time of hardening], the composition and the comparative composition were used to evaluate the composition. The physical properties (transparency and heat-resistant transparency) of the cured product, the curing initiation temperature, and the appearance of the cured product. The results are shown in Table 4, Figure 2 and Figure 3.

As shown in Table 4, no foaming or cracking was observed in the cured products of Composition 1-1 to Composition 1-5, Composition 4-1 to Composition 4-3, and Comparative Composition 4-1, and the appearance was observed. It is "good". In particular, the appearances of the compositions 1-5 and 4-3 having a platinum atom content of 0.003 mass ppm are also "good" with respect to the total amount of the composition, and thus the components (A) and (B) of the compositions are shown. The ingredients have good hardenability. On the other hand, in the comparative composition 1-1 containing no platinum catalyst, it was "unhardened", and no cured product was obtained. Therefore, various physical properties of the cured product in the comparative composition 1-1 were not evaluated.

Further, regarding the curing initiation temperature, the content of the platinum atom decreases, and the curing initiation temperature becomes high. The curing initiation temperature of the composition 1-5 was higher than 150 ° C, but the cured product was smoothly obtained under the curing conditions (heating at 90 ° C for 1 hour and further heating at 150 ° C for 4 hours).

The transmittance of all hardened materials is in the range of 88 to 91% at a wavelength of 405 nm, and is in the range of 89 to 91% at a wavelength of 365 nm, showing high transparency. On the other hand, regarding the transparency (heat-resistant transparency) after continuously heating the cured product at 200 ° C for 100 hours, all the cured products maintained a high transmittance of 85% or more at a wavelength of 405 nm, but were used for comparison at a wavelength of 365 nm. The transmittance of the cured product of the composition 4-1 was 70%, and the decrease in transparency was observed. On the other hand, the cured products of the composition 1-1 to the composition 1-5 and the composition 4-1 to the composition 4-4 were maintained at a transparency of 75% or more.

According to the above, it is shown that the compositions 1-1 to 1-5 and the compositions 4-1 to 4-4 in the scope of the present invention have good hardenability and high heat-resistant transparency.

<Evaluation of hardening retarder and heat-resistant transparency>

The polyanthracene resin (A1) as the component (A) and the polyoxynoxy resin (B1) as the component (B) are blended in a mass ratio of 2:1, and the platinum catalyst of the component (C) is mixed to prepare various kinds. Compositions 1-6 to 1-9 were prepared by hardening the retarder. Here, as the platinum catalyst, platinum-divinyltetramethyldioxane is used in such a manner that the content of platinum atoms is 2.0 ppm by mass based on the total mass of the components (A) to (C). Complex compound. For hardening retarders In the case where the content of the platinum atom is 2.0 ppm by mass, it is added in an amount of 70 to 80 equivalents. Specifically, in the preparation of the composition 1-6, 118 μg of dimethyl maleate as a hardening retarder was added to 1 g of the total amount of the composition, in the preparation of the composition 1-7, relative to the combination. To a total amount of 1 g, 67 μg of 3-butyn-2-ol-2-methyl group was added, and in the preparation of the composition 1-8, 94 μg of 1-ethynyl-1-cyclohexanol was added to 1 g of the total amount of the composition, 86 μg of tetramethylethylenediamine was added to the composition 1-9 in an amount of 1 g based on the total amount of the composition.

According to the above-mentioned [transparency of cured product], [heat-resistant transparency of cured product], [appearance at the time of hardening], and the method described in the following [hardening start time], the compositions 1-6 to the composition are used. Composition 1-1 of 1-9, which is an example of a composition which is an unbonded hardening retarder, was evaluated for physical properties (transparency and heat-resistant transparency) of the cured product, appearance of the cured product, and curing start time. The results are shown in Table 5 and Figure 4.

[hardening start time]

The composition which was allowed to stand for 10 minutes after preparation was subjected to a rotational viscometer (manufactured by Brookfield. Engineering. Laboratories. Inc., product name: DV-II+PRO) and a temperature control unit (manufactured by Brookfield. Engineering. Laboratories. Inc., product name: THERMOSEL The viscosity was measured every 1 minute at a shear rate of 30 [1/s] at 25 ° C for a period of 3 hours. The time when the viscosity at the start of the measurement exceeded 30,000 cP was evaluated as the hardening start time.

As shown in Table 5, no foaming or cracking was observed in the cured products of Composition 1-1 and Composition 1-6 to Composition 1-9, and the appearance was "good". As the curing start time, after 26 minutes in the composition 1-1, the composition 1-6 to the composition 1-9 to which the hardening retarder is added is more than 2 hours, and thus it is known that the hardening retardant can be added by adding And control hardenability. Further, the transmittance of the cured product of the composition 1-6 to 1-9 was 89% or more at a wavelength of 405 nm, and was 87% or more at a wavelength of 365 nm, and it was found that the transparency was not impaired by the hardening retarder. . Further, the transparency (heat-resistant transparency) after continuously heating the cured product at 200 ° C for 100 hours is 85% or more at a wavelength of 405 nm and 74% or more at a wavelength of 365 nm. Therefore, it is understood that the cured products of the compositions 1-6 to 1-9 exhibit almost the same heat resistance and transparency as the cured product of the composition 1-1 to which the hardening retarder is not added.

<Evaluation of light stabilizers and antioxidants and heat-resistant transparency>

The polyoxynoxy resin (A4) as the component (A) and the polyoxynoxy resin (B4) as the component (B) are blended in a mass ratio of 2:1, and the platinum catalyst of the component (C) is mixed, thereby preparing various kinds. Composition 4-4 to Composition 4-6 were prepared as a light stabilizer or an antioxidant. Here, as the platinum catalyst, platinum-divinyltetramethyldioxane is used in such a manner that the content of platinum atoms is 0.2 ppm by mass based on the total mass of the components (A) to (C). Complex compound. The light stabilizer and the antioxidant are added in an amount of 0.05 to 0.2% by mass based on the total mass of the components (A) to (C). Specifically, in the preparation of the composition 4-4, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate as a light stabilizer is added in an amount of 1 g based on the total amount of the composition. Ester 0.5 mg. In the preparation of the composition 4-5, 1.0 mg of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate as a light stabilizer was added to 1 g of the total amount of the composition. In the preparation of the compositions 4-6, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1 as an antioxidant was separately added to 1 g of the total amount of the composition. , 3,5-three -2,4,6-(1H,3H,5H)-trione 1.5 mg and 2,2-bis({[3-(dodecylthio)propenyl)oxy}methyl)-1 3-propyldiyl=bis[3-(dodecylthio)propionate] 0.5 mg.

Using the composition 4-4 to the composition 4-6 and the composition 4-1 as an example of the composition of the unadjusted light stabilizer and the antioxidant, according to the above [appearance at the time of hardening] and the following [containing an anti- The method described in the heat-resistant transparency of the cured product of the oxidizing agent is used to evaluate the physical properties (transparency and heat-resistant transparency) of the cured product and the appearance of the cured product.

[Heat-resistant transparency of hardened materials containing antioxidants]

The prepared composition was heated in air at 90 ° C for 1 hour, and further heated at 150 ° C for 4 hours to make 22 mm. , 2mm thick hardened material. The transmittance of the cured product in the wavelength region of 405 nm and 365 nm was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV-3150). The cured product was further heated at 200 ° C, and temporarily cooled to room temperature over the period of 100 hours and 200 hours. The transmittance of the cured product after cooling was also measured. From the results of the measurement, the ratio of the transmittance of the cured product after further heating was calculated based on the transmittance of the cured product before further heating.

The evaluation results of the cured product of the composition 4-1 and the composition 4-4 to the composition 4-6 are shown in Table 6.

As shown in Table 6, no foaming or cracking was observed in the cured product of the composition 4-1 and the composition 4-4 to the composition 4-6, and the appearance was "good". The cured product of all the compositions was further heated at 200 ° C, and the transmittance after 100 hours and after 200 hours was 0 hours later (the cured product before further hardening was in the wavelength region of 405 nm and 365 nm). The transmittance was slightly decreased on the basis of the standard, but in the composition 4-4 to 4-6 to which the light stabilizer or the antioxidant was added, the change in transmittance was smaller than that of the composition 4-1. In the composition 4-6 to which the antioxidant was added, the variation ratio of the transmittance was particularly small. From their results, it has been shown that the addition of a light stabilizer or an antioxidant contributes to an improvement in the heat-resistant transparency of the cured product.

[Synthesis Example 7-1]

<Polymerization of polyoxyl resin (I-1)>

With fluororesin mixing blade, Dean-Stark device, Daisy reflow device In a 4-liter 2-liter flask, 1,000 g of a polyoxyxylene resin based on the polyfluorene oxide resin (I-1) described in Synthesis Example 1-1 was used. Then, 250 g of toluene was added, and the flask was continuously heated at 130 ° C for 24 hours to carry out hydrolysis and condensation reaction. Thereafter, the reaction liquid was returned to room temperature to prepare a polyoxyxylene resin (II) containing toluene.

The polyoxymethylene resin (II) has a mass average molecular weight (Mw) of 5,200, a composition ratio of (Me ₂ SiO _2/2 ) _0.50 (PhSiO _3/2 ) _0.50 , and a HO-Si group content of 4.5 mmol/g (6.7). Mass%), the toluene content was 20.49 mass%.

[Synthesis Example 7-2]

<Synthesis of polyoxyl resin (A7)>

130.00 g of polyoxyl resin (II), 288.91 g of toluene, 103.36 g of methanol, 10.25 g of 1,1,3,3-tetramethyldioxane and 0.24 mL of 70% concentrated nitric acid were added to The flask was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 310 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. A transparent viscous liquid polyoxyl resin (A7).

The yield of polyoxyxylene resin (A7) was 103.23 g, the mass average molecular weight (Mw) was 6,100, the viscosity was 5,100 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.39 (PhSiO _3/2 ) _0.47 (H(Me). ₂ SiO _1/2 ) _0.14 , the content of the H-Si group was 1.26 mmol/g, and the content of the HO-Si group was 2.66 mmol/g (4.5% by mass).

[Synthesis Example 7-3]

<Synthesis of polyoxyl resin (B7)>

65.00 g of polyoxyl resin (II), 144.45 g of toluene, 51.68 g of methanol, 6.50 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane and 2.24 70% concentrated nitric acid in mL was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was moved to liquid separation. In the funnel, 155 g of water was added, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. Transparent viscous liquid polyoxyl resin (B7).

The yield of polyoxyxylene resin (B7) was 49.34 g, the mass average molecular weight (Mw) was 4,800, the viscosity was 6,500 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.42 (PhSiO _3/2 ) _0.49 (CH ₂ = The content of CH(Me) ₂ SiO _1/2 ) _0.9 , CH ₂ =CH-Si group was 0.87 mmol/g, and the content of HO-Si group was 2.6 mmol/g (4.3% by mass).

[Synthesis Example 8-1]

<Synthesis of polyoxyl resin (A8)>

130.00 g of polyoxyl resin (II), 288.91 g of toluene, 103.36 g of methanol, 12.49 g of 1,1,3,3-tetramethyldioxane and 0.30 mL of 70% concentrated nitric acid were added to The flask was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 310 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. A transparent viscous liquid polyoxyl resin (A8).

The yield of the polyoxyxylene resin (A8) was 107.48 g, the mass average molecular weight (Mw) was 5,600, the viscosity was 2,800 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.40 (PhSiO _3/2 ) _0.48 (H (Me). ₂ SiO _1/2 ) _0.12 , the content of the H-Si group was 1.40 mmol/g, and the content of the HO-Si group was 2.1 mmol/g (3.6% by mass).

[Synthesis Example 8-2]

<Synthesis of polyoxyl resin (B8)>

65.00 g of polyoxyl resin (II), 144.45 g of toluene, 51.68 g of methanol, 8.67 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane and 2.98 mL of 70% concentrated nitric acid were added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 155 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. A transparent viscous liquid polyoxyl resin (B8).

The yield of polyoxyxylene resin (B8) was 51.78 g, the mass average molecular weight (Mw) was 5,300, the viscosity was 5,000 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.39 (PhSiO _3/2 ) _0.44 (CH ₂ = CH(Me) ₂ SiO _1/2 ) _0.17 , the content of CH ₂ =CH-Si group was 1.05 mmol/g, and the content of HO-Si group was 2.3 mmol/g (4.0% by mass).

[Synthesis Example 9-1]

<Synthesis of polyoxyl resin (A9)>

130.00 g of polyoxyl resin (II), 288.91 g of toluene, 103.36 g of methanol, 15.62 g of 1,1,3,3-tetramethyldioxane and 0.37 mL of 70% concentrated nitric acid were added to The flask was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 310 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. Transparent viscous liquid polyoxyl resin (A9).

The yield of the polyoxyxylene resin (A9) was 106.52 g, the mass average molecular weight (Mw) was 5,800, the viscosity was 2,100 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.38 (PhSiO _3/2 ) _0.42 (H (Me) ₂ SiO _1/2 ) _0.20 , the content of the H-Si group was 1.81 mmol/g, and the content of the HO-Si group was 1.7 mmol/g (2.9% by mass).

[Synthesis Example 9-2]

<Synthesis of polyoxyl resin (B9)>

65.00 g of polyoxyl resin (II), 144.45 g of toluene, 51.68 g of methanol, 10.84 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane and 3.73 70% concentrated nitric acid in mL was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 155 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. Transparent viscous liquid polyoxyl resin (B9).

The yield of polyoxyxylene resin (B9) was 49.16 g, the mass average molecular weight (Mw) was 5,200, the viscosity was 3,900 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.39 (PhSiO _3/2 ) _0.48 (CH ₂ = The content of CH(Me) ₂ SiO _1/2 ) _0.13 , CH ₂ =CH-Si group was 1.17 mmol/g, and the content of HO-Si group was 2.2 mmol/g (3.7 mass%).

[Synthesis Example 10-1]

<Synthesis of polyoxyl resin (A10)>

120.00 g of polyoxyl resin (II), 306.93 g of toluene, 106.34 g of methanol, 24.59 g of 1,1,3,3-tetramethyldioxane and 0.59 mL of 70% concentrated nitric acid were added to The flask was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 320 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. Transparent viscous liquid polyoxyl resin (A10).

The yield of the polyoxyxylene resin (A10) was 110.66 g, the mass average molecular weight (Mw) was 5,700, the viscosity was 1,600 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.35 (PhSiO _3/2 ) _0.41 (H (Me). ₂ SiO _1/2 ) _0.24 , the content of the H-Si group was 2.25 mmol/g, and the content of the HO-Si group was 1.18 mmol/g (2.0% by mass).

[Synthesis Example 10-2]

<Synthesis of polyoxyl resin (B10)>

60.00 g of polyoxyl resin (II), 153.47 g of toluene, 53.17 g of methanol, 17.07 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane and 5.87 70% concentrated nitric acid in mL was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 160 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. A transparent viscous liquid polyoxyl resin (B10).

The yield of polyoxyxylene resin (B10) was 55.70 g, the mass average molecular weight (Mw) was 4,800, the viscosity was 3,000 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.40 (PhSiO _3/2 ) _0.45 (CH ₂ = The content of CH(Me) ₂ SiO _1/2 ) _0.15 , CH ₂ =CH-Si group was 1.43 mmol/g, and the content of HO-Si group was 1.9 mmol/g (3.0% by mass).

[Synthesis Example 11-1]

<Synthesis of polyoxyl resin (A11)>

130.00 g of polyoxyl resin (II), 288.91 g of toluene, 103.36 g of methanol, 31.23 g of 1,1,3,3-tetramethyldioxane and 0.75 mL of 70% concentrated nitric acid were added to The flask was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 310 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. Transparent viscous liquid polyoxyl resin (A11).

The yield of the polyoxyxylene resin (A11) was 113.15 g, the mass average molecular weight (Mw) was 5,700, the viscosity was 1,000 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.36 (PhSiO _3/2 ) _0.38 (H (Me). ₂ SiO _1/2 ) _0.26 , the content of the H-Si group was 2.7 mmol/g, and the content of the HO-Si group was 0.86 mmol/g (1.5% by mass).

[Synthesis Example 11-2]

<Synthesis of polyoxyl resin (B11)>

65.00 g of polyoxyl resin (II), 144.45 g of toluene, 51.68 g of methanol, 21.68 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane and 7.45 70% concentrated nitric acid in mL was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 155 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. A transparent viscous liquid polyoxyl resin (B11).

The yield of polyoxyxylene resin (B11) was 53.64 g, the mass average molecular weight (Mw) was 5,200, the viscosity was 2,500 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.38 (PhSiO _3/2 ) _0.45 (CH ₂ = CH(Me) ₂ SiO _1/2 ) _0.17 , the content of CH ₂ =CH-Si group was 1.6 mmol/g, and the content of HO-Si group was 1.8 mmol/g (3.0% by mass).

[Synthesis Example 12-1]

<Synthesis of polyoxyl resin (A12)>

39.7 g of polyoxynoxy resin (I-1), 119 g of toluene, 39.7 g of methanol, 8.3 g of 1,1,3,3-tetramethyldioxane and 0.20 mL of 70% concentrated nitric acid were added. The flask was stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 119 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. Transparent viscous liquid polyoxyl resin (A12).

The yield of polyoxyxylene resin (A12) was 42.5 g, the mass average molecular weight (Mw) was 1,900, the viscosity was 200 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.31 (PhSiO _3/2 ) _0.42 (H(Me) ₂ SiO _1/2 ) _0.27 , the content of the H-Si group was 2.8 mmol/g, and the content of the HO-Si group was 2.0 mmol/g (3.4% by mass).

[Synthesis Example 12-2]

<Synthesis of polyoxyl resin (B12)>

19.9 g of polydecane resin (I-1), 59.7 g of toluene, 19.9 g of methanol, 5.76 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane And 1.98 mL of 70% concentrated nitric acid was added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 59.7 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. Toluene was distilled off from the organic layer by an evaporator, and then distilled under reduced pressure by heating at 150 ° C for 1 hour, and then distilled under reduced pressure by heating at 170 ° C for 1 hour to obtain colorlessness. Transparent viscous liquid polyoxyl resin (B12).

The yield of polyoxyxylene resin (B12) was 20.6 g, the mass average molecular weight (Mw) was 1,800, the viscosity was 350 cP, and the composition ratio was (Me ₂ SiO _2/2 ) _0.32 (PhSiO _3/2 ) _0.45 (CH ₂ =CH). (Me) ₂ SiO _1/2 ) _0.23 , a CH ₂ =CH-Si group content of 2.3 mmol/g, and a HO-Si group content of 2.1 mmol/g (3.6 mass%).

The composition ratio and the physical property values of the synthesized polyoxynoxy resin (A7)~(A12) and polyoxyxylene resin (B7)~(B12) (the content of HO-Si group, SiH group or Si-CH=CH ₂ group) The content, mass average molecular weight, viscosity, refractive index, and transparency are shown in Table 7. In Table 7, Vi represents a vinyl group (CH ₂ =CH- group).

<Curable polyoxyn resin composition and cured product thereof>

The viscosity of the prepared composition, the physical properties (hardness, adhesion, transparency, linear thermal expansion coefficient, 5% weight reduction temperature, adhesion strength) of the cured product obtained from the composition, and the appearance at the time of hardening according to the above examples The measurement methods of 1 to 6 and Comparative Examples 1 to 3 were measured. Further, the adhesion of the cured product was measured by using a 6050 SMD type PPA resin package instead of the 3528 SMD type PPA resin package, and the measurement method is as follows. The punching formability of the cured product is as shown in the following measurement method. Further, the composition used in the measurement is a polyfluorene oxide resin (polyoxygen resin (A7) to (A12)] of the component (A) and a polyoxyl resin (polyoxyl resin) of the component (B). B7)~(B12)] was prepared by mixing with a mass ratio of 2:1 and mixing with a platinum catalyst of the component (C) to prepare Examples 7 to 12 Composition. Here, as the platinum catalyst, a platinum-divinyltetramethyldioxane complex is used in such a manner that the content of platinum atoms is 0.03 ppm by mass based on the total amount of the composition.

[Adhesiveness of hardened material (6050SMD type PPA resin package)]

The prepared mixture was poured into a 6050 SMD type PPA (6.0 mm × 5.0 mm × 2.0 mm), heated in air at 90 ° C for 1 hour, and further heated at 150 ° C for 4 hours to prepare 9 samples as hardened materials. . The specimens were confirmed by an optical microscope, and the cured product was evaluated as "peeling" from the package, and the unpeeled was evaluated as "close contact". Among the nine samples, the number of samples evaluated as "closed" was listed as "qualified number".

[Pore forming test]

The prepared composition was poured into a mold (90 mm × 90 mm × 2 mm), heated in air at 90 ° C for 1 hour, and further heated at 150 ° C for 4 hours to prepare a plate-like cured product. The plate-shaped cured product was perforated into a dumbbell-shaped No. 8 shape in accordance with JIS K 6251. When the hardened body was punched, no cracking or resin leakage occurred, and the punched product was evaluated as "good". The situation other than this is "bad".

The evaluation results of the compositions and cured products of Examples 7 to 12 are shown in Table 8.

As shown in Table 8, the cured products produced in Examples 7 to 12 all had excellent heat-resistant transparency. Further, in the adhesion test, excellent adhesion was exhibited to the 3528 SMD type PPA resin package substrate in any of the cured products. In particular, the cured products of Examples 7 to 9 having a higher mass average molecular weight and a higher Si-OH group content than the cured products of Examples 10 to 12 were larger than the 3528 SMD type PPA resin package. The 6050SMD type PPA resin package also exhibits excellent adhesion. Further, in the punched formability test, in the cured product of Example 12 having a low mass average molecular weight, the resin strength was insufficient and the test piece could not be perforated, and Examples 7 to 11 having a higher mass average molecular weight were used. In the hardened material, the hardened body can be perforated without problems.

1‧‧‧ sealing material

2‧‧‧Optical semiconductor components

3‧‧‧bonding line

4‧‧‧Reflecting material

5‧‧‧ lead frame

6‧‧‧Optical semiconductor substrate

10‧‧‧Optical semiconductor devices

Claims (15)

A curable polyoxyxene resin composition containing at least (A) a component: a polyoxyxylene resin having a hydrogen atom (SiH group) bonded to a ruthenium atom and a component (B) represented by the following formula [1] a polyfluorene oxide resin having a vinyl group (Si-CH=CH ₂ group) bonded to a ruthenium atom and a component (C): a platinum catalyst, and a component (A) and a compound represented by the following formula [2] The total content of the stanol group (Si-OH group) in the component (B) is 0.5 to 5.0 mmol/g, and the content of the platinum atom in the component (C) is relative to the component (A) and the component (B) and (C). The total mass of the components, in terms of mass units, is 0.003 to 3.0 ppm, [25] (H-SiR ¹ ₂ O _1/2 ) _a (SiR ² ₂ O _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d [1] (wherein R ¹ is an alkyl group having 1 to 3 carbon atoms, two R ^{1 's} may be the same or different from each other, and R ² is an alkane having 1 to 3 carbon atoms; The two R ² groups may be the same or different from each other, and R ³ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a, b and c are each more than 0 and not up to 1 The number of d is 0 or more and less than 1, satisfying a+b+c+d=1, (SiR ² ₂ O _2/2 ), (R ³ SiO _3/2 ), and (SiO _4/2 ) The oxygen atoms in the structural unit represented represent the formation of a decane bond Oxygen atom or oxygen atom forming a stanol group) (CH ₂ =CH-SiR ⁴ ₂ O _1/2 ) _e (SiR ⁵ ₂ O _2/2 ) _f (R ⁶ SiO _3/2 ) _g (SiO _4/2 ) _h [2] (wherein R ⁴ is an alkyl group having 1 to 3 carbon atoms, 2 R ⁴ may be the same or different from each other, and R ⁵ is an alkyl group having 1 to 3 carbon atoms 2 R ⁵ may be the same or different types, and R ⁶ is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and e, f and g are each more than 0 and not up to 1 Number, h is 0 or more and less than 1, satisfying e+f+g+h=1, (SiR ⁵ ₂ O _2/2 ), (R ⁶ SiO _3/2 ), and (SiO _4/2 ) The oxygen atom in the structural unit represented represents an oxygen atom forming a siloxane chain or an oxygen atom forming a stanol group, respectively. The hardenable polyoxyxene resin composition of claim 1, wherein the number of moles of the hydrogen atom bonded to the ruthenium atom in the component (A): the vinyl group bonded to the ruthenium atom in the component (B) The number of ears is 0.8:0.2~0.5:0.5. The hardened polyoxyxene resin composition according to claim 1 or 2, wherein among the components (A), a, b, c and d are a: b: c: d = 0.10 to 0.40: 0.10 to 0.80: 0.10 0.80:0~0.70, in the component (B), e, f, g, and h are e:f:g:h=0.10~0.40:0.10~0.80:0.10~0.80:0~0.70. The sclerosing polyoxymethylene resin composition of claim 3, wherein in the component (A), a, b, c and d are a: b: c: d = 0.20 to 0.40: 0.10 to 0.40: 0.30 to 0.60: 0.10~0.30, in the component (B), e, f, g and h are e:f:g:h=0.20~0.40:0.10~0.40:0.30~0.60:0.10~0.30. The sclerosing polyoxymethylene resin composition of claim 1 or 2, wherein in the component (A), d = 0, a, b and c are a: b: c = 0.05 to 0.40: 0.10 to 0.80: 0.10 0.80, in the component (B), h=0, e, f, and g are e:f:g=0.05~0.40:0.10~0.80:0.10~0.80. The curable polyoxyxene resin composition of claim 1 or 2, which further contains a hardening retarder. The curable polyoxyxylene resin composition of claim 1 or 2, which further contains an antioxidant or a light stabilizer. The curable polyoxyxene resin composition according to claim 1 or 2, further comprising one or more selected from the group consisting of a subsequent imparting agent, a phosphor, and inorganic particles. The curable polyoxyxene resin composition of claim 1 or 2, which further comprises a release agent, a resin modifier, a colorant, a diluent, an antibacterial agent, an antifungal agent, a leveling agent, and an anti-sagging agent. One or more of the group consisting of agents. A hardened material which is a hardenable polyoxygen tree as claimed in any one of claims 1 to 9. The lipid composition is hardened. A sealant comprising the hardener of the curable polyoxyxene resin composition according to any one of claims 1 to 9. A method for producing a cured product of a curable polyoxynene resin composition, which comprises heating the curable polyanthracene resin composition according to any one of claims 1 to 9 at 45 ° C or higher and 300 ° C or lower. Hardening. An optical semiconductor device obtained by sealing at least an optical semiconductor element with a cured product of the curable polyoxyxene resin composition according to any one of claims 1 to 9. An adhesive for a semiconductor comprising the cured product of the curable polyoxyxene resin composition according to any one of claims 1 to 9. An optical semiconductor device using the semiconductor adhesive of claim 14.