KR20210148069A - Curable composition, cured product, and method of using the curable composition - Google Patents

Abstract

〔R¹ 은, 무치환의 탄소수 1 ∼ 10 의 알킬기, 치환기 (에폭시 고리를 갖는 기를 제외한다) 를 갖는 탄소수 1 ∼ 10 의 알킬기, 무치환의 탄소수 6 ∼ 12 의 아릴기, 및, 치환기 (에폭시 고리를 갖는 기를 제외한다) 를 갖는 탄소수 6 ∼ 12 의 아릴기로 이루어지는 군에서 선택되는 적어도 1 개이다.〕
(B) 성분 : 3 관능 실란 화합물 유래의 반복 단위를 갖는 특정한 실리콘 올리고머The present invention relates to a curable composition containing the following components (A) and (B), a cured product obtained by curing the curable composition, and the use of the curable composition as an adhesive for an optical device fixing material or an optical device fixing material sealing material way to do it The curable composition of this invention is excellent in sclerosis|hardenability.
(A) component: Curable polysilsesquioxane compound which has a repeating unit represented by following formula (a-1)

[R ¹ is an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a substituent (excluding the group having an epoxy ring), an unsubstituted aryl group having 6 to 12 carbon atoms, and a substituent (epoxy at least one selected from the group consisting of an aryl group having 6 to 12 carbon atoms.]
(B) component: a specific silicone oligomer having a repeating unit derived from a trifunctional silane compound

Description

Curable composition, cured product, and method of using the curable composition

The present invention relates to a curable composition excellent in curability, a cured product obtained by curing the curable composition, and a method of using the curable composition as an adhesive for an optical device fixing material or an optical device fixing material sealing material.

Conventionally, various improvements are made according to the use of a curable composition, and it has been widely used in industry as a raw material of an optical component or a molded object, an adhesive agent, a coating agent, etc.

Moreover, a curable composition has attracted attention also as a composition for optical element fixing materials, such as an adhesive agent for optical element fixing materials, and a sealing material for optical element fixing materials.

Examples of the optical element include various lasers such as semiconductor lasers (LD), light-emitting elements such as light-emitting diodes (LEDs), light-receiving elements, composite optical elements, and optical integrated circuits.

In recent years, optical elements of blue light or white light having a shorter peak wavelength of light emission have been developed and are widely used. The high luminance of the light emitting device having such a short peak wavelength of light emission progresses rapidly, and the amount of heat generated by the optical device tends to increase with this.

However, with the recent increase in luminance of optical devices, the cured product of the optical device fixing material composition is exposed to high energy light or high temperature heat generated from the optical device for a long time, resulting in a decrease in adhesive strength. occurred.

In order to solve this problem, the composition for optical element fixing materials which has a polysilsesquioxane compound as a main component is proposed by patent documents 1-3.

By the way, when an optical element etc. are fixed using a curable composition, in order to shorten work time and prevent contamination, the curable composition which can harden|cure in a shorter time has been calculated|required.

Japanese Laid-Open Patent Publication No. 2004-359933 Japanese Laid-Open Patent Publication No. 2005-263869 Japanese Laid-Open Patent Publication No. 2006-328231

The present invention has been made in view of the circumstances of the prior art described above, and comprises a curable composition excellent in curability, a cured product obtained by curing the curable composition, and an adhesive for an optical device fixing material or an optical device fixing material encapsulant. The purpose is to provide a method for using as

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors repeated earnest examination about the curable composition containing a curable polysilsesquioxane compound.

As a result, the curable composition containing a curable polysilsesquioxane compound and the specific silicone oligomer which has an epoxy ring discovered that it was excellent in sclerosis|hardenability, and came to complete this invention.

In addition, in this invention, "excellent in sclerosis|hardenability" means the characteristic that a curable composition hardens|cures in a short time.

In this way, according to the present invention, there is provided a method of using the curable compositions of the following [1] to [7], the cured products of [8] and [9], and the curable compositions of [10] and [11].

[1] A curable composition comprising the following component (A) and component (B).

(A) component: Curable polysilsesquioxane compound which has a repeating unit represented by following formula (a-1)

[Formula 1]

[R ¹ is an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a substituent (excluding the group having an epoxy ring), an unsubstituted aryl group having 6 to 12 carbon atoms, and a substituent (epoxy at least one selected from the group consisting of an aryl group having 6 to 12 carbon atoms.]

(B) component: a silicone oligomer having a repeating unit derived from a trifunctional silane compound and having or not having a repeating unit derived from a tetrafunctional silane compound, a repeating unit derived from a trifunctional silane compound and a tetrafunctional silane compound A silicone oligomer in which the total amount of the derived repeating units is 80 mol% or more of the total repeating units, and at least one of the trifunctional silane compounds is a trifunctional silane compound having a group having an epoxy ring.

[2] The curable composition according to [1], wherein the mass average molecular weight (Mw) of the component (A) is 800 to 30,000.

[3] The curable composition according to [1] or [2], wherein the mass average molecular weight (Mw) of the component (B) is 500 to 5,000.

[4] The curable composition according to any one of [1] to [3], wherein the epoxy equivalent of component (B) is 50 to 2,000 g/eq.

[5] The curable composition according to any one of [1] to [4], wherein the content of the component (B) is 0.1 to 100 parts by mass relative to 100 parts by mass of the component (A).

[6] The curable composition according to any one of [1] to [5], wherein the total amount of the component (A) and the component (B) is 30 to 100% by mass based on the solid content of the curable composition.

[7] The curable composition according to any one of [1] to [6], further comprising the following component (C).

(C) component: silane coupling agent

[8] A cured product obtained by curing the curable composition according to any one of [1] to [7].

[9] The cured product according to [8], which is an optical element fixing material.

[10] A method in which the curable composition according to any one of [1] to [7] is used as an adhesive for an optical element fixing material.

[11] A method in which the curable composition according to any one of [1] to [7] is used as a sealing material for an optical element fixing material.

According to the present invention, there are provided a curable composition excellent in curability, a cured product obtained by curing the curable composition, and a method of using the curable composition as an adhesive for an optical element fixing material or an optical element fixing material sealing material.

Hereinafter, the present invention will be described in detail by classifying it into 1) a curable composition, 2) a cured product, and 3) a method of using the curable composition.

1) curable composition

The curable composition of this invention contains the following (A) component and (B) component.

(A) component: Curable polysilsesquioxane compound which has a repeating unit represented by following formula (a-1)

(B) component: a silicone oligomer having a repeating unit derived from a trifunctional silane compound and having or not having a repeating unit derived from a tetrafunctional silane compound, a repeating unit derived from a trifunctional silane compound and a tetrafunctional silane compound A silicone oligomer in which the total amount of the derived repeating units is 80 mol% or more of the total repeating units, and at least one of the trifunctional silane compounds is a trifunctional silane compound having a group having an epoxy ring.

In the present invention, the "curable polysilsesquioxane compound" refers to a polysilsesquioxane compound that independently changes into a cured product by satisfying predetermined conditions such as heating, or functions as a curable component in a curable composition. polysilsesquioxane compound.

[(A) component]

Component (A) constituting the curable composition of the present invention is a curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1) (hereinafter referred to as “polysilsesquioxane compound (A)”) There are cases).

[Formula 2]

(In formula (a-1), R ¹ is an unsubstituted C 1 to C 10 alkyl group, a substituent (excluding groups having an epoxy ring) having 1 to 10 C alkyl group, and an unsubstituted C 6 to C 12 alkyl group It is at least 1 selected from the group which consists of an aryl group and a C6-C12 aryl group which has a substituent (except the group which has an epoxy ring).

1-6 are preferable and, as for carbon number of "the unsubstituted C1-C10 alkyl group" represented by R<^{1>, 1-3 are more preferable.}

Examples of the "unsubstituted C1-C10 alkyl group" include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned.

1-6 are preferable and, as for carbon number of the "C1-C10 alkyl group which has a substituent (except the group which has an epoxy ring)" represented by R<^{1>, 1-3 are more preferable.} In addition, this carbon number means carbon number of the part (part of an alkyl group) excluding a substituent. Accordingly, when R ¹ is “an alkyl group having 1 to 10 carbon atoms having a substituent (excluding a group having an epoxy ring)”, ^{the number of carbon atoms in R 1} may exceed 10 in some cases.

Examples of the alkyl group of the “alkyl group having 1 to 10 carbon atoms having a substituent (excluding the group having an epoxy ring)” include the same ones as described as “unsubstituted alkyl group having 1 to 10 carbon atoms”.

The number of atoms (however, excluding the number of hydrogen atoms) of the substituent of the "alkyl group having 1 to 10 carbon atoms having a substituent (excluding the group having an epoxy ring)" is usually 1 to 30, preferably 1 to 20 am.

As a substituent of "a C1-C10 alkyl group which has a substituent (except the group which has an epoxy ring)", Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; cyano group; Formula: group represented by OG; and the like.

Here, G represents a protecting group of a hydroxyl group. There is no restriction|limiting in particular as a protecting group of a hydroxyl group, Well-known protecting group known as a protecting group of a hydroxyl group is mentioned. For example, an acyl-type protecting group; silyl-based protecting groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group and t-butyldiphenylsilyl group; acetal protecting groups such as a methoxymethyl group, a methoxyethoxymethyl group, a 1-ethoxyethyl group, a tetrahydropyran-2-yl group, and a tetrahydrofuran-2-yl group; Alkoxycarbonyl-type protecting groups, such as a t-butoxycarbonyl group; Ether protecting groups, such as a methyl group, an ethyl group, t-butyl group, an octyl group, an allyl group, a triphenylmethyl group, a benzyl group, p-methoxybenzyl group, a fluorenyl group, a trityl group, and a benzhydryl group; and the like.

The number of carbon atoms of the "unsubstituted aryl group having 6 to 12 carbon atoms" represented by R ^{1 is preferably 6 .}

As "unsubstituted C6-C12 aryl group", a phenyl group, 1-naphthyl group, 2-naphthyl group, etc. are mentioned.

The number of carbon atoms of the "alkyl group having 1 to 12 carbon atoms having a substituent (excluding the group having an epoxy ring)" represented by R ^{1 is preferably 6;} In addition, this carbon number means carbon number of the part (part of an aryl group) excluding a substituent. Accordingly, when R ¹ is “an aryl group having 6 to 12 carbon atoms and having a substituent (excluding a group having an epoxy ring)”, ^{the number of carbon atoms in R 1} may exceed 12 in some cases.

Examples of the aryl group for "aryl having 6 to 12 carbon atoms having a substituent (excluding groups having an epoxy ring)" include the same ones as described for "unsubstituted aryl group having 6 to 12 carbon atoms".

The number of atoms (however, excluding the number of hydrogen atoms) of the substituent of "an aryl group having 6 to 12 carbon atoms having a substituent (excluding a group having an epoxy ring)" is 1 to 30, preferably 1 to It is 20.

As a substituent of "an aryl group having 6 to 12 carbon atoms having a substituent (excluding a group having an epoxy ring)", a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, and iso Alkyl groups, such as a butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and isooctyl group; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; Alkoxy groups, such as a methoxy group and an ethoxy group; and the like.

Among these, R ¹ is an unsubstituted C1-C10 alkyl group, a fluorine atom-containing C1-C10 alkyl group, an unsubstituted C6-C12 aryl group, or a C1-C10 alkyl group having a cyano group. is preferable

By using the polysilsesquioxane compound (A) in which R ¹ is an unsubstituted C1-C10 alkyl group, the curable composition used as the hardened|cured material more excellent in heat resistance and adhesiveness is obtained easily.

In this specification, "hardened|cured material excellent in adhesiveness" means "hardened|cured material with high adhesive strength".

By using the polysilsesquioxane compound (A) in which R<^1> is a C1-C10 alkyl group which has a fluorine atom, a low refractive index curable composition and hardened|cured material are obtained easily.

By using the polysilsesquioxane compound (A) in which R<^1> is an unsubstituted C1-C12 aryl group, a high refractive index curable composition and hardened|cured material are obtained easily.

By using the polysilsesquioxane compound (A) in which R ¹ is an alkyl group having 1 to 10 carbon atoms having a cyano group, a curable composition having high adhesive strength to a highly polar adherend can be easily obtained.

The repeating unit represented by the formula (a-1) is represented by the following formula. In the present specification, O _1/2 represents that an oxygen atom is shared with an adjacent repeating unit.

[Formula 3]

As shown by formula (a-2), polysilsesquioxane compound (A) has 3 oxygen atoms couple|bonded with the silicon atom generally called T site, and group (R<^1> ) other than that is 1 It has a partial structure made up of dog bonds.

Examples of the T site contained in the polysilsesquioxane compound (A) include those represented by the following formulas (a-3) to (a-5).

[Formula 4]

In formulas (a-3) to (a-5), R ¹ has the same meaning as above. R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. As a C1-C10 alkyl group of R<^2> , a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, etc. are mentioned. A plurality of R ^{2 s may} all be the same or different. In addition, the Si atom is couple|bonded with * in said Formula (a-3) - (a-5).

The polysilsesquioxane compound (A) is a ketone solvent such as acetone; aromatic hydrocarbon-based solvents such as benzene; sulfur-containing solvents such as dimethyl sulfoxide; Ether solvents, such as tetrahydrofuran; ester solvents such as ethyl acetate; halogen-containing solvents such as chloroform; and a mixed solvent composed of two or more thereof; Since it is soluble in various organic solvents, such as, ²⁹ Si-NMR in the solution state of a polysilsesquioxane compound (A) can be measured using these solvent.

^{By measuring 29} Si-NMR in a solution state of the polysilsesquioxane compound (A), the T3 site represented by the formula (a-3), the T2 site represented by the formula (a-4), and the formula (a-5) ), the content ratio of T1 sites can be calculated.

From the viewpoint of improving the adhesive strength, the polysilsesquioxane compound (A) used in the present invention preferably contains 10 to 45 mol% of T2 sites, more preferably 15 to 40 mol%, It is more preferable to contain 20-35 mol%.

Moreover, it is preferable that the polysilsesquioxane compound (A) used by this invention contains 50-90 mol% of T3 sites from a viewpoint of obtaining the hardened|cured material excellent in hard and heat resistance, and 55-85 mol% It is more preferable to contain, and it is still more preferable to contain 60-80 mol%.

40-100 mol% is preferable with respect to all the repeating units, and, as for the content rate of the repeating unit represented by said formula (a-1) in a polysilsesquioxane compound (A), 70-100 mol% is more preferable, , 90-100 mol% is more preferable, and 100 mol% is especially preferable.

^{When 29} Si-NMR is measured in the solution state of the polysilsesquioxane compound (A) ^{, for example, when R 1} is a methyl group, a peak derived from a silicon atom in the structure represented by the formula (a-3) above ( T3) is observed in the region of -70 ppm or more and less than -61 ppm, and the peak (T2) derived from the silicon atom in the structure represented by the formula (a-4) is -60 ppm or more and less than -54 ppm The peak (T1) which is observed in the region and derived from the silicon atom in the structure represented by the formula (a-5) is observed in the region of -53 ppm or more and less than -45 ppm.

In addition, when R ¹ is a phenyl group, T3 is observed in a region of -82 ppm or more and less than -73 ppm, T2 is observed in a region of -73 ppm or more and less than -65 ppm, T1 is -65 ppm or more, It is observed in the region below -55 ppm.

From a viewpoint of acquiring the more excellent effect of this invention, as for the polysilsesquioxane compound (A), it is preferable that the integral of T3 is 60 to 90 % with respect to the total value of the integral of T1, T2, and T3.

²⁹ Si-NMR spectrum can be measured by the method as described in an Example, for example.

In addition, in this specification, "T1", "T2", "T3", etc. may represent the structure of a repeating unit, and may represent the NMR peak corresponding to the structure.

40 mol% or more is preferable with respect to all repeating units, and, as for the content rate of the repeating unit represented by the said Formula (a-1) in a polysilsesquioxane compound (A), 70 mol% or more is more preferable, 90 mol% or more is more preferable, and 100 mol% is especially preferable.

The content rate of the repeating unit represented by the said Formula (a-1) in a polysilsesquioxane compound (A) can be calculated|required by measuring ^{29 Si-NMR of a polysilsesquioxane compound (A), for example.} have.

Further, even when the polysilsesquioxane compound (A) has a repeating unit other than the repeating unit represented by the formula (a-1), the polysilsesquioxane compound (A) does not have a group having an epoxy ring. will be. From this point, a polysilsesquioxane compound (A) and the silicone oligomer of (B) component are distinguished clearly.

^{What has 1 type of R<1>} (homopolymer) may be sufficient as a polysilsesquioxane compound (A), and what has 2 or more types of R<^1> (copolymer) may be sufficient as it.

When the polysilsesquioxane compound (A) is a copolymer, the polysilsesquioxane compound (A) may be any of random copolymers, block copolymers, graft copolymers, and alternating copolymers, but ease of manufacture, etc. A random copolymer is preferable from the viewpoint of

In addition, the structure of a polysilsesquioxane compound (A) may be any structure of a ladder structure, a double decker type|mold structure, a cage structure, a partial cleavage cage structure, a cyclic structure, and a random structure.

Although the mass average molecular weight (Mw) of a polysilsesquioxane compound (A) is not specifically limited, Usually, 800-30,000, Preferably 1,200-20,000, More preferably, 1,500-18,000, More preferably, 2,500-16,000 , particularly preferably 4,000 to 14,000. By using the polysilsesquioxane compound (A) having a mass average molecular weight (Mw) within the above range, a curable composition that provides a cured product having more excellent heat resistance and adhesiveness can be easily obtained.

Although the molecular weight distribution (Mw/Mn) of a polysilsesquioxane compound (A) is not specifically limited, Usually, it is 1.0-10.0, Preferably it is 1.1-6.0. By using the polysilsesquioxane compound (A) having a molecular weight distribution (Mw) within the above range, a curable composition that provides a cured product having more excellent heat resistance and adhesiveness can be easily obtained.

A mass average molecular weight (Mw) and a number average molecular weight (Mn) can be calculated|required as a standard polystyrene conversion value by gel permeation chromatography (GPC) which uses tetrahydrofuran (THF) as a solvent, for example.

In this invention, a polysilsesquioxane compound (A) can be used individually by 1 type or in combination of 2 or more type.

The manufacturing method of a polysilsesquioxane compound (A) is not specifically limited. For example, the following formula (a-6)

[Formula 5]

(Wherein, R ¹ has the same meaning as above. R ³ represents an alkyl group having 1 to 10 carbon atoms, X ¹ represents a halogen atom, and p represents an integer of 0 to 3. A plurality of R ³ and a plurality of X ¹ may each be the same as or different from each other.)

A polysilsesquioxane compound (A) can be manufactured by polycondensing at least 1 type of the silane compound (1) represented by.

Examples of the alkyl group having 1 to 10 carbon atoms for R ³ include the same groups as those shown as the alkyl group having 1 to 10 carbon atoms for ^{R 2 .}

As a halogen atom of X<^1> , a chlorine atom, a bromine atom, etc. are mentioned.

Specific examples of the silane compound (1) include alkyl trialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltripropoxysilane;

Methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane, etc. of alkylhalogenoalkoxysilane compounds;

alkyltrihalogenosilane compounds such as methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, and ethyltribromosilane;

3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, etc. of substituted alkyltrialkoxysilane compounds;

3,3,3-trifluoropropylchlorodimethoxysilane, 3,3,3-trifluoropropylchlorodiethoxysilane, 3,3,3-trifluoropropyldichloromethoxysilane, 3,3,3 -Trifluoropropyldichloroethoxysilane, 2-cyanoethylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 2-cyanoethyldichloromethoxysilane, 2-cyanoethyldichloroethoxysilane, etc. of substituted alkylhalogenoalkoxysilane compounds;

substituted alkyltrihalogenosilane compounds such as 3,3,3-trifluoropropyltrichlorosilane and 2-cyanoethyltrichlorosilane;

Phenyltrialkoxysilane compounds which have a substituent, such as phenyltrimethoxysilane and 4-methoxyphenyltrimethoxysilane, or do not have a substituent;

Phenylhalogenoalkoxysilane with or without a substituent, such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane, and 4-methoxyphenyldichloromethoxysilane compounds;

Phenyltrihalogenosilane compounds which have a substituent, such as phenyltrichlorosilane and 4-methoxyphenyltrichlorosilane, or do not have a substituent; and the like.

These silane compounds (1) can be used individually by 1 type or in combination of 2 or more type.

The method of polycondensing the said silane compound (1) is not specifically limited. For example, in a solvent or without a solvent, the method of adding a predetermined amount of a polycondensation catalyst to a silane compound (1), and stirring at predetermined temperature is mentioned. More specifically, (a) a method in which a predetermined amount of an acid catalyst is added to the silane compound (1) and stirred at a predetermined temperature; (b) a predetermined amount of a base catalyst is added to the silane compound (1) at a predetermined temperature A method of stirring in (c) adding a predetermined amount of an acid catalyst to the silane compound (1), stirring at a predetermined temperature, adding an excess amount of a base catalyst to make the reaction system basic, and stirring at a predetermined temperature and the like. Among these, the method of (a) or (c) is preferable at the point which can obtain the target polysilsesquioxane compound (A) efficiently.

Any of an acid catalyst and a base catalyst may be sufficient as the polycondensation catalyst to be used. Moreover, although you may use combining two or more polycondensation catalysts, it is preferable to use an acid catalyst at least.

Examples of the acid catalyst include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, and nitric acid; organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; and the like. Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid is preferable.

As a base catalyst, Ammonia water; Trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, aniline, picoline, 1,4- organic bases such as diazabicyclo[2.2.2]octane and imidazole; organic hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide and potassium t-butoxide; metal hydrides such as sodium hydride and calcium hydride; metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, and magnesium carbonate; metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; and the like.

The usage-amount of a polycondensation catalyst is 0.05-10 mol% normally with respect to the total mol amount of a silane compound (1), Preferably it is the range of 0.1-5 mol%.

When using a solvent at the time of polycondensation, the solvent to be used can be suitably selected according to the kind etc. of a silane compound (1). For example, water; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol and t-butyl alcohol; and the like. These solvents can be used individually by 1 type or in combination of 2 or more type. In addition, when the method of (c) is adopted, an organic solvent and an excess amount of a base catalyst (such as ammonia water) are added to the reaction solution after polycondensation reaction is performed in an aqueous system in the presence of an acid catalyst, and basic conditions You may make it perform a polycondensation reaction further under the following conditions.

The amount of the solvent used is 0.1 liters or more and 10 liters or less, preferably 0.1 liters or more and 2 liters or less, per 1 mol of the total molar amount of the silane compound (1).

The temperature at the time of polycondensing a silane compound (1) is the temperature range from 0 degreeC to the boiling point of the solvent used normally, Preferably it is the range of 20 degreeC or more and 100 degrees C or less. When the reaction temperature is too low, the progress of the polycondensation reaction may become insufficient. On the other hand, when the reaction temperature becomes too high, suppression of gelation becomes difficult. The reaction is usually completed in 30 minutes to 30 hours.

Moreover, depending on the kind of monomer to be used, it may be difficult to make high molecular weight. For example, the alkyl group of R ¹ is a monomer having a fluorine atom, R ¹ may have less tendency than the conventional reactive group of the monomer. In such a case, the polysilsesquioxane compound (A) of the target molecular weight can be obtained easily by performing reaction for a long time on mild conditions and reducing a catalyst amount.

After completion of the reaction, when an acid catalyst is used, neutralization is performed by adding an aqueous alkali solution such as sodium hydrogen carbonate to the reaction solution, and when a base catalyst is used, neutralization is performed by adding an acid such as hydrochloric acid to the reaction solution, , the salt generated at that time can be removed by filtration, washing with water, or the like to obtain the target polysilsesquioxane compound (A).

By the above method, when manufacturing the polysilsesquioxane compound (A), OR ³ or X ¹ part of, that was a de-alcohol such as occur in the silane compound (1), polysilsesquioxane compound (A) remaining in the For this reason, in the polysilsesquioxane compound (A), the case where the repeating unit represented by said Formula (a-4) and Formula (a-5) other than the repeating unit represented by said Formula (a-3) is contained have.

[(B) component]

The component (B) constituting the curable composition of the present invention is a silicone oligomer having a repeating unit derived from a trifunctional silane compound and having or not having a repeating unit derived from a tetrafunctional silane compound, and a trifunctional silane compound The total amount of the repeating unit derived from the tetrafunctional silane compound and the repeating unit derived from the tetrafunctional silane compound is 80 mol% or more of the total repeating units of component (B), and at least one of the trifunctional silane compounds is a trifunctional group having an epoxy ring. It is a silicone oligomer (Hereinafter, it may represent as "silicone oligomer (B)") which is a silane compound.

In the present invention, the silicone oligomer is a silane compound polymer that does not have a high degree of polymerization. The polymerization degree of a silicone oligomer (B) is 2-100 normally.

The silicone oligomer (B) has a repeating unit derived from a trifunctional silane compound.

A trifunctional silane compound is a compound which has one silicon atom and three hydrolysable groups couple|bonded with this silicon atom. In this specification, a hydrolysable group means groups which have hydrolysis and polycondensability, such as an alkoxy group and a halogen atom.

As a trifunctional silane compound, the silane compound (1) represented by Formula (a-6) shown as a manufacturing raw material of a polysilsesquioxane compound (A) is mentioned.

The silicone oligomer (B) may or may not have a repeating unit derived from a tetrafunctional silane compound.

A tetrafunctional silane compound is a compound which has one silicon atom and 4 hydrolysable groups couple|bonded with this silicon atom.

Examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, methoxyethoxysilane, dimethoxydiethoxysilane, trimethoxyethoxysilane, trimethoxycyclorosilane, triethoxycyclorosilane, Dimethoxydichlorosilane, diethoxydichlorosilane, methoxytrichlorosilane, ethoxytrichlorosilane, tetrachlorosilane, tetrabromosilane, etc. are mentioned.

The total of the repeating units derived from the trifunctional silane compound and the repeating units derived from the tetrafunctional silane compound contained in the silicone oligomer (B) is 80 mol% or more, preferably 80 to 100 mol%, more Preferably it is 90-100 mol%.

The curable composition in which the sum total of the repeating unit derived from a trifunctional silane compound and the repeating unit derived from a tetrafunctional silane compound is less than 80 mol% of all repeating units is inferior to sclerosis|hardenability.

The amount of the repeating unit derived from the trifunctional silane compound contained in the silicone oligomer (B) is preferably 5 to 40 mol% of the total of the repeating unit derived from the trifunctional silane compound and the repeating unit derived from the tetrafunctional silane compound, , More preferably, it is 10-30 mol%.

By containing many repeating units derived from a trifunctional silane compound, compatibility with a polysilsesquioxane compound (A) of a silicone oligomer (B) becomes high. On the other hand, by hardening the curable composition containing the silicone oligomer (B) containing many repeating units derived from a tetrafunctional silane compound, hardened|cured material and excellent heat resistance can be obtained easily.

The type and content of each repeating unit contained in the silicone oligomer (B) is determined by the same method as described above as the method for determining the structure of the polysilsesquioxane compound (A) (a method based on the measurement result of ^{29 Si-NMR)} ) can be obtained by

The silicone oligomer (B) has a repeating unit derived from a trifunctional silane compound having a group having an epoxy ring. That is, at least 1 sort(s) of the trifunctional silane compound used when synthesize|combining a silicone oligomer (B) is a compound which has group which has an epoxy ring.

Examples of the trifunctional silane compound having a group having an epoxy ring include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy silane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-glycidoxyoctyltriethoxysilane, etc. are mentioned.

As described above, the silicone oligomer (B) has an epoxy ring in the molecule. In this invention, the curable composition excellent in sclerosis|hardenability can be obtained by using such an oligomer with a sclerosing|hardenable polysilsesquioxane compound (A).

Such an effect cannot be obtained even if a silicone oligomer having a functional group (for example, a thiol group) other than an epoxy ring-containing group (for example, a thiol group) or a monomer having an epoxy ring is used instead of the silicone oligomer (B).

Moreover, rather than introduce|transducing an epoxy ring into a polysilsesquioxane compound (A), it is sufficient to use a polysilsesquioxane compound (A) and a silicone oligomer (B) together with the introduction amount of a smaller epoxy ring, hardenability can be realized.

Although the mass average molecular weight (Mw) of a silicone oligomer (B) is not specifically limited, Usually, it is 500-5,000, Preferably it is 1,000-4,500, More preferably, it is 1,500-4,000, More preferably, it is 2,000-3,500. By using the silicone oligomer (B) having a mass average molecular weight (Mw) within the above range, a curable composition having more excellent curability can be easily obtained. Moreover, the hardened|cured material of such a curable composition tends to be excellent in adhesiveness.

Although the molecular weight distribution (Mw/Mn) of a silicone oligomer (B) is not specifically limited, Usually, it is 1.0-10.0, Preferably it is 1.1-6.0. By using the silicone oligomer (B) having a molecular weight distribution (Mw) within the above range, a curable composition having more excellent curability can be easily obtained. Moreover, the hardened|cured material of such a curable composition tends to be excellent in adhesiveness.

A mass average molecular weight (Mw) and a number average molecular weight (Mn) can be calculated|required as a standard polystyrene conversion value by gel permeation chromatography (GPC) which uses tetrahydrofuran (THF) as a solvent, for example.

Although the epoxy equivalent of a silicone oligomer (B) is not specifically limited, Usually 50-2,000 g/eq, Preferably it is 100-1,500 g/eq, More preferably, 150-1200 g/eq, More preferably, it is 200- 1,000 g/eq. By using the silicone oligomer (B) having an epoxy equivalent within the above range, a curable composition having more excellent curability can be easily obtained. Moreover, the hardened|cured material of such a curable composition tends to be excellent in adhesiveness.

The epoxy equivalent of the silicone oligomer (B) can be measured according to JIS K7236 (2001).

In this invention, a silicone oligomer (B) can be used individually by 1 type or in combination of 2 or more type.

The manufacturing method of a silicone oligomer (B) is not specifically limited. In the method similar to what was demonstrated as a manufacturing method of a polysilsesquioxane compound (A) WHEREIN: The target silicone oligomer (B) can be manufactured by changing reaction conditions etc. suitably.

Moreover, as a silicone oligomer (B), you may use a commercially available silicone oligomer.

[Curable composition]

The curable composition of this invention contains a polysilsesquioxane compound (A) and a silicone oligomer (B).

The total amount of the polysilsesquioxane compound (A) and the silicone oligomer (B) is in the solid content of the curable composition, preferably 30 to 100 mass%, more preferably 40 to 95 mass%, still more preferably 50 -90 mass %, Especially preferably, it is 55-85 mass %.

In the present invention, "solid content" means components other than the solvent in the curable composition.

To [ content of silicone oligomer (B) / 100 mass parts of polysilsesquioxane compound (A)), Preferably it is 0.1-100 mass parts, More preferably, it is 0.5-80 mass parts, More preferably, it is 1.0-60 mass parts. It is a mass part, Especially preferably, it is 1.5-40 mass parts. When there is too little content of (B) component, there exists a possibility that the effect of this invention may not be acquired, and when there is too much, there exists a possibility of gelatinization.

The curable composition of this invention may contain a silane coupling agent as (C)component. By using the curable composition containing a silane coupling agent, it becomes easy to form the hardened|cured material which is more excellent in adhesiveness.

A silane coupling agent means the silane compound which has a silicon atom, a functional group, and the hydrolysable group couple|bonded with the said silicon atom.

The functional group refers to a group having reactivity with another compound (mainly an organic substance), for example, an amino group, a substituted amino group, an isocyanate group, a ureido group, a group having a nitrogen atom such as a group having an isocyanurate skeleton; acid anhydride group (acid anhydride structure); vinyl group; allyl group; epoxy group; (meth)acryl group; mercapto group; and the like.

In this invention, a silane coupling agent can be used individually by 1 type or in combination of 2 or more type.

When the curable composition of this invention contains a silane coupling agent, the content is not specifically limited, According to the objective, it can determine suitably.

As a silane coupling agent, the silane coupling agent which has a nitrogen atom in a molecule|numerator, and the silane coupling agent which has an acid anhydride structure in a molecule|numerator are preferable.

A curable composition containing a silane coupling agent having a nitrogen atom in its molecule or a silane coupling agent having an acid anhydride structure in its molecule tends to provide a cured product having better heat resistance and adhesion.

As a silane coupling agent which has a nitrogen atom in a molecule|numerator, for example, a trialkoxysilane compound represented by the following formula (c-1), a dialkoxyalkylsilane compound represented by a formula (c-2), a dialkoxyarylsilane compound, etc. can be heard

[Formula 6]

In the formula, R ^a represents an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. A plurality of R ^{2 s may be the} same or different.

R ^b is an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group; or an aryl group having a substituent or not having a substituent, such as a phenyl group, 4-chlorophenyl group, 4-methylphenyl group, and 1-naphthyl group; indicates

R ^c represents an organic group having 1 to 10 carbon atoms and having a nitrogen atom. In addition, R ^c may be further bonded to a group containing a silicon atom.

Specific examples of the organic group having 1 to 10 carbon atoms for R ^c include N-2-(aminoethyl)-3-aminopropyl group, 3-aminopropyl group, N-(1,3-dimethyl-butylidene) aminopropyl group, 3-ureidopropyl group, N-phenyl-aminopropyl group, etc. are mentioned.

Among the compounds represented by the formula (c-1) or (c-2), in the case where R ^c is an organic group bonded to a group containing another silicon atom, a silane coupling agent having an isocyanurate skeleton ( isocyanurate-based silane coupling agent) and a silane coupling agent having a urea skeleton (urea-based silane coupling agent).

Among these, as the silane coupling agent having a nitrogen atom in the molecule, an isocyanurate-based silane coupling agent and a urea-based silane coupling agent are preferable from the viewpoint of easily obtaining a cured product having superior adhesiveness, and It is preferable to have 4 or more alkoxy groups bonded to a silicon atom in it.

Having 4 or more alkoxy groups bonded to a silicon atom means that the sum total of the alkoxy groups bonded to the same silicon atom and the alkoxy groups bonded to different silicon atoms is 4 or more.

As an isocyanurate-type silane coupling agent which has 4 or more alkoxy groups couple|bonded with the silicon atom, the compound represented by a following formula (c-3) is mentioned. As a urea-type silane coupling agent which has 4 or more alkoxy groups couple|bonded with the silicon atom, the compound represented by a following formula (c-4) is mentioned.

[Formula 7]

(In the formula, R ^a has the same meaning as above. t1 to t5 each independently represent an integer of 1 to 10, preferably an integer of 1 to 6, particularly preferably 3.

Among these, as the silane coupling agent having a nitrogen atom in the molecule, 1,3,5-N-tris(3-trimethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3- Triethoxysilylpropyl)isocyanurate (hereinafter referred to as "isocyanurate compound"), N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3- It is preferable to use triethoxysilylpropyl)urea (hereinafter referred to as "urea compound") and a combination of the isocyanurate compound and the urea compound.

When the curable composition of the present invention contains a silane coupling agent having a nitrogen atom in the molecule, the content is not particularly limited, but the amount is determined by the mass ratio of the component (A) and the silane coupling agent having a nitrogen atom in the molecule [( A) component: a silane coupling agent having a nitrogen atom in the molecule], preferably 100:0.1 to 100:90, more preferably 100:0.3 to 100:60, more preferably 100:1 to 100:50 , more preferably 100:3 to 100:40, particularly preferably 100:5 to 100:35.

The cured product of the curable composition containing the component (A) and the silane coupling agent having a nitrogen atom in the molecule in such a proportion is more excellent in heat resistance and adhesiveness.

The silane coupling agent which has an acid-anhydride structure in a molecule|numerator is an organosilicon compound which has both the group which has an acid-anhydride structure, and a hydrolysable group in one molecule. Specifically, a compound represented by the following formula (c-5) is exemplified.

[Formula 8]

In the formula, Q represents a group having an acid anhydride structure, R ^d represents an alkyl group having 1 to 6 carbon atoms or a phenyl group having or not having a substituent, and R ^e is an alkoxy group having 1 to 6 carbon atoms or halogen An atom is represented, i and k represent the integer of 1-3, j represents the integer of 0-2, and i+j+k=4. When j is 2, R ^{d may be the} same or different. When k is 2 or 3, a plurality of Re may be the same or different. When i is 2 or 3, a plurality of Qs may be the same or different.

As Q, the following formula

[Formula 9]

(in formula, h represents the integer of 0-10) etc. are mentioned, The group represented by (Q1) is especially preferable.

Examples of the silane coupling agent having an acid anhydride structure in the molecule include 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, 3-(trimethoxysilyl)propyl succinic anhydride, 3 tri(C1-C6) alkoxysilyl (C2-C8) alkyl succinic anhydride, such as -(triethoxysilyl)propyl succinic anhydride;

di(C1-C6) alkoxymethylsilyl (C2-C8) alkyl succinic anhydride, such as 2-(dimethoxymethylsilyl)ethyl succinic anhydride;

(C1-C6) alkoxy dimethylsilyl (C2-C8) alkyl succinic anhydride, such as 2-(methoxydimethylsilyl) ethyl succinic anhydride;

trihalogenosilyl (C2-8)alkyl succinic anhydride, such as 2-(trichlorosilyl)ethyl succinic anhydride and 2-(tribromosilyl)ethyl succinic anhydride;

dihalogenomethylsilyl (C2-8)alkyl succinic anhydride, such as 2-(dichloromethylsilyl)ethyl succinic anhydride;

halogenomethylsilyl (C2-8)alkyl succinic anhydride, such as 2-(chloromethylsilyl)ethyl succinic anhydride; and the like.

Among these, as a silane coupling agent which has an acid anhydride structure in a molecule|numerator, tri(C1-C6) alkoxysilyl (C2-C8) alkyl succinic anhydride is preferable, 3-(trimethoxysilyl)propyl succinic anhydride, or Particular preference is given to 3-(triethoxysilyl)propyl succinic anhydride.

When the curable composition of the present invention contains a silane coupling agent having an acid anhydride structure in the molecule, the content is not particularly limited, but the amount is the mass ratio of the component (A) and the silane coupling agent having an acid anhydride structure in the molecule [ (A) component: a silane coupling agent having an acid anhydride structure in the molecule], preferably 100:0.1 to 100:30, more preferably 100:0.3 to 100:20, more preferably 100:0.5 to 100 : 15, more preferably 100:1 to 100:10.

The hardened|cured material of the curable composition containing (A) component and the silane coupling agent which has an acid-anhydride structure in a molecule|numerator in such a ratio becomes more excellent in adhesiveness.

The curable composition of this invention may contain other components in the range which does not impair the objective of this invention.

As other components, microparticles|fine-particles, antioxidant, a ultraviolet absorber, a light stabilizer, etc. are mentioned.

When microparticles|fine-particles are added, the curable composition excellent in the workability|operativity in an application|coating process may be obtained. As a material of microparticles|fine-particles, it is a metal; metal oxides; Mineral ; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; metal hydroxides such as aluminum hydroxide; Metal silicates, such as an aluminum silicate, a calcium silicate, and a magnesium silicate; inorganic components such as silica; silicon ; Organic components, such as an acrylic polymer; and the like.

In addition, the microparticles|fine-particles to be used may be what was modified on the surface.

These microparticles|fine-particles can be used individually by 1 type or in combination of 2 or more type. Although content of microparticles|fine-particles is not specifically limited, Usually, 50 mass % or less is preferable with respect to (A) component, 40 mass % or less is more preferable, and 35 mass % or less is still more preferable.

An antioxidant is added to prevent oxidative deterioration upon heating. As antioxidant, phosphorus antioxidant, phenolic antioxidant, sulfur-type antioxidant, etc. are mentioned.

Phosphite, oxaphosphaphenanthrene oxide, etc. are mentioned as phosphorus antioxidant. Monophenols, bisphenols, polymer type phenols etc. are mentioned as a phenolic antioxidant. Examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc. can be heard

These antioxidants can be used individually by 1 type or in combination of 2 or more type. Although content of antioxidant is not specifically limited, It is 10 mass % or less normally with respect to (A) component.

A ultraviolet absorber is added in order to improve the light resistance of the hardened|cured material obtained.

Examples of the ultraviolet absorber include salicylic acids, benzophenones, benzotriazoles, and hindered amines.

A ultraviolet absorber can be used individually by 1 type or in combination of 2 or more type. Although content of a ultraviolet absorber is not specifically limited, It is 10 mass % or less normally with respect to (A) component.

An optical stabilizer is added in order to improve the light resistance of the hardened|cured material obtained.

As the light stabilizer, for example, poly[b6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-triazine-2,4-diylb(2,2) and hindered amines such as ,6,6-tetramethyl-4-piperidine)imino｝hexamethylene(2,2,6,6-tetramethyl-4-piperidine)imino｝]. can

These light stabilizers can be used individually by 1 type or in combination of 2 or more type. Content of an optical stabilizer is 20 mass % or less normally with respect to (A) component.

The curable composition of this invention may contain a solvent. A solvent will not be specifically limited if it can melt|dissolve or disperse|distribute the component of the curable composition of this invention.

Examples of the solvent include acetates such as diethylene glycol monobutyl ether acetate and 1,6-hexanediol diacetate; tripropylene glycol-n-butyl ether; Glycerin diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether, cyclohexanedimethanol diglycidyl ether, alkylenedi glycidyl ether, polyglycol diglycidyl ether diglycidyl ethers such as dil ether and polypropylene glycol diglycidyl ether; triglycidyl ethers such as trimethylolpropane triglycidyl ether and glycerin triglycidyl ether; vinyl hexene oxides such as 4-vinyl cyclohexene monoxide, vinyl cyclohexene dioxide, and methylated vinyl cyclohexene dioxide; and the like.

A solvent can be used individually by 1 type or in combination of 2 or more type.

When the curable composition of this invention contains a solvent, the content is solid content concentration, Preferably it is 50-95 mass %, It is a quantity used more preferably 60-85 mass %. When solid content concentration is in this range, the curable composition excellent in the workability|operativity in an application|coating process can be obtained easily.

A curable composition that satisfies these requirements regarding the amount of solvent has an appropriate balance of adhesiveness and wet diffusivity (above, properties related to the diffusion of droplets).

The curable composition of this invention can be manufactured by mixing and defoaming the said (A) component and (B) component, and another component in predetermined ratio as needed, for example.

A mixing method and a defoaming method are not specifically limited, A well-known method can be used.

The curable composition of this invention contains a polysilsesquioxane compound (A) and a silicone oligomer (B). For this reason, the curable composition of this invention is excellent in sclerosis|hardenability.

It can be confirmed that the curable composition of this invention is excellent in sclerosis|hardenability, for example as follows.

That is, using an automatic curing time measuring device (manufactured by Cyber Co., Ltd., trade name “Madoka”), a sample of the curable composition is put on a stainless plate heated to 150° C., and then the injected sample is stirred, and the stirring torque is increased. , measure the time until it becomes 0.049 N·cm.

Usually, it is preferable that it is 1200 second or less, and, as for time until it becomes 0.049 N*cm, it is more preferable that it is 1000 second or less, It is more preferable that it is 600 second or less.

As mentioned above, the curable composition of this invention is excellent in sclerosis|hardenability. Therefore, by using the curable composition of this invention, compared with the case where the conventional curable composition is used, working time can be shortened.

2) cured product

The cured product of the present invention is obtained by curing the curable composition of the present invention.

Heat hardening is mentioned as a method of hardening the curable composition of this invention. The heating temperature at the time of hardening is 100-200 degreeC normally, and a heating time is 10 minutes - 20 hours normally, Preferably it is 30 minutes - 10 hours.

The hardened|cured material of this invention is excellent in heat resistance and adhesiveness.

It can be confirmed that the hardened|cured material of this invention has these characteristics as follows, for example. That is, a predetermined amount of the curable composition of the present invention is applied to the mirror surface of a silicon chip, the coated surface is placed on an adherend, pressed, and cured by heat treatment. This is left on the measurement stage of the bond tester heated in advance to a predetermined temperature (for example, 100° C.) for 30 seconds, from a position of 100 µm from the adherend to the adhesive surface in the horizontal direction (shear direction) Apply stress to measure the adhesion between the test piece and the adherend.

It is preferable that it is 30 N/4 mm<2> or more in 100 degreeC, as for the adhesive force of the hardened|cured material of this invention, it is more preferable that it is 35 N/4 mm<2> or more, It is more preferable that it is 40 N/4 mm<2>/ or more.

In this specification, "4 mm2" means "2 mm square", that is, 2 mm x 2 mm (a square with a side of 2 mm).

Since it has the said characteristic, the hardened|cured material of this invention is used suitably as an optical element fixing material.

3) How to use the curable composition

The method of the present invention is a method of using the curable composition of the present invention as an adhesive for an optical element fixing material or a sealing material for an optical element fixing material.

Examples of the optical element include light-emitting elements such as LED and LD, light-receiving elements, composite optical elements, and optical integrated circuits.

<Adhesive for Optical Device Fixing Material>

The curable composition of this invention can be used suitably as an adhesive agent for optical element fixing materials.

As a method of using the curable composition of the present invention as an adhesive for an optical device fixing material, the composition is applied to one or both bonding surfaces of a material to be bonded (optical device and its substrate, etc.), pressed, and heated A method of hardening and strongly adhering the materials to be adhered to each other is exemplified. The amount of application of the curable composition of the present invention is not particularly limited, and by curing, the amount of materials to be adhered can be firmly adhered to each other. Usually, the thickness of the coating film of a curable composition is 0.5-5 micrometers, Preferably it is an quantity used as 1-3 micrometers.

Examples of the substrate material for bonding the optical element include glasses such as soda lime glass and heat-resistant hard glass; ceramics; Sapphire ; metals such as iron, copper, aluminum, gold, silver, platinum, chromium, titanium, alloys of these metals, and stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); Polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyphenylenesulfide, polyetherimide , synthetic resins such as polyimide, polyamide, acrylic resin, norbornene-based resin, cycloolefin resin, and free epoxy resin; and the like.

Although the heating temperature at the time of heat-hardening changes with the curable composition etc. to be used, it is 100-200 degreeC normally. Heating time is 10 minutes - 20 hours normally, Preferably they are 30 minutes - 10 hours.

<Encapsulant for optical element fixing material>

The curable composition of this invention can be used suitably as an adhesive agent for optical element fixing materials.

As a method of using the curable composition of the present invention as an encapsulant for an optical element fixing material, for example, the composition is molded into a desired shape to obtain a molded article enclosing an optical element, and then heat-cured to cure the optical element rod. The method of manufacturing a body member, etc. are mentioned.

It does not specifically limit as a method of shape|molding the curable composition of this invention into a desired shape, Well-known molding methods, such as a normal transfer molding method and a casting method, are employable.

Although the heating temperature at the time of heat-hardening changes with the curable composition etc. to be used, it is 100-200 degreeC normally. Heating time is 10 minutes - 20 hours normally, Preferably they are 30 minutes - 10 hours.

Since the optical element sealing body obtained uses the curable composition of this invention, it is excellent in heat resistance and adhesiveness.

Example

Hereinafter, the present invention will be described in more detail by way of Examples. However, the present invention is not limited to the following examples at all.

(Measurement of average molecular weight)

The mass average molecular weight (Mw) and number average molecular weight (Mn) of the curable polysilsesquioxane compound obtained in Production Examples and the silicone oligomer of component B were measured in terms of standard polystyrene with the following apparatus and conditions.

Device name: HLC-8220GPC, manufactured by Tosoh Corporation

Column: sequentially connected TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL

Solvent: tetrahydrofuran

Injection volume: 80 μl

Measuring temperature: 40℃

Flow rate: 1 ml/min

Detector: Differential Refractometer

(IR spectrum measurement)

The IR spectrum of the curable polysilsesquioxane compound obtained by the manufacture example was measured using the Fourier transform infrared spectrophotometer (The Parkin-Elmer company make, Spectrum 100).

( ²⁹ Si-NMR measurement)

In order to investigate the repeating unit and the amount of the silane compound polymer [component (A) and component (B)], ²⁹ Si-NMR measurement was performed under the following conditions.

Equipment: AV-500 manufactured by Bruker Biospin

²⁹ Si-NMR resonance frequency: 99.352 MHz

Probe: 5 mmφ solution probe

Measurement temperature: room temperature (25℃)

Sample rotation speed: 20 ㎑

Measurement method: Inverse gate decoupling method

²⁹ Si flip angle: 90°

²⁹ Si 90° pulse width: 8.0 ㎲

Repetition time: 5 s

Integration count: 9200 times

Observation width: 30 ㎑

( ²⁹ Si-NMR sample preparation method)

In order to shorten the relaxation time, Fe(acac) ₃ was added as a relaxation reagent and measured.

Silane compound polymer concentration: 30% by mass

Fe(acac) ₃ concentration: 0.7 mass%

Measuring solvent: acetone

Internal standard: TMS

(Waveform processing analysis)

For each peak of the spectrum after Fourier transform, a chemical shift was calculated|required according to the position of a peak top, and it integrated.

(Production Example 1)

After putting 71.37 g (400 mmol) of methyltriethoxysilane in a 300 ml eggplant flask, and stirring this, 0.10 g of 35 mass% hydrochloric acid (0.25 mol% with respect to methyltriethoxysilane) in 21.6 ml of distilled water was added, and the total volume was stirred at 30°C for 2 hours, then at 70°C, and stirred for 5 hours.

140 g of propyl acetate and 0.12 g of 28 mass % aqueous ammonia (0.5 mol% with respect to methyltriethoxysilane) were added there, continuing stirring of the content, and it stirred at 70 degreeC as it is for 3 hours.

After the reaction solution was allowed to cool to room temperature, purified water was added thereto to perform liquid separation treatment, and this operation was repeated until the pH of the aqueous layer became 7. 55.7 g of curable polysilsesquioxane compounds (A1) were obtained by concentrating an organic layer with an evaporator and vacuum-drying a concentrate. Its mass average molecular weight (Mw) was 7,800, and molecular weight distribution (Mw/Mn) was 4.52.

The IR spectrum data of the curable polysilsesquioxane compound (A1) is shown below.

Si-CH ₃ : 1272 cm ^-1 , 1409 cm ^-1 , Si-O : 1132 cm ^-1

Moreover, as a ^{result of performing 29} Si-NMR spectrum measurement, the peak integral ratio of T1, T2, and T3 was 0:24:76.

(Production Example 2)

In a 300 ml eggplant-type flask, 17.0 g (77.7 mmol) of 3,3,3-trifluoropropyltrimethoxysilane and 32.33 g (181.3 mmol) of methyltriethoxysilane were charged, and this While stirring, an aqueous solution obtained by dissolving 0.0675 g of 35 mass % hydrochloric acid (the amount of HCl is 0.65 mmol, 0.25 mol% with respect to the total amount of the silane compound) in 14.0 g of distilled water is added, and the total volume is heated at 30°C for 2 hours, Then, it heated up at 70 degreeC and stirred for 20 hours.

A mixed solution of 0.0394 g of 28 mass % aqueous ammonia ( _{the amount of NH 3} is 0.65 mmol) and 46.1 g of propyl acetate is added thereto while stirring the contents, the pH of the reaction solution is set to 6.9, and 40 at 70°C as it is. stirred for minutes.

After standing to cool a reaction liquid to room temperature, 50 g of propyl acetate and 100 g of water were added there, liquid separation processing was performed, and the organic layer containing a reaction product was obtained. Magnesium sulfate was added to this organic layer, and the drying process was performed. Curable polysilsesquioxane compound (A2) was obtained by vacuum-drying the concentrate obtained after concentrating an organic layer with an evaporator after separation-removing magnesium sulfate by filtration. The mass average molecular weight (Mw) of this was 5,500, and molecular weight distribution was 3.40.

IR spectrum data of curable polysilsesquioxane compound (A2) is shown below.

Si-CH ₃ : 1272 cm ^-1 , 1409 cm ^-1 , Si-O : 1132 cm ^-1 , CF : 1213 cm ^-1

Moreover, as a ^{result of performing 29} Si-NMR spectrum measurement, the ratio of the peak integral values of T1, T2, and T3 was 2:27:71.

(Production Example 3)

In a 300 ml eggplant-type flask, 20.2 g (102 mmol) of phenyltrimethoxysilane, 3.15 g (18 mmol) of 2-cyanoethyltrimethoxysilane, 96 ml of acetone as a solvent and 24 ml of distilled water were added After that, 0.15 g (1.5 mmol) of phosphoric acid was added as a catalyst while stirring the contents, followed by stirring at 25°C for further 16 hours.

After completion of the reaction, the reaction solution was concentrated to 50 ml with an evaporator, and 100 ml of ethyl acetate was added to the concentrate, followed by neutralization with a saturated aqueous sodium hydrogen carbonate solution. After standing for a while, the organic layer was separated and collected. Then, the organic layer was washed twice with distilled water, and then dried over anhydrous magnesium sulfate. After the magnesium sulfate was separated by filtration, the filtrate was concentrated to 50 ml with an evaporator, and the resulting concentrate was added dropwise to a large amount of n-hexane for precipitation, and the precipitate was separated by decantation. The obtained precipitate was dissolved in methyl ethyl ketone (MEK) and recovered, and the solvent was distilled off under reduced pressure with an evaporator. 13.5 g of curable polysilsesquioxane compounds (A3) were obtained by vacuum-drying a residue. Its mass average molecular weight (Mw) was 1,870, and molecular weight distribution (Mw/Mn) was 1.42.

The IR spectrum data of the curable polysilsesquioxane compound (A3) is shown below.

Si-Ph: 698 cm ^-1 , 740 cm ^-1 , Si-O: 1132 cm ^-1 , -CN: 2259 cm ^-1

Moreover, as a ^{result of performing 29} Si-NMR spectrum measurement, the peak integral ratio of T1, T2, and T3 was 0:33:67.

The compounds used in Examples and Comparative Examples are shown below.

(Component A)

Curable polysilsesquioxane compound (A1) [Curable PSQ (A1)]: Curable polysilsesquioxane compound obtained in Production Example 1

Curable polysilsesquioxane compound (A2) [Curable PSQ (A2)]: Curable polysilsesquioxane compound obtained in Production Example 2

Curable polysilsesquioxane compound (A3) [Curable PSQ (A3)]: Curable polysilsesquioxane compound obtained in Production Example 3

(component B and comparative compound)

Silicone oligomer (B1): commercially available silicone oligomer containing epoxy ring, mass average molecular weight (Mw) 2,400, molecular weight distribution (Mw/Mn) 1.53, epoxy equivalent 830 g/eq

Silicone oligomer (B2): commercially available silicone oligomer containing an epoxy ring, mass average molecular weight (Mw) 2,300, molecular weight distribution (Mw/Mn) 1.48, epoxy equivalent 350 g/eq

Silicone oligomer (B3): commercially available silicone oligomer containing a mercapto group, mass average molecular weight (Mw) 1,800, molecular weight distribution (Mw/Mn) 1.79, mercapto equivalent 800 g/eq

Silicone oligomer (B4): commercially available silicone oligomer containing an epoxy ring, mass average molecular weight (Mw) 2,200, molecular weight distribution (Mw/Mn) 2.24

Silicone oligomer (B5): commercially available silicone oligomer containing epoxy ring, mass average molecular weight (Mw) 1,500, molecular weight distribution (Mw/Mn) 1.39, epoxy equivalent 490 g/eq

Silicone oligomer (B6): commercially available silicone oligomer containing epoxy ring [polycondensate of 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane (cyclic tetramer)], epoxy equivalent 200 g/eq

Silane coupling agent (B7): 3-glycidoxypropyltrimethoxysilane

The types of repeating units of silicone oligomers (B1) to (B6) and their content rates calculated from the ^{29 Si-NMR measurement results are shown below.}

In addition, in the said table|surface, M, D, T, and Q show that the number of the oxygen atoms couple|bonded with the silicon atom is 1, 2, 3, and 4, respectively. In addition, the number after M, D, T and Q indicates the number of Si-O- bonds bonded to the silicon atom. Therefore, for example, in the case of a silicone oligomer in which the non-hydrolyzable group is a methyl group and the hydrolyzable group is a methoxy group, the specific structure is as follows. In the formula, "Me" represents a methyl group.

[Formula 10]

(component C)

Silane coupling agent (C1): 1,3,5-N-tris[3-(trimethoxysilyl)propyl]isocyanurate

Silane coupling agent (C2): 3- (trimethoxysilyl) propyl succinic anhydride

(Example 1)

To 100 parts by mass of the curable polysilsesquioxane compound (A1), a mixed solvent of diethylene glycol monobutyl ether acetate: tripropylene glycol-n-butyl ether = 40: 60 (mass ratio) was added, and the total volume was stirred. . 5 mass parts of silicone oligomer (B1), 30 mass parts of silane coupling agents (C1), and 3 mass parts of silane coupling agents (C2) were added to this, and the curable composition was obtained by fully mixing and defoaming the total volume.

(Examples 2 to 8, Comparative Examples 1 to 8)

In Example 1, except having changed each component into what was shown in Table 2, it carried out similarly to Example 1, and obtained the curable composition.

The following measurements and tests were performed using the curable compositions obtained in Examples and Comparative Examples, respectively. A result is shown in Table 2.

[Curability evaluation]

As described below, the curing time of the curable composition was measured using an automatic curing time measuring device "Madoka" (manufactured by Cyber Co., Ltd.).

On the stainless steel plate heated to 150 degreeC, 0.30 mL sample was thrown in, and it stirred. Since the stirring torque increases with time, the time (seconds) until the stirring torque becomes 0.049 N·cm was measured. Stirring conditions are as follows.

Rotational rotation speed of the stirring blade: 200 rpm

Idle rotation speed of the stirring blade: 80 rpm

·Gap (distance between heating plate and stirring blade): 0.3 mm

[Adhesive strength evaluation]

The curable compositions obtained in Examples and Comparative Examples were respectively applied to the mirror surface of a square (area 4 mm2) silicon chip having a side length of 2 mm so that the thickness was about 2 µm, and the coated surface was applied to the adherend (silver plated copper plate) and pressed. Then, it heat-processed and hardened at 130 degreeC for 2 hours, and the to-be-adhered body with a test piece was obtained. This adherend with a test piece was left for 30 seconds on the measurement stage of a bond tester (manufactured by Daisy, series 4000) that had been previously heated to 100° C., from a position 100 μm high from the adherend, at a speed of 200 μm/s. Stress was applied in the horizontal direction (shear direction) with respect to the adhesive surface, and the adhesive force (N/4 mm<2>) of the test piece and to-be-adhered body in 100 degreeC was measured.

[Transmittance after heating]

The curable compositions obtained in Examples and Comparative Examples were poured into a mold having a length of 25 mm and a width of 20 mm, each having a thickness of 1 mm, and heated and cured at 150°C for 3 hours to obtain a test piece. After heating this test piece at 200 degreeC for 100 hours, the transmittance|permeability of wavelength 450nm was measured using the spectrophotometer.

Table 2 shows the following.

The curable composition of Examples 1-8 is a sclerosis|hardenability evaluation test. WHEREIN: Hardened|cured material is obtained in the short time of 1000 second or less, and it is excellent in sclerosis|hardenability.

Moreover, in the evaluation test of the adhesive strength of the hardened|cured material obtained in Examples 1-8, adhesive strength is 30 N/4 mm<2> or more, and it is excellent in adhesiveness.

Moreover, the hardened|cured material of the curable composition of an Example has sufficient light transmittance even after heating.

On the other hand, in the curable composition of Comparative Examples 1-8, the curing time exceeding 1000 second was required in the sclerosis|hardenability evaluation test, and sclerosis|hardenability was inferior.

Moreover, in the evaluation test of the adhesive strength of the hardened|cured material obtained in Examples 1-8, adhesive strength is 30 N/4 mm<2> or more, and it is excellent in adhesiveness.

Claims (11)

Curable composition containing following (A) component and (B) component.
(A) component: Curable polysilsesquioxane compound which has a repeating unit represented by following formula (a-1)

(R ¹ is an unsubstituted C1-C10 alkyl group, a C1-C10 alkyl group having a substituent (excluding the group having an epoxy ring), an unsubstituted C6-C12 aryl group, and a substituent (epoxy It is at least one selected from the group consisting of an aryl group having 6 to 12 carbon atoms (excluding groups having a ring).
(B) component: a silicone oligomer having a repeating unit derived from a trifunctional silane compound and having or not having a repeating unit derived from a tetrafunctional silane compound, a repeating unit derived from a trifunctional silane compound and a tetrafunctional silane compound A silicone oligomer in which the total amount of the derived repeating units is 80 mol% or more of the total repeating units, and at least one of the trifunctional silane compounds is a trifunctional silane compound having a group having an epoxy ring. The method of claim 1,
(A) The curable composition whose mass average molecular weights (Mw) of a component are 800-30,000. 3. The method according to claim 1 or 2,
(B) The curable composition whose mass average molecular weights (Mw) of a component are 500-5,000. 4. The method according to any one of claims 1 to 3,
(B) Curable composition whose epoxy equivalent of component is 50-2,000 g/eq. 5. The method according to any one of claims 1 to 4,
(B) Curable composition whose content of component is 0.1-100 mass parts with respect to 100 mass parts of (A) component. 6. The method according to any one of claims 1 to 5,
The curable composition whose total amount of (A) component and (B) component is 30-100 mass % in solid content of a curable composition. 7. The method according to any one of claims 1 to 6,
Furthermore, the curable composition containing the following (C)component.
(C) component: silane coupling agent Hardened|cured material obtained by hardening|curing the curable composition in any one of Claims 1-7. 9. The method of claim 8,
A cured product that is an optical device fixing material. The method of using the curable composition in any one of Claims 1-7 as an adhesive agent for optical element fixing materials. The method of using the curable composition in any one of Claims 1-7 as a sealing material for optical element fixing materials.