KR20220074817A - Curable compositions, cured products and methods of using the curable compositions - Google Patents

Abstract

〔R¹ 은, 무치환의 탄소수 6 ∼ 12 의 아릴기, 또는 치환기를 갖는 탄소수 6 ∼ 12 의 아릴기를 나타낸다.〕로 나타내는 반복 단위 (반복 단위 (1) ) 를 갖고, 하기 식 (a-2)

〔R² 는, 무치환의 탄소수 1 ∼ 10 의 알킬기, 또는, 치환기를 갖는 탄소수 1 ∼ 10 의 알킬기를 나타낸다.〕로 나타내는 반복 단위〔반복 단위 (2)〕를 갖거나 또는 갖지 않는 폴리실세스퀴옥산 화합물이며, 분자 구조에 관한 특정한 요건을 만족시키는 것을 특징으로 하는 폴리실세스퀴옥산 화합물
(C) 성분 : 실란 커플링제The present invention is a curable composition containing the following components (A) and (C), 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 a sealing material for an optical device fixing material . The curable composition of the present invention has a high refractive index and is preferably used in the optical field.
(A) Component: the following formula (a-1)

[R ¹ represents an unsubstituted aryl group having 6 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms having a substituent.] has a repeating unit (repeating unit (1)) represented by the following formula (a-2 )

Polysilces having or not having a repeating unit [repeating unit (2)] represented by [R ² represents an unsubstituted C1-C10 alkyl group or a substituted C1-C10 alkyl group.] Polysilsesquioxane compound, characterized in that it is a quioxane compound and satisfies specific requirements regarding molecular structure
(C) component: silane coupling agent

Description

Curable compositions, cured products and methods of using the curable compositions

The present invention relates to a curable composition having a high refractive index and preferably used in the optical field, 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 is about

BACKGROUND ART Conventionally, various improvements have been made according to the use of curable compositions, and they are widely used in industry as raw materials for optical parts and molded articles, adhesives, coatings, and the like.

Moreover, a curable composition attracts 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 whose peak wavelength of light emission has a shorter wavelength have been developed and 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 composition for optical device fixing materials is exposed to high-energy light or heat higher than that generated from optical devices for a long period of time, resulting in a decrease in adhesive strength. has 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 fixing an optical element etc. using a curable composition, in order to improve light extraction efficiency, according to the refractive index of the surrounding member, the curable composition of an appropriate refractive index may be selected.

For example, in order to suppress reflection at the interface between the sealing material and the fixing material and to increase the light extraction efficiency, it is preferable that the difference between the refractive index of the sealing material and the refractive index of the fixing material is small.

Therefore, when using the sealing material which has a comparatively high refractive index, it becomes necessary to form a fixing material using the curable composition which has a similarly high refractive index.

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 having a high refractive index and preferably used in the optical field, a cured product obtained by curing the curable composition, and the curable composition as an optical device. An object of the present invention is to provide a method for use as an adhesive for fixing or an encapsulant for fixing an optical device.

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

As a result,

(i) a curable composition having a high refractive index is obtained by using a polysilsesquioxane compound containing many aryl groups as the polysilsesquioxane compound;

(ii) the cured product of the curable composition containing a polysilsesquioxane compound containing a large number of aryl groups may cause cracks;

(iii) a cured product of a curable composition containing a polysilsesquioxane compound containing many aryl groups tends to have poor adhesion;

(iv) introducing a specific molecular structure into the polysilsesquioxane compound containing many aryl groups, and adding a silane coupling agent to the curable composition, which can solve the problems of (ii) and (iii) thing,

To find out, it came to complete the present invention.

In this way, according to the present invention, the following [1] to [7] curable composition, the cured product of [8] and [9], and the method of using the curable composition of [10] and [11] are provided.

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

(A) Component: the following formula (a-1)

[Formula 1]

[R ¹ represents an unsubstituted aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms having a substituent.]

has a repeating unit [repeating unit (1)] represented by the following formula (a-2)

[Formula 2]

[ ^R2 represents an unsubstituted C1-C10 alkyl group or a C1-C10 alkyl group having a substituent.]

A polysilsesquioxane compound having or not having a repeating unit [repeating unit (2)] represented by

[Requirement 1]

The amount of the repeating unit (1) is 80 to 100 mol% with respect to the total amount of the repeating unit (1) and the repeating unit (2).

[Requirement 2]

To the total amount of the T site (T1 site) represented by the following formula (a-3), the T site (T2 site) represented by the following formula (a-4), and the T site (T3 site) represented by the following formula (a-5) In contrast, the amount of the T2 site is 30 to 70 mol%.

[Formula 3]

[G represents a group represented by R ¹ or R ² . R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. A silicon atom is bonded to *.]

(C) component: silane coupling agent

[2] The curable composition according to [1], wherein the component (A) has a mass average molecular weight (Mw) of 500 to 3,000.

[3] The curable composition according to [1] or [2], wherein the total amount of the repeating unit (1) and the repeating unit (2) in the component (A) is 90 to 100 mol% based on the total repeating units of the component (A).

[4] The curable composition according to any one of [1] to [3], wherein the content of the component (C) is 0.1 to 70 parts by mass with respect to 100 parts by mass of the component (A).

[5] The curable composition according to any one of [1] to [4], wherein the total amount of the component (A) and the component (C) is 50 to 100 mass% of the solid content of the curable composition.

[6] The curable composition according to any one of [1] to [5], further comprising a diluent and having a solid content concentration of 60 mass% or more and less than 100 mass%.

[7] The curable composition according to any one of [1] to [6], wherein the refractive index (nD) at 25°C is 1.500 to 1.600.

[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, a curable composition having a high refractive index and preferably used in the optical field, a cured product obtained by curing the curable composition, and the curable composition are used as an adhesive for an optical element fixing material or an optical element fixing material sealing material. How to use is provided.

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 the present invention contains the following component (A) and component (C).

Component (A): A polysilsesquioxane compound having a repeating unit represented by the formula (a-1) and having or not having a repeating unit represented by the formula (a-2), the requirements 1 and 2 above A polysilsesquioxane compound that satisfies

(C) component: silane coupling agent

[(A) component]

Component (A) constituting the curable composition of the present invention is a polysilsesquioxane compound having a repeating unit [repeating unit (1)] represented by the following formula (a-1), and satisfies the above requirements 1 and 2 It is a polysilsesquioxane compound, characterized in that

[Formula 4]

[R ¹ represents an unsubstituted aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms having a substituent.]

Since the repeating unit (1) has R ¹ , the polysilsesquioxane compound having the repeating unit (1) has a high refractive index. For this reason, the curable composition of this invention becomes a thing with a high refractive index.

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

As for carbon number of "an unsubstituted C6-C12 aryl group" of R< ¹ >, 6 is preferable.

As for carbon number of "C6-C12 aryl group which has a substituent" of R< ¹ >, 6 is preferable. In addition, this carbon number means the 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 having a substituent”, the number of carbon atoms in R ¹ may exceed 12 in some cases.

Examples of the aryl group of the “substituted aryl group having 6 to 12 carbon atoms” for R ¹ include the same groups as those described as “unsubstituted aryl group having 6 to 12 carbon atoms”.

The number of substituents (however, excluding the number of hydrogen atoms) of the "C6-C12 aryl group having a substituent" of R ¹ is usually 1 to 30, preferably 1 to 20.

As a substituent of the "C6-C12 aryl group having a substituent" of R ¹ , a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t- Alkyl groups, such as a 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; can be heard

Among these, as R< ¹ >, a C6-C12 aryl group is preferable and a phenyl group is more preferable at the point which can prepare efficiently a curable composition with a high refractive index.

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 a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer, etc. From the viewpoint of , a random copolymer is preferable.

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

The polysilsesquioxane compound (A) may further have a repeating unit [repeating unit (2)] represented by the following formula (a-2) (copolymer).

[Formula 5]

[ ^R2 represents an unsubstituted C1-C10 alkyl group or a C1-C10 alkyl group having a substituent.]

Generally, when a polysilsesquioxane compound has a repeating unit (2), while making it high molecular weight, the softness|flexibility of a molecular chain improves. For this reason, when a curable composition contains the polysilsesquioxane compound which has a repeating unit (2), it is thought that it becomes difficult to generate|occur|produce a crack in the hardened|cured material.

However, as will be described later, in the present invention, a polysilsesquioxane compound having a low content of the repeating unit (2) is used, and it is expected that this effect due to the repeating unit (2) will hardly be utilized. .

1-6 are preferable and, as for carbon number of "unsubstituted C1-C10 alkyl group" of R< ² >, 1-3 are more preferable.

As the "unsubstituted C1-C10 alkyl group" of R ² , a methyl group, an 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 "C1-C10 alkyl group which has a substituent" of R< ² >, 1-3 are more preferable. In addition, this carbon number means the carbon number of the part (part of an alkyl group) excluding a substituent. Accordingly, when R ² is “an alkyl group having 1 to 10 carbon atoms having a substituent”, the number of carbon atoms in R ² may exceed 10 in some cases.

Examples of the alkyl group of the “alkyl group having 1 to 10 substituents” of R ² include the same ones as those described as “unsubstituted alkyl group of 1 to 10 carbons”.

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

As a substituent of "a C1-C10 alkyl group which has a substituent", Halogen atoms, such as a chlorine atom and a bromine atom; cyano group; and the like.

Among these, as R ² , an unsubstituted C1-C10 alkyl group is preferable, an unsubstituted C1-C6 alkyl group is more preferable, and an unsubstituted C1-C3 alkyl group is still more preferable.

By using the polysilsesquioxane compound (A) in which R< ² > is an unsubstituted C1-C10 alkyl group, the molecular weight of a polysilsesquioxane compound (A) is controllable efficiently.

When the polysilsesquioxane compound (A) has a repeating unit (2), the polysilsesquioxane compound (A) may have one type of R ² or two or more types of R ² . okay

The repeating unit (1) and the repeating unit (2) are represented by the following formula (a-6).

[Formula 6]

[G represents a group represented by R ¹ or R ² . R ¹ and R ² each have the same meaning as above. O _1/2 indicates that an oxygen atom is shared with an adjacent repeating unit.]

As represented by the formula (a-6), the polysilsesquioxane compound (A) has three oxygen atoms bonded to a silicon atom generally referred to as a T site, and other groups (group represented by G) has a partial structure formed by combining one

As the T site contained in the polysilsesquioxane compound (A), the T site (T1 site) represented by the following formula (a-3), the T site (T2 site) represented by the following formula (a-4), the following formula The T site (T3 site) represented by (a-5) is mentioned.

[Formula 7]

In formulas (a-3), (a-4) and (a-5), G has the same meaning as above. R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. As "a C1-C10 alkyl group" of R< ³ >, 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 ³ s may all be the same or different. In addition, the silicon atom is couple|bonded with * in said Formula (a-3) - (a-5).

When synthesizing the polysilsesquioxane compound (A), immediately after the start of the reaction, the product contains many T1 sites and T2 sites, but the amount of these sites decreases as the reaction proceeds, and the amount of T3 sites gradually decreases increases

Therefore, a polysilsesquioxane compound having a high T1 site or T2 site content is a relatively low molecular compound, whereas a polysilsesquioxane compound having a high T3 site content is a relatively high molecular weight compound, Movement is limited.

Moreover, as shown from the number of remaining reactive groups (-OR ³ ), the polysilsesquioxane compound having a high content of T1 sites or T2 sites has a high content of T3 sites compared to those having sufficient reactivity. Polysilsesquioxane compounds tend to have poor reactivity.

The polysilsesquioxane compound (A) satisfies the above requirement 1.

That is, in the polysilsesquioxane compound (A), the amount of the repeating unit (1) is 80 to 100 mol% based on the total amount of the repeating unit (1) and the repeating unit (2).

Since the curable composition of this invention contains the polysilsesquioxane compound which satisfy|fills the requirement 1, it becomes a thing with a high refractive index.

From the viewpoint of obtaining a curable composition having a higher refractive index, the amount of the repeating unit (1) is preferably 92 to 100 mol%, and 98 to 100 mol% with respect to the total amount of the repeating unit (1) and the repeating unit (2). more preferably, 100 mol% is particularly preferable.

The polysilsesquioxane compound (A) which satisfies the requirement 1 contains little or no repeating unit (2). Therefore, it is thought that the polysilsesquioxane compound which satisfy|fills the requirement 1 hardly has the characteristic resulting from the repeating unit (2).

That is, when a curable composition contains the polysilsesquioxane compound which satisfy|fills the requirement 1, there exists a possibility that the hardened|cured material may crack or the adhesiveness of hardened|cured material may deteriorate.

As will be described later, the present invention solves these problems by satisfying the requirement 2 and using the component (C).

The ratio of the repeating unit (1) and the repeating unit (2) in a polysilsesquioxane compound (A) can be calculated|required by measuring ²⁹ Si-NMR of a polysilsesquioxane compound (A), for example.

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; It is soluble in various organic solvents, such as For this reason, ²⁹ Si-NMR in the solution state of a polysilsesquioxane compound (A) can be measured using these solvents.

The polysilsesquioxane compound (A) satisfies the requirement 2 above.

That is, in the polysilsesquioxane compound (A), the amount of the T2 site is 30 to 70 mol% with respect to the total amount of the T1 site, the T2 site, and the T3 site, and contains a relatively large amount of the T2 site.

The curable composition of this invention contains the polysilsesquioxane compound which satisfy|fills the said requirement 1, The effect resulting from the repeating unit (2) can hardly be utilized.

However, when the polysilsesquioxane compound which satisfies the requirement 1 satisfies the requirement 2, the hardened|cured material of the curable composition of this invention becomes a thing hard to generate|occur|produce a crack.

That is, when the curable composition that satisfies the above requirement 1 and contains a polysilsesquioxane compound containing a large amount of T1 sites is cured, a hydrolysis reaction or a condensation reaction occurs excessively, and due to curing shrinkage, It becomes easy to generate|occur|produce a crack in the hardened|cured material.

In addition, since the polysilsesquioxane compound that satisfies the above requirement 1 and contains a large amount of T3 sites is a relatively high molecular compound and has poor mobility, the curable composition containing such a polysilsesquioxane compound The cargo tends to generate residual stress and is prone to cracking.

On the other hand, since the curable composition containing the polysilsesquioxane compound containing many T2 sites is a thing which can be hardened|cured without raising|generating a hydrolysis reaction or a condensation reaction excessively, it is hard to generate|occur|produce a crack in the hardened|cured material.

In addition, since the polysilsesquioxane compound containing many T2 sites does not have a very high molecular weight and has moderate mobility, the hardened|cured material of the curable composition containing the polysilsesquioxane compound containing many T2 sites, Residual stress is hard to generate|occur|produce and it is hard to generate|occur|produce a crack.

Moreover, there exists a tendency for the adhesiveness of the hardened|cured material of a curable composition to improve by using the polysilsesquioxane compound containing many T2 sites.

Since the above effect is easily obtained, the amount of T2 sites relative to the total amount of T1 sites, T2 sites and T3 sites is 30 to 70 mol%, preferably 35 to 66 mol%, more preferably 40 to 62 mol%, , more preferably 45 to 58 mol%.

In addition, the amount of T1 sites relative to the total amount of T1 sites, T2 sites and T3 sites is preferably 0 to 40 mol%, more preferably 0 to 30 mol%, still more preferably 0 to 20 mol%, , more preferably 0 to 10 mol%.

When a polysilsesquioxane compound (A) contains a T1 site suitably, the curable composition excellent in sclerosis|hardenability can be obtained.

The amount of T3 sites relative to the total amount of T1 sites, T2 sites and T3 sites is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 30 to 50 mol%. .

When the polysilsesquioxane compound (A) contains the T3 site appropriately, generation of a by-product generated by a condensation reaction during curing can be suppressed.

The content rate of T1 site, T2 site, and T3 site can be calculated|required by measuring ²⁹ Si-NMR in the solution state of a polysilsesquioxane compound (A).

For example, when acetone is used as the measurement solvent and TMS (tetramethylsilane) is used as the internal standard, in formulas (a-3) to (a-6), G is at the silicon atom in the T site of the phenyl group The derived signal is observed at -65 to -58 ppm at the T1 site, -74 to -65 ppm at the T2 site, and -82 to -75 ppm at the T3 site, and formulas (a-3) to (a-6) In , the signal derived from the silicon atom in the T site of the methyl group of G is observed at -50 to -46 ppm at the T1 site, -61 to -52 ppm at the T2 site, and -70 to -61 ppm at the T3 site. .

The mass average molecular weight (Mw) of the polysilsesquioxane compound (A) is preferably 500 to 3,000, more preferably 550 to 2,650, still more preferably 600 to 2,300, still more preferably 650 to 2,000 to be. When a mass average molecular weight (Mw) uses the polysilsesquioxane compound (A) in the said range, it becomes easy to obtain the curable composition which a crack does not generate|occur|produce easily after hardening.

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, More preferably, it is 1.1-4.0. By using the polysilsesquioxane compound (A) whose molecular weight distribution (Mw/Mn) exists in the said range, it becomes easy to obtain the curable composition which provides the hardened|cured material excellent in heat resistance and 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.

The total amount of the repeating unit (1) and the repeating unit (2) in the polysilsesquioxane compound (A) is preferably from 90 to 100 mol% in all the repeating units of the polysilsesquioxane compound (A), more Preferably it is 95-100 mol%, More preferably, it is 98-100 mol%.

The refractive index (nD) at 25°C of the polysilsesquioxane compound (A) is preferably 1.500 to 1.600, more preferably 1.505 to 1.590, still more preferably 1.510 to 1.580.

When the refractive index (nD) in 25 degreeC of a polysilsesquioxane compound (A) exists in the range of 1.500-1.600, a curable composition and hardened|cured material with a high refractive index become easy to be obtained.

The refractive index (nD) of the polysilsesquioxane compound (A) can be measured using an Abbe refractometer.

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

The synthesis method of a polysilsesquioxane compound (A) is not specifically limited. For example, a polysilsesquioxane compound (A) is compoundable by polycondensing at least 1 type of the silane compound (1) represented by a following formula (a-7).

[Formula 8]

(Wherein, R ¹ has the same meaning as above. R ⁴ 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 ⁴ and a plurality of of X ¹ may be the same as or different from each other.)

Moreover, polysilsesquioxane compound by polycondensing at least 1 type of silane compound (1) represented by Formula (a-7), and at least 1 type of silane compound (2) represented by following formula (a-8) (A) can be synthesized.

[Formula 9]

(Wherein, R ² has the same meaning as above. R ⁵ represents an alkyl group having 1 to 10 carbon atoms, X ² represents a halogen atom, and q represents an integer of 0 to 3. A plurality of R ⁵ and a plurality of X ² of each may be the same as or different from each other.)

Examples of the “alkyl group having 1 to 10 carbon atoms” for R ⁴ and R ⁵ include the same ones as those shown for the “alkyl group having 1 to 10 carbon atoms” for R ³ .

Examples of the halogen atom for X ¹ and X ² include a chlorine atom and a bromine atom.

As a specific example of a silane compound (1),

unsubstituted aryltrialkoxysilane compounds such as phenyltrimethoxysilane and phenyltriethoxysilane;

unsubstituted arylhalogenoalkoxysilane compounds such as phenylchlorodimethoxysilane, phenylchlorodiethoxysilane, phenyldichloromethoxysilane and phenyldichloroethoxysilane;

unsubstituted aryltrihalogenosilane compounds such as phenyltrichlorosilane;

4-methylphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 4-methylphenyltriethoxysilane, 4-methoxyphenyltriethoxysilane, 4-chlorophenyltri aryltrialkoxysilane compounds having a substituent such as ethoxysilane;

4-Methylphenylchlorodimethoxysilane, 4-methoxyphenylchlorodimethoxysilane, 4-chlorophenylchlorodimethoxysilane, 4-methylphenyldichloromethoxysilane, 4-methoxyphenyldichloromethoxysilane, 4-chlorophenyldichloro arylhalogenoalkoxysilane compounds having a substituent such as methoxysilane;

aryltrihalogenosilane compounds having a substituent such as 4-methylphenyltrichlorosilane, 4-methoxyphenyltrichlorosilane and 4-chlorophenyltrichlorosilane; and the like.

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

As a specific example of a silane compound (2),

unsubstituted alkyltrialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltripropoxysilane;

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

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

alkyltrialkoxysilane compounds having a substituent such as 2-cyanoethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 2-cyanoethyltriethoxysilane and 3-chloropropyltriethoxysilane;

2-Cyanoethylchlorodimethoxysilane, 3-chloropropylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 3-chloropropylchlorodiethoxysilane, 2-cyanoethyldichloromethoxysilane, 3- alkylhalogenoalkoxysilane compounds having a substituent such as chloropropyldichloromethoxysilane, 2-cyanoethyldichloroethoxysilane and 3-chloropropyldichloroethoxysilane;

alkyltrihalogenosilane compounds having a substituent such as 2-cyanoethyltrichlorosilane and 3-chloropropyltrichlorosilane; and the like.

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

The method of polycondensing the said silane compound 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, and stirring at predetermined temperature is mentioned. More specifically, (a) a method of adding a predetermined amount of an acid catalyst to the silane compound and stirring at a predetermined temperature; (b) a method of adding a predetermined amount of a base catalyst to the silane compound and stirring at a predetermined temperature; ( c) a method of adding a predetermined amount of an acid catalyst to the silane compound, 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) 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 salt 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 amount of the polycondensation catalyst used is usually in the range of 0.05 to 10 mol%, preferably 0.1 to 5 mol%, based on the total mol of the silane compound.

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. 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.

The amount of the solvent to be used is 0.1 liters or more and 10 liters or less, preferably 0.1 liters or more and 2 liters or less, per mole of the total molar amount of the silane compound.

The temperature at the time of polycondensing a silane compound is the temperature range from 0 degreeC to the boiling point of the solvent used normally, Preferably it is the range of 20 degreeC - 100 degreeC. 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.

When the reaction is performed using a large amount of the compound represented by the formula (a-7), it is difficult to obtain a polymer having a large molecular weight. And even if the reaction is performed for a long time, it is difficult to increase the molecular weight while leaving the T2 site.

Moreover, in order to acquire the effect of this invention, the one where the molecular weight of a polysilsesquioxane compound (A) is not too large is preferable.

Therefore, in order to synthesize|combine a polysilsesquioxane compound (A), as mentioned above, it is preferable to add a predetermined amount of an acid catalyst to a silane compound, to stir at predetermined temperature, and to finish reaction in a comparatively short time.

By the above method, when synthesizing the polysilsesquioxane compound (A), no alcohol or the like occurs among OR ⁴ or X ¹ of the silane compound (1) or OR ⁵ or X ² of the silane compound (2). The part which does not remain|survives in a polysilsesquioxane compound (A). For this reason, in the polysilsesquioxane compound (A), the case where the repeating unit represented by said formula (a-3) and formula (a-4) other than the repeating unit represented by said formula (a-5) is contained have.

[(C) component]

The component (C) constituting the curable composition of the present invention is a silane coupling agent.

The curable composition of this invention contains the polysilsesquioxane compound which satisfy|fills the said requirement 1, The effect resulting from the repeating unit (2) can hardly be utilized.

However, since the curable composition of the present invention contains component (C) together with the polysilsesquioxane compound satisfying the requirement 1, the cured product of the curable composition of the present invention has adhesion at room temperature or high temperature. will be of excellent quality.

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 (group having an 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.

To [ content of a silane coupling agent / 100 mass parts of polysilsesquioxane compound (A) ], Preferably it is 0.1-70 mass parts, More preferably, it is 1-60 mass parts, More preferably, it is 5-55 mass parts. part, More preferably, it is 10-50 mass parts, Especially preferably, it is 15-45 mass parts.

By using the curable composition in which content of a silane coupling agent exists in the said range, the hardened|cured material more excellent in the adhesiveness at the time of normal temperature or high temperature can be formed.

As the silane coupling agent, a silane coupling agent having a nitrogen atom in the molecule or a silane coupling agent having an acid anhydride structure in the molecule is preferable, a silane coupling agent having an isocyanurate structure in the molecule, or a succinic anhydride structure in the molecule The silane coupling agent which has is more preferable.

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 10]

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 ^a 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 which has a substituent, such as a phenyl group, 4-chlorophenyl group, 4-methylphenyl group, and 1-naphthyl group, or does not have a substituent; indicates

R ^c represents an organic group having 1 to 10 carbon atoms and having a nitrogen atom. In addition, R ^c may further couple|bond with the group containing another 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), as the compound in the case where R ^c is an organic group bonded to a group containing another silicon atom, a compound with another silicon atom via an isocyanurate skeleton Examples thereof include bonding to form an isocyanurate-based silane coupling agent, and bonding to other silicon atoms via a urea skeleton to form a 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 more excellent adhesiveness, It is preferable to have 4 or more alkoxy groups couple|bonded with the silicon atom in a molecule|numerator.

To have 4 or more of the alkoxy groups couple|bonded with the silicon atom means that the total coefficient of the alkoxy group couple|bonded with the same silicon atom and the alkoxy group couple|bonded with the 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 11]

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

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 -triethoxysilylpropyl)urea (hereinafter referred to as "urea compound"), and a combination of the isocyanurate compound and the urea compound are preferably used.

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 100:65, 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 having an acid anhydride structure in a molecule is an organosilicon compound having both a group having an acid anhydride structure and a hydrolyzable group in one molecule. Specifically, a compound represented by the following formula (c-5) is exemplified.

[Formula 12]

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 A halogen 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 ^Res 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 13]

(in formula, h represents the integer of 0-10.) group 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;

halogenodimethylsilyl (C2-8) alkyl succinic anhydride, such as 2-(chlorodimethylsilyl)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 [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 It is 100:15, More preferably, it is an amount used as 100:1 - 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.

[Curable composition]

It is preferable that the total amount of (A) component and (C)component is 50-100 mass % in solid content of curable composition, and, as for the curable composition of this invention, it is more preferable that it is 70-100 mass %.

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

The curable composition of the present invention may contain, as component (B), fine particles having an average primary particle size of 5 nm or more and 40 nm or less (hereinafter referred to as “fine particles (B)”).

The curable composition containing the microparticles|fine-particles (B) is excellent in workability|operativity in an application|coating process.

Since this effect is more easily acquired, the average primary particle diameter of microparticles|fine-particles (B) becomes like this. Preferably it is 5-30 nm, More preferably, it is 5-20 nm.

The average primary particle diameter of the microparticles|fine-particles (B) is calculated|required by observing the shape of microparticles|fine-particles using a transmission electron microscope.

As a material of microparticles|fine-particles (B), 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 (B) to be used may be the thing by which the surface was modified.

The microparticles|fine-particles (B) can be used individually by 1 type or in combination of 2 or more type.

When the curable composition of the present invention contains fine particles (B) [component (B)], the content of the component (B) is not particularly limited, but the amount is determined by the mass ratio of the component (A) to the component (B) [(A) ) component: (B) component], Preferably it is 100:0.1-100:90, More preferably, 100:0.2-100:60, More preferably, 100:0.3-100:50, More preferably, 100 : 0.5-100:40, More preferably, it is an amount used as 100:0.8-100:30. (B) By using component in the said range, the effect of adding (B) component can be expressed more.

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

As another component, antioxidant, a ultraviolet absorber, a light stabilizer, etc. are mentioned.

An antioxidant is added in order to prevent oxidative deterioration at the time of 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, Usually, it is 10 mass % or less with respect to (A) component.

A ultraviolet absorber is added for the purpose of improving 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 in particular of a ultraviolet absorber is not specifically limited, It is 10 mass % or less normally with respect to (A) component.

A light stabilizer is added for the purpose of improving the light resistance of the hardened|cured material obtained.

As the light stabilizer, for example, poly[{6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(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 diluent. A diluent will not be specifically limited if it can melt|dissolve or disperse|distribute the component of the curable composition of this invention. One type may be sufficient as a diluent, and two or more types may be used together.

When the curable composition of the present invention contains a diluent, the content thereof has a solid content concentration of preferably 60 mass% or more and less than 100 mass%, more preferably 65 to 98 mass%, still more preferably 70 to The amount is 95% by mass.

The polysilsesquioxane compound (A) used for this invention has comparatively small molecular weight in many cases. In the curable composition containing such a polysilsesquioxane compound (A), even if it does not contain a diluent in large quantities (that is, even if solid content concentration is high), it has favorable applicability|paintability.

When a curable composition with a high solid content concentration is used, even if the drying conditions or curing conditions of the coating film are not strictly controlled, the cured product contains almost no solvent, so a cured product having certain characteristics can be stably formed. .

Since the curable composition of this invention contains a polysilsesquioxane compound (A), refractive index is high.

The curable composition of the present invention has a refractive index (nD) at 25°C of usually 1.500 or more, preferably 1.500 to 1.600, more preferably 1.505 to 1.590, still more preferably 1.510 to 1.580.

The refractive index (nD) of a curable composition can be measured using the method as described in an Example.

The curable composition of this invention can be prepared, for example by mixing the said (A) component and (C) component, and components other than these in predetermined ratios as needed, and defoaming.

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

2) cured product

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

Heat curing 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 the heating time is 10 minutes - 20 hours normally, Preferably it is 30 minutes - 10 hours.

The cured product of the present 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 a 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 (eg, 23 ° C., 100 ° C) for 30 seconds, and from a position 50 µm high from the adherend, in a horizontal direction ( shear direction), and the adhesive force between the test piece and the adherend is measured.

It is preferable that it is 100 N/4 mm<2> or more at 23 degreeC, and, as for the adhesive force of the hardened|cured material of this invention, it is more preferable that it is 120 N/4 mm<2> or more.

It is preferable that it is 40 N/4 mm<2> or more at 100 degreeC, and, as for the adhesive force of the hardened|cured material of this invention, it is more preferable that it is 45 N/4 mm<2> or more.

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

The cured product of the present invention has a high refractive index and excellent adhesiveness. Therefore, the hardened|cured material of this invention is used suitably as an adhesive bond layer etc. with high refractive index.

The cured product of the present invention has a refractive index (nD) at 25°C of usually 1.500 or more, preferably 1.500 to 1.600, more preferably 1.505 to 1.590, still more preferably 1.510 to 1.580.

The refractive index (nD) of hardened|cured material can be measured using an Abbe refractometer.

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, a predetermined amount of the composition is applied to the bonding surfaces of one or both of the materials to be bonded (optical device and its substrate, etc.), followed by compression. , a method in which the materials to be adhered are firmly adhered to each other by heating and curing. 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 may 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 amount 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 a sealing material 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 encapsulating an optical element, and then heat-cured to cure the optical element encapsulant. and a method of manufacturing it.

It does not specifically limit as a method of shape|molding the curable composition of this invention into a desired shape, A well-known molding method, such as a normal transfer molding method and a casting method, is 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 curable composition of this invention is used for the optical element sealing body obtained, 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 polysilsesquioxane compound were set as standard polystyrene conversion values, and were measured on the following apparatus and conditions.

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

Column: sequentially connected TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL

Solvent: tetrahydrofuran

Injection volume: 20 μl

Measuring temperature: 40℃

Flow rate: 0.6 ml/min

Detector: Differential Refractometer

( ²⁹ Si-NMR measurement)

In order to investigate the repeating unit of a polysilsesquioxane compound and its quantity, ²⁹ Si-NMR measurement was performed under the following conditions.

Apparatus: 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 rate: 20 kHz

Measurement method: Inverse gate decoupling method

²⁹ Si flip angle: 90°

²⁹ Si 90° pulse width: 8.0 μs

Repetition time: 5 s

Integration count: 9200 times

Measuring width: 30 kHz

( ²⁹ Si-NMR sample preparation method)

To shorten the relaxation time, it was measured by adding Fe(acac) ₃ as a relaxation reagent.

Polysilsesquioxane compound concentration: 15% by mass

Fe(acac) ₃ concentration: 0.6 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 by the position of a peak top, and each peak was integrated in the following range. Based on the obtained value, the ratio of the T1 site, the T2 site, and the T3 site was calculated.

T site having a phenyl group (T1: -65 to -58 ppm, T2: -74 to -65 ppm, T3: -82 to -75 ppm)

T site having a methyl group (T1: -50 to -46 ppm, T2: -61 to -52 ppm, T3: -70 to -61 ppm)

(refractive index)

The refractive index (nD) of the polysilsesquioxane compound was measured at 25 degreeC using the multi-wavelength Abbe refractometer (made by Atago Corporation, DR-M2).

(Production Example 1)

In a 300 ml eggplant-type flask, 28.91 g (145.8 mmol) of phenyltrimethoxysilane was put, and then, while stirring, 0.0376 g of 35 mass% hydrochloric acid in 7.874 g of distilled water (with respect to phenyltrimethoxysilane, 0.25 mol of HCl) %) was added, the whole was heated up at 30 degreeC for 2 hours, then at 70 degreeC, and it stirred for 5 hours.

After allowing the reaction liquid to cool to room temperature, 50 g of propyl acetate and 100 g of water were added thereto to perform a liquid separation treatment, and an organic layer containing a reaction product was obtained. Magnesium sulfate was added to this organic layer, and the drying process was performed. The polysilsesquioxane compound (A1) was obtained by concentrating the organic layer with an evaporator, then vacuum-drying the obtained concentrate after filtration separation removal of magnesium sulfate.

(Production Example 2)

In Production Example 1, hydrochloric acid was added to phenyltrimethoxysilane, and the whole was stirred at 30°C for 2 hours. Then, except not having performed the process of heating up at 70 degreeC and stirring for 5 hours, it carried out similarly to manufacture example 1, and obtained the polysilsesquioxane compound (A2).

(Production Example 3)

In a 300 ml eggplant-type flask, 28.77 g (145.1 mmol) of phenyltrimethoxysilane and 0.2675 g (1.5 mmol) of methyltriethoxysilane were put, and then, while stirring, 0.477 g of 35 mass% hydrochloric acid in 8.24 g of distilled water An aqueous solution in which (HCl is 3 mol% based on the total amount of the silane compound) was added, and the whole was heated at 30°C for 2 hours, then at 80°C, and stirred for 20 hours.

After standing to cool a reaction liquid to room temperature, the polysilsesquioxane compound (A3) was obtained by performing liquid separation, a drying process, etc. similarly to manufacture example 1.

(Production Example 4)

In a 300 ml eggplant-type flask, 28.10 g (141.7 mmol) of phenyltrimethoxysilane and 1.337 g (7.5 mmol) of methyltriethoxysilane were put, and then, while stirring, 0.466 g of 35 mass% hydrochloric acid in 8.05 g of distilled water An aqueous solution in which (Hcl is 3 mol% with respect to the total amount of the silane compound) was added, and the whole was heated at 30°C for 2 hours, then at 80°C, and stirred for 20 hours.

After standing to cool a reaction liquid to room temperature, the polysilsesquioxane compound (A3) was obtained by performing liquid separation, a drying process, etc. similarly to manufacture example 1.

(Preparation Example 5)

In a 300 ml eggplant-type flask, 13.62 g (68.7 mmol) of phenyltrimethoxysilane and 1.36 g (6.3 mmol) of methyltriethoxysilane were put, and then, while stirring, 0.02 g of 35 mass% hydrochloric acid in 4.12 g of distilled water An aqueous solution in which (HCl is 0.25 mol% relative to the total amount of the silane compound) was added, and the whole was heated at 30°C for 2 hours, then at 80°C, and stirred for 20 hours.

After standing to cool a reaction liquid to room temperature, the polysilsesquioxane compound (A5) was obtained by performing liquid separation, a drying process, etc. similarly to manufacture example 1.

(Comparative Preparation Example 1)

In a 300 ml eggplant-type flask, 14.455 g (72.9 mmol) of phenyltrimethoxysilane was put, and then, while stirring, 0.0188 g of 35 mass % hydrochloric acid in 3.937 g of distilled water (with respect to phenyltrimethoxysilane, 0.25 mol of HCl) %) was added, the whole was heated up at 30 degreeC for 2 hours, then 70 degreeC, and it stirred for 22 hours.

While stirring of the contents was continued, 15 g of propyl acetate and 0.0109 g of 28 mass% aqueous ammonia (0.25 mol% relative to phenyltriethoxysilane) were added thereto, the temperature was raised to 80°C, and the mixture was stirred for 20 hours.

After standing to cool a reaction liquid to room temperature, the polysilsesquioxane compound (A6) was obtained by performing liquid separation, a drying process, etc. similarly to manufacture example 1.

(Reference Preparation Example 1)

In a 300 ml eggplant-type flask, 9.34 g (47.1 mmol) of phenyltrimethoxysilane and 8.40 g (47.1 mmol) of methyltriethoxysilane were put, and then, while stirring, 0.025 g of 35 mass% hydrochloric acid in 5.09 g of distilled water An aqueous solution in which (HCl is 0.25 mol% relative to the total amount of the silane compound) was added, and the whole was heated at 30°C for 2 hours, then at 80°C, and stirred for 20 hours.

After standing to cool a reaction liquid to room temperature, the polysilsesquioxane compound (A7) was obtained by performing liquid separation, a drying process, etc. similarly to manufacture example 1.

(Reference Preparation Example 2)

In a 300 ml eggplant-type flask, 12.55 g (63.3 mmol) of phenyltrimethoxysilane and 4.83 g (27.1 mmol) of methyltriethoxysilane were put, and then, while stirring, 0.024 g of 35 mass% hydrochloric acid in 4.88 g of distilled water An aqueous solution in which (HCl is 0.25 mol% based on the total amount of the silane compound) was added, and the whole was heated at 30°C for 2 hours, then at 80°C, and stirred for 20 hours.

While stirring the contents, 17 g of propyl acetate and 0.149 g of 28 mass% aqueous ammonia (2.5 mol% relative to phenyltriethoxysilane) were added thereto, and the temperature was raised to 80°C and stirred for 20 hours.

After standing to cool a reaction liquid to room temperature, the polysilsesquioxane compound (A8) was obtained by performing liquid separation, a drying process, etc. similarly to manufacture example 1.

Table 1 shows the details of the obtained polysilsesquioxane compound (PSQ).

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

(Silane coupling agent)

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

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

(filler)

Silica fine particles: (manufactured by Nippon Aerosil Co., Ltd., product name “AEROSIL RX300”, average primary particle diameter: 7 nm, specific surface area: 210 m 2 /g)

(Example 1)

5 parts by mass of silica fine particles are added to 100 parts by mass of the polysilsesquioxane compound (A1), and a mixed solvent of diethylene glycol monobutyl ether acetate: tripropylene glycol-n-butyl ether = 40: 60 (mass ratio) is added was added, and the whole was stirred. 3 After dispersion treatment by this roll mill, 30 parts by mass of a silane coupling agent (C1) and 3 parts by mass of a silane coupling agent (C2) are added, and the whole is sufficiently mixed and defoamed to obtain a curable composition having a solid content concentration of 80% by mass. got it

(Example 2)

In Example 1, except that the content of the silica fine particles was changed to 20 parts by mass and the amount of the mixed solvent was further changed, in the same manner as in Example 1, a curable composition having a solid content concentration of 80% by mass was obtained.

(Example 3)

In Example 1, except that the polysilsesquioxane compound (A2) was used instead of the polysilsesquioxane compound (A1) and the mixed solvent amount was changed, it carried out similarly to Example 1, and solid content concentration was 90 A curable composition which is mass % was obtained.

(Example 4)

In Example 3, except that the content of the silica fine particles was changed to 0 parts by mass and the amount of the mixed solvent was further changed, in the same manner as in Example 3, a curable composition having a solid content concentration of 90% by mass was obtained.

(Example 5)

In Example 1, it carried out similarly to Example 1, except that the polysilsesquioxane compound (A3) was used instead of the polysilsesquioxane compound (A1), and having changed the amount of mixed solvents, and the solid content concentration was 82 A curable composition which is mass % was obtained.

(Example 6)

In Example 1, it carried out similarly to Example 1, except that the polysilsesquioxane compound (A4) was used instead of the polysilsesquioxane compound (A1), and having changed the mixing solvent amount, and the solid content concentration was 82 A curable composition which is mass % was obtained.

(Example 7)

In Example 1, except that the polysilsesquioxane compound (A5) was used instead of the polysilsesquioxane compound (A1) and the mixed solvent amount was changed, it carried out similarly to Example 1, and solid content concentration was 80 A curable composition which is mass % was obtained.

(Comparative Example 1)

Except that in Example 1, the polysilsesquioxane compound (A6) was used instead of the polysilsesquioxane compound (A1), the content of the silica fine particles was changed to 20 parts by mass, and the mixed solvent amount was changed. , A curable composition having a solid content concentration of 80% by mass was obtained in the same manner as in Example 1.

(Comparative Example 2)

In Example 5, except that the silane coupling agent (C1) and the silane coupling agent (C2) were not used, it carried out similarly to Example 5, and obtained the curable composition whose solid content concentration is 90 mass %.

(Reference Example 1)

In Example 1, except that the polysilsesquioxane compound (A7) was used instead of the polysilsesquioxane compound (A1), it was carried out similarly to Example 1, and the curable composition whose solid content concentration is 80 mass % was obtained.

(Reference Example 2)

In Example 1, the polysilsesquioxane compound (A8) was used instead of the polysilsesquioxane compound (A1), the content of the silica fine particles was changed to 20 parts by mass, and the amount of the mixed solvent was changed except that , It carried out similarly to Example 1, and obtained the curable composition whose solid content concentration is 80 mass %.

The following measurements and tests were performed using the curable compositions obtained in Examples, Comparative Examples, and Reference Examples, respectively.

[Refractive Index Measurement]

The refractive index (nD) of the curable composition was measured at 25 degreeC using the multi-wavelength Abbe refractometer (The Atago Corporation make, DR-M2).

[Evaluation of Crack Resistance]

On the mirror surface of a square glass chip having a side length of 0.5 mm, the curable compositions obtained in Examples and Comparative Examples were applied to a thickness of about 2 µm, respectively, and the coated surface was placed on an adherend (silver-plated copper plate). pressed Then, it heat-processed and hardened at 170 degreeC for 2 hours, and the to-be-adhered body with a test piece was obtained. Moreover, 20 pieces of to-be-adhered bodies with a test piece were produced with respect to 1 type of curable composition. The resin portion (fillet portion) protruding from the glass chip was observed using a scanning electron microscope (manufactured by Keyence Corporation, VE-9800S), the number of samples having cracks was counted, and the crack occurrence rate was 0% or more and 25% Less than "A", 25% or more and less than 50% were evaluated as "B", and 50% or more and 100% or less were evaluated as "C".

[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 to a thickness of about 2 µm, and the coated surface was applied to the adherend ( It was placed on a silver-plated copper plate) and was crimped. Then, it heat-processed and hardened at 170 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) heated in advance to a predetermined temperature (23° C., 100° C.), and the speed from a position 50 μm high from the adherend. Stress was applied in the horizontal direction (shear direction) with respect to the adhesive surface at 200 µm/s, and the adhesive force (N/4 mm 2 ) between the test piece and the adherend at 23°C and 100°C was measured.

Table 2 shows the measurement results and evaluation results.

The following can be seen from the said Example, a comparative example, and a reference example.

Since the curable composition of Examples 1-7 contains the polysilsesquioxane compound with a high content rate of a repeating unit (1), refractive index is high.

Similarly, since the curable composition of the comparative example 1 also contains the polysilsesquioxane compound with a high content rate of the repeating unit (1), the refractive index is high.

However, since the polysilsesquioxane compound (A6) used in Comparative Example 1 did not have a high ratio of T2 sites, the hardened|cured material of the curable composition of Comparative Example 1 was inferior in crack resistance.

Moreover, since the curable composition of Examples 1-7 contains a silane coupling agent, even if it contains a polysilsesquioxane compound with a high content rate of a repeating unit (1), the hardened|cured material has sufficient adhesive strength. have it

On the other hand, since the curable composition obtained by the comparative example 2 does not contain a silane coupling agent, the hardened|cured material does not have sufficient adhesive strength.

In addition, when the results of Reference Example 1 and Reference Example 2 are compared, it can be seen that when the ratio of the repeating unit (1) is low, the refractive index of the curable composition is lowered, but in the results of Examples 1 to 7 and Reference Example 1, According to this, it is considered that the refractive index is sufficiently high in the range of 80 to 100 mol% of the repeating unit (1) relative to the total amount of the repeating unit (1) and the repeating unit (2).

Claims (11)

The curable composition containing the following (A) component and (C) component.
(A) Component: the following formula (a-1)

[R ¹ represents an unsubstituted aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms having a substituent.]
has a repeating unit [repeating unit (1)] represented by the following formula (a-2)

[ ^R2 represents an unsubstituted C1-C10 alkyl group or a C1-C10 alkyl group having a substituent.]
A polysilsesquioxane compound having or not having a repeating unit [repeating unit (2)] represented by
[Requirement 1]
The amount of the repeating unit (1) is 80 to 100 mol% with respect to the total amount of the repeating unit (1) and the repeating unit (2).
[Requirement 2]
To the total amount of the T site (T1 site) represented by the following formula (a-3), the T site (T2 site) represented by the following formula (a-4), and the T site (T3 site) represented by the following formula (a-5) In contrast, the amount of the T2 site is 30 to 70 mol%.

[G represents a group represented by R ¹ or R ² . R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. A silicon atom is bonded to *.]
(C) Component: Silane Coupling Agent The method of claim 1,
(A) The curable composition whose mass average molecular weights (Mw) of a component are 500-3,000. 3. The method of claim 1 or 2,
A curable composition in which the total amount of the repeating unit (1) and the repeating unit (2) in component (A) is 90 to 100 mol% based on the total amount of repeating units in component (A). 4. The method according to any one of claims 1 to 3,
(C) Curable composition whose content of component is 0.1-70 mass parts with respect to 100 mass parts of (A) component. 5. The method according to any one of claims 1 to 4,
The curable composition whose total amount of (A) component and (C) component is 50-100 mass % in solid content of a curable composition. 6. The method according to any one of claims 1 to 5,
A curable composition further comprising a diluent and having a solid content concentration of 60% by mass or more and less than 100% by mass. 7. The method according to any one of claims 1 to 6,
The curable composition whose refractive index (nD) in 25 degreeC is 1.500-1.600. 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.