TW202118832A - Curable composition, cured product, and method for using curable composition - Google Patents

Abstract

The present invention pertains to: a curable composition containing component (A) and component (C); a cured product obtained by curing said curable composition; and a method for using said curable composition as an adhesive agent for optical element-fixing materials or as a sealing material for optical element-fixing materials. The curable composition according to the present invention has a high refractive index and is suitably used in the field of optics. Component (A): A polysilsesquioxane compound that has a repeating unit [repeating unit (1)] represented by formula (a-1) [R1 represents an unsubstituted aryl group having 6-12 carbon atoms or an aryl group having a substituent and having 6-12 carbon atoms] and that optionally has a repeating unit [repeating unit (2)] represented by formula (a-2) [R2 represents an unsubstituted alkyl group having 1-10 carbon atoms and an alkyl group having a substituent and having 1-10 carbon atoms]. The polysilsesquioxane compound is characterized by satisfying a specific requirement regarding the molecular structure. Component (C): A silane coupling agent. (a-1): R1SiO3/2 (a-2): R2SiO3/2.

Description

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

The present invention relates to a curable composition having a high refractive index and suitable for the optical field, a cured product obtained by curing the above-mentioned curable composition; and the use of the above-mentioned curable composition as an adhesive or optical element fixing material. The method of using sealing material for component fixing material.

Conventional curable compositions have been modified in various ways according to their applications, and are widely used industrially as raw materials for optical parts and molded articles, adhesives, coating agents, and the like. Furthermore, the curable composition is attracting attention for use as an optical element fixing material composition such as an adhesive for an optical element fixing material and a sealing material for an optical element fixing material.

Optical components include various lasers such as semiconductor lasers (LD), light-emitting components such as light-emitting diodes (LED), light-receiving components, composite optical components, and optical integrated circuits. In recent years, blue light and white light light elements with shorter peak wavelengths have been developed, and they have been widely used. The high brightness of such light-emitting elements with a shorter light-emitting peak wavelength has been greatly improved, and with this phenomenon, the heat generation of the light-emitting elements tends to become greater.

However, with the increase in brightness of optical elements in recent years, the cured product of the composition for fixing optical elements will be exposed to higher energy light for a long time, and the higher temperature heat generated by the optical element will cause a problem of decreased adhesion. .

In order to solve this problem, Patent Documents 1 to 3 propose a composition for an optical element fixing material containing a polysilsesquioxane compound as a main component.

However, when a curable composition is used to fix an optical element or the like, in order to improve the light extraction efficiency, a curable composition with an appropriate refractive index is selected according to the refractive index of the surrounding members. For example, in order to suppress reflection at the interface between the sealant and the fixing material, and to improve the light extraction efficiency, it is preferable that the difference between the refractive index of the sealant and the fixing material be small. Therefore, when a sealant with a higher refractive index is used, it is necessary to use a curable composition that also has a high refractive index to form the fixing material. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-359933 [Patent Document 2] Japanese Patent Laid-Open No. 2005-263869 [Patent Document 3] Japanese Patent Laid-Open No. 2006-328231

[The problem to be solved by the invention]

The present invention was completed in view of the above-mentioned conventional technical facts, and its object is to provide: a curable composition having a high refractive index and suitable for use in the optical field, a cured product obtained by curing the above-mentioned curable composition, and the above-mentioned curable composition A method of using the composition as an adhesive for an optical element fixing material or a sealing material for an optical element fixing material. [Means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive studies on curable compositions containing polysilsesquioxane compounds. turn out: (i) As a polysilsesquioxane compound, a polysilsesquioxane compound containing more aryl groups can be used to obtain a curable composition with a high refractive index; (ii) For hardenable compositions containing polysilsesquioxane compounds with more aryl groups, the hardened material may crack; (iii) Curable compositions containing polysilsesquioxane compounds with more aryl groups have a tendency to have poor adhesion in the cured product; (iv) The problems (ii) and (iii) above can be solved by introducing a specific molecular structure into a polysilsesquioxane compound containing polyaryl groups and adding a silane coupling agent to the curable composition , Then completed the present invention.

Therefore, according to the present invention, the following methods of using the curable composition of [1]~[7], the cured product of [8], [9], and the curable composition of [10], [11] will be provided .

[1] A curable composition containing the following components (A) and (C): (A) Component: Having a repeating unit represented by the following formula (a-1) [Repeat unit (1)]

[R ¹ represents an unsubstituted aryl group with 6 to 12 carbons or a substituted aryl group with 6 to 12 carbons]; and has or does not have the repeating unit represented by the following formula (a-2) [ Repeating unit (2)]

[R ² represents an unsubstituted alkyl group with 1 to 10 carbons or a substituted alkyl group with 1 to 10 carbons] polysilsesquioxane compound that satisfies the following requirements 1 and 2 Polysilsesquioxane compound [Requirement 1] The amount of the repeating unit (1) is 80-100 mol% based on the total amount of the repeating unit (1) and the repeating unit (2). [Requirement 2] Relative to the T site (T1 site) shown in the following formula (a-3), the T site (T2 site) shown in the following formula (a-4), and the following formula (a-5) The total amount of T sites (T3 sites) shown, the amount of the above T2 sites is 30-70 mol%.

[G system represents the group ^{represented by R 1} or R ^2. R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. *The silicon atom is bonded. ] (C) Ingredient: Silane coupling agent. [2] The curable composition as described in [1], wherein the mass average molecular weight (Mw) of the component (A) is 500 to 3,000. [3] The curable composition as described in [1] or [2], wherein the total amount of the repeating unit (1) and the repeating unit (2) in the component (A) accounts for the total repeating unit of the component (A) 90~100mol% of it. [4] The curable composition according to any one of [1] to [3], wherein the content of the (C) component is 0.1 to 70 parts by mass relative to 100 parts by mass of the (A) component. [5] The curable composition as described in any one of [1] to [4], wherein the total amount of (A) component and (C) component accounts for 50 to 100 of the solid content of the curable composition quality%. [6] The curable composition according to any one of [1] to [5], which further contains a diluent, and the solid content concentration is 60% by mass or more and less than 100% by 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 described in any one of [1] to [7] above. [9] The cured product described in [8] is an optical element fixing material. [10] A method of using the curable composition described in any one of [1] to [7] as an adhesive for an optical element fixing material. [11] A method of using the curable composition described in any one of [1] to [7] as a sealing material for an optical element fixing material. [Compared with the effect of previous technology]

According to the present invention, it is possible to provide: a curable composition having a high refractive index and suitable for the optical field, a cured product cured from the above-mentioned curable composition, and the use of the above-mentioned curable composition as an adhesive for optical element fixing materials The method of sealing material for fixing material of optical element or optical element.

Hereinafter, the method of using the present invention according to: 1) the curable composition, 2) the curable product, and 3) the curable composition will be described in detail.

1) Hardening composition The curable composition of the present invention contains the following (A) component and (C) component. (A) Component: a polysilsesquioxane compound having a repeating unit represented by the above formula (a-1) and having (or not having) a repeating unit represented by the above formula (a-2), characterized by satisfying the above requirements The polysilsesquioxane compound of 1 and Requirement 2 [hereinafter referred to as "polysilsesquioxane compound (A)"]. (C)Component: Silane coupling agent

[(A) Ingredient] The 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), characterized by satisfying the above-mentioned requirement 1 and requirement 2 polysilsesquioxane compound.

[R ¹ represents an unsubstituted aryl group with 6 to 12 carbons or a substituted aryl group with 6 to 12 carbons. ]

Because the repeating unit (1) has R ¹ , the polysilsesquioxane compound having the repeating unit (1) has a higher refractive index. Therefore, the curable composition of the present invention has a higher refractive index.

Examples of the "unsubstituted aryl group having 6 to 12 carbons" for R ^{1 include phenyl, 1-naphthyl, and 2-naphthyl.} The carbon number of the "unsubstituted aryl group having 6 to 12 carbons" for R ^{1 is preferably 6.}

The "substituted aryl group having 6 to 12 carbons" for R ^{1 preferably has 6 carbon atoms.} In addition, this carbon number means the carbon number of the part except a substituent (aryl part). Therefore, when R ¹ is a "substituted aryl group with 6 to 12 carbons", the carbon number of ^{R 1 may exceed 12.} For ^{the "substituted aryl group having 6 to 12 carbons" for R 1} , the aryl group may be the same as that exemplified for the "unsubstituted 6 to 12 carbon aryl group".

The number of substituent atoms (except for the number of hydrogen atoms) of the "substituted aryl group having 6 to 12 carbon atoms" for ^{R 1 is usually 1 to 30, preferably 1 to 20.} For ^{the "substituted aryl group with 6 to 12 carbons" for R 1} , the substituents include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and isobutyl Alkyl group, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl and other alkyl groups; halogen atoms such as chlorine and bromine atoms; alkoxy groups such as methoxy and ethoxy groups, etc. .

Among them, from the viewpoint of efficiently preparing a high refractive index curable composition, R ^{1 is} preferably an unsubstituted aryl group having 6 to 12 carbon atoms, more preferably a phenyl group.

The polysilsesquioxane compound (A) may have one type of R ¹ (monomer), or may have two or more types of R ¹ (copolymer). When the polysilsesquioxane compound (A) is a copolymer, the polysilsesquioxane compound (A) can be a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer, etc. Any one of them is preferably a random copolymer from the viewpoint of ease of manufacture and the like. Furthermore, the structure of the polysilsesquioxane compound (A) can be any of a ladder-like structure, a double-layer structure, a cage-type structure, a partially-cracked cage-type structure, a ring-type structure, and a random structure. One structure.

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

[R ² represents an unsubstituted alkyl group with 1 to 10 carbons, or a substituted alkyl group with 1 to 10 carbons. ]

Generally, the polysilsesquioxane compound has a repeating unit (2), which can be high molecular weight, and can improve the flexibility of the molecular chain. Therefore, since the curable composition contains the polysilsesquioxane compound having the repeating unit (2), it is judged that the cured product is less likely to crack. However, as described later, the present invention uses a polysilsesquioxane compound with a low content of the repeating unit (2), and it is predicted that this effect caused by the repeating unit (2) can hardly be utilized.

The "unsubstituted alkyl group with 1 to 10 carbons" for R ² preferably has 1 to 6 carbon atoms, more preferably 1 to 3. The "unsubstituted alkyl group with 1 to 10 carbons" for R ² includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tertiary Butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, etc.

The "substituted alkyl group having 1 to 10 carbons" for R ² preferably has 1 to 6 carbon atoms, more preferably 1 to 3. In addition, the carbon number refers to the carbon number of the substituent excluding the outer part (alkyl part). Therefore, when R ² is an "substituted alkyl group with 1 to 10 carbons", the carbon number of ^{R 2 may exceed 10.} Examples of the "substituted alkyl group having 1 to 10 carbon atoms" for R ² include the same ones as those exemplified in the "unsubstituted alkyl group having 1 to 10 carbon atoms".

In the "substituted alkyl group having 1 to 10 carbon atoms", the number of substituent atoms (except for the number of hydrogen atoms) is usually 1 to 30, preferably 1 to 20. The "substituted alkyl group having 1 to 10 carbon atoms" includes, for example, halogen atoms such as a chlorine atom and a bromine atom; and a cyano group.

Among them, R ^{2 is} preferably an unsubstituted alkyl group with 1 to 10 carbons, more preferably an unsubstituted alkyl group with 1 to 6 carbons, and particularly preferably an unsubstituted alkyl group with 1 to 3 carbons. base. The molecular weight of the polysilsesquioxane compound (A) can be controlled efficiently by using the polysilsesquioxane compound (A) having an unsubstituted C1-C10 alkyl group for R ^2.

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 .

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

[G system represents the group ^{represented by R 1} or R ^2. R ¹ and R ² respectively represent the same as above. O _1/2 system means that it shares oxygen atoms with adjacent repeating units]

As shown in formula (a-6), the polysilsesquioxane compound (A) has three oxygen atoms bonded to the silicon atom generally referred to as "T site", and the other group (shown by G) The radical) is a partial structure formed by bonding one oxygen atom. Examples of the T site system contained in the polysilsesquioxane compound (A) include: T site (T1 site) represented by the following formula (a-3), T site represented by the following formula (a-4) Point (T2 site), T site (T3 site) shown in the following formula (a-5).

In formulas (a-3), (a-4) and (a-5), the G series has the same meaning as above. R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the "alkyl group with 1 to 10 carbons" for R ³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tertiary butyl, etc. . The plural R ³ may be completely the same or different from each other. In addition, in the above formulas (a-3) to (a-5), * is a silicon atom bonded.

When the polysilsesquioxane compound (A) is synthesized, the product contains more T1 sites and T2 sites immediately after the reaction starts, but as the reaction progresses, the amount of these sites also follows Decrease, and gradually increase the amount of T3 sites. Therefore, polysilsesquioxane compounds with a higher proportion of T1 or T2 sites belong to lower molecular compounds. In contrast, polysilsesquioxane compounds with a higher proportion of T3 sites belong to For higher molecular compounds, the movement of the molecular chain is restricted. Furthermore, based on the ^{number of remaining reactive groups (-OR 3} ), polysilsesquioxane compounds with a higher proportion of T1 site or T2 site have sufficient reactivity. In contrast, T3 site contains Polysilsesquioxane compounds with higher proportions tend to have poor reactivity.

The polysilsesquioxane compound (A) satisfies the above-mentioned requirement 1. That is, in the polysilsesquioxane compound (A), 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). The curable composition of the present invention contains a polysilsesquioxane compound that satisfies Requirement 1, and therefore has a high refractive index. From the viewpoint of obtaining a curable composition with a higher refractive index, the amount of the repeating unit (1) is preferably 92 to 100 mol%, and more preferably 98 to the total amount of the repeating unit (1) and the repeating unit (2). 100mol%, especially good system 100mol%.

The polysilsesquioxane compound (A) that satisfies the requirement 1 contains almost (or completely) no repeating unit (2). Therefore, it can be considered that the polysilsesquioxane compound that satisfies the requirement 1 has almost no characteristics due to the repeating unit (2). That is, since the curable composition contains the polysilsesquioxane compound that satisfies Requirement 1, there is a possibility that the cured product may crack or the adhesiveness of the cured product may be poor. As described later, the present invention can solve these problems by satisfying requirement 2 and using component (C).

The ratio of the repeating unit (1) to the repeating unit (2) in the polysilsesquioxane compound (A) can be obtained by measuring ^{29 Si-NMR of the polysilsesquioxane compound (A), for example.} The polysilsesquioxane compound (A) is soluble in, for example, ketone solvents such as acetone; aromatic hydrocarbon solvents such as benzene; sulfur-containing solvents such as dimethyl sulfoxide; ether solvents such as tetrahydrofuran; ethyl acetate, etc. Ester solvents; halogen-containing solvents such as chloroform; and various organic solvents such as mixed solvents composed of two or more of these. ^{Therefore, by using these solvents, 29} Si-NMR in which the polysilsesquioxane compound (A) is in a solution state can be measured.

The polysilsesquioxane compound (A) satisfies the above-mentioned requirement 2. That is, in the polysilsesquioxane compound (A), the amount of the above-mentioned T2 site is 30 to 70 mol% with respect to the total amount of the T1 site, T2 site, and T3 site, and contains many T2 sites. The curable composition of the present invention contains a polysilsesquioxane compound that satisfies the above-mentioned requirement 1, and the effect due to the repeating unit (2) is hardly utilized. However, the polysilsesquioxane compound that satisfies the requirement 1 meets the requirement 2, so that the cured product of the curable composition of the present invention is less likely to crack.

That is, a curable composition containing a polysilsesquioxane compound that satisfies the above-mentioned requirements 1 and contains a large number of T1 sites will undergo excessive hydrolysis and condensation reactions during curing, which will cause curing due to curing shrinkage. Cracks easily occur in the material. Furthermore, the polysilsesquioxane compound that satisfies the above requirements 1, and contains more T3 sites, is a higher molecular compound and has poor mobility, so it contains a curable combination of such polysilsesquioxane compounds Hardened objects are prone to residual stress and cracks.

On the other hand, a curable composition with a polysilsesquioxane compound containing more T2 sites can be hardened without excessive hydrolysis and condensation reactions, so cracks are unlikely to occur in the hardened material. Furthermore, because the molecular weight of the polysilsesquioxane compound containing more T2 sites is not too high and has moderate mobility, it has a curable combination of polysilsesquioxane compounds containing more T2 sites The hardened material is not prone to residual stress and cracks. In addition, by using a polysilsesquioxane compound containing more T2 sites, there is a tendency to improve the adhesiveness of the cured product of the curable composition.

From the viewpoint of easily obtaining the above effects, the amount of T2 site is 30~70mol%, preferably 35~66mol%, more preferably 40~62mol relative to the total amount of T1 site, T2 site and T3 site. %, especially good line 45~58mol%.

Furthermore, relative to the total amount of T1 site, T2 site and T3 site, the amount of T1 site is preferably 0-40 mol%, more preferably 0-30 mol%, particularly preferably 0-20 mol%, most preferably It is 0~10mol%. When the polysilsesquioxane compound (A) contains the T1 site appropriately, a curable composition with more excellent curability can be obtained. Furthermore, relative to the total amount of T1 site, T2 site and T3 site, the amount of T3 site is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, particularly preferably 30 to 50 mol%. When the polysilsesquioxane compound (A) contains the T3 site moderately, the formation of by-products due to the condensation reaction during curing can be suppressed.

The content ratio of T1 site, T2 site and T3 site can be obtained ^{by 29 Si-NMR measuring the polysilsesquioxane compound (A) in a solution state.} For example, when the measurement solvent is acetone and the internal standard is TMS (tetramethylsilane), in formulas (a-3)~(a-6), G is the signal derived from the silicon atom in the T site of the phenyl group , T1 site is observed at -65~-58ppm, T2 site is observed at -74~-65ppm, T3 site is observed at -82~-75ppm; in formula (a-3)~(a -6), G is the signal derived from the silicon atom in the T site of the methyl group, the T1 site is observed at -50~-46ppm, the T2 site is observed at -61~-52ppm, and the T3 site It is observed at -70~-61ppm.

The mass average molecular weight (Mw) of the polysilsesquioxane compound (A) is preferably 500 to 3,000, more preferably 550 to 2,650, particularly preferably 600 to 2,300, and most preferably 650 to 2,000. By using the polysilsesquioxane compound (A) having a mass average molecular weight (Mw) in the above range, a curable composition that is less likely to crack after curing can be easily obtained.

The molecular weight distribution (Mw/Mn) of the polysilsesquioxane compound (A) is not particularly limited, and is usually 1.0 to 10.0, preferably 1.1 to 6.0, and more preferably 1.1 to 4.0. By using the polysilsesquioxane compound (A) having a molecular weight distribution (Mw/Mn) within the above range, a curable composition that can provide a cured product with more excellent heat resistance and adhesion can be easily obtained. The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using a gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent to obtain a standard polystyrene conversion value.

The total amount of repeating unit (1) and repeating unit (2) in the polysilsesquioxane compound (A) accounts for 90-100 mol% of the total repeating unit of the polysilsesquioxane compound (A), More preferably 95~100mol%, especially good 98~100mol%.

The 25°C refractive index (nD) of the polysilsesquioxane compound (A) is preferably 1.500 to 1.600, more preferably 1.505 to 1.590, particularly preferably 1.510 to 1.580. When the 25°C refractive index (nD) of the polysilsesquioxane compound (A) is in the range of 1.500 to 1.600, a curable composition and cured product with a high refractive index can be easily obtained. The refractive index (nD) of the polysilsesquioxane compound (A) can be measured using an Abbe refractometer.

In the present invention, the polysilsesquioxane compound (A) can be used singly or in combination of two or more.

The synthesis method of the polysilsesquioxane compound (A) is not particularly limited. For example, by subjecting at least one of the silane compounds (1) represented by the following formula (a-7) to polycondensation, the polysilsesquioxane compound (A) can be synthesized.

(In the formula, R ¹ represents the same meaning as above. R ⁴ represents an alkyl group with 1 to 10 carbon atoms; X ¹ represents a halogen atom, and p represents an integer from 0 to 3. The plural R ⁴ and the plural X ¹ represent They may be the same or different from each other.)

Furthermore, by polycondensing at least one of the silane compounds (1) represented by the formula (a-7) and at least one of the silane compounds (2) represented by the following formula (a-8), the poly The silsesquioxane compound (A).

(In the formula, R ² represents the same meaning as above. R ⁵ represents an alkyl group with 1 to 10 carbon atoms; X ² represents a halogen atom; q represents an integer from 0 to 3. The plural R ⁵ and the plural X ² represent They may be the same or different from each other.)

The "alkyl group with 1 to 10 carbons" for R ⁴ and R ⁵ may be the same as that shown for the "alkyl group with 1 to 10 carbons" ^{for R 3, for example.} Examples of the halogen atom system of X ¹ and X ² include a chlorine atom and a bromine atom.

Specific examples of the silane compound (1) include: Unsubstituted aryltrialkoxysilane compounds such as phenyltrimethoxysilane and phenyltriethoxysilane; Unsubstituted aryl haloalkoxysilane compounds such as phenylchlorodimethoxysilane, phenylchlorodiethoxysilane, phenyldichloromethoxysilane, phenyldichloroethoxysilane, etc.; Unsubstituted aryl trihalosilane compounds such as phenyltrichlorosilane; 4-methylphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 4-methylphenyltriethoxysilane, 4-methoxy Phenyltriethoxysilane, 4-chlorophenyltriethoxysilane and other substituted aryltrialkoxysilane compounds; 4-methylphenylchlorodimethoxysilane, 4-methoxyphenylchlorodimethoxysilane, 4-chlorophenylchlorodimethoxysilane, 4-methylphenyldichloromethoxysilane Silane, 4-methoxyphenyldichloromethoxysilane, 4-chlorophenyldichloromethoxysilane and other substituted aryl haloalkoxysilane compounds; 4-methylphenyltrichlorosilane, 4-methoxyphenyltrichlorosilane, 4-chlorophenyltrichlorosilane and other substituted aryl trihalosilane compounds, etc. These silane compounds (1) can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the silane compound (2) include: Unsubstituted alkyl trialkoxy silane compounds such as methyl trimethoxy silane, methyl triethoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, ethyl tripropoxy silane, etc. ； Methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethyl Unsubstituted alkyl halide alkoxysilane compounds such as oxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane, etc.; Unsubstituted alkyl trihalosilane compounds such as methyl trichlorosilane, methyl tribromosilane, ethyl trichlorosilane, ethyl tribromosilane, etc.; Alkyl trianes with substituents such as 2-cyanoethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 3-chloropropyltriethoxysilane, etc. Oxysilane compounds; 2-cyanoethylchlorodimethoxysilane, 3-chloropropylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 3-chloropropylchlorodiethoxysilane, 2- Cyanoethyldichloromethoxysilane, 3-chloropropyldichloromethoxysilane, 2-cyanoethyldichloroethoxysilane, 3-chloropropyldichloroethoxysilane, etc. with substituents Alkyl halide alkoxy silane compounds; Alkyl trihalosilane compounds with substituents such as 2-cyanoethyltrichlorosilane and 3-chloropropyltrichlorosilane. These silane compounds (2) can be used individually by 1 type or in combination of 2 or more types.

The method of polycondensing the above-mentioned silane compound is not particularly limited. For example, in a solvent (or without a solvent), a predetermined amount of polycondensation catalyst is added to the silane compound, and then stirred at a predetermined temperature. More specifically, for example: (a) Add a predetermined amount of acid catalyst to the silane compound, and then perform agitation at a predetermined temperature; (b) Add a predetermined amount of alkali catalyst to the silane compound, and then follow the established method The method of stirring at temperature; (c) Add a predetermined amount of acid catalyst to the silane compound, after stirring at a predetermined temperature, add an excess amount of alkali catalyst to make the reaction system alkaline, and then perform stirring at the predetermined temperature Method and so on. Among them, the method (a) is preferred from the viewpoint that the target polysilsesquioxane compound (A) can be obtained efficiently.

The polycondensation catalyst used may be either an acid catalyst or an alkali catalyst. In addition, two or more polycondensation catalysts may be used in combination, but it is preferable to use at least an acid catalyst. Examples of the acid catalyst system 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, it is preferable to select at least one from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid.

Examples of alkali catalyst systems include: ammonia; trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, pyridine, 1,8-diazabicyclo[5.4.0] -7-Myrcene, aniline, picoline, 1,4-diazabicyclo[2.2.2]octane, imidazole and other organic bases; tetramethylammonium hydroxide, tetraethylammonium hydroxide and other organic hydroxides; Metal alkoxides such as sodium oxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-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 bicarbonates such as sodium bicarbonate and potassium bicarbonate, etc.

Relative to the total mol of the silane compound, the usage amount of the polycondensation catalyst is usually in the range of 0.05-10 mol%, preferably 0.1-5 mol%.

When a solvent is used during polycondensation, the solvent used can be appropriately selected according to the type of silane compound, etc. For example: water; aromatic hydrocarbons such as benzene, toluene, xylene; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone and other ketones; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, tertiary butanol and other alcohols. These solvent systems can be used individually by 1 type or in combination of 2 or more types.

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

The temperature at the time of polycondensation of the silane compound is usually the temperature range from 0°C to the boiling point of the solvent used, and preferably the range from 20°C to 100°C. If the reaction temperature is too low, there will be insufficient progress of the polycondensation reaction. On the other hand, if the reaction temperature is too high, it is more difficult to suppress gelation. The reaction is usually completed in 30 minutes to 30 hours.

When a large amount of the compound represented by formula (a-7) is used for the reaction, it is not easy to obtain a polymer with a larger molecular weight. However, even if it reacts for a long time, it is difficult to increase the molecular weight when the T2 site remains. Furthermore, in order to obtain the effects of the present invention, the molecular weight of the polysilsesquioxane compound (A) is preferably not too large. Therefore, in order to synthesize the polysilsesquioxane compound (A), as described above, it is better to add a predetermined amount of acid catalyst to the silane compound, then stir at a predetermined temperature, and complete the reaction in a short time.

When the polysilsesquioxane compound (A) is synthesized by the above method, the OR ⁴ or X ¹ of the silane compound (1) and the OR ⁵ or X ² of the silane compound (2) will not cause dealcoholization. It remains in the polysilsesquioxane compound (A). Therefore, in the polysilsesquioxane compound (A), in addition to the repeating unit represented by the above formula (a-5), it also contains the repeating unit represented by the above formula (a-3) and formula (a-4) unit.

[(C) Ingredient] The (C) component constituting the curable composition of the present invention is a silane coupling agent. The curable composition of the present invention contains a polysilsesquioxane compound that satisfies the above-mentioned requirement 1, and the effect due to the repeating unit (2) is hardly utilized. However, since the curable composition of the present invention contains the polysilsesquioxane compound that satisfies Requirement 1, and the component (C), the cured product of the curable composition of the present invention has the same adhesiveness at room temperature and high temperature. Excellent.

The "silane coupling agent" refers to a silane compound having a silicon atom, a functional group, and a hydrolyzable group bonded to the silicon atom. The so-called "functional group" refers to groups that are reactive with other compounds (mainly organic), such as amino groups, substituted amino groups, isocyanate groups, urea groups, groups with trimeric isocyanate skeletons, and other groups with nitrogen atoms; acid anhydrides Group (with acid anhydride structure group); vinyl group; allyl group; epoxy group; (meth) propenyl group; mercapto group, etc. In the present invention, the silane coupling agent system may be used singly or in combination of two or more kinds.

The content of the silane coupling agent, relative to 100 parts by mass of the polysilsesquioxane compound (A), is preferably 0.1 to 70 parts by mass, more preferably 1 to 60 parts by mass, particularly preferably 5 to 55 parts by mass, The best system is 10-50 parts by mass, and the best system is 15-45 parts by mass. By using a curable composition having a silane coupling agent content of silicon within the above-mentioned range, a cured product having better adhesiveness at room temperature and high temperature can be formed.

The silane coupling agent is preferably a silane coupling agent having a nitrogen atom in the molecule, a silane coupling agent having an acid anhydride structure in the molecule, more preferably a silane coupling agent having a triisocyanate structure in the molecule, and a silane coupling agent having a succinic anhydride structure in the molecule. mixture.

Silane coupling agents having nitrogen atoms in the molecule include, for example, trialkoxysilane compounds represented by the following formula (c-1), dialkoxyalkylsilane compounds represented by formula (c-2) or dioxanes Oxyaryl silane compounds, etc.

In the above formulas, R ^a represents a line methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy and the like carbons, alkoxy of 1 to 6. Plural R ^a may be the same line with each other, it may also be mutually different. R ^b represents a C1-C6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, etc.; or phenyl, 4-chlorophenyl, 4-methyl Substituent (or unsubstituted) aryl groups such as phenyl and 1-naphthyl.

R ^c represents an organic group having 1 to 10 carbon atoms with a nitrogen atom. In addition, R ^c may be further bonded to other silicon-containing groups. Specific examples of the organic group with 1 to 10 carbon atoms in R ^c include: N-2-(aminoethyl)-3-aminopropyl, 3-aminopropyl, N-(1,3-dimethyl) -Butylene)aminopropyl, 3-ureapropyl, N-phenyl-aminopropyl and the like.

In the compound represented by the above formula (c-1) or (c-2), when R ^c is bonded to another organic group containing a silicon atom group, the compound system may, for example, be bonded to other groups via a trimeric isocyanate skeleton. Silicon atoms constitute a trimeric isocyanate-based silane coupling agent, and other silicon atoms are bonded via a urea skeleton to constitute a urea-based silane coupling agent.

Among them, the silane coupling agent with nitrogen atom in the molecule, from the viewpoint of easily obtaining a cured product with more excellent adhesion, is preferably a triisocyanate-based silane coupling agent and a urea-based silane coupling agent, and more preferably is a silane coupling agent In the molecule, there are more than 4 alkoxy groups bonded to the silicon atom. The so-called "the number of alkoxy groups bonded to a silicon atom reaches 4 or more" means that only alkoxy groups are bonded to the same silicon atom, and the total number of alkoxy groups bonded to different silicon atoms is 4 or more.

A trimeric isocyanate-based silane coupling agent having an alkoxy group of 4 or more bonded to the silicon atom can be exemplified by the compound represented by the following formula (c-3). The urea-based silane coupling agent with 4 or more alkoxy groups bonded to the silicon atom can be exemplified by the compound represented by the following formula (c-4).

Wherein, R ^a represents a system as defined above. t1~t5 each represent an independent integer of 1-10, preferably an integer of 1-6, more preferably 3.

Among them, the silane coupling agent having a nitrogen atom in the molecule is preferably used, for example: 1,3,5-N-(3-trimethoxysilylpropyl) trimeric isocyanate, 1,3,5- N-ginseng (3-triethoxysilylpropyl) trimeric isocyanate (hereinafter referred to as ``trimeric isocyanate compound''), N,N'-bis(3-trimethoxysilylpropyl)urea, N, N'-bis(3-triethoxysilylpropyl)urea (hereinafter referred to as "urea compound"), and a combination of the above-mentioned trimeric isocyanate compound and urea compound.

When the curable composition of the present invention contains a silane coupling agent with a nitrogen atom in the molecule, the content is not particularly limited, and the amount depends on the mass of the above component (A) and the silane coupling agent with a nitrogen atom in the molecule Compared with [(A) component: silane coupling agent with nitrogen atom in the molecule], preferably 100:0.1~100:65, more preferably 100:0.3~100:60, especially preferred 100:1~100: 50. The best system is 100: 3~100: 40, and the best system is 100: 5~100:35. In this ratio, the curable composition containing the component (A) and the silane coupling agent having nitrogen atoms in the molecule will have more excellent heat resistance and adhesiveness of the cured product.

The silane coupling agent having an acid anhydride structure in the molecule is an organosilicon compound having both an acid anhydride structure group and a hydrolyzable group in one molecule. Specific systems can be exemplified by the compound represented by the following formula (c-5):

Formula, Q represents a system configuration having an acid anhydride group; R ^d are diagrams alkyl group having 1 to 6 carbon atoms, the group or a phenyl substituted (or unsubstituted with substituents); R ^e represents a system having 1 to 6 carbon atoms, alkoxy of Oxy group or halogen atom; i and k represent integers from 1 to 3, j represents integers from 0 to 2, i+j+k=4. When j is 2, R ^d may be the same or different from each other. When k is 2 or 3, plural R ^e may be the same line with each other, may also be mutually different. When i is 2 or 3, the plural Qs may be the same or different from each other. The Q system can be exemplified by the following formula:

(In the formula, h represents an integer from 0 to 10), etc., more preferably the base shown in (Q1).

Examples of silane coupling agents with acid anhydride structure in the molecule include: 2-(Trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, 3-(trimethoxysilyl)propyl succinic anhydride, 3-(triethoxy) Silyl group) propyl succinic anhydride and other tris (carbon number 1~6) alkoxysilyl group (carbon number 2~8) alkyl succinic anhydride; 2-(Dimethoxysilyl)ethyl succinic anhydride and other two (carbon number 1~6) alkoxysilyl (carbon number 2~8) alkyl succinic anhydride; 2-(Methoxydisilyl)ethyl succinic anhydride, etc. (carbon number 1~6) alkoxy disilyl(carbon number 2~8) alkyl succinic anhydride;

2-(Trichlorosilyl) ethyl succinic anhydride, 2-(tribromosilyl) ethyl succinic anhydride and other trihalosilyl (carbon number 2~8) alkyl succinic anhydride; Dihalosilyl (carbon number 2~8) alkyl succinic anhydride such as 2-(dichlorosilyl) ethyl succinic anhydride; 2-(Chlorodisilyl) ethyl succinic anhydride and other halogen disilyl groups (carbon number 2-8) alkyl succinic anhydride, etc.

Among them, the silane coupling agent having an acid anhydride structure in the molecule is preferably tris (carbon number 1~6) alkoxysilyl (carbon number 2~8) alkyl succinic anhydride, particularly preferably 3-(trimethoxy) Silyl)propyl succinic anhydride or 3-(triethoxysilyl)propyl succinic anhydride.

When the curable composition of the present invention is a silane coupling agent having an acid anhydride structure in the molecule, the content is not particularly limited, and is based on the mass ratio of the above component (A) to the silane coupling agent having an acid anhydride structure in the molecule [( A) Ingredients: silane coupling agent with acid anhydride structure in the molecule], the amount is preferably 100:0.1~100:30, more preferably 100:0.3~100:20, especially preferred 100:0.5~100:15 , The best system is 100:1~100:10. With this ratio, the curable composition containing the component (A) and the silane coupling agent having an acid anhydride structure in the molecule will have more excellent adhesion of the cured product.

[Curable composition] The curable composition of the present invention is the total amount of the (A) component and the (C) component, which accounts for 50 to 100% by mass, more preferably 70 to 100% by mass in the solid content of the curable composition. In the present invention, the "solid content" refers to components other than the solvent in the curable composition.

The curable composition of the present invention may contain fine particles (hereinafter referred to as "fine particles (B)") having an average primary particle diameter of 5 nm or more and 40 nm or less of the component (B). The curable composition containing fine particles (B) is excellent in workability in the coating step. From the viewpoint of easily obtaining this effect, the average primary particle size of the fine particles (B) is preferably 5 to 30 nm, more preferably 5 to 20 nm.

The average primary particle size of the fine particles (B) can be obtained by observing the shape of the fine particles using a transmission electron microscope.

The material system of the fine particles (B) includes, for example, metals; metal oxides; minerals; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; metal hydroxides such as aluminum hydroxide; silicic acid Metal silicates such as aluminum, calcium silicate, and magnesium silicate; inorganic components such as silicon dioxide; silicones; organic components such as acrylic polymers. Furthermore, the microparticles (B) used can also be surface-modified.

The fine particle (B) system can be used individually by 1 type or in combination of 2 or more types. When the curable composition of the present invention contains fine particles (B) [(B) component], the content of (B) component is not particularly limited, and is based on the mass ratio of the above-mentioned (A) component to (B) component [(A) component: (B) component], the amount is preferably 100:0.1~100:90, more preferably 100:0.2~100:60, especially best 100:0.3~100:50, the best System 100: 0.5~100:40, the best system 100: 0.8~100:30. By using the component (B) within the above range, the effect of weighting the component (B) can be more apparent.

The curable composition of the present invention may contain other components within a range that does not impair the purpose of the present invention. Examples of such other component systems include antioxidants, ultraviolet absorbers, and light stabilizers.

Antioxidants are added to prevent oxidative degradation during heating. Examples of antioxidants include phosphorus-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

Examples of phosphorus-based antioxidants include phosphites, oxaphosphaphenanthrene oxides, and the like. Examples of phenolic antioxidants include monophenols, bisphenols, and polymer phenols. Examples of sulfur-based antioxidants include: 3,3'-thiodipropionate dilauryl ester, 3,3'-thiodipropionate dimyristate, 3,3'-thiodipropionate distearate Fatty esters and so on.

These antioxidants can be used individually by 1 type or in combination of 2 or more types. The antioxidant content is not particularly limited, but is usually 10% by mass or less with respect to the (A) component.

The ultraviolet absorber is added for the purpose of improving the light resistance of the cured product obtained. Examples of ultraviolet absorbers include salicylic acids, diphenylketones, benzotriazoles, hindered amines, and the like. The ultraviolet absorber system can be used individually by 1 type or in combination of 2 or more types. The content of the ultraviolet absorber is not particularly limited, but is usually 10% by mass or less with respect to the (A) component.

The light stabilizer is added for the purpose of improving the light resistance of the obtained cured product. Examples of light stabilizers include: poly[{6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-tri-2,4-diyl}{( 2,2,6,6-Tetramethyl-4-piperidine)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidine)imino}] etc. Hindered amines, etc. These light stabilizers can be used individually by 1 type or in combination of 2 or more types. The content of the light stabilizer is usually 20% by mass or less with respect to the component (A).

The curable composition of the present invention may also contain a diluent. The diluent can dissolve (or disperse) the components of the curable composition of the present invention, and the rest is not particularly limited. One type of diluent system may be used, or two or more types may be used in combination.

When the curable composition of the present invention contains a diluent, the solid content concentration is preferably 60% by mass or more and less than 100% by mass, more preferably 65 to 98% by mass, and particularly preferably 70 to 95% by mass. % Of the amount. Most of the polysilsesquioxane compounds (A) used in the present invention have relatively low molecular weights. The curable composition containing such a polysilsesquioxane compound (A) has good coating properties even if it does not contain a large amount of diluent (that is, even if the solid content concentration is high). When a curable composition with a high solid content concentration is used, even if the drying conditions and curing conditions of the coating film are not strictly controlled, the cured product contains almost no solvent, so it can be stably formed into a cured product with certain characteristics.

Since the curable composition of the present invention contains the polysilsesquioxane compound (A), it has a high refractive index. The 25°C refractive index (nD) of the curable composition of the present invention is usually above 1.500, preferably 1.500 to 1.600, more preferably 1.505 to 1.590, particularly preferably 1.510 to 1.580. The refractive index (nD) of the curable composition can be measured using the method described in the examples.

The curable composition of the present invention can be prepared by mixing the above-mentioned (A) component and (C) component, and other components as necessary, in a predetermined ratio, and defoaming. The mixing method and the defoaming method are not particularly limited, and a known method can be used.

2) Hardened object The cured product of the present invention is obtained by curing the curable composition of the present invention. The method of curing the curable composition of the present invention can be, for example, heat curing. The heating temperature during curing is usually 100 to 200°C, and the heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

The cured product of the present invention is excellent in heat resistance and adhesiveness. The fact that the cured product of the present invention has these characteristics can be confirmed as follows, for example. That is, a predetermined amount of the curable composition of the present invention is coated on the mirror surface of the silicon wafer, the coated surface is placed on the adherend, and the coating surface is pressure-bonded and subjected to heat treatment to harden it. Place it on the measurement platform of the welding tester that has been preheated to a predetermined temperature (for example, 23°C, 100°C) for 30 seconds, from a position of 50μm from the adherend to the horizontal direction (shearing Direction) apply stress, and measure the adhesion between the test piece and the adherend.

The adhesive force of the cured product of the present invention is preferably 100 N/4 mm ² or more, more preferably 120 N/4 mm ² or more at 23°C. The adhesive force of the cured product of the present invention is preferably 40N/4mm ² or more, more preferably 45N/4mm ² or more at 100°C. In this manual, the so-called "4mm ² "means "2mm square", that is, 2mm×2mm (a square with a side length of 2mm).

The cured product of the present invention has a high refractive index and excellent adhesiveness. Therefore, the cured product of the present invention is preferably used as an adhesive layer with a high refractive index. The 25°C refractive index (nD) of the cured product of the present invention is usually 1.500 or higher, preferably 1.500-1.600, more preferably 1.505-1.590, particularly preferably 1.510-1.580. The refractive index (nD) of the cured product can be measured using an Abbe refractometer.

Because of the above characteristics, the cured product of the present invention is preferably used 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 system include light-emitting elements such as LEDs and LDs, as well as light-receiving elements, composite optical elements, and optical integrated circuits.

＜Adhesives for optical element fixing materials＞ The curable composition of the present invention is preferably used as an adhesive for optical element fixing materials. The method of using the curable composition of the present invention as an adhesive for an optical element fixing material can be, for example, by coating the combination on the adhesive surface of one (or both) of the material to be adhered (optical element and its substrate, etc.) After the object is crimped, it is heated and hardened to make the material to be adhered firmly adhere to each other. The coating amount of the curable composition of the present invention is not particularly limited, as long as the amount is used to harden the materials to be adhered firmly to each other. Usually, the thickness of the coating film of the curable composition is 0.5 to 5 μm, preferably 1 to 3 μm.

Substrate materials for adhering optical components can include, for example: soda-lime glass, heat-resistant hard glass and other glasses; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium and these metal alloys; Stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.) and other metals; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, poly Styrene, polycarbonate, polymethylpentene, polyether, polyetheretherketone, polyetherether, polyphenylene sulfide, polyetherimide, polyimide, polyamide, acrylic resin, camphor Synthetic resins such as olefin resin, cycloolefin resin, glass epoxy resin, etc.

The heating temperature during heat curing varies depending on the curable composition used, etc., and is usually 100 to 200°C. The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

＜Sealing material for optical element fixing material＞ The curable composition of the present invention is quite suitable as a sealing material for optical element fixing materials. The method of using the curable composition of the present invention as a sealing material for an optical element fixing material can be, for example, by forming the composition into a desired shape to obtain a molded body containing an optical element, and then heating it Hardening, and a method of manufacturing an optical element sealing body, etc. The method for molding the curable composition of the present invention into a desired shape is not particularly limited, and well-known molding methods such as a general transfer molding method and an injection molding method can be used.

The heating temperature during heat curing varies depending on the curable composition used, etc., and is usually 100 to 200°C. The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

Since the obtained optical element sealing body 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 with examples. However, the present invention is not limited to the following examples.

(Determination of average molecular weight) The mass average molecular weight (Mw) and number average molecular weight (Mn) of polysilsesquioxane compounds are standard polystyrene conversion values and are measured in accordance with the following equipment and conditions. Device name: HLC-8220GPC, manufactured by Tosoh Corporation Column: connected by TSKgelGMHXL, TSKgelGMHXL, and TSKge12000HXL in sequence Solvent: Tetrahydrofuran Injection volume: 20μl Measuring temperature: 40℃ Flow rate: 0.6ml/min Detector: Differential refractometer

( ²⁹ Si-NMR measurement) In order to investigate the repeating unit and amount of polysilsesquioxane compounds, ²⁹ Si-NMR measurement was performed under the following conditions. ^{Apparatus: AV-500 29} Si-NMR manufactured by Bruker BioSpin Co., Ltd. Resonance frequency: 99.352MHz Probe: 5mmΦ solution probe Measuring temperature: Room temperature (25°C) Sample revolution: 20kHz Measuring method: Anti-gating decoupling method ²⁹ Si Deflection angle: 90° ²⁹ Si 90° Pulse width: 8.0μs Repetition time: 5s Integration times: 9200 times Observation width: 30kHz

( ²⁹ Si-NMR sample preparation method) In order to shorten the relaxation time, Fe(acac) _{3 of} relaxation reagent was added for measurement. Polysilsesquioxane compound concentration: 15% by mass Fe(acac) ₃ concentration: 0.6% by mass Measurement solvent: Acetone Internal standard: TMS

(Waveform processing analysis) For each peak of the mass spectrum after Fourier transformation, the chemical shift is calculated from the position of the peak top, and the integration of each peak is performed in the following range. Calculate the ratio of T1 site, T2 site, and T3 site from the obtained value. T site with phenyl (T1: -65~-58ppm, T2: -74~-65ppm, T3: -82~-75ppm) T site with methyl group (T1: -50~-46ppm, T2: -61~-52ppm, T3: -70~-61ppm)

(Refractive index) Using a multi-wavelength Abbe refractometer (manufactured by ATAGO Co., Ltd., DR-M2), the refractive index (nD) of the polysilsesquioxane compound was measured at 25°C.

(Manufacturing example 1) Put 28.91g (145.8mmol) of phenyltrimethoxysilane in a 300ml eggplant-shaped flask, and while stirring, add 0.0376g of 35% by mass hydrochloric acid dissolved in 7.874g of distilled water (relative to phenyltrimethoxysilane) , HCl is 0.25 mol%) aqueous solution, the whole is stirred at 30°C for 2 hours, and the adhesive is heated to 70°C and stirred for 5 hours. After the reaction liquid was left to cool to room temperature, 50 g of propyl acetate and 100 g of water were added thereto, and liquid separation treatment was performed to obtain an organic layer containing a reaction product. Magnesium sulfate was added to the organic layer to perform drying treatment. After the magnesium sulfate was removed by filtration, the organic layer was concentrated by an evaporator, and the obtained concentrate was adhered and vacuum dried to obtain a polysilsesquioxane compound (A1).

(Manufacturing Example 2) Except in Production Example 1, hydrochloric acid was added to phenyltrimethoxysilane, and the whole was stirred at 30°C for 2 hours. Then, the polysilsesquioxane compound (A2) was obtained in the same manner as in Production Example 1, except that the step of raising the temperature to 70° C. and stirring for 5 hours was not performed.

(Manufacturing Example 3) Put 28.77g (145.1mmol) of phenyltrimethoxysilane and 0.2675g (1.5mmol) of methyltriethoxysilane in a 300ml eggplant-shaped flask, while stirring, add 35 masses dissolved in 8.24g of distilled water % Hydrochloric acid 0.477 g (with respect to the total amount of silane compounds, HCl is 3 mol%) aqueous solution, the whole was stirred at 30°C for 2 hours, the adhesion was heated to 80°C and stirred for 20 hours. After the reaction liquid was left to cool to room temperature, liquid separation, drying treatment, etc. were performed in the same manner as in Production Example 1, to obtain a polysilsesquioxane compound (A3).

(Manufacturing Example 4) Put 28.10g (141.7mmol) of phenyltrimethoxysilane and 1.337g (7.5mmol) of methyltriethoxysilane in a 300ml eggplant-shaped flask. While stirring, add 35 masses dissolved in 8.05g of distilled water % Hydrochloric acid 0.466 g (with respect to the total amount of the silane compound, HCl is 3 mol%) aqueous solution, the whole was stirred at 30°C for 2 hours, and the adhesion was heated to 80°C and stirred for 20 hours. After the reaction liquid was left to cool to room temperature, liquid separation, drying treatment, etc. were performed in the same manner as in Production Example 1, to obtain a polysilsesquioxane compound (A4).

(Manufacturing Example 5) Put 13.62g (68.7mmol) of phenyltrimethoxysilane and 1.36g (6.3mmol) of methyltriethoxysilane in a 300ml eggplant-shaped flask. While stirring, add 35 masses dissolved in 4.12g of distilled water % Hydrochloric acid 0.02 g (with respect to the total amount of the silane compound, HCl is 0.25 mol%) aqueous solution, the whole was stirred at 30°C for 2 hours, and the adhesion was heated to 80°C and stirred for 20 hours. After the reaction liquid was left to cool to room temperature, liquid separation, drying treatment, etc. were performed in the same manner as in Production Example 1, to obtain a polysilsesquioxane compound (A5).

(Comparative Manufacturing Example 1) After putting 14.455g (72.9mmol) of phenyltrimethoxysilane in a 300ml eggplant-shaped flask, while stirring, add 0.0188g of 35% by mass hydrochloric acid dissolved in 3.937g of distilled water (relative to phenyltrimethoxysilane, HCl (0.25 mol%) aqueous solution, the whole was stirred at 30°C for 2 hours, and the adhesive was heated to 70°C and stirred for 22 hours. While continuing to stir the contents, 15 g of propyl acetate and 0.0109 g of 28% by mass ammonia water (0.25 mol% with respect to phenyltriethoxysilane) were added thereto, and the mixture was heated to 80° C. and stirred for 20 hours. After the reaction liquid was left to cool to room temperature, liquid separation, drying treatment, etc. were performed in the same manner as in Production Example 1, to obtain a polysilsesquioxane compound (A6).

(Refer to Manufacturing Example 1) A 300ml eggplant-shaped flask was charged with 9.34g (47.1mmol) of phenyltrimethoxysilane and 8.40g (47.1mmol) of methyltriethoxysilane and added, while stirring, 35 masses dissolved in 5.09g of distilled water were added. % Hydrochloric acid 0.025g (with respect to the total amount of silane compounds, HCl is 0.25 mol%) aqueous solution, the whole is stirred at 30°C for 2 hours, the adhesion is heated to 80°C and stirred for 20 hours. After the reaction liquid was left to cool to room temperature, liquid separation, drying treatment, etc. were performed in the same manner as in Production Example 1, to obtain a polysilsesquioxane compound (A7).

(Refer to Manufacturing Example 2) Put 12.55g (63.3mmol) of phenyltrimethoxysilane and 4.83g (27.1mmol) of methyltriethoxysilane in a 300ml eggplant-shaped flask. While stirring, add 35 masses dissolved in 4.88g of distilled water An aqueous solution of 0.024 g of% hydrochloric acid (with respect to the total amount of silane compounds, HCl is 0.25 mol%), the whole was stirred at 30°C for 2 hours, and the adhesion was heated to 80°C and stirred for 20 hours. While continuously stirring the contents, 17 g of propyl acetate and 0.149 g of 28% by mass ammonia water (2.5 mol% with respect to phenyltriethoxysilane) were added thereto, and the mixture was heated to 80° C. and stirred for 20 hours. After the reaction liquid was left to cool to room temperature, liquid separation, drying treatment, etc. were performed in the same manner as in Production Example 1, to obtain a polysilsesquioxane compound (A8).

The details of the obtained polysilsesquioxane compound (PSQ) are shown in Table 1.

[Table 1] Table 1 Repeating unit (1) (mol%) Repeating unit (2) (mol%) Mass average molecular weight (Mw) Molecular weight distribution (Mw/Mn) Refractive index (nD) Proportion of T sites (mol%) T1 T2 T3 Manufacturing example 1 PSQ(A1) 100 0 1100 1.2 1.566 5 53 42 Manufacturing example 2 PSQ(A2) 100 0 750 1.3 1.543 16 53 31 Manufacturing example 3 PSQ(A3) 99 1 1700 1.3 1.563 0 36 64 Manufacturing example 4 PSQ(A4) 95 5 1700 1.4 1.561 0 33 67 Manufacturing example 5 PSQ(A5) 90 10 1300 1.3 1.555 0 38 62 Comparative Manufacturing Example 1 PSQ(A6) 100 0 1700 1.3 1.566 4 27 69 Reference manufacturing example 1 PSQ(A7) 50 50 2800 1.9 1.513 0 31 69 Reference manufacturing example 2 PSQ(A8) 70 30 2400 1.5 1.539 0 28 72

The compounds used in the Examples, Comparative Examples and Reference Examples are as follows:

(Silane coupling agent) Silane coupling agent (C1): 1,3,5-N-[3-(trimethoxysilyl)propyl] isocyanate Silane coupling agent (C2): 3-(trimethoxysilyl)propyl succinic anhydride

(Filling agent) Silica particles: (manufactured by Nippon Silica Co., Ltd., product name "AEROSIL RX300", average primary particle size: 7nm, specific surface area: 210m ² /g)

(Example 1) To 100 parts by mass of polysilsesquioxane compound (A1), 5 parts by mass of silica fine particles are added, and diethylene glycol monobutyl ether acetate: tripropylene glycol n-butyl ether = 40: 60 (mass ratio ) The mixed solvents are stirred as a whole. After dispersing by a three-roll mill, 30 parts by mass of silane coupling agent (C1) and 3 parts by mass of silane coupling agent (C2) are added, and the whole is thoroughly mixed and defoamed to obtain a curable composition with a solid content of 80% by mass .

(Example 2) In Example 1, except that the content of the silica particles was changed to 20 parts by mass and the amount of the mixed solvent was changed, the same procedure as in Example 1 was followed to obtain a curable composition with a solid concentration of 80% by mass. .

(Example 3) Except that in Example 1, instead of the polysilsesquioxane compound (A1), the polysilsesquioxane compound (A2) was used instead, and the amount of mixed solvent was changed, the rest were the same as in Example 1. A curable composition with a solid content concentration of 90% by mass was obtained.

(Example 4) Except that in Example 3, the content of silica fine particles was changed to 0 parts by mass, and the amount of mixed solvent was changed, the rest was the same as in Example 3 to obtain a curable composition with a solid content concentration of 90% by mass. .

(Example 5) Except that in Example 1, instead of polysilsesquioxane compound (A1), polysilsesquioxane compound (A3) was used instead, and the amount of mixed solvent was changed, the rest were the same as in Example 1. A curable composition having a solid content concentration of 82% by mass was obtained.

(Example 6) Except that in Example 1, instead of the polysilsesquioxane compound (A1), the polysilsesquioxane compound (A4) was used instead, and the amount of the mixed solvent was changed, the rest were the same as in Example 1. A curable composition having a solid content concentration of 82% by mass was obtained.

(Example 7) Except that in Example 1, instead of polysilsesquioxane compound (A1), polysilsesquioxane compound (A5) was used instead, and the amount of mixed solvent was changed, the rest were the same as in Example 1. A curable composition with a solid content concentration of 80% by mass was obtained.

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

(Comparative example 2) Except that in Example 5, the silane coupling agent (C1) and the silane coupling agent (C2) were not used, in the same manner as in Example 5, a curable composition with a solid content concentration of 90% by mass was obtained.

(Reference example 1) Except that in Example 1, instead of the polysilsesquioxane compound (A1), the polysilsesquioxane compound (A7) was used instead, and the rest were the same as in Example 1 to obtain a solid content concentration of 80 mass. % Hardening composition.

(Reference example 2) Except that in Example 1, instead of polysilsesquioxane compound (A1), polysilsesquioxane compound (A8) was used instead, and the content of silica fine particles was changed to 20 parts by mass. Except for the amount of the mixed solvent, in the same manner as in Example 1, a curable composition having a solid content concentration of 80% by mass was obtained.

Using the curable compositions obtained in Examples, Comparative Examples, and Reference Examples, the following measurements and tests were performed, respectively. [Measurement of refractive index] Using a multi-wavelength Abbe refractometer (manufactured by ATAGO Co., Ltd., DR-M2), the refractive index (nD) of the curable composition was measured at 25°C.

[Crack resistance evaluation] On the mirror surface of a square glass wafer with a side length of 0.5 mm, the curable compositions obtained in the examples and comparative examples were applied to a thickness of about 2 μm, respectively, and the coated surface was placed on the adherend (silver-plated copper plate ) And perform crimping. Then, heat treatment was performed at 170°C for 2 hours to harden, and an adherend with a test piece was obtained. In addition, 20 adherends with test pieces were produced for one curable composition. Using a scanning electron microscope (KEYENCE Corporation, VE-9800S), observe the resin part (corner fill part) oozing from the glass wafer, and count the number of samples with cracks. The crack generation rate is 0% or more and less than 25 % Is rated as "A", 25% or more and less than 50% is rated as "B", and 50% or more and 100% or less is rated as "C".

^{[Adhesion strength evaluation] On the mirror surface of a square (area 4mm 2} ) silicon wafer with a side length of 2 mm, the curable compositions obtained in the examples and comparative examples were applied to a thickness of approximately 2 μm, and the coated surface Place it on the adherend (silver-plated copper plate) and perform crimping. Then, heat treatment was performed at 170°C for 2 hours to harden, and an adherend with a test piece was obtained. Place the adherend with the test piece on the measurement platform of a welding tester (manufactured by Dage Corporation, series 4000) preheated to a predetermined temperature (23°C, 100°C) for 30 seconds. At the 50μm height of the object, apply stress to the adhesive surface in the horizontal direction (shear direction) at a speed of 200μm/s, and measure the adhesion between the test piece and the adherend (N/4mm ² ) at 23°C and 100°C.

The measurement results and evaluation results are shown in Table 2.

[Table 2] Table 2 Composition of hardening composition (parts by mass) Solid content (mass%) Refractive index (nD) Evaluation of crack resistance Adhesion strength (N/4mm ² ) PSQ Silane coupling agent Silica particles (C1) (C2) 23℃ 100°C Example 1 PSQ(A1)100 30 3 5 80 1.512 A 157.6 87.7 Example 2 PSQ(A1)100 30 3 20 80 1.510 A 120.2 67.6 Example 3 PSQ(A2)100 30 3 5 90 1.513 A 193.0 99.2 Example 4 PSQ(A2)100 30 3 0 90 1.512 A 150.7 109.7 Example 5 PSQ(A3)100 30 3 5 82 1.515 A 126.9 46.4 Example 6 PSQ(A4)100 30 3 5 82 1.514 A 135.4 51.8 Example 7 PSQ(A5)100 30 3 5 80 1.508 A 136.9 57.5 Comparative example 1 PSQ(A6)100 30 3 20 80 1.507 C 116.0 59.3 Comparative example 2 PSQ(A3)100 0 0 5 78 1.532 A 26.8 9.5 Reference example 1 PSQ(A7)100 30 3 5 80 1.488 A 129.7 51.4 Reference example 2 PSQ(A8)100 30 3 20 80 1.495 A 149.1 83.4

The following can be understood from the above-mentioned Examples, Comparative Examples, and Reference Examples. The curable composition of Examples 1 to 7 has a higher refractive index because it has a polysilsesquioxane compound with a higher content of repeating unit (1). Similarly, the curable composition of Comparative Example 1 also has a higher refractive index because it has a polysilsesquioxane compound with a higher content of repeating unit (1). However, since the polysilsesquioxane compound (A6) used in Comparative Example 1 has a low ratio of T2 sites, the cured product of the curable composition of Comparative Example 1 exhibits poor crack resistance. Furthermore, the curable compositions of Examples 1 to 7 contain a silane coupling agent, so even if they have a polysilsesquioxane compound with a high content of repeating unit (1), the cured product still has sufficient adhesive strength . On the other hand, since the curable composition obtained in Comparative Example 2 did not contain a silane coupling agent, the cured product did not have sufficient adhesive strength. In addition, comparing the results of Reference Example 1 and Reference Example 2, it is found that if the proportion of the repeating unit (1) is low, the refractive index of the curable composition will decrease. However, according to Examples 1 to 7, and Reference Example 1 As a result, if the amount of the repeating unit (1) is in the range of 80-100 mol% with respect to the total amount of the repeating unit (1) and the repeating unit (2), it is judged that it will have a sufficiently high refractive index.

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Claims (11)

A curable composition containing the following (A) component and (C) component: (A) component: having a repeating unit represented by the following formula (a-1) [repeating unit (1)]; and having or A polysilsesquioxane compound that does not have the repeating unit [repeating unit (2)] represented by the following formula (a-2),

[R ¹ represents an unsubstituted aryl group with 6 to 12 carbons, or a substituted aryl group with 6 to 12 carbons]

[R ² represents an unsubstituted alkyl group with 1 to 10 carbons, or a substituted alkyl group with 1 to 10 carbons] and a polysilsesquioxane compound that satisfies the following requirements 1 and 2; [Requirement 1] Relative to the total amount of the repeating unit (1) and the repeating unit (2), the amount of the repeating unit (1) is 80-100 mol%; [Requirement 2] Relative to the T site shown in the following formula (a-3) (T1 site), the total amount of the T site (T2 site) shown in the following formula (a-4), and the T site (T3 site) shown in the following formula (a-5), the above T2 site The amount is 30~70mol%;

[G represents a ^{group represented by R 1} or R ² , R ³ represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, * is a silicon atom bonded], (C) component: silane coupling agent. The curable composition according to claim 1, wherein the mass average molecular weight (Mw) of the component (A) is 500 to 3,000. The curable composition according to claim 1, wherein the total amount of the repeating unit (1) and the repeating unit (2) in the component (A) accounts for 90-100 mol% of the total repeating unit of the component (A). The curable composition according to claim 1, wherein the content of the component (C) is 0.1 to 70 parts by mass relative to 100 parts by mass of the component (A). The curable composition according to claim 1, wherein the total amount of the component (A) and the component (C) accounts for 50 to 100% by mass in the solid content of the curable composition. The curable composition according to claim 1, which further contains a diluent, and the solid content concentration is 60% by mass or more and less than 100% by mass. The curable composition according to claim 1, wherein the refractive index (nD) at 25°C is 1.500 to 1.600. A hardened product obtained by hardening the hardenable composition according to any one of claims 1 to 7. The cured product described in claim 8 is an optical element fixing material. A method is to use the curable composition described in any one of claims 1 to 7 as an adhesive for optical element fixing materials. A method is to use the curable composition described in any one of claims 1 to 7 as a sealing material for an optical element fixing material.