JP6830565B1 - Curable composition, cured product, and how to use the curable composition - Google Patents

Abstract

The present invention adheres a curable composition containing the following components (A) and (B), a cured product obtained by curing the curable composition, and the curable composition to an optical device fixing material. It is a method used as an agent or a sealing material for an optical element fixing material. The curable composition of the present invention is excellent in curability. Component (A): Curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1) [R1 has an unsubstituted alkyl group having 1 to 10 carbon atoms and a substituent (having an epoxy ring). Alkyl groups having 1 to 10 carbon atoms having (excluding groups), aryl groups having 6 to 12 carbon atoms unsubstituted, and aryl groups having 6 to 12 carbon atoms having substituents (excluding groups having an epoxy ring). At least one selected from the group consisting of. (B) Component: A specific silicone oligomer having a repeating unit derived from a trifunctional silane compound.

Description

In the present invention, a curable composition having excellent curability, a cured product obtained by curing the curable composition, and the curable composition are sealed with an adhesive for an optical element fixing material or a sealing material for an optical element fixing material. Regarding the method of using it as a material.

Conventionally, curable compositions have been variously improved according to their uses, and have been widely used industrially as raw materials for optical parts and molded products, adhesives, coating agents, and the like.
Further, the curable composition has also attracted attention as a composition for an optical element fixing material such as an adhesive for an optical element fixing material and a sealing material for an optical element fixing material.

Optical elements include various lasers such as semiconductor lasers (LDs), light emitting elements such as light emitting diodes (LEDs), light receiving elements, composite optical elements, optical integrated circuits, and the like.
In recent years, optical elements of blue light and white light having a shorter peak wavelength of light emission have been developed and widely used. The brightness of such a light emitting element having a short peak wavelength of light emission is dramatically increased, and the amount of heat generated by the optical element tends to be further increased accordingly.

However, with the increase in brightness of optical devices in recent years, the cured product of the composition for fixing the optical element is exposed to higher energy light or higher temperature heat generated from the optical element for a long time, and the adhesive strength is reduced. There was a problem of doing.

In order to solve this problem, Patent Documents 1 to 3 propose compositions for optical device fixing materials containing a polysilsesquioxane compound as a main component.

By the way, when an optical element or the like is fixed using a curable composition, a curable composition that can be cured in a shorter time is required in order to shorten the working time and prevent contamination. It was.

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

The present invention has been made in view of the above-mentioned actual conditions of the prior art, and a curable composition having excellent curability, a cured product obtained by curing the curable composition, and the curable composition. It is an object of the present invention to provide a method for use as an adhesive for an optical element fixing material or a sealing material for an optical element fixing material.

In order to solve the above problems, the present inventors have made extensive studies on a curable composition containing a curable polysilsesquioxane compound.
As a result, they have found that a curable composition containing a curable polysilsesquioxane compound and a specific silicone oligomer having an epoxy ring has excellent curability, and have completed the present invention.
In the present invention, "excellent in curability" means the property that the curable composition is cured in a short time.

Thus, according to the present invention, the following methods of using the curable compositions [1] to [7], the cured products [8] and [9], and the curable compositions [10] and [11] are provided. Will be done.

[1] A curable composition containing the following component (A) and component (B).
Component (A): Curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1)

[R ¹ is an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a substituent (excluding a group having an epoxy ring), and an unsubstituted aryl group having 6 to 12 carbon atoms. , And at least one selected from the group consisting of an aryl group having 6 to 12 carbon atoms having a substituent (excluding a group having an epoxy ring). ]
Component (B): A silicone oligomer having or not having a repeating unit derived from a trifunctional silane compound and having or not having a repeating unit derived from a tetrafunctional silane compound, which is a repeating unit derived from a trifunctional silane compound and tetrafunctional. The total amount of the repeating units derived from the silane compound is 80 mol% or more in all the repeating units, and at least one of the trifunctional silane compounds is a trifunctional silane compound having a group having an epoxy ring. Silicone oligomer [2] The curable composition according to [1], wherein the mass average molecular weight (Mw) of the component (A) is 800 to 30,000.
[3] The curable composition according to [1] or [2], wherein the mass average molecular weight (Mw) of the component (B) is 500 to 5,000.
[4] The curable composition according to any one of [1] to [3], wherein the epoxy equivalent of the component (B) is 50 to 2,000 g / eq.
[5] The curable composition according to any one of [1] to [4], wherein the content of the component (B) is 0.1 to 100 parts by mass with respect to 100 parts by mass of the component (A). ..
[6] The curable composition according to any one of [1] to [5], wherein the total amount of the component (A) and the component (B) is 30 to 100% by mass in the solid content of the curable composition. ..
[7] The curable composition according to any one of [1] to [6], which further contains the following component (C).
Component (C): Silane coupling agent [8] A cured product obtained by curing the curable composition according to any one of the above [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] above 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] above is used as a sealing material for an optical element fixing material.

According to the present invention, a curable composition having excellent curability, a cured product obtained by curing the curable composition, and the curable composition can be used as an adhesive for a light element fixing material or a light element fixing material. A method of use as a sealing material is provided.

Hereinafter, the present invention will be described in detail by dividing 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 components (A) and (B).
Component (A): Curable polysilsesquioxane compound having a repeating unit represented by the above formula (a-1) Component (B): A tetrafunctional silane compound having a repeating unit derived from a trifunctional silane compound. A silicone oligomer having or not having a repeating unit derived from the above, wherein the total amount of the repeating unit derived from the trifunctional silane compound and the repeating unit derived from the tetrafunctional silane compound is 80 mol% or more in all the repeating units, and the above 3 Silicone oligomer in which at least one of the functional silane compounds is a trifunctional silane compound having a group having an epoxy ring In the present invention, the "curable polysilsesquioxane compound" satisfies a predetermined condition such as heating. It refers to a polysilsesquioxane compound that changes into a cured product by itself, or a polysilsesquioxane compound that functions as a curable component in a curable composition.

[(A) component]
The component (A) constituting the curable composition of the present invention is a curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1) (hereinafter, "polysilsesquioxane compound (A)". ) ”.).

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

The number of carbon atoms of the "unsubstituted alkyl group having 1 to 10 carbon atoms" represented by R ^1, 1 to 6 preferably 1 to 3 is more preferable.
Examples of the "unsubstituted alkyl group having 1 to 10 carbon atoms" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group and an n-. Examples thereof include a pentyl group, an n-hexyl group, an n-octyl group, an n-nonyl group and an n-decyl group.

R carbon number of ¹ represented by "optionally substituted alkyl group having 1 to 10 carbon atoms having a (excluding a group having an epoxy ring)" is 1 to 6 preferably 1 to 3 is more preferable. It should be noted that this carbon number means the carbon number of the portion excluding the substituent (the portion of the alkyl group). Therefore, when R ¹ is an "alkyl group having 1 to 10 carbon atoms having a substituent (excluding a group having an epoxy ring)", the carbon number of R ¹ may exceed 10.
The alkyl group of the "alkyl group having 1 to 10 carbon atoms having a substituent (excluding the group having an epoxy ring)" is the same as that shown as the "unsubstituted alkyl group having 1 to 10 carbon atoms". Can be mentioned.

The number of atoms (excluding the number of hydrogen atoms) of the substituent of the "alkyl group having 1 to 10 carbon atoms having a substituent (excluding the group having an epoxy ring)" is usually 1 to 30, preferably 1 to 20. Is.
The substituent of the "alkyl group having 1 to 10 carbon atoms having a substituent (excluding the group having an epoxy ring)" is a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a cyano group; a formula: represented by OG. Groups to be; etc.
Here, G represents a hydroxyl-protecting group. The hydroxyl-protecting group is not particularly limited, and examples thereof include known protecting groups known as hydroxyl-protecting groups. For example, acyl-based protecting groups; silyl-based protecting groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group; methoxymethyl group, methoxyethoxymethyl group, 1-ethoxyethyl group. Acetal-based protecting groups such as tetrahydropyran-2-yl group and tetrahydrofuran-2-yl group; alkoxycarbonyl-based protecting groups such as t-butoxycarbonyl group; methyl group, ethyl group, t-butyl group, octyl group , Allyl group, triphenylmethyl group, benzyl group, p-methoxybenzyl group, fluorenyl group, trityl group, benzhydryl group and other ether-based protecting groups; and the like.

The number of carbon atoms of the "unsubstituted aryl group having 6 to 12 carbon atoms" represented by R ¹ 6 is preferred.
Examples of the "unsubstituted aryl group having 6 to 12 carbon atoms" include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.

Carbon number of represented by R ¹ "substituted aryl group having 6 to 12 carbon atoms having a (excluding a group having an epoxy ring)" 6 are preferred. It should be noted that this carbon number means the carbon number of the portion excluding the substituent (the portion of the aryl group). Therefore, when R ¹ is an "aryl group having 6 to 12 carbon atoms having a substituent (excluding a group having an epoxy ring)", the carbon number of R ¹ may exceed 12.
The aryl group of the "aryl group having 6 to 12 carbon atoms having a substituent (excluding the group having an epoxy ring)" is the same as that shown as the "aryl group having 6 to 12 carbon atoms unchanged". Can be mentioned.

The number of atoms (excluding the number of hydrogen atoms) of the substituent of the "aryl group having 6 to 12 carbon atoms having a substituent (excluding the group having an epoxy ring)" is usually 1 to 30, preferably 1 to 20. Is.
Examples of the substituent of the "aryl group having 6 to 12 carbon atoms having a substituent (excluding the group having an epoxy ring)" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and s-. Alkyl groups such as butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and isooctyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom. An alkoxy group such as a methoxy group and an ethoxy group; and the like.

Among these, R ¹ is an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a fluorine atom, an unsubstituted aryl group having 6 to 12 carbon atoms, or a cyano group. Alkyl groups having 1 to 10 carbon atoms are preferable.
By using the polysilsesquioxane compound (A) in which R ¹ is an unsubstituted alkyl group having 1 to 10 carbon atoms, it is easy to obtain a curable composition which is a cured product having excellent heat resistance and adhesiveness. Become.
In the present specification, "a cured product having excellent adhesiveness" means "a cured product having high adhesive strength".
By using the polysilsesquioxane compound (A) in which R ¹ is an alkyl group having 1 to 10 carbon atoms having a fluorine atom, a curable composition or a cured product having a low refractive index can be easily obtained.
By using the polysilsesquioxane compound (A) in which R ¹ is an unsubstituted aryl group having 6 to 12 carbon atoms, a curable composition or a cured product having a high refractive index can be easily obtained.
By using the polysilsesquioxane compound (A) in which R ¹ is an alkyl group having a cyano group and having 1 to 10 carbon atoms, it is easy to obtain a curable composition having high adhesive strength to a highly polar adherend. Become.

The repeating unit represented by the above formula (a-1) is represented by the following formula. As used herein, O _1/2 means that an oxygen atom is shared with adjacent repeating units.

As represented by the formula (a-2), the polysilsesquioxane compound (A) has three oxygen atoms bonded to a silicon atom, which is generally called a T site, and other groups (R ¹ ). Has a partial structure in which one is bonded.
Examples of the T-site contained in the polysilsesquioxane compound (A) include those represented by the following formulas (a-3) to (a-5).

In the formulas (a-3) to (a-5), R ¹ has the same meaning as described above. R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms R ^2, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, s- butyl group, an isobutyl group, a t- butyl group and the like can be mentioned. A plurality of R ² to each other may all be different mutually be the same. Further, in the above formulas (a-3) to (a-5), a Si atom is bonded to *.

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

By measuring ²⁹ Si-NMR in a solution state of the polysilsesquioxane compound (A), the T3 site represented by the above formula (a-3), the T2 site represented by the formula (a-4), and the formula The content ratio of the T1 site represented by (a-5) can be determined.
The polysilsesquioxane compound (A) used in the present invention preferably contains 10 to 45 mol% of T2 sites, more preferably 15 to 40 mol%, from the viewpoint of improving the adhesive strength. Those containing 35 mol% are even more preferable.
Further, the polysilsesquioxane compound (A) used in the present invention preferably contains 50 to 90 mol% of T3 sites from the viewpoint of obtaining a cured product which is hard and has excellent heat resistance, and contains 55 to 85 mol%. Those containing 60 to 80 mol% are more preferable, and those containing 60 to 80 mol% are even more preferable.

The content ratio of the repeating unit represented by the above formula (a-1) in the polysilsesquioxane compound (A) is preferably 40 to 100 mol%, more preferably 70 to 100 mol%, based on all the repeating units. 90 to 100 mol% is more preferable, and 100 mol% is particularly preferable.

When ²⁹ Si-NMR in a solution state of the polysilsesquioxane compound (A) is measured, for example, when R ¹ is a methyl group, a peak derived from a silicon atom in the structure represented by the above formula (a-3) is obtained. (T3) is observed in the region of -70 ppm or more and less than -61 ppm, and the peak (T2) derived from the silicon atom in the structure represented by the formula (a-4) is in the region of -60 ppm or more and less than -54 ppm. The peak (T1) derived from the silicon atom in the structure represented by the above formula (a-5) is observed in the region of −53 ppm or more and less than −45 ppm.
When R ¹ is a phenyl group, T3 is observed in the region of -82 ppm or more and less than -73 ppm, T2 is observed in the region of -73 ppm or more and less than -65 ppm, and T1 is observed in the region of -65 ppm or more and -65 ppm or more. It is observed in the region of less than 55 ppm.
From the viewpoint of obtaining the better effect of the present invention, the integral value of T3 of the polysilsesquioxane compound (A) is 60 to 90% of the total value of the integral values of T1, T2, and T3. The one is preferable.
^{29 The} Si-NMR spectrum can be measured, for example, by the method described in Examples.
In addition, in this specification, "T1", "T2", "T3" and the like may represent the structure of a repeating unit, and may represent the NMR peak corresponding to the structure.

The content ratio of the repeating unit represented by the formula (a-1) in the polysilsesquioxane compound (A) is preferably 40 mol% or more, more preferably 70 mol% or more, and 90 mol, based on all the repeating units. % Or more is more preferable, and 100 mol% is particularly preferable.
The content ratio of the repeating unit represented by the above formula (a-1) in the polysilsesquioxane compound (A) can be determined, for example, by measuring ²⁹ Si-NMR of the polysilsesquioxane compound (A). Can be sought.

Even when the polysilsesquioxane compound (A) has a repeating unit other than the repeating unit represented by the formula (a-1), the polysilsesquioxane compound (A) has an epoxy ring. It does not have a group having. In this respect, the polysilsesquioxane compound (A) and the silicone oligomer of the component (B) are clearly distinguished.

The polysilsesquioxane compound (A) may be one having one kind of R ¹ (homogeneous polymer) or ^one having two or more kinds of R ¹ (copolymer).

When the polysilsesquioxane compound (A) is a copolymer, the polysilsesquioxane compound (A) is any of a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer and the like. However, from the viewpoint of ease of production and the like, a random copolymer is preferable.
Further, the structure of the polysilsesquioxane compound (A) may be any of a ladder type structure, a double decker type structure, a cage type structure, a partially cleaved cage type structure, a cyclic type structure, and a random type structure. ..

The mass average molecular weight (Mw) of the polysilsesquioxane compound (A) is not particularly limited, but is usually 800 to 30,000, preferably 1,200 to 20,000, and more preferably 1,500 to 18,000. It is more preferably 2,500 to 16,000, and particularly preferably 4,000 to 14,000. By using the polysilsesquioxane compound (A) having a mass average molecular weight (Mw) within the above range, it becomes easy to obtain a curable composition that gives a cured product having better heat resistance and adhesiveness.

The molecular weight distribution (Mw / Mn) of the polysilsesquioxane compound (A) is not particularly limited, but is usually 1.0 to 10.0, preferably 1.1 to 6.0. By using the polysilsesquioxane compound (A) having a molecular weight distribution (Mw / Mn) within the above range, it becomes easy to obtain a curable composition that gives a cured product having better heat resistance and adhesiveness.
The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, as standard polystyrene-equivalent values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

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

The method for producing the polysilsesquioxane compound (A) is not particularly limited. For example, the following equation (a-6)

(In the formula, R ¹ has the same meaning as described above. R ³ represents an alkyl group having 1 to 10 carbon atoms, X ¹ represents a halogen atom, and p represents an integer of 0 to ^3. Multiple R ³ and a plurality of X ¹ are each, be the same as each other, may be different from each other.)
The polysilsesquioxane compound (A) can be produced by polycondensing at least one of the silane compounds (1) represented by (1).
Examples of the alkyl group having 1 to 10 carbon atoms of R ³ include those similar to those shown as the alkyl group having 1 to 10 carbon atoms of R ² .
Examples of the halogen atom of X ¹ include a chlorine atom and a bromine atom.

Specific examples of the silane compound (1) include alkyltrialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltripropoxysilane;
Alkylhalogenoalkoxysilane compounds such as methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane;
Alkyltrihalogenosilane compounds such as methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, and ethyltribromosilane;

Substituted alkyltrialkoxysilane compounds such as 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, and 2-cyanoethyltriethoxysilane;
3,3,3-Trifluoropropylchlorodimethoxysilane, 3,3,3-trifluoropropylchlorodiethoxysilane, 3,3,3-trifluoropropyldichloromethoxysilane, 3,3,3-trifluoropropyldichloro Substituted alkylhalogenoalkoxysilane compounds such as ethoxysilane, 2-cyanoethylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 2-cyanoethyldichloromethoxysilane, 2-cyanoethyldichloroethoxysilane;
Substituted alkyltrihalogenosilane compounds such as 3,3,3-trifluoropropyltrichlorosilane and 2-cyanoethyltrichlorosilane;

Phenyltrialkoxysilane compounds having or not having a substituent, such as phenyltrimethoxysilane and 4-methoxyphenyltrimethoxysilane;
Phenylhalogenoalkoxysilane compounds having or not having a substituent, such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane, 4-methoxyphenyldichloromethoxysilane;
Examples thereof include phenyltrihalogenosilane compounds having or not having a substituent such as phenyltrichlorosilane and 4-methoxyphenyltrichlorosilane; and the like.
These silane compounds (1) can be used alone or in combination of two or more.

The method for polycondensing the silane compound (1) is not particularly limited. For example, a method of adding a predetermined amount of polycondensation catalyst to the silane compound (1) in a solvent or without a solvent and stirring at a predetermined temperature can be mentioned. More specifically, (a) a method of adding a predetermined amount of an acid catalyst to the silane compound (1) and stirring at a predetermined temperature, and (b) adding a predetermined amount of a base catalyst to the silane compound (1). A method of stirring at a predetermined temperature, (c) a predetermined amount of acid catalyst is added to the silane compound (1), and after stirring at a predetermined temperature, an excess amount of base catalyst is added to make the reaction system basic. , A method of stirring at a predetermined temperature and the like. Among these, the method (a) or (c) is preferable because the desired polysilsesquioxane compound (A) can be efficiently obtained.

The polycondensation catalyst used may be either an acid catalyst or a base catalyst. Further, two or more polycondensation catalysts may be used in combination, but at least an acid catalyst is preferably used.
Examples of the acid catalyst include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid and nitric acid; and organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; Can be mentioned. 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 the base catalyst, aqueous ammonia; trimethylamine, triethylamine, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, pyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, aniline, picolin, 1,4- Organic bases such as diazabicyclo [2.2.2] octane and imidazole; organic hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; sodium methoxydone, sodium ethoxydo, sodium t-butoxide, potassium t-butoxide. Metal alkoxides such as; 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; Metallic 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 amount of the silane compound (1).

When a solvent is used at the time of polycondensation, the solvent to be used can be appropriately selected depending on the type of the silane compound (1) and the like. 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, t-butyl alcohol; and the like. These solvents can be used alone or in combination of two or more. When the method (c) above is adopted, a polycondensation reaction is carried out in an aqueous system in the presence of an acid catalyst, and then an organic solvent and an excessive amount of a base catalyst (ammonia water or the like) are added to the reaction solution. The polycondensation reaction may be further carried out under basic conditions.

The amount of the solvent used 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 mol amount of the silane compound (1).

The temperature at which the silane compound (1) is polycondensed is usually in the temperature range from 0 ° C. to the boiling point of the solvent used, preferably in the range of 20 ° C. or higher and 100 ° C. or lower. If the reaction temperature is too low, the progress of the polycondensation reaction may be insufficient. On the other hand, if the reaction temperature becomes too high, it becomes difficult to suppress gelation. The reaction is usually complete in 30 minutes to 30 hours.

Depending on the type of monomer used, it may be difficult to increase the molecular weight. For example, the monomer R ¹ is an alkyl group having a fluorine atom, it tends to be inferior in reactivity than the monomer wherein R ¹ is normal alkyl group. In such a case, by reducing the amount of catalyst and carrying out the reaction for a long time under mild conditions, the polysilsesquioxane compound (A) having the desired molecular weight can be easily obtained.

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

When the polysilsesquioxane compound (A) is produced by the above method, the portion of OR ³ or X ¹ of the silane compound (1) in which dealcoholization or the like does not occur is the polysilsesquioxane compound (A). ) Remains in. Therefore, in the polysilsesquioxane compound (A), in addition to the repeating unit represented by the formula (a-3), the repeating unit represented by the formulas (a-4) and (a-5) is contained. May be included.

[Component (B)]
The component (B) constituting the curable composition of the present invention is a silicone oligomer having or not having a repeating unit derived from a trifunctional silane compound and having or not having a repeating unit derived from a tetrafunctional silane compound. The total amount of the repeating unit derived from the trifunctional silane compound and the repeating unit derived from the tetrafunctional silane compound is 80 mol% or more in all the repeating units of the component (B), and at least one of the trifunctional silane compounds is an epoxy ring. It is a silicone oligomer (hereinafter, may be referred to as "silicone oligomer (B)") which is a trifunctional silane compound having a group having.
In the present invention, the silicone oligomer refers to a silane compound polymer having a low degree of polymerization. The degree of polymerization of the silicone oligomer (B) is usually 2 to 100.

The silicone oligomer (B) has a repeating unit derived from a trifunctional silane compound.
The trifunctional silane compound is a compound having one silicon atom and three hydrolyzable groups bonded to the silicon atom. In the present specification, the hydrolyzable group refers to a group having hydrolyzable / polycondensable properties such as an alkoxy group and a halogen atom.
Examples of the trifunctional silane compound include the silane compound (1) represented by the formula (a-6) shown as a raw material for producing the polysilsesquioxane compound (A).

The silicone oligomer (B) may or may not have a repeating unit derived from a tetrafunctional silane compound.
The tetrafunctional silane compound is a compound having one silicon atom and four hydrolyzable groups bonded to the silicon atom.
Examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, trimethoxyethoxysilane, trimethoxychlorosilane, triethoxychlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, and methoxytrichlorosilane. , Ethoxytrichlorosilane, tetrachlorosilane, tetrabromosilane and the like.

The total of the repeating unit derived from the trifunctional silane compound and the repeating unit derived from the tetrafunctional silane compound contained in the silicone oligomer (B) is 80 mol% or more, preferably 80 to 100 mol%, more preferably 80 mol% or more in all the repeating units. It is 90 to 100 mol%.
A curable composition in which the total of the repeating unit derived from the trifunctional silane compound and the repeating unit derived from the tetrafunctional silane compound is less than 80 mol% in all the repeating units is inferior in curability.

The amount of the repeating unit derived from the trifunctional silane compound contained in the silicone oligomer (B) is preferably 5 to 40 mol% of the total of the repeating unit derived from the trifunctional silane compound and the repeating unit derived from the tetrafunctional silane compound. , More preferably 10 to 30 mol%.
By containing a large amount of repeating units derived from the trifunctional silane compound, the compatibility of the silicone oligomer (B) with the polysilsesquioxane compound (A) is enhanced. On the other hand, by curing the curable composition containing the silicone oligomer (B) derived from the tetrafunctional silane compound and containing a large amount of repeating units, it becomes easy to obtain a cured product that is hard and has excellent heat resistance.

The type of each repeating unit contained in the silicone oligomer (B) and its content ratio are the same as those described above as the method for determining the structure of the polysilsesquioxane compound (A) (measurement result of ²⁹ Si-NMR). It can be obtained by the method based on).

The silicone oligomer (B) has a repeating unit derived from a trifunctional silane compound having a group having an epoxy ring. That is, at least one of the trifunctional silane compounds used in synthesizing the silicone oligomer (B) is a compound having a group having an epoxy ring.

Examples of the trifunctional silane compound having a group having an epoxy ring include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxidecyclohexyl) ethyltrimethoxysilane, and 2 -(3,4-Epoxide cyclohexyl) ethyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-glycidoxyoctyltriethoxysilane, and the like can be mentioned.

As described above, the silicone oligomer (B) has an epoxy ring in the molecule. In the present invention, by using such an oligomer together with the curable polysilsesquioxane compound (A), a curable composition having excellent curability can be obtained.
Such an effect cannot be obtained by using a silicone oligomer having a functional group (for example, a thiol group) other than the epoxy ring-containing group or a monomer having an epoxy ring instead of the silicone oligomer (B).

Further, the combined use of the polysilsesquioxane compound (A) and the silicone oligomer (B) requires a smaller amount of epoxy ring to be introduced than the introduction of the epoxy ring into the polysilsesquioxane compound (A). Sufficient curability can be realized.

The mass average molecular weight (Mw) of the silicone oligomer (B) is not particularly limited, but is usually 500 to 5,000, preferably 1,000 to 4,500, more preferably 1,500 to 4,000, and even more preferably 2. It is 000 to 3,500. By using the silicone oligomer (B) having a mass average molecular weight (Mw) within the above range, it becomes easy to obtain a curable composition having more excellent curability. Further, the cured product of such a curable composition tends to have excellent adhesiveness.

The molecular weight distribution (Mw / Mn) of the silicone oligomer (B) is not particularly limited, but is usually 1.0 to 10.0, preferably 1.1 to 6.0. By using the silicone oligomer (B) having a molecular weight distribution (Mw / Mn) within the above range, it becomes easy to obtain a curable composition having better curability. Further, the cured product of such a curable composition tends to have excellent adhesiveness.
The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, as standard polystyrene-equivalent values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

The epoxy equivalent of the silicone oligomer (B) is not particularly limited, but is usually 50 to 2,000 g / eq, preferably 100 to 1,500 g / eq, more preferably 150 to 1,200 g / eq, still more preferably 200 to 1. It is 000 g / eq. By using the silicone oligomer (B) having an epoxy equivalent within the above range, it becomes easy to obtain a curable composition having better curability. Further, the cured product of such a curable composition tends to have excellent adhesiveness.
The epoxy equivalent of the silicone oligomer (B) can be measured according to JIS K7236 (2001).

In the present invention, the silicone oligomer (B) can be used alone or in combination of two or more.

The method for producing the silicone oligomer (B) is not particularly limited. The target silicone oligomer (B) can be produced by appropriately changing the reaction conditions and the like in the same method as described as the method for producing the polysilsesquioxane compound (A).
Further, as the silicone oligomer (B), a commercially available silicone oligomer may be used.

[Curable composition]
The curable composition of the present invention contains a polysilsesquioxane compound (A) and a silicone oligomer (B).
The total amount of the polysilsesquioxane compound (A) and the silicone oligomer (B) is preferably 30 to 100% by mass, more preferably 40 to 95% by mass, still more preferably 40% by mass, based on the solid content of the curable composition. Is 50 to 90% by mass, particularly preferably 55 to 85% by mass.
In the present invention, the "solid content" refers to a component other than the solvent in the curable composition.

The content of the silicone oligomer (B) is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 80 parts by mass, still more preferably, with respect to 100 parts by mass of the polysilsesquioxane compound (A). It is 1.0 to 60 parts by mass, particularly preferably 1.5 to 40 parts by mass. If the content of the component (B) is too small, the effect of the present invention may not be obtained, and if it is too large, gelation may occur.

The curable composition of the present invention may contain a silane coupling agent as the component (C). By using a curable composition containing a silane coupling agent, it becomes easy to form a cured product having better adhesiveness.
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 functional group refers to a group having a reactivity with another compound (mainly an organic substance), for example, a group having a nitrogen atom such as an amino group, a substituted amino group, an isocyanate group, a ureido group, or a group having an isocyanurate skeleton. Acid anhydride group (acid anhydride structure); vinyl group; allyl group; epoxy group; (meth) acrylic group; mercapto group; and the like.
In the present invention, the silane coupling agent can be used alone or in combination of two or more.
When the curable composition of the present invention contains a silane coupling agent, the content thereof is not particularly limited and can be appropriately determined depending on the intended purpose.

As the silane coupling agent, a silane coupling agent having a nitrogen atom in the molecule and a silane coupling agent having an acid anhydride structure in the molecule are preferable.

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

Examples of the silane coupling agent having a nitrogen atom in the molecule include a trialkoxysilane compound represented by the following formula (c-1), a dialkoxyalkylsilane compound represented by the formula (c-2), or dialkoxy. Examples thereof include arylsilane compounds.

In the above formulas, ^{R a} represents a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, an alkoxy group having 1 to 6 carbon atoms such as t- butoxy. A plurality of R ^a each other may be different from each be the same.
R ^b is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a t-butyl group; or a phenyl group, a 4-chlorophenyl group and a 4-. Represents an aryl group having or not having a substituent, such as a methylphenyl group or a 1-naphthyl group.

R ^c represents an organic group having 1 to 10 carbon atoms and having a nitrogen atom. Further, R ^c may be bonded to a group containing another silicon atom.
Specific examples of the organic group having 1 to 10 carbon atoms R ^c is, N-2- (aminoethyl) -3-aminopropyl group, 3-aminopropyl group, N-(1,3-dimethyl - butylidene) amino Examples thereof include a propyl group, a 3-ureidopropyl group and an N-phenyl-aminopropyl group.

Of the above formula (c-1) or compounds represented by ^(c-2), R c is, as the compound where an organic group bonded with groups containing other silicon atoms, having an isocyanurate skeleton Examples thereof include a silane coupling agent (isocyanurate-based silane coupling agent) and a silane coupling agent having a urea skeleton (urea-based silane coupling agent).

Among these, as the silane coupling agent having a nitrogen atom in the molecule, an isocyanurate-based silane coupling agent and a urea-based silane coupling agent are preferable because a cured product having better adhesiveness can be easily obtained. , It is preferable that the molecule has 4 or more alkoxy groups bonded to a silicon atom.
Having 4 or more alkoxy groups bonded to a silicon atom means that the total count of the alkoxy groups bonded to the same silicon atom and the alkoxy groups bonded to different silicon atoms is 4 or more.

Examples of the isocyanurate-based silane coupling agent having 4 or more alkoxy groups bonded to a silicon atom include a compound represented by the following formula (c-3). Examples of the urea-based silane coupling agent having 4 or more alkoxy groups bonded to a silicon atom include a compound represented by the following formula (c-4).

In the formula, ^Ra 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, and particularly preferably 3.

Among these, 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate and 1,3,5-N-tris (3-) are examples of the silane coupling agent having a nitrogen atom in the molecule. 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 above isocyanurate compound and urea compound is preferably used.

When the curable composition of the present invention contains a silane coupling agent having a nitrogen atom in the molecule, the content thereof is not particularly limited, but the amount thereof has the above component (A) and the nitrogen atom in the molecule. The mass ratio of the silane coupling agent [(A component: silane coupling agent having a nitrogen atom in the molecule], preferably 100: 0.1 to 100: 90, more preferably 100: 0.3 to 100: The amount is 60, more preferably 100: 1 to 100: 50, still more preferably 100: 3 to 100: 40, and 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 at such a ratio becomes excellent in heat resistance and adhesiveness.

A 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. Specific examples thereof include compounds represented by the following formula (c-5).

Wherein, Q represents a group having an acid anhydride structure, R ^d represents an alkyl group having 1 to 6 carbon atoms, or has a substituent, or a phenyl group having no substituent, R ^e is a carbon It represents an alkoxy group or a halogen atom of the number 1 to 6, i and k represent an integer of 1 to 3, j represents an integer of 0 to 2, and i + j + k = 4. When j is 2, R ^ds may be the same or different from each other. when k is 2 or 3, among a plurality of R ^e may be different from each be the same. When i is 2 or 3, a plurality of Qs may be the same or different from each other.
The following formula is used as Q

Examples thereof include groups represented by (in the formula, h represents an integer of 0 to 10), and the group represented by (Q1) is particularly preferable.

Examples of the silane coupling agent having an acid anhydride structure in the molecule include 2- (trimethoxysilyl) ethyl anhydride succinic anhydride, 2- (triethoxysilyl) ethyl anhydride succinic anhydride, and 3- (trimethoxysilyl) propyl anhydride succinic anhydride. Tri (1-6 carbon atoms) alkoxysilyl (2-8 carbon atoms) alkyl succinic anhydride, such as acid, 3- (triethoxysilyl) propyl succinic anhydride;
Di (1 to 6 carbon atoms) alkoxymethylsilyl (2 to 8 carbon atoms) alkyl succinic anhydride, such as 2- (dimethoxymethylsilyl) ethyl succinic anhydride;
(1-6 carbon atoms) alkoxydimethylsilyl (2-8 carbon atoms) alkyl succinic anhydride, such as 2- (methoxydimethylsilyl) ethyl succinic anhydride;

Trihalogenosilyl (2-8 carbon atoms) alkyl succinic anhydride, such as 2- (trichlorosilyl) ethyl succinic anhydride, 2- (tribromosilyl) ethyl succinic anhydride;
Dihalogenomethylsilyl (2-8 carbon atoms) alkyl succinic anhydride, such as 2- (dichloromethylsilyl) ethyl succinic anhydride;
Examples thereof include halogenodimethylsilyl (2 to 8 carbon atoms) alkyl succinic anhydride, such as 2- (chlorodimethylsilyl) ethyl succinic anhydride.

Among these, as the silane coupling agent having an acid anhydride structure in the molecule, tri (1 to 6 carbon atoms) alkoxysilyl (2 to 8 carbon atoms) alkyl succinic anhydride is preferable, and 3- (trimethoxysilyl) is preferable. ) Succinic anhydride or 3- (triethoxysilyl) propyl succinic anhydride is particularly preferred.

When the curable composition of the present invention contains a silane coupling agent having an acid anhydride structure in the molecule, the content thereof is not particularly limited, but the amount thereof is acid anhydride in the above component (A) and the molecule. Mass ratio of silane coupling agent having a physical structure [(A component: silane coupling agent having an acid anhydride structure in the molecule], preferably 100: 0.1 to 100:30, more preferably 100: The amount is 0.3 to 100: 20, more preferably 100: 0.5 to 100: 15, and even more preferably 100: 1 to 100:10.
The cured product of the curable composition containing the component (A) and the silane coupling agent having an acid anhydride structure in the molecule at such a ratio becomes more excellent in adhesiveness.

The curable composition of the present invention may contain other components as long as the object of the present invention is not impaired.
Examples of other components include fine particles, antioxidants, ultraviolet absorbers, light stabilizers and the like.

When fine particles are added, a curable composition having excellent workability in the coating process may be obtained. The materials of the fine particles include 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; aluminum silicate and silicic acid. Examples thereof include metal silicates such as calcium and magnesium silicate; inorganic components such as silica; silicones; organic components such as acrylic polymers; and the like.
Further, the fine particles used may have a modified surface.

These fine particles can be used alone or in combination of two or more. The content of the fine particles is not particularly limited, but is usually preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, based on the component (A).

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

Examples of the phosphorus-based antioxidant include phosphites, oxaphosphaphenanthrene oxides and the like. Examples of the phenolic antioxidant include monophenols, bisphenols, and high molecular weight phenols. Examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate and the like.

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

The UV absorber is added for the purpose of improving the light resistance of the obtained cured product.
Examples of the ultraviolet absorber include salicylic acids, benzophenones, benzotriazoles, hindered amines and the like.
The ultraviolet absorber may be used alone or in combination of two or more. The content of the ultraviolet absorber is not particularly limited, but is usually 10% by mass or less with respect to the component (A).

The light stabilizer is added for the purpose of improving the light resistance of the obtained cured product.
Examples of the light stabilizer include poly [{6- (1,1,3,3, -tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6). , 6-Tetramethyl-4-piperidin) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidine) imino}] and other hindered amines.
These light stabilizers can be used alone or in combination of two or more. 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 contain a solvent. The solvent is not particularly limited as long as it can dissolve or disperse the components of the curable composition of the present invention.
Examples of the solvent include acetates such as diethylene glycol monobutyl ether acetate and 1,6-hexanediol diacetate; tripropylene glycol-n-butyl ether; glycerin diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether. , Cyclohexanedimethanol diglycidyl ether, alkylene diglycidyl ether, polyglycol diglycidyl ether, polypropylene glycol diglycidyl ether and other diglycidyl ethers; trimethylolpropane triglycidyl ether, glycerin triglycidyl ether and other triglycidyl ethers; -Vinylhexene oxides such as vinylcyclohexene monooxide, vinylcyclohexendioxide, methylated vinylcyclohexendioxide; and the like.
The solvent can be used alone or in combination of two or more.

When the curable composition of the present invention contains a solvent, the content thereof is an amount such that the solid content concentration is preferably 50 to 95% by mass, more preferably 60 to 85% by mass. When the solid content concentration is within this range, it becomes easy to obtain a curable composition having excellent workability in the coating process.

A curable composition that satisfies these requirements regarding the amount of solvent has an appropriate balance of adhesiveness and wettability (the above-mentioned characteristics regarding the spread of droplets).

The curable composition of the present invention can be prepared, for example, by mixing the above-mentioned component (A), component (B), and, if desired, other components at a predetermined ratio and defoaming.
The mixing method and defoaming method are not particularly limited, and known methods can be used.

The curable composition of the present invention contains a polysilsesquioxane compound (A) and a silicone oligomer (B). Therefore, the curable composition of the present invention is excellent in curability.
It can be confirmed, for example, that the curable composition of the present invention has excellent curability as follows.
That is, using an automatic curing time measuring device (manufactured by Cyber Co., Ltd., trade name "Madoka"), a sample of the curable composition is placed on a stainless steel plate heated to 150 ° C., and then the charged sample is stirred. Then, the time until the stirring torque increases to 0.049 N · cm is measured.
The time until it reaches 0.049 N · cm is usually preferably 1200 seconds or less, more preferably 1000 seconds or less, and more preferably 600 seconds or less.

As described above, the curable composition of the present invention is excellent in curability. Therefore, by using the curable composition of the present invention, the working time can be shortened as compared with the case of using the conventional curable composition.

2) Cured product The cured product of the present invention is obtained by curing the curable composition of the present invention.
Examples of the method for curing the curable composition of the present invention include heat curing. The heating temperature at the time of 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.
It can be confirmed that the cured product of the present invention has these properties, for example, as follows. That is, a predetermined amount of the curable composition of the present invention is applied to the mirror surface of the silicon chip, the coated surface is placed on the adherend, pressure-bonded, and heat-treated to cure. This is left on the measurement stage of a bond tester preheated to a predetermined temperature (for example, 100 ° C.) for 30 seconds, and from a position at a height of 100 μm from the adherend, in the horizontal direction (shear direction) with respect to the adhesive surface. Apply stress and measure the adhesive strength between the test piece and the adherend.

Adhesion of the cured product of the present invention is preferably at 100 ° C. is 30 N / 4 mm ² or more, more preferably 35N / 4 mm ² or more, and still more preferably 40N / 4 mm ² or more.
In the present specification, "4 mm ² " means "2 mm square", that is, 2 mm x 2 mm (a square having a side of 2 mm).

Since it has the above characteristics, the cured product of the present invention is preferably used as an optical element fixing material.

3) Method of using 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 a light emitting element such as an LED and an LD, a light receiving element, a composite optical element, and an optical integrated circuit.

<Adhesive for optical element fixing material>
The curable composition of the present invention can be suitably used as an adhesive for an optical element fixing material.
As a method of using the curable composition of the present invention as an adhesive for an optical element fixing material, the composition is applied to one or both adhesive surfaces of a material to be adhered (optical element and its substrate, etc.). , After crimping, heat-curing to firmly bond the materials to be bonded to each other. The amount of the curable composition of the present invention applied is not particularly limited as long as it can firmly bond the materials to be bonded to each other by curing. 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 elements include glasses such as soda lime glass and heat-resistant hard glass; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium and alloys of these metals. , Stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone , Polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, acrylic resin, norbornene resin, cycloolefin resin, synthetic resin such as glass epoxy resin; and the like.

The heating temperature at the time of heat-curing depends on the curable composition used and the like, but is usually 100 to 200 ° C. The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

<Encapsulating material for optical element fixing material>
The curable composition of the present invention can be suitably used as a sealing material for an optical element fixing material.
As a method of using the curable composition of the present invention as a sealing material for an optical element fixing material, for example, the composition is molded into a desired shape to obtain a molded product containing an optical element, and then this Examples thereof include a method of manufacturing an optical device encapsulant by heating and curing the material.
The method for molding the curable composition of the present invention into a desired shape is not particularly limited, and a known molding method such as a normal transfer molding method or a casting method can be adopted.

The heating temperature at the time of heat curing depends on the curable composition used and the like, but 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 device encapsulant uses the curable composition of the present invention, it is excellent in heat resistance and adhesiveness.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(Measurement of average molecular weight)
The mass average molecular weight (Mw) and number average molecular weight (Mn) of the curable polysilsesquioxane compound obtained in the production example and the silicone oligomer of component B are standard polystyrene conversion values, and are set to the following equipment and conditions. It was measured.
Device name: HLC-8220GPC, manufactured by Tosoh Corporation Columns: TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL are sequentially linked. Solvent: tetrahydrofuran Injection amount: 80 μl
Measurement temperature: 40 ° C
Flow velocity: 1 ml / min Detector: Differential refractometer

(Measurement of IR spectrum)
The IR spectrum of the curable polysilsesquioxane compound obtained in the production example was measured using a Fourier transform infrared spectrophotometer (Spectrum 100, manufactured by PerkinElmer).

( ²⁹ Si-NMR measurement)
In order to investigate the repeating unit of the silane compound polymer [component (A) and component (B)] and its amount, ²⁹ Si-NMR measurement was performed under the following conditions.
Equipment: AV-500 manufactured by Bruker Biospin
²⁹ Si-NMR resonance frequency: 99.352 MHz
Probe: 5 mmφ solution Probe measurement temperature: Room temperature (25 ° C)
Sample rotation speed: 20 kHz
Measurement method: inverse gate decoupling method
²⁹ Si flip angle: 90 °
²⁹ Si 90 ° pulse width: 8.0 μs
Repeat time: 5s
Number of integrations: 9200 observations Width: 30 kHz

( ²⁹ Si-NMR sample preparation method)
In order to shorten the relaxation time, Fe (acac) ₃ was added as a relaxation reagent and measured.
Silane compound polymer concentration: 30% by mass
Fe (acac) ₃ concentration: 0.7% by mass
Measuring solvent: Acetone Internal standard: TMS

(Waveform processing analysis)
For each peak of the spectrum after Fourier transform, the chemical shift was obtained from the position of the peak top and integrated.

(Manufacturing Example 1)
71.37 g (400 mmol) of methyltriethoxysilane was charged in a 300 ml eggplant-shaped flask, and then 0.10 g of 35 mass% hydrochloric acid (0 with respect to methyltriethoxysilane) was added to 21.6 ml of distilled water while stirring the mixture. An aqueous solution in which .25 mol%) was dissolved was added, and the whole volume was heated to 30 ° C. for 2 hours and then to 70 ° C. for 5 hours.
While continuing to stir the contents, 140 g of propyl acetate and 0.12 g of 28 mass% aqueous ammonia (0.5 mol% with respect to methyltriethoxysilane) were added thereto, and the mixture was stirred as it was at 70 ° C. for 3 hours.
After allowing the reaction solution to cool to room temperature, purified water was added thereto for liquid separation treatment, and this operation was repeated until the pH of the aqueous layer reached 7. The organic layer was concentrated with an evaporator and the concentrate was vacuum dried to obtain 55.7 g of curable polysilsesquioxane compound (A1). The mass average molecular weight (Mw) of this product was 7,800, and the molecular weight distribution (Mw / Mn) was 4.52.
The IR spectral data of the curable polysilsesquioxane compound (A1) is shown below.
Si-CH ₃ : 1272 cm ^-1 , 1409 cm ^-1 , Si-O: 1132 cm ^-1
Moreover, as a result of performing ²⁹ Si-NMR spectrum measurement, the peak integral value ratio of T1, T2, and T3 was 0:24:76.

(Manufacturing Example 2)
17.0 g (77.7 mmol) of 3,3,3-trifluoropropyltrimethoxysilane and 32.33 g (181.3 mmol) of methyltriethoxysilane were placed in a 300 mL eggplant-shaped flask, and the mixture was stirred. While doing so, an aqueous solution obtained by dissolving 0.0675 g of 35 mass% hydrochloric acid (the amount of HCl was 0.65 mmol, 0.25 mol% with respect to the total amount of the silane compound) was added to 14.0 g of distilled water. The whole volume was heated to 30 ° C. for 2 hours and then to 70 ° C. for 20 hours.
While continuing to stir the contents, a mixed solution of 0.0394 g of 28 mass% ammonia water (0.65 mmol of NH ₃ ) and 46.1 g of propyl acetate was added thereto to adjust the pH of the reaction solution to 6.9. And stirred as it was at 70 ° C. for 40 minutes.
After allowing the reaction solution to cool to room temperature, 50 g of propyl acetate and 100 g of water were added thereto to carry out a liquid separation treatment to obtain an organic layer containing a reaction product. Magnesium sulfate was added to this organic layer and dried. After removing magnesium sulfate by filtration, the organic layer was concentrated by an evaporator, and then the obtained concentrate was vacuum-dried to obtain a curable polysilsesquioxane compound (A2). The mass average molecular weight (Mw) of this product was 5,500, and the molecular weight distribution was 3.40.
The IR spectral data of the curable polysilsesquioxane compound (A2) is shown below.
Si-CH ₃ : 1272 cm ^-1 , 1409 cm ^-1 , Si-O: 1132 cm ^-1 , CF: 1213 cm ^-1
Moreover, as a result of performing ²⁹ Si-NMR spectrum measurement, the peak integral value ratio of T1, T2, and T3 was 2:27:71.

(Manufacturing Example 3)
After charging 20.2 g (102 mmol) of phenyltrimethoxysilane, 3.15 g (18 mmol) of 2-cyanoethyltrimethoxysilane, and 96 ml of acetone and 24 ml of distilled water as a solvent in a 300 ml eggplant-shaped flask, the contents are added. While stirring, 0.15 g (1.5 mmol) of phosphoric acid was added as a catalyst, and the mixture was further stirred at 25 ° C. for 16 hours.
After completion of the reaction, the reaction solution was concentrated to 50 ml with an evaporator, 100 ml of ethyl acetate was added to the concentrate, and the mixture was neutralized with a saturated aqueous sodium hydrogen carbonate solution. After allowing to stand for a while, the organic layer was separated. Then, the organic layer was washed twice with distilled water and then dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered off, the filtrate was concentrated to 50 ml with an evaporator, and the obtained concentrate was added dropwise to a large amount of n-hexane to precipitate, and the precipitate was separated by decantation. The obtained precipitate was dissolved in methyl ethyl ketone (MEK) and recovered, and the solvent was distilled off under reduced pressure with an evaporator. The residue was vacuum dried to obtain 13.5 g of curable polysilsesquioxane compound (A3). The mass average molecular weight (Mw) of this product was 1,870, and the molecular weight distribution (Mw / Mn) was 1.42.
The IR spectral data of the curable polysilsesquioxane compound (A3) is shown below.
Si-Ph: 698cm ^-1 , 740cm ^-1 , Si-O: 1132cm ^-1 , -CN: 2259cm ^-1
As a result of ²⁹ Si-NMR spectrum measurement, the peak integral value ratio of T1, T2 and T3 was 0:33:67.

The compounds used in Examples and Comparative Examples are shown below.
(Component A)
Curable polysilsesquioxane compound (A1) [curable PSQ (A1)]: Curable polysilsesquioxane compound obtained in Production Example 1 Curable polysilsesquioxane compound (A2) [curable PSQ (A2)]: Curable polysilsesquioxane compound obtained in Production Example 2 Curable polysilsesquioxane compound (A3) [Curable PSQ (A3)]: Curable polysis obtained in Production Example 3. Lucesquioxane compound

(B component and comparative compound)
Silicone oligomer (B1): Commercially available epoxy ring-containing silicone oligomer, mass average molecular weight (Mw) 2,400, molecular weight distribution (Mw / Mn) 1.53, epoxy equivalent 830 g / eq
Silicone oligomer (B2): Commercially available epoxy ring-containing silicone oligomer, mass average molecular weight (Mw) 2,300, molecular weight distribution (Mw / Mn) 1.48, epoxy equivalent 350 g / eq
Silicone oligomer (B3): Commercially available mercapto group-containing silicone oligomer, mass average molecular weight (Mw) 1,800, molecular weight distribution (Mw / Mn) 1.79, mercapto equivalent 800 g / eq
Silicone oligomer (B4): Commercially available silicone oligomer containing no epoxy ring, mass average molecular weight (Mw) 2,200, molecular weight distribution (Mw / Mn) 2.24
Silicone oligomer (B5): Commercially available epoxy ring-containing silicone oligomer, mass average molecular weight (Mw) 1,500, molecular weight distribution (Mw / Mn) 1.39, epoxy equivalent 490 g / eq
Silicone oligomer (B6): Commercially available epoxy ring-containing silicone oligomer [2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane polycondensate (cyclic tetramer)], epoxy equivalent 200 g / eq
Silane coupling agent (B7): 3-glycidoxypropyltrimethoxysilane

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

In the above table, M, D, T and Q indicate that the number of oxygen atoms bonded to the silicon atom is 1, 2, 3 and 4, respectively. The numbers after M, D, T and Q represent the number of Si—O— bonds attached to the silicon atom. Therefore, for example, in the case of a silicone oligomer in which the non-hydrolyzable group is a methyl group and the hydrolyzable group is a methoxy group, the specific structure is as follows. In the formula, "Me" represents a methyl group.

(C component)
Silane Coupling Agent (C1): 1,3,5-N-Tris [3- (trimethoxysilyl) propyl] Isocyanurate Silane Coupling Agent (C2): 3- (Trimethoxysilyl) Propyl succinic anhydride

(Example 1)
A mixed solvent of diethylene glycol monobutyl ether acetate: tripropylene glycol-n-butyl ether = 40: 60 (mass ratio) was added to 100 parts by mass of the curable polysilsesquioxane compound (A1), and the whole volume was stirred. 5 parts by mass of silicone oligomer (B1), 30 parts by mass of silane coupling agent (C1), and 3 parts by mass of silane coupling agent (C2) are added to this, and the whole content is thoroughly mixed and defoamed to cure. A sex composition was obtained.

(Examples 2 to 8 and Comparative Examples 1 to 8)
A curable composition was obtained in the same manner as in Example 1 except that each component was changed to that shown in Table 2.

The following measurements and tests were carried out using the curable compositions obtained in Examples and Comparative Examples, respectively. The results are shown in Table 2.

[Evaluation of curability]
As described below, the curing time of the curable composition was measured using an automatic curing time measuring device "Madoka" (manufactured by Cyber Co., Ltd.).
A 0.30 mL sample was placed on a stainless steel plate heated to 150 ° C. and stirred. Since the stirring torque increases with time, the time (seconds) until the stirring torque reaches 0.049 N · cm was measured. The stirring conditions are as follows.
・ Rotation speed of stirring blade: 200 rpm
・ Revolution speed of stirring blade: 80 rpm
・ Gap (distance between heating plate and stirring blade): 0.3 mm

[Adhesive strength evaluation]
The curable compositions obtained in Examples and Comparative Examples were applied to the mirror surface of a square (area 4 mm ² ) silicon chip having a side length of 2 mm so as to have a thickness of about 2 μm. The coated surface was placed on an adherend (silver-plated copper plate) and crimped. Then, it was heat-treated at 130 ° C. for 2 hours and cured to obtain an adherend with a test piece. The adherend with the test piece was left on the measurement stage of a bond tester (manufactured by Daige, Series 4000) preheated to 100 ° C. for 30 seconds, and the speed was 200 μm / from a position at a height of 100 μm from the adherend. A stress was applied to the adhesive surface in the horizontal direction (shear direction) with s, and the adhesive force (N / 4 mm ² ) between the test piece and the adherend at 100 ° C. was measured.

[Transmittance after heating]
The curable compositions obtained in Examples and Comparative Examples were poured into a mold having a length of 25 mm and a width of 20 mm so as to have a thickness of 1 mm, and heated at 150 ° C. for 3 hours to cure the test piece. Obtained. After heating this test piece at 200 ° C. for 100 hours, the transmittance at a wavelength of 450 nm was measured using a spectrophotometer.

The following can be seen from Table 2.
In the curability evaluation test, the curable compositions of Examples 1 to 8 were obtained in a short time of 1000 seconds or less, and are excellent in curability.
Further, in the evaluation test of the adhesive strength of the cured product obtained in Examples 1 to 8, the adhesive strength is 30 N / 4 mm ² or more, and the adhesive property is excellent.
Further, the cured product of the curable composition of the example has sufficient light transmittance even after heating.
On the other hand, the curable compositions of Comparative Examples 1 to 8 are inferior in curability because they require a curing time of more than 1000 seconds in the curability evaluation test.
Further, in the evaluation test of the adhesive strength of the cured product obtained in Comparative Examples 1 to 8, the adhesive strength was less than 30 N / 4 mm ² , and the adhesive strength was inferior.

Claims (11)

A curable composition containing the following components (A) and (B), and the content of the component (B) is 1 to 60 parts by mass with respect to 100 parts by mass of the component (A) .
Component (A): have a repeating unit represented by the following formula (a-1), the proportion of the repeating unit represented by the formula (a-1) is, Ru 70～100Mol% der the total repeating units Curable polysilsesquioxane compound

[R ¹ is an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a substituent (excluding a group having an epoxy ring), and an unsubstituted aryl group having 6 to 12 carbon atoms. , And at least one selected from the group consisting of an aryl group having 6 to 12 carbon atoms having a substituent (excluding a group having an epoxy ring). ]
Component (B): a repeating unit derived from trifunctional silane compound, and 4 a sheet recone oligomer having repeating units derived from functional silane compounds, derived from trifunctional silane compound derived repeating units and tetrafunctional silane compound The total amount of the repeating units is 80 mol% or more in all the repeating units, and the content of the repeating units derived from the trifunctional silane compound is the repeating units derived from the trifunctional silane compound and the repeating units derived from the tetrafunctional silane compound. Silicone oligomer which is 5 to 40 mol% based on the total amount and at least one of the trifunctional silane compounds is a trifunctional silane compound having a group having an epoxy ring. A curable composition containing the following components (A) and (B), wherein the content of the component (B) is 1 to 60 parts by mass with respect to 100 parts by mass of the component (A).
Component (A): Cured having a repeating unit represented by the following formula (a-1), and the ratio of the repeating unit represented by the formula (a-1) is 70 to 100 mol% with respect to all the repeating units. Sex polysilsesquioxane compound

[R ¹ is an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a substituent (excluding a group having an epoxy ring), and an unsubstituted aryl group having 6 to 12 carbon atoms. , And at least one selected from the group consisting of an aryl group having 6 to 12 carbon atoms having a substituent (excluding a group having an epoxy ring). ]
Component (B): Silicone oligomer having or not having a repeating unit derived from a trifunctional silane compound and having or not having a repeating unit derived from a tetrafunctional silane compound, and having an epoxy equivalent of 50 to 2,000 g / eq. Yes, the total amount of the repeating unit derived from the trifunctional silane compound and the repeating unit derived from the tetrafunctional silane compound is 80 mol% or more in all the repeating units, and at least one of the trifunctional silane compounds is a group having an epoxy ring. Silicone oligomer which is a trifunctional silane compound having The curable composition according to claim 1 or 2 , wherein the mass average molecular weight (Mw) of the component (A) is 800 to 30,000. The curable composition according to any one of claims 1 to 3 , wherein the mass average molecular weight (Mw) of the component (B) is 500 to 5,000. The curable composition according to claim 1 , 3 or 4 , wherein the epoxy equivalent of the component (B) is 50 to 2,000 g / eq. The curable composition according to any one of claims 1 to 5, wherein the total amount of the component (A) and the component (B) is 30 to 100% by mass in the solid content of the curable composition. The curable composition according to any one of claims 1 to 6, further comprising the following component (C).
Ingredient (C): Silane coupling agent A cured product obtained by curing the curable composition according to any one of claims 1 to 7. The cured product according to claim 8, which is an optical element fixing material. A method in which the curable composition according to any one of claims 1 to 7 is used as an adhesive for an optical element fixing material. A method in which the curable composition according to any one of claims 1 to 7 is used as a sealing material for an optical element fixing material.