JP7310047B2 - Curable composition, cured product, method for producing cured product, and method for using curable composition - Google Patents

Description

The present invention provides a curable composition that provides a cured product having excellent peel resistance and heat resistance and high adhesive strength, a cured product obtained by curing the composition, a method for producing the same, and the composition. as an adhesive for fixing optical elements or a sealing material for fixing optical elements.

Conventionally, curable compositions have been variously improved according to their uses, and are widely used industrially as raw materials for optical parts and moldings, adhesives, coating agents, and the like.
In addition, the curable composition is also attracting attention as an optical element fixing material such as an optical element fixing adhesive or an optical element fixing encapsulant when manufacturing an optical element sealing body.

Optical devices include various lasers such as semiconductor lasers (LD), light emitting devices such as light emitting diodes (LED), light receiving devices, composite optical devices, optical integrated circuits, and the like. In recent years, blue-light and white-light optical elements with shorter peak emission wavelengths have been developed and widely used. The brightness of such light-emitting elements having a short peak wavelength of light emission is rapidly increasing, and accordingly, the amount of heat generated by the optical elements tends to increase further.

However, as the brightness of optical elements has increased in recent years, the cured product of the optical element fixing composition is exposed to higher energy light and higher temperature heat generated from the optical element for a long time, and deteriorates and peels off. or the adhesive force is lowered.

In order to solve this problem, Patent Documents 1 to 3 disclose a composition for an optical element fixing material containing a polysilsesquioxane compound as a main component, and Patent Document 4 discloses a hydrolyzate/polycondensate of a silane compound. Semiconductor light-emitting device members and the like to be used have been proposed.
However, even with the cured products such as the compositions and members described in Patent Documents 1 to 4, it was sometimes difficult to obtain peel resistance and heat resistance while maintaining sufficient adhesive strength.

On the other hand, the present inventors have discovered a curable composition that gives a cured product that is excellent in peel resistance and heat resistance and has high adhesive strength (Patent Documents 5 and 6).
However, in order to cure these curable compositions, it was necessary to heat them at a high temperature (170° C. or higher) for about 2 hours. Therefore, when these curable compositions are used in an optical semiconductor light-emitting device or the like, they are exposed to high temperatures during curing, which may damage package peripheral members.

JP-A-2004-359933 JP 2005-263869 A JP 2006-328231 A JP 2007-112975 A WO2012/073988 WO2016/031728 (US2017/253781 A1)

The present invention has been made in view of the above circumstances, and is a curable composition that provides a cured product having high adhesive strength, which can be cured by heating at a lower temperature than conventional curable compositions. The object of the present invention is to provide a product, a cured product obtained by curing the composition, a method for producing the same, and a method of using the composition as an adhesive for fixing an optical element and a sealant for fixing an optical element.

The present inventors have made intensive studies to solve the above problems. As a result, a composition containing a specific silane compound polymer and at least one metal compound selected from the group consisting of a bismuth compound, an aluminum compound and a zirconium compound in a specific ratio can be cured by heating at a low temperature. The inventors have found that the resulting cured product has high adhesive strength, and have completed the present invention.

Thus, according to the present invention, the following [1] to [7] curable compositions, [8] and [9] cured products, [10] method for producing cured products, [11] for fixing optical elements A method of using it as an adhesive and a method of using it as a sealing material for fixing optical elements of [12] are provided.

[1] A curable composition containing the following components (A) and (B), wherein the content of component (B) is more than 0 parts by mass and 3 parts by mass with respect to 100 parts by mass of component (A) part or less.
(A) component: the following formula (a)

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms with or without a substituent, or an aryl group with or without a substituent. R ¹ may be the same or different, Z represents a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, p represents a positive integer, and q and r Each independently represents 0 or a positive integer.)
Silane compound polymer (B) component represented by: at least one metal compound selected from the group consisting of bismuth compounds, aluminum compounds and zirconium compounds

[2] The curable composition according to [1], wherein the weight average molecular weight (Mw) of the silane compound polymer of component (A) is 800 to 50,000.
[3] The curable composition according to [1] or [2], wherein the silane compound polymer is a polycondensation product of one or more silane compounds represented by the following formula (1).

(In the formula, R ¹ has the same meaning as above, X ¹ represents a halogen atom, and s represents an integer of 0 to 3. Multiple R ² and multiple X ¹ are identical to each other. may be different.
[4] The curable composition according to any one of [1] to [3], further comprising the following component (C).
Component (C): a silane coupling agent having a nitrogen atom in the molecule [5] The curable composition according to any one of [1] to [4], further comprising the following component (D).
Component (D): The curable composition according to any one of [1] to [5], further comprising a silane coupling agent [6] having an acid anhydride structure in the molecule and a diluent.
[7] The curable composition according to [6], wherein the curable composition has a solid content concentration of 50% by mass or more and less than 100% by mass.

[8] A cured product obtained by curing the curable composition according to any one of [1] to [7].
[9] The cured product of [8], which is an optical element fixing material.
[10] A method for producing a cured product, wherein the curable composition according to any one of [1] to [7] is heated to 110°C to 130°C to be cured.

[11] A method of using the curable composition according to any one of [1] to [7] as an adhesive for fixing optical elements.
[12] A method of using the curable composition according to any one of [1] to [7] as a sealing material for fixing an optical element.

The curable composition of the present invention can be cured by heating at a lower temperature than conventional compositions. When the curable composition of the present invention is used as a fixing material for an optical element of an optical semiconductor light-emitting device, it is not necessary to set the composition to a high temperature during curing, so that the package member is not damaged by heat.
A cured product obtained by curing the curable composition of the present invention has excellent adhesive strength. Therefore, the curable composition of the present invention can be suitably used as an adhesive for fixing optical elements and a sealant for fixing optical elements.

Hereinafter, the present invention will be described in detail by dividing into 1) a curable composition, 2) a cured product and its production method, and 3) a method for using the curable composition.

1) Curable composition The curable composition of the present invention is a curable composition containing the following components (A) and (B), wherein the content of component (B) is 100 mass of component (A) It is characterized by being more than 0 parts by mass and 3 parts by mass or less with respect to parts.
(A) component: a silane compound polymer represented by the following formula (a)

Component (B): at least one metal compound selected from the group consisting of bismuth compounds, aluminum compounds and zirconium compounds

(A) Component The (A) component used in the curable composition of the present invention is a silane compound polymer represented by the formula (a) (hereinafter sometimes referred to as "silane compound polymer (A)"). is.

In the above formula (a), the repeating unit represented by the formula: -(R ¹ SiO _3/2 )-, the repeating unit represented by the formula: -(R ¹ SiZO _2/2 )-, and the formula: - The repeating units represented by (R ¹ SiZ ₂ O _1/2 )- can be represented by the following (a1) to (a3) respectively. In (a1) to (a3), “—O—” represents an oxygen atom shared by two adjacent Si atoms.

In the silane compound polymer (A) used in the present invention, when each of p, q, and r in formula (a) is 2 or more, the repeating units represented by formulas (a1) to (a3) are , may be the same or different.

In the above formulas (a), (a1), (a2) and (a3), R ¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted , or represents an aryl group having no substituents.
That is, R ¹ is selected from the group consisting of a substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group having a substituent, and an unsubstituted aryl group. It is.
The number of carbon atoms in the "substituted alkyl group having 1 to 10 carbon atoms" means the number of carbon atoms in the alkyl group portion. Therefore, the total carbon number of R ¹ may exceed 10 in some cases.

The alkyl group having 1 to 10 carbon atoms for R ¹ includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group and n-pentyl. group, n-hexyl group, n-octyl group, n-nonyl group and the like.

Examples of substituents of the substituted alkyl group having 1 to 10 carbon atoms of R ¹ include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; cyano group; group represented by formula: OG; is mentioned.
G represents a hydroxyl-protecting group. The hydroxyl-protecting group is not particularly limited, and includes known protecting groups known as hydroxyl-protecting groups. For example, acyl protecting group; silyl protecting group such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group; methoxymethyl group, methoxyethoxymethyl group, 1-ethoxyethyl group , tetrahydropyran-2-yl group, acetal protecting group such as tetrahydrofuran-2-yl group; alkoxycarbonyl protecting group such as t-butoxycarbonyl group; methyl group, ethyl group, t-butyl group, octyl group , an allyl group, a triphenylmethyl group, a benzyl group, a p-methoxybenzyl group, a fluorenyl group, a trityl group, a benzhydryl group, and the like.

The aryl group for R ¹ includes aryl groups having 6 to 20 carbon atoms such as phenyl group, 1-naphthyl group and 2-naphthyl group.
Examples of substituents of the aryl group having a substituent for R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n- Alkyl groups such as 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; alkoxy groups such as methoxy group and ethoxy group; be done.

Among these, R ¹ is a substituted alkyl group having 1 to 6 carbon atoms, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an unsubstituted aryl group, more preferably a substituted alkyl group having 1 to 6 carbon atoms, an unsubstituted alkyl group having 1 to 6 carbon atoms, or a phenyl group, an alkyl group having 1 to 6 carbon atoms having a cyano group, fluorine More preferably, an alkyl group having 1 to 6 carbon atoms having an atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or a phenyl group, an alkyl group having 1 to 3 carbon atoms having a cyano group, and a carbon number having a fluorine atom A 1 to 3 alkyl group, an unsubstituted alkyl group having 1 to 3 carbon atoms, or a phenyl group is particularly preferred.
Plural R ^1s may all be the same or different.

Z represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
The alkoxy group having 1 to 10 carbon atoms for Z includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, pentyloxy and the like. A chlorine atom, a bromine atom, etc. are mentioned as a halogen atom.
Among these, Z is preferably a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.
p represents a positive integer, and q and r each independently represents 0 or a positive integer.
Plural R ^1s may all be the same or different.
Moreover, all of a plurality of Z's may be the same or different.

The method for producing the silane compound polymer (A) is not particularly limited.
For example, it can be produced by polycondensing one or more silane compounds represented by the following formula (1) (hereinafter sometimes referred to as "silane compound (1)"). Here, "polycondensation" is used as a broad concept including hydrolysis and polycondensation reactions.

In formula (1), R ¹ has the same meaning as above. R ² represents an alkyl group having 1-10 carbon atoms, X ¹ represents a halogen atom, and s represents an integer of 0-3.

Examples of the alkyl group having 1 to 10 carbon atoms for R ² include those exemplified as the alkyl group having 1 to 10 carbon atoms for R ¹ .
A chlorine atom, a bromine atom, etc. are mentioned as a halogen atom of ^X1 .
When s is 2 or more, a plurality of OR ² may be the same or different. Also, when (3-s) is 2 or more, a plurality of X ^1s may be the same or different.

Preferred specific examples of silane compound (1) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane and n-propyltriethoxysilane. , n-propyltripropoxysilane, n-propyltributoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, isooctyltrimethoxysilane, isooctyltri Alkyltrialkoxysilane compounds such as ethoxysilane;

methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane, n-propylchlorodimethoxysilane, n - alkylhalogenoalkoxysilane compounds such as propyldichloromethoxysilane, n-butylchlorodimethoxysilane, n-butyldichloromethoxysilane;

methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, ethyltribromosilane, n-propyltrichlorosilane, n-propyltribromosilane, n-butyltrichlorosilane, isobutyltrichlorosilane, n-pentyltrichlorosilane, n-hexyl Alkyltrihalogenosilane compounds such as trichlorosilane, isooctyltrichlorosilane;

phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 2-chlorophenyltrimethoxysilane, phenyltriethoxysilane, 2-methoxyphenyltriethoxysilane, phenyldimethoxyethoxysilane, phenyldiethoxymethoxysilane, etc. phenyltrialkoxysilane compounds that may be
optionally substituted phenylhalogenoalkoxysilane compounds such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, phenylchloromethoxyethoxysilane, phenylchlorodiethoxysilane, and phenyldichloroethoxysilane;
optionally substituted phenyltrihalogenosilane compounds such as phenyltrichlorosilane, phenyltribromosilane, 4-methoxyphenyltrichlorosilane, phenyltrichlorosilane, 2-ethoxyphenyltrichlorosilane, and 2-chlorophenyltrichlorosilane;

Cyanomethyltrimethoxysilane, Cyanomethyltriethoxysilane, 1-Cyanoethyltrimethoxysilane, 2-Cyanoethyltrimethoxysilane, 2-Cyanoethyltriethoxysilane, 2-Cyanoethyltripropoxysilane, 3-Cyanopropyltrimethoxysilane, 3- Cyanopropyltriethoxysilane, 3-cyanopropyltripropoxysilane, 3-cyanopropyltributoxysilane, 4-cyanobutyltrimethoxysilane, 5-cyanopentyltrimethoxysilane, 2-cyanopropyltrimethoxysilane, 2-(cyano methoxy)ethyltrimethoxysilane, 2-(2-cyanoethoxy)ethyltrimethoxysilane, o-(cyanomethyl)phenyltripropoxysilane, m-(cyanomethyl)phenyltrimethoxysilane, p-(cyanomethyl)phenyltriethoxysilane, Cyanoalkyltrialkoxysilane compounds such as p-(2-cyanoethyl)phenyltrimethoxysilane;

Cyanomethyltrichlorosilane, cyanomethylbromodimethoxysilane, 2-cyanoethyldichloromethoxysilane, 2-cyanoethyldichloroethoxysilane, 3-cyanopropyltrichlorosilane, 3-cyanopropyltribromosilane, 3-cyanopropyldichloromethoxysilane, 3- Cyanopropyldichloroethoxysilane, 3-cyanopropylchlorodimethoxysilane, 3-cyanopropylchlorodiethoxysilane, 4-cyanobutylchlorodiethoxysilane, 3-cyano-n-butylchlorodiethoxysilane, 2-(2-cyano ethoxy)ethyltrichlorosilane, 2-(2-cyanoethoxy)ethylbromodiethoxysilane, 2-(2-cyanoethoxy)ethyldichloropropoxysilane, o-(2-cyanoethyl)phenyltrichlorosilane, m-(2-cyanoethyl ) cyanoalkylhalogenosilane compounds such as phenylmethoxydibromosilane, p-(2-cyanoethyl)phenyldimethoxychlorosilane, p-(2-cyanoethyl)phenyltribromosilane;

fluoroalkyltrialkoxysilane compounds such as 3,3,3-trifluoropropyltrimethoxysilane and 3,3,3-trifluoropropyltriethoxysilane;
3,3,3-trifluoropropylchlorodimethoxysilane, 3,3,3-trifluoropropylchlorodiethoxysilane, 3,3,3-trifluoropropyldichloromethoxysilane, 3,3,3-trifluoropropyldichloro fluoroalkylhalogenoalkoxysilane compounds such as ethoxysilane;
fluoroalkyltrihalogenosilane compounds such as 3,3,3-trifluoropropyltrichlorosilane; and the like.
The silane compound (1) can be used singly or in combination of two or more.

Among these, the silane compound (1) is preferably a trialkoxysilane compound because a cured product having better adhesiveness can be easily obtained, and (i) an alkyltrialkoxysilane compound having 1 to 10 carbon atoms. , (ii) a combination of a phenyltrialkoxysilane compound and a trialkoxysilane compound having a cyanoalkyl group having 1 to 10 carbon atoms, or (iii) an alkyltrialkoxysilane compound having 1 to 10 carbon atoms and 1 carbon atom. A combination with a trialkoxysilane compound having ˜10 fluoroalkyl groups is more preferred.

When the phenyltrialkoxysilane compound and the cyanoalkyltrialkoxysilane compound having 1 to 10 carbon atoms are used in combination, the ratio of the phenyltrialkoxysilane compound and the cyanoalkyltrialkoxysilane compound having 1 to 10 carbon atoms is the molar ratio. and [phenyltrialkoxysilane compound]:[cyanoalkyltrialkoxysilane compound having 1 to 10 carbon atoms] = 95:5 to 50:50, more preferably 90:10 to 60:40.

When an alkyltrialkoxysilane compound having 1 to 10 carbon atoms and a trialkoxysilane compound having a fluoroalkyl group having 1 to 10 carbon atoms are used in combination, the alkyltrialkoxysilane compound having 1 to 10 carbon atoms and the alkyltrialkoxysilane compound having 1 to 10 carbon atoms are combined. The molar ratio of the trialkoxysilane compound having a fluoroalkyl group of up to 10 to be used is [alkyltrialkoxysilane compound having 1 to 10 carbon atoms]:[trialkoxysilane having a fluoroalkyl group having 1 to 10 carbon atoms. compound]=95:5 to 10:90 is preferred, 90:10 to 30:70 is more preferred, and 85:15 to 50:50 is even more preferred.

The method of polycondensing the silane compound (1) is not particularly limited, but a method of adding a predetermined amount of catalyst to the silane compound (1) in a solvent or without solvent and stirring the whole at a predetermined temperature. mentioned.

The catalyst used may be either an acid catalyst or a base catalyst.
Also, an acid catalyst and a base catalyst can be used in combination. For example, after conducting the polycondensation reaction of the silane compound in the presence of an acid catalyst, the reaction solution may be made basic by adding a base catalyst, and the polycondensation reaction may be further conducted under basic conditions.
Acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid and trifluoroacetic acid; be done.

Base catalysts include ammonia (water); trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), aniline, picoline. , 1,4-diazabicyclo[2.2.2]octane, imidazole and other organic bases; tetramethylammonium hydroxide, tetraethylammonium hydroxide and other organic salt hydroxides; sodium methoxide, sodium ethoxide, sodium t-butoxide , metal alkoxides such as potassium t-butoxide; metal hydrides such as sodium hydride and calcium hydride; metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide; sodium carbonate, potassium carbonate, magnesium carbonate and the like metal carbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; and the like.

The amount of the catalyst used is usually in the range of 0.1 mol % to 10 mol %, preferably 1 mol % to 5 mol %, relative to the total molar amount of silane compound (1).

The solvent to be used can be appropriately selected according to the type of 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 and t-butyl alcohol; These solvents can be used singly or in combination of two or more.

The amount of the solvent to be used is not particularly limited, but it is usually 0.1 to 10 liters, preferably 0.1 to 2 liters per 1 mol of the total molar amount of the silane compound (1).

The temperature at which the silane compound (1) is polycondensed (reacted) is usually in the range of 0°C to the boiling point of the solvent used, preferably in the range of 20°C to 100°C. If the reaction temperature is too low, the condensation reaction may not progress sufficiently. On the other hand, if the reaction temperature is too high, it becomes difficult to suppress gelation. The reaction is usually completed in 30 minutes to 30 hours.

Depending on the type of silane compound (1) used, it may be difficult to increase the molecular weight. For example, silane compounds in which R ¹ is a fluoroalkyl group tend to be less reactive than silane compounds in which R ¹ is a normal alkyl group. In such a case, by reducing the amount of catalyst and conducting the reaction under mild conditions for a long time, gelation can be suppressed and the silane compound polymer (A) having the desired molecular weight can be easily obtained.

After the completion of the reaction, when an acid catalyst is used, an alkaline aqueous solution such as sodium hydrogen carbonate is added to the reaction solution, and when a base catalyst is used, an acid such as hydrochloric acid is added to the reaction solution. The mixture is combined, and the salt generated at that time is removed by filtration or washing with water to obtain the target silane compound polymer.

When the silane compound polymer (A) is produced by the above method, the portion of OR ² or X ¹ of the silane compound (1) that has not been dehydrated and/or dealcoholized is included in the silane compound polymer (A). remain in That is, when there is one remaining OR ² or X ¹ , it remains as (R ¹ SiZO _2/2 ) in the formula (a), and when there are two remaining OR ² or X ¹ , in formula (a), remains as (R ¹ SiZ ₂ O _1/2 ).

The silane compound polymer (A) may be a homopolymer (a polymer having one type of R ¹ ) or a copolymer (a polymer having two or more types of R ¹ ).
When the silane compound polymer (A) is a copolymer (a polymer having two or more ^R1 ), the silane compound polymer (A) may be a random copolymer, a block copolymer, a graft copolymer, Although any copolymer such as an alternating copolymer may be used, a random copolymer is preferable from the viewpoint of ease of production.
Further, the structure of the silane compound polymer (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 weight average molecular weight (Mw) of the silane compound polymer (A) is usually in the range of 800-50,000, preferably 3,000-30,000, more preferably 5,000-15,000. Within this range, a cured product having excellent handleability of the composition, adhesiveness and heat resistance can be obtained.
The mass average molecular weight (Mw) and number average molecular weight (Mn) can be obtained as standard polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent (same below is.).

Although the molecular weight distribution (Mw/Mn) of the silane compound polymer (A) is not particularly limited, it is usually in the range of 1.0-10.0, preferably 1.1-6.0. By being in the said range, the hardened|cured material which is excellent in adhesiveness and heat resistance is obtained.
The silane compound polymer (A) can be used singly or in combination of two or more.

The content of the silane compound polymer (A) is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, and still more preferably 60 to 85% by mass in the solid content of the curable composition. .

Component (B) The curable composition of the present invention contains, as component (B), at least one metal compound selected from the group consisting of bismuth compounds, aluminum compounds and zirconium compounds.
Since the curable composition of the present invention contains the component (B), it can be cured at a lower temperature in a short time, and a cured product having excellent adhesion can be obtained. .

The metal compound of component (B) is not particularly limited as long as it is a compound containing bismuth, aluminum or zirconium. and compounds of tetravalent zirconium are preferred.

Bismuth compounds, aluminum compounds and zirconium compounds include, for example, bismuth, aluminum or zirconium halides, metal hydroxides, metal oxides, inorganic salts (nitrates, sulfates, carbonates, hydrogen carbonates, phosphates etc.), alkoxides, carboxylates, chelate compounds and the like.

More specific examples include, but are not limited to, the following.
Halides such as bismuth chloride, bismuth bromide, aluminum chloride, aluminum bromide, zirconium chloride, zirconium bromide;
metal oxides such as bismuth oxide, bismuth oxide chloride, aluminum oxide, zirconium dioxide;
metal hydroxides such as bismuth hydroxide, aluminum hydroxide, zirconium hydroxide;
Nitrates such as bismuth nitrate, aluminum nitrate, zirconium nitrate;
Sulfates such as bismuth sulfate, aluminum sulfate, and zirconium sulfate;
carbonates such as bismuth carbonate, aluminum carbonate, zirconium carbonate;
Hydrogen carbonates such as bismuth hydrogen carbonate, aluminum hydrogen carbonate, zirconium hydrogen carbonate;
Phosphates such as bismuth phosphate, aluminum phosphate, zirconium phosphate;

^A _metal ^alkoxide ₍ ^R _{_} ⁴ is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, etc. Alkyl group having 1 to 20 carbon atoms; Alkenyl group having 2 to 20 carbon atoms such as 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, and 3-butenyl group; Phenyl group, etc. Aromatic groups having 6 to 20 carbon atoms; aralkyl groups having 7 to 20 carbon atoms such as benzyl group and phenethyl group; represents a cycloalkyl group; etc.);

Bismuth, aluminum or zirconium acetate, propionate, octanoate, nonanoate, dodecanoate (laurate), tetradecanoate (myristate), hexadecanoate (palmitate), octadecane Fatty acid salts such as acid salts (stearate), naphthenate, octylate, neodecanoate, isostearate; aromatic carboxylates such as benzoates; polyvalent carboxylates such as succinates; Unsaturated carboxylates such as maleates, linolenates, linoleates, oleates, arachidonates; rosinates; carboxylates such as;
Bismuth, aluminum or zirconium and a polydentate ligand (e.g., β-diketone compounds such as acetylacetone and benzoylacetone; β-ketoesters such as methyl acetoacetate and ethyl acetoacetate; carbonato; ethylenediamine; compound) and a chelate compound.

Also, the metal compound of component (B) may have a structure in which multiple types of ligands are bonded to bismuth, aluminum, or zirconium.
Ligands include halide ions, hydride ions (hydride), oxygen atoms (oxo, peroxo), hydroxy (hydroxo), water (aqua or aco), carbon monoxide (carbonyl), carbonate ions (carbonato, CO ₃ ^2- ) and other inorganic ligands;
Oxalate ion (oxalato, C ₂ O ₄ ^2- ), alkoxy group (eg methoxy group, ethoxy group), acyl group (eg acetyl group, propionyl group, benzoyl group), carboxylate group, acetylacetonato, ethyl Acetoacetate, cycloalkadienyl (e.g., cyclopentadienyl, dicyclopentadienyl), ether (e.g., diethyl ether), hydrocarbon group (e.g., methyl group, alkyl group such as ethyl group; phenyl group, naphthyl aryl group such as group);
Nitrogen-containing ligands such as ammonia, nitro, nitrite (NO ₂ ⁻ ), cyano, cyanato, isocyanato, alkylamides (e.g. dimethylamide), ethylenediamine, diethylenetriamine, pyridine, phenanthroline;
organic ligands such as sulfur-containing ligands such as thiocyanato and isothiocyanato;

Preferable specific examples of the (B) component metal compound include the following.
(bismuth compound)
Bismuth halides such as bismuth chloride oxide, bismuth chloride and bismuth bromide; inorganic salts of bismuth such as bismuth hydroxide, bismuth nitrate and bismuth sulfate; bismuth acetate, bismuth benzoate, bismuth octylate, bismuth naphthenate, oxysalicylic acid Bismuth carboxylates such as bismuth, bismuth neodecanoate, bismuth rosinate, bismuth versate, bismuth 2-ethylhexanoate [bismuth tris (2-ethylhexanoate)], bismuth stearate; -O]triphenylbismuth; etc.

(aluminum compound)
aluminum halides such as aluminum chloride; aluminum alkoxides such as aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum trisec-butylate, aluminum tributyrate; aluminum tris(acetylacetonate), aluminum aluminum chelate compounds such as tris(ethylacetoacetate), aluminum monoacetylacetonate bis(ethylacetoacetate), aluminum diisopropoxyacetylacetonate;

(zirconium compound)
zirconium halides such as zirconium oxychloride; inorganic zirconium salts such as zirconium sulfate and zirconium nitrate; zirconium carboxylates such as zirconium acetate, zirconium octylate and zirconium stearate; zirconium alkoxides such as n-butoxide and zirconium octoxy/tridecooxide; zirconium chelate compounds such as zirconium tetrakisacetylacetonate, zirconium tributoxy monoacetylacetonate, and zirconium tributoxy/monoacetylacetonate;

Among these, bismuth halides, bismuth carboxylates, [carbonato(2-)-O]triphenylbismuth, aluminum chelate compounds, and zirconium carboxylates are more preferable, and bismuth halides and bismuth carbon More preferred are carboxylates having 6 to 20 carbon atoms, [carbonato(2-)-O]triphenylbismuth, aluminum chelate compounds, zirconium carboxylates having 6 to 20 carbon atoms, bismuth chloride, bismuth octylate, [ Carbonato(2-)-O]triphenylbismuth, aluminum chelate compounds, and zirconium octylate are particularly preferred.

The lower limit of the content of component (B) is more than 0 parts by mass, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, per 100 parts by mass of component (A). The upper limit of the content of component (B) is 3 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less per 100 parts by mass of component (A).
A curable composition that can be cured at a low temperature (110 to 130° C.) in a short time can be obtained by blending the component (B) in such a ratio.

Component (C) The curable composition of the present invention further includes component (C): a silane coupling agent having a nitrogen atom in the molecule (hereinafter sometimes referred to as "silane coupling agent (C)"). preferably contains
The curable composition containing the component (C) provides a cured product that is excellent in workability in the coating step and also excellent in adhesiveness, peeling resistance, and heat resistance.

The silane coupling agent (C) is not particularly limited as long as it is a silane coupling agent having a nitrogen atom in its molecule. Examples thereof include a trialkoxysilane compound represented by the following formula (c-1), and a dialkoxyalkylsilane compound or dialkoxyarylsilane compound represented by the formula (c-2).

In the above formula, R ^a represents an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and t-butoxy. A plurality of R ^a may be the same or different.
R ^b is an alkyl group having 1 to 6 carbon atoms such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group; or a phenyl group, 4-chlorophenyl group, 4- an aryl group with or without a substituent, such as a methylphenyl group;

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

Among the compounds represented by the formula (c-1) or (c-2), the compound in which R ^c is an organic group bonded to another silicon atom-containing group includes an isocyanurate skeleton. Examples include those that form an isocyanurate-based silane coupling agent by bonding with other silicon atoms, and those that form a urea-based silane coupling agent by bonding with other silicon atoms via a urea skeleton.

Among these, the silane coupling agent (C) is preferably an isocyanurate-based silane coupling agent and a urea-based silane coupling agent because a cured product having higher adhesive strength can be easily obtained. Among them, those having 4 or more silicon-bonded alkoxy groups are preferred.
Having 4 or more silicon-bonded alkoxy groups means that the total number of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is 4 or more.

As the isocyanurate-based silane coupling agent having 4 or more silicon-bonded alkoxy groups, a compound represented by the following formula (c-3) is a urea-based silane cup having 4 or more silicon-bonded alkoxy groups. Ring agents include compounds 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, particularly preferably 3.

Specific examples of the compound represented by formula (c-3) include 1,3,5-N-tris(3-trimethoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-tri 1, such as ethoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-triisopropoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-tributoxysilylpropyl) isocyanurate , 3,5-N-tris[(tri(C1-6)alkoxy)silyl(C1-10)alkyl]isocyanurate; 1,3,5-N-tris(3-dithoxymethylsilylpropyl ) isocyanurate, 1,3,5-N-tris(3-dimethoxyethylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-dimethoxyisopropylsilylpropyl) isocyanurate, 1,3,5- N-tris(3-dimethoxy n-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-dimethoxyphenylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-diethoxy methylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diethoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diethoxyisopropylsilylpropyl)isocyanurate, 1 , 3,5-N-tris(3-diethoxy n-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-diethoxyphenylsilylpropyl) isocyanurate, 1,3,5-N- Tris (3-diisopropoxymethylsilylpropyl) isocyanurate, 1,3,5-N-tris (3-diisopropoxyethylsilylpropyl) isocyanurate, 1,3,5-N-tris (3-diiso Propoxyisopropylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diisopropoxyn-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diisopropoxyphenylsilylpropyl) ) isocyanurate, 1,3,5-N-tris(3-dibutoxymethylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-dibutoxyethylsilylpropyl) isocyanurate, 1,3, 5-N-tris(3-dibutoxyisopropylsilylpropyl) isocyanurate, 1,3,5-N-tris(3-dibutoxy n-propylsilylpropyl) isocyanurate, 1,3,5-N-tris(3 1,3,5-N-tris[(di(C1-6)alkoxy)silyl(C1-10)alkyl]isocyanurate such as -dibutoxyphenylsilylpropyl)isocyanurate;

Specific examples of the compound represented by formula (c-4) include N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea, N , N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, N,N'-bis(2-trimethoxysilylethyl)urea, etc. N'-bis[(tri(C1-6)alkoxysilyl)(C1-10)alkyl]urea; N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis (3-dimethoxyethylsilylpropyl)urea, N,N'-bis(3-diethoxymethylsilylpropyl)urea and other N,N'-bis[(di(C 1-6) alkoxy (C 1- 6) Alkylsilyl (C1-C10) aryl)urea; N,N'-bis(3-dimethoxyphenylsilylpropyl)urea, N,N'-bis(3-diethoxyphenylsilylpropyl)urea such as N,N'-bis[(di(C1-6)alkoxy(C6-20)arylsilyl(C1-10)alkyl)urea;

Among these, the silane coupling agent (C) includes 1,3,5-N-tris(3-trimethoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-triethoxysilylpropyl) ) Isocyanurate (hereinafter referred to as "isocyanurate compound"), N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea (hereinafter, " urea compound"), and a combination of the isocyanurate compound and the urea compound are preferably used.

When the isocyanurate compound and the urea compound are used in combination, the ratio by mass of the (isocyanurate compound) and the (urea compound) is preferably 100:1 to 100:200, preferably 100: 10 to 100:110 is more preferred. By using the isocyanurate compound and the urea compound in combination in such a ratio, it is possible to obtain a curable composition that gives a cured product with excellent heat resistance and adhesiveness.
Silane coupling agents (C) can be used alone or in combination of two or more.

When the curable composition of the present invention contains component (C), the amount of component (C) used is such that the proportion of component (A) and component (C) used is equal to component (A) and component (C). The mass ratio [(A) component: (C) component] is preferably 100:0.3 to 100:50, more preferably 100:1 to 100:40, and still more preferably 100:3 to 100:35. is the amount.
By using the components (A) and (C) in such proportions, the cured product of the curable composition of the present invention becomes more excellent in heat resistance and adhesiveness.

Component (D) In the curable composition of the present invention, component (D): a silane coupling agent having an acid anhydride structure in the molecule (hereinafter sometimes referred to as "silane coupling agent (D)"). preferably contains
The curable composition containing the component (D) gives a cured product that is superior in workability in the coating step and also superior in adhesiveness, peeling resistance, and heat resistance.

The silane coupling agent (D) is an organosilicon compound having both a group (Q) having an acid anhydride structure and a hydrolyzable group (R ^e ) in one molecule. Specifically, it is a compound represented by the following formula (d).

In the formula, Q represents a group having an acid anhydride structure, R ^d represents an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted phenyl group, and R ^e represents a carbon represents an alkoxy group of numbers 1 to 6 or a halogen atom, i and k represent integers of 1 to 3, j represents an integer of 0 to 2, and i+j+k=4. When j is 2, ^Rd 's may be the same or different. When k is 2 or 3, a plurality of R ^e may be the same or different. When i is 2 or 3, multiple Qs may be the same or different.
As Q, the following formula

(Wherein, h represents an integer of 0 to 10.) and the like, and the group represented by (Q1) is particularly preferred.
In formula (d), the C1-6 alkyl group for R ^d includes the same groups as those exemplified as the C1-6 alkyl group for R ¹ .
The substituents of the phenyl group having a substituent for R ^d include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group and n-pentyl. alkyl groups such as groups and n-hexyl groups; halogen atoms such as fluorine atoms, chlorine atoms and bromine atoms; alkoxy groups such as methoxy groups and ethoxy groups;
The alkoxy group having 1 to 6 carbon atoms of R ^e includes a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group and a t-butoxy group.
A chlorine atom, a bromine atom, etc. are mentioned as a halogen atom of R ^e .

Among these, as the compound represented by formula (d), the following formula (d-1)

(In the formula, R ^e , h, i, j, and k have the same meanings as above.)
A compound represented by is preferred. In the formula, h is preferably 2 to 8, more preferably 2 or 3, particularly preferably 3.

Specific examples of the silane coupling agent represented by the formula (d-1) include 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, 3-(trimethoxy Tri(C1-6)alkoxysilyl(C2-8)alkylsuccinic anhydride such as silyl)propylsuccinic anhydride, 3-(triethoxysilyl)propylsuccinic anhydride; 2-(dimethoxymethylsilyl) di(C1-C6) alkoxymethylsilyl (C2-8) alkyl succinic anhydride such as ethyl succinic anhydride; 2-(methoxydimethylsilyl) ethyl succinic anhydride (C1-6 ) alkoxydimethylsilyl (2-8 carbon atoms) alkyl succinic anhydride;

Trihalogenosilyl (C 2-8) alkyl succinic anhydride such as 2-(trichlorosilyl)ethyl succinic anhydride, 2-(tribromosilyl)ethyl succinic anhydride; 2-(dichloromethylsilyl)ethyl succinic anhydride dihalogenomethylsilyl (2-8 carbon atoms) alkyl succinic anhydride such as acid; halogenodimethylsilyl (2-8 carbon atoms) alkyl succinic anhydride such as 2-(chlorodimethylsilyl)ethyl succinic anhydride; is mentioned.
Silane coupling agents (D) can be used alone or in combination of two or more.

Among these, the silane coupling agent (D) is preferably tri(C 1-6) alkoxysilyl (C 2-8) alkyl succinic anhydride, 3-(trimethoxysilyl) propyl succinic anhydride, 3-(Triethoxysilyl)propyl succinic anhydride is particularly preferred.

When the curable composition of the present invention contains component (D), the content of component (D) is not particularly limited, but the mass ratio of component (A) and component (D) [component (A): (D) component], preferably 100:0.01 to 100:30, more preferably 100:0.1 to 100:10.
A cured product of the curable composition containing the components (A) and (D) in such a ratio has excellent heat resistance and adhesiveness.

(E) Diluent The curable composition of the invention may further contain a diluent for the purpose of imparting fluidity.
The diluent is not particularly limited as long as it is compatible with the components (A) and (B). For example, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, nitrogen-containing compounds such as dimethylimidazolidinone; sulfur-containing compounds such as dimethylsulfoxide; diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , dipropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol-n-butyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Ether Acetate, Diethylene Glycol Monobutyl Ether Acetate, Dipropylene Glycol Methyl Ether Acetate, Propylene Glycol Phenyl Ether, 2,2,4-Trimethyl-1,3-Pentanediol Monoisobutyrate (Texanol), γ-Butyrolactone, Ethyl Lactate, 1 -oxygen-containing compounds such as methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol mono-n-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol;

These diluents can be used singly or in combination of two or more.
When the curable composition of the present invention contains a diluent, from the viewpoint of workability, the amount of the diluent used is such that the solid content concentration of the curable composition of the present invention is 50% by mass or more and less than 100% by mass. An amount of 60 to 90% by mass is more preferable, and an amount of 70 to 85% by mass is even more preferable.

(F) Other Components The curable composition of the present invention may contain “other components” other than the components (A) to (E) as long as the objects of the present invention are not hindered.
Other components include fine particles, antioxidants, UV absorbers, light stabilizers, and the like.

By adding fine particles, it may be possible to obtain a curable composition having excellent workability in the coating process. Materials of the fine particles include silica; resins such as acryl and silicone; metal oxides such as aluminum oxide and titanium oxide; and minerals such as boehmite.
These microparticles|fine-particles can be used individually by 1 type or in combination of 2 or more types. The amount of fine particles to be used is generally 10% by mass or less relative to component (A).

Antioxidants are added to prevent oxidative deterioration during heating. Antioxidants include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and the like.

Phosphorus-based antioxidants include phosphites, oxaphosphaphenanthrene oxides, and the like. Phenolic antioxidants include monophenols, bisphenols, polymeric phenols, and the like. Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and the like.

These antioxidants can be used singly or in combination of two or more. The amount of antioxidant to be used is generally 10% by mass or less relative to the component (A).

A UV absorber is added for the purpose of improving the light resistance of the resulting cured product.
Examples of ultraviolet absorbers include salicylic acids, benzophenones, benzotriazoles, hindered amines and the like.
Ultraviolet absorbers can be used singly or in combination of two or more.
The amount of the ultraviolet absorber to be used is generally 10% by mass or less relative to the component (A).

A light stabilizer is added for the purpose of improving the light resistance of the resulting cured product.
Light stabilizers include, for example, poly[{6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6 ,6-tetramethyl-4-piperidine)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidine)imino}] and other hindered amines.
These light stabilizers can be used singly or in combination of two or more.
The amount of light stabilizer used is usually 10% by mass or less relative to component (A).

The curable composition of the present invention is prepared, for example, by blending the components (A), (B), and optionally (C) to (F) in a predetermined proportion, and mixing and defoaming by a known method. can be obtained by

The curable composition of the present invention can be cured by heating at a lower temperature than conventional ones, and the resulting cured product has excellent peel resistance, heat resistance, and high adhesive strength.
When the curable composition of the present invention is used in an optical element device, it does not need to be heated at a high temperature when curing the curable composition. do not have.
Therefore, the curable composition of the present invention is suitably used as a raw material for optical parts and moldings, an adhesive, a coating agent, and the like.

2) Cured Product and Production Method Thereof The cured product of the present invention is obtained by curing the curable composition of the present invention.
A method of curing the curable composition of the present invention includes a method of curing by heating.
The cured product of the present invention is obtained by heating the curable composition of the present invention to generally 100° C. to 150° C., preferably 110° C. to 140° C., more preferably 110° C. to 130° C. for curing. can be done. The heating time is usually 10 minutes to 5 hours, preferably 30 minutes to 3 hours.
The cured product of the present invention can be obtained by curing at such a low temperature and by heating for a short period of time. Therefore, when used in an optical semiconductor light-emitting device or the like, there is no possibility of exposing the peripheral members of the package to high temperature and damaging them.

For example, it can be confirmed as follows that the cured product of the present invention can be obtained in a short time by heating the curable composition of the present invention at a low temperature.
That is, using an automatic curing time measuring device (manufactured by Cyber Co., Ltd., product name "Madoka"), a sample of the curable composition was put on a stainless steel plate heated to 120 ° C. and stirred, and the stirring torque increased. and measure the time until it reaches 0.392 N·cm.
The time required to reach 0.392 N·cm is preferably 8,000 seconds or less.

In addition, it can be confirmed, for example, in the following manner that the cured product of the present invention has high adhesive strength even if it is obtained by curing by heating at a low temperature.
That is, a curable composition is applied to the mirror surface of a silicon chip, the applied surface is placed on an adherend and pressed, and heat-treated at a low temperature (for example, 120° C.) to cure. This adherend with the test piece is left on the measurement stage of a bond tester preheated to a predetermined temperature (for example, 23 ° C.) for 30 seconds, and from a position of 100 μm above the adherend, the horizontal direction to the adhesive surface A stress is applied (in the shear direction) to measure the adhesion between the test piece and the adherend.
The adhesive strength of the cured product thus measured is preferably 50 N/4 mm ² or more, more preferably 70 N/4 mm ² or more at 23°C.
Here, “N/4 mm ² ” is the adhesive force [N] per area of 2 mm×2 mm.

3) Method of using curable composition The method of using the curable composition of the present invention is a method of using the curable composition of the present invention as an adhesive for fixing optical elements or a sealant for fixing optical elements.
Examples of optical devices include light-emitting devices such as LEDs and LDs, light-receiving devices, composite optical devices, optical integrated circuits, and the like.

<Adhesive for fixing optical elements>
The curable composition of the present invention can be suitably used as an adhesive for fixing optical elements.
As a method of using the curable composition of the present invention as an adhesive for fixing optical elements, a predetermined amount of the composition is applied to one or both bonding surfaces of the materials to be bonded (optical element and its substrate, etc.). Then, after pressure bonding, heat curing is performed to firmly bond the materials to be bonded together.

In the present invention, as described above, the heat curing of the curable composition can be performed at a lower temperature and in a shorter time than conventional ones, so that the peripheral members of the optical semiconductor light emitting device do not need to be exposed to high temperatures. It does not damage package materials.

Glass 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 as substrate materials for bonding optical elements , metals such as 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-based resin, cycloolefin resin, glass epoxy resin, and other synthetic resins;

<Encapsulant for fixing optical element>
The curable composition of the present invention can be suitably used as a sealing material for an optical element sealing body.
As a method of using the curable composition of the present invention as a sealing material for fixing an optical element, for example, the composition is molded into a desired shape to obtain a molded article enclosing an optical element, and then the molded article is obtained. and a method of manufacturing an optical element encapsulant by heat curing.
A method for molding the curable composition of the present invention into a desired shape is not particularly limited, and a conventional transfer molding method or a known molding method such as a casting method can be employed.

In the present invention, as described above, the heat curing of the curable composition can be performed at a lower temperature and in a shorter time than conventional ones, so that the peripheral members of the optical semiconductor light emitting device do not need to be exposed to high temperatures. It does not damage package materials.
The resulting optical element encapsulant uses the curable composition of the present invention and therefore has high adhesive strength.

EXAMPLES Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, "%" and "parts" are based on mass.

(Mass average molecular weight measurement)
The mass-average molecular weight (Mw) and number-average molecular weight (Mn) of the silane compound polymers obtained in the following production examples were converted to standard polystyrene values and measured using the following equipment and conditions.
Apparatus name: HLC-8220GPC, manufactured by Tosoh Corporation Column: TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL sequentially linked Solvent: THF
Injection volume: 80 μl
Measurement temperature: 40°C
Flow rate: 1 ml/min Detector: Differential refractometer

(Measurement of IR spectrum)
The IR spectrum of the silane compound polymer obtained in Production Example was measured using a Fourier transform infrared spectrophotometer (Spectrum 100, manufactured by PerkinElmer).

(Production example 1)
After charging 71.37 g (400 mmol) of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBE-13) in a 300 ml eggplant-shaped flask, 0.10 g (400 mmol) of 35% hydrochloric acid was added to 21.6 ml of distilled water. 0.25 mol % with respect to the total amount of silane compounds) was added with stirring, and the total volume was stirred at 30°C for 2 hours, then heated to 70°C and stirred for 5 hours, and then propyl acetate was added. 140 g was added and stirred. 0.12 g of 28% aqueous ammonia (0.5 mol % with respect to the total amount of silane compounds) was added thereto while stirring, and the whole volume was heated to 70° C. and further stirred for 3 hours. Purified water was added to the reaction solution, the phases were separated, 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 dried in vacuum to obtain 55.7 g of silane compound polymer (A1). This product had a mass average molecular weight (MW) of 7,800 and a molecular weight distribution (PDI) of 4.52.
IR spectral data of the silane compound polymer (A1) are shown below.
Si—CH ₃ : 1272 cm ⁻¹ , 1409 cm ⁻¹ , Si—O: 1132 cm ⁻¹

(Production example 2)
In a 300 ml eggplant-shaped flask, 20.2 g (102 mmol) of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.15 g (18 mmol) of 2-cyanoethyltrimethoxysilane (manufactured by Azumax Co., Ltd.), and as a solvent , 96 ml of acetone and 24 ml of distilled water were charged, and then 0.15 g (1.5 mmol) of phosphoric acid (manufactured by Kanto Kagaku Co., Ltd.) was added as a catalyst while stirring the contents, followed by further stirring 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 hydrogencarbonate solution. After standing for a while, the organic layer was separated. The organic layer was then washed twice with distilled water and then dried over anhydrous magnesium sulfate. After removing magnesium sulfate by filtration, the filtrate was concentrated to 50 ml by an evaporator, and the obtained concentrate was dropped into a large amount of n-hexane to precipitate, and the precipitate was separated by decantation. The resulting precipitate was dissolved in methyl ethyl ketone (MEK) and recovered, and the solvent was distilled off under reduced pressure using an evaporator. By vacuum drying the residue, 13.5 g of polysilsesquioxane compound (A2) was obtained. This product had a mass average molecular weight (Mw) of 1,870 and a molecular weight distribution (Mw/Mn) of 1.42.
IR spectral data of the polysilsesquioxane compound (A2) are shown below.
Si—Ph: 698 cm ⁻¹ , 740 cm ⁻¹ , Si—O: 1132 cm ⁻¹ , —CN: 2259 cm ⁻¹

(Example 1)
To 100 parts of the silane compound polymer (A1) obtained in Production Example 1 as component (A), diethylene glycol monobutyl ether acetate (BDGAC): tripropylene glycol-n-butyl ether (TPnB) = 40:60 as component (E). (mass ratio) mixed solvent was added and stirred. Thereafter, 30 parts by mass of 1,3,5-N-tris[3-(trimethoxysilyl)propyl]isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-9659) as component (C), and component (D) , 3-(Trimethoxysilyl) propyl succinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd.: X-12-967C) 3 parts by mass, as the component (B), Pucat 25 (manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.25 A curable composition was obtained by adding parts by mass and thoroughly mixing and defoaming the entire contents.

(Examples 2-12, Comparative Examples 1-4)
In Example 1, Example 2 was prepared in the same manner as in Example 1, except that the type of component (A), the type of component (B), and the amount (parts) used were changed as shown in Table 1 below. 12 curable compositions and comparative examples 1-4 were obtained.
In the table below, the types of the (B) component or the following (b) component used instead of the (B) component: B1 to B5, b1 and b2 represent the following.
In the table, the amount [parts] of component (B) or component (b) used represents parts by mass per 100 parts of component (A).

(B) Component B1: Pucat 25 (manufactured by Nippon Kagaku Sangyo Co., Ltd., bismuth octylate compound)
B2: Orgatics ZC-200 (manufactured by Matsumoto Fine Chemical Co., Ltd., zirconium octylate compound B3: M-5A (manufactured by Soken Chemical Co., Ltd., aluminum chelate compound)
B4: Bismuth chloride B5: [Carbonato(2-)-O]triphenylbismuth (b) Component b1: ORGATIX TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis(ethylacetoacetate))
b2: diazabicycloundecene (DBU)

The cured products of the curable compositions obtained in Examples and Comparative Examples were measured for adhesive strength and evaluated for curability as follows.
The measurement results and evaluation are shown in Table 1 below.

(Measurement of adhesive strength)
Each of the curable compositions obtained in Examples and Comparative Examples was applied to the mirror surface of a silicon chip having a square (2 mm × 2 mm = 4 mm ² ) thickness of 350 µm with a side length of 2 mm and a thickness of about The coating was applied to a thickness of 2 μm, and the coated surface was placed on an adherend (silver-plated copper plate) and pressure-bonded. After that, the curable composition was cured by heating at 120° C. for 2 hours to obtain an adherend with a test piece. This adherend with the test piece is left on the measurement stage of a bond tester (series 4000, manufactured by Daisy) preheated to a predetermined temperature (23 ° C.) for 30 seconds, and from a position at a height of 100 μm from the adherend, Stress was applied horizontally (shear direction) to the adhesive surface at a speed of 200 μm/s, and the adhesive strength [N/4 mm ² ] between the test piece and the adherend at 23° C. was measured.

(Curability evaluation)
The curing time 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 120° C. and stirred. The time (seconds) until the stirring torque increased with time and reached 0.392 N·cm was measured. 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

(Production example 3)
In a 300 mL eggplant-shaped flask, 17.0 g (77.7 mmol) of 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Azumax Co., Ltd.) and methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name After charging 32.33 g (181.3 mmol) of "KBE-13"), this was stirred while adding 0.0675 g of 35% hydrochloric acid to 14.0 g of distilled water (the amount of HCl was 0.65 mmol, the total amount of silane compounds was 0.25 mol %) was added, and the whole volume was stirred at 30° C. for 2 hours, then heated to 70° C. and stirred for 20 hours.
While continuing to stir the contents, a mixed solution of 0.0394 g of 28% aqueous ammonia (the amount of _NH3 is 0.65 mmol) and 46.1 g of propyl acetate was added to adjust the pH of the reaction solution to 6.9. , and stirred 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 for liquid separation treatment to obtain an organic layer containing a reaction product. Drying treatment was performed by adding magnesium sulfate to this organic layer. After the magnesium sulfate was removed by filtration, the organic layer was concentrated with an evaporator, and the obtained concentrate was vacuum-dried to obtain a polysilsesquioxane compound (A3). This product had a mass average molecular weight (Mw) of 5,500 and a molecular weight distribution of 3.40.
IR spectral data of the curable polysilsesquioxane compound (A3) are shown below.
Si—CH ₃ : 1272 cm ⁻¹ , 1409 cm ⁻¹ , Si—O: 1132 cm ⁻¹ , CF: 1213 cm ⁻¹

(Examples 13 and 14, Comparative Example 5)
Example 13 was prepared in the same manner as in Example 1, except that the type of component (A), the type of component (B), and the amount (parts) used were changed as shown in Table 2 below. , 14, and a curable composition of Comparative Example 5 were obtained.
The cured product of the obtained curable composition was measured for adhesive strength and evaluated for curability.
The measurement results and evaluation are shown in Table 2 below.

From Tables 1 and 2, all the curable compositions of Examples 1 to 14 were cured in a short time of 8,000 seconds or less in the curability evaluation test, indicating excellent curability. .
Moreover, even when cured at 120° C. for 2 hours, the adhesive strength of the obtained cured product is 50 N/4 mm ² or more, indicating that the adhesive strength is excellent.
On the other hand, it can be seen that the curable compositions of Comparative Examples 1, 4 and 5 are inferior in curability to the curable compositions of Examples in the curability evaluation test.
Moreover, when the curable compositions of Comparative Examples 1 to 5 were cured at 120° C. for 2 hours, the adhesive strength of the resulting cured products was less than 50 N/4 mm ² , indicating poor adhesive strength.

Claims (10)

An adhesive for fixing an optical element,
Contains the following components (A) and (B), the content of component (B) is more than 0 parts by mass and 3 parts by mass or less per 100 parts by mass of component (A), and an epoxy resin A curable composition characterized by not containing.
(A) component: the following formula (a)

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms with or without a substituent, or an aryl group with or without a substituent. R ¹ may be the same or different, Z represents a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, p represents a positive integer, and q and r Each independently represents 0 or a positive integer.)
Silane compound polymer (B) component represented by: from the group consisting of bismuth halide, bismuth carboxylate, carbonate [(2-)-O] triphenylbismuth, aluminum chelate compound and zirconium carboxylate at least one selected metal compound 2. The curable composition according to claim 1 , wherein the weight average molecular weight (Mw) of the silane compound polymer of component (A) is 800 to 50,000. 3. The curable composition according to claim 1, wherein the silane compound polymer of component (A) is a polycondensation product of one or more silane compounds represented by the following formula (1).

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms with or without a substituent, or an aryl group with or without a substituent. R ¹ may be the same or different, R ² represents an alkyl group having 1 to 10 carbon atoms, X ¹ represents a halogen atom, and s represents an integer of 0 to 3. Multiple R ² groups and multiple X ¹ groups may be the same or different. 4. The curable composition according to any one of claims 1 to 3 , further comprising the following component (C).
(C) component: a silane coupling agent having a nitrogen atom in the molecule 5. The curable composition according to any one of claims 1 to 4 , further comprising the following component (D).
(D) component: silane coupling agent having an acid anhydride structure in the molecule The curable composition according to any one of claims 1 to 5 , further comprising a diluent. The curable composition according to claim 6 , wherein the curable composition has a solid content concentration of 50% by mass or more and less than 100% by mass. 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 for producing a cured product, wherein the curable composition according to any one of claims 1 to 7 is cured by heating at 110°C to 130°C.