KR20200131228A - Curable composition, cured product, method of producing cured product, and method of using curable composition - Google Patents

Abstract

(A) 성분 : 식 (a) 로 나타내는 실란 화합물 중합체 (R¹ 은, 치환기를 갖거나, 혹은 치환기를 갖지 않는 탄소수 1 ∼ 10 의 알킬기, 또는, 치환기를 갖거나, 혹은 치환기를 갖지 않는 아릴기를, Z 는, 하이드록시기, 탄소수 1 ∼ 10 의 알콕시기, 또는, 할로겐 원자를, p 는 양의 정수를, q, r 은, 0 또는 양의 정수를 나타낸다.)
(B) 성분 : 비스무트 화합물, 알루미늄 화합물 및 지르코늄 화합물로 이루어지는 군에서 선택되는 적어도 1 종의 금속 화합물.The present invention is a curable composition comprising the following component (A) and component (B), wherein the content of the component (B) is more than 0 parts by mass and 3 parts by mass or less based on 100 parts by mass of the component (A) , A cured product obtained by curing the composition, and a method of using the composition as an adhesive for fixing an optical device or a sealing material for fixing an optical device. The curable composition of the present invention can be cured by low temperature heating, and a cured product having a high adhesive strength is obtained.

Component (A): silane compound polymer represented by formula (a) (R ¹ is an alkyl group having 1 to 10 carbon atoms having a substituent or not having a substituent, or an aryl group having a substituent or not having a substituent , 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 represents 0 or a positive integer.)
Component (B): at least one metal compound selected from the group consisting of bismuth compounds, aluminum compounds, and zirconium compounds.

Description

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

The present invention is a curable composition from which a cured product having excellent peeling resistance and heat resistance, and having a high adhesive strength is obtained, a cured product obtained by curing the composition, a method for producing the same, and an adhesive for fixing an optical element or It relates to a method of using as a sealing material for fixing optical elements.

BACKGROUND ART Conventionally, various improvements have been made depending on the use of the curable composition, and it is widely used industrially as a raw material for optical parts or molded articles, adhesives, coating agents, and the like.

Further, the curable composition has also attracted attention as an optical element fixing material such as an adhesive for fixing an optical element or a sealing material for fixing an optical element when manufacturing an optical element sealing body.

Examples of optical elements include various lasers such as semiconductor lasers (LD), light-emitting elements such as light-emitting diodes (LEDs), light-receiving elements, composite optical elements, and optical integrated circuits. In recent years, optical devices of blue light or white light having a shorter peak wavelength of light emission have been developed and have been widely used. The increase in luminance of a light-emitting device having a short peak wavelength of light emission is rapidly progressing, and the amount of heat generated by the optical device tends to be further increased.

However, with the recent increase in luminance of optical elements, the cured product of the composition for optical element fixing materials is exposed to higher energy light or heat at a higher temperature than that generated from the optical element for a long time, deteriorated and peeled off, There was a problem that the adhesion was lowered.

In order to solve this problem, in Patent Documents 1 to 3, a composition for an optical device fixing material containing a polysilsesquioxane compound as a main component, and in Patent Document 4, semiconductor light emission using a hydrolysis/polycondensation product of a silane compound Device members and the like have been proposed.

However, even in the case of a cured product such as a composition or member described in Patent Documents 1 to 4, it may be difficult to obtain peeling resistance and heat resistance while maintaining sufficient adhesive strength.

On the other hand, the present inventors have found a curable composition which is excellent in peeling resistance and heat resistance, and a cured product having high adhesive strength is obtained (Patent Documents 5 and 6).

However, in order to cure these curable compositions, it was necessary to heat 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, there is a case where they are exposed to high temperatures during curing, and the members around the package are damaged.

Japanese Unexamined Patent Publication No. 2004-359933 Japanese Patent Laid-Open Publication No. 2005-263869 Japanese Patent Laid-Open Publication No. 2006-328231 Japanese Unexamined Patent Publication No. 2007-112975 WO2012/073988 WO2016/031728 (US2017/253781 A1)

The present invention has been made in view of the above circumstances, as a curable composition from which a cured product having high adhesive strength is obtained, a curable composition that can be cured by heating at a low temperature compared to the conventional one, a cured product obtained by curing the composition, and a method for producing the same And, it is an object to provide a method of using the composition as an adhesive for fixing an optical device and a sealing material for fixing an optical device.

In order to solve the above problems, the present inventors have conducted extensive research. 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 low temperature, The cargo was found to have a high adhesive force, and the present invention was completed.

In this way, according to the present invention, the curable composition of the following [1] to [7], the cured product of [8] and [9], the method of producing the cured product of [10], and the adhesive for fixing an optical element of [11]. And a method of using as a sealing material for fixing an optical element of [12].

[1] A curable composition comprising the following component (A) and component (B), wherein the content of component (B) is more than 0 parts by mass and 3 parts by mass or less based on 100 parts by mass of component (A). Curable composition.

(A) component: the following formula (a)

[Formula 1]

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms having a substituent or not having a substituent group, or an aryl group having a substituent group or not having a substituent. A plurality of R ^{1s 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 represent 0 or a positive integer.)

Silane compound polymer represented by

(B) component: 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 mass average molecular weight (Mw) of the silane compound polymer of the component (A) is 800 to 50,000.

[3] The curable composition according to [1] or [2], wherein the silane compound polymer is one or two or more polycondensation products of the silane compound represented by the following formula (1).

[Formula 2]

(In the formula, R ¹ represents the same meaning as above, X ¹ represents a halogen atom, and s represents an integer of 0 to 3. A plurality of R ² and a plurality of X ^{1 may} be the same as each other, It may be different.

[4] The curable composition according to any one of [1] to [3], further containing the following component (C).

(C) Component: Silane coupling agent having a nitrogen atom in the molecule

[5] The curable composition according to any one of [1] to [4], further containing the following (D) component.

(D) Component: Silane coupling agent having an acid anhydride structure in the molecule

[6] The curable composition according to any one of [1] to [5], further containing a diluent.

[7] The curable composition according to [6], wherein the solid content concentration of the curable composition is 50 mass% or more and less than 100 mass%.

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

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

[10] A method for producing a cured product in which the curable composition according to any one of [1] to [7] is heated and cured at 110°C to 130°C.

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

[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 low temperature compared to the conventional one. 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, since it is not necessary to heat it at the time of curing, the package member is not damaged by heat.

The cured product obtained by curing the curable composition of the present invention has excellent adhesion. Therefore, the curable composition of the present invention can be preferably used as an adhesive for fixing an optical element and a sealing material for fixing an optical element.

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

1) curable composition

The curable composition of the present invention is a curable composition comprising the following component (A) and component (B), wherein the content of component (B) is greater than 0 parts by mass and 3 parts by mass based on 100 parts by mass of component (A) It is characterized by the following.

(A) component: silane compound polymer represented by following formula (a)

[Formula 3]

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

(A) component

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

In the 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: -(R ¹ The repeating units represented by SiZ ₂ O _1/2 )- can be represented by the following (a1) to (a3), respectively. In addition, in (a1) to (a3), "-O-" represents an oxygen atom shared by two adjacent Si atoms.

[Formula 4]

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

In the above formulas (a), (a1), (a2) and (a3), R ¹ is an alkyl group having 1 to 10 carbon atoms which has a substituent or does not have a substituent, or has a substituent or a substituent It represents an aryl group which does not have.

That is, R ¹ is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms having a substituent, an alkyl group having 1 to 10 carbon atoms unsubstituted, an aryl group having a substituent, and an unsubstituted aryl group.

In addition, the number of carbon atoms in the "alkyl group having 1 to 10 carbon atoms having a substituent" means the number of carbon atoms in the alkyl group portion. Accordingly, the number of carbon atoms in the entire R ¹ may exceed 10 in some cases.

Examples of the alkyl group having 1 to 10 carbon atoms of R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, etc. are mentioned.

Examples of the substituent for R ¹ 's alkyl group having 1 to 10 carbon atoms include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; Cyano group; Formula: Group represented by OG; Can be mentioned.

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

Examples of the aryl group for R ¹ include aryl groups having 6 to 20 carbon atoms such as a phenyl group, 1-naphthyl group, and 2-naphthyl group.

Examples of the substituent 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-pentyl group , alkyl groups such as n-hexyl group, n-heptyl group, n-octyl group, and isooctyl group; Halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom; Alkoxy groups, such as a methoxy group and an ethoxy group; Can be mentioned.

Among these, R ¹ is preferably an alkyl group having 1 to 6 carbon atoms having a substituent, an alkyl group having 1 to 6 carbon atoms, or an unsubstituted aryl group having a substituent, since the effect of the present invention is easily obtained. A C1-C6 alkyl group, an unsubstituted C1-C6 alkyl group, or a phenyl group is more preferable, and a C1-C6 alkyl group which has a cyano group, a C1-C6 alkyl group which has a fluorine atom, and an unsubstituted carbon number A 1-6 alkyl group or a phenyl group is more preferable, and a C1-C3 alkyl group having a cyano group, a C1-C3 alkyl group having a fluorine atom, an unsubstituted C1-C3 alkyl group, or a phenyl group is particularly preferred. Do.

All of a plurality of R ^1s may be the same or different.

Z represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.

Examples of the alkoxy group having 1 to 10 carbon atoms for Z include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a t-butoxy group, and a pentyloxy group. As a halogen atom, a chlorine atom, a bromine atom, etc. are mentioned.

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 represent 0 or a positive integer.

All of a plurality of R ^1s may be the same or different.

In addition, a plurality of Z may be all the same or different.

The production method of the silane compound polymer (A) is not particularly limited.

For example, it can manufacture by polycondensing 1 type or 2 or more types of a silane compound represented by following formula (1) (it may be called "silane compound (1)" hereafter). Here, "polycondensation" is used in a broad concept including hydrolysis and polycondensation reactions.

[Formula 5]

In formula (1), R ¹ represents the same meaning as above. 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.

Examples of the alkyl group having 1 to 10 carbon atoms for R ² include the same as those exemplified as the alkyl group having 1 to 10 carbon atoms for R ¹ .

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

When s is 2 or more, a plurality of ORs ^{2 may be the} same or different. In addition, when (3-s) is 2 or more, a plurality of X ^{1s may be the} same or different.

Preferred specific examples of the silane compound (1) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n-pentyltrimethoxysilane, n-hexyl Alkyl trialkoxysilane compounds such as trimethoxysilane, isooctyltrimethoxysilane, and isooctyltriethoxysilane;

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

Methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, ethyltribromosilane, n-propyltrichlorosilane, n-propyltribromosilane, n-butyltrichlorosilane, isobutyltrichlorosilane, n-pentyl Alkyl trihalogenosilane compounds such as trichlorosilane, n-hexyltrichlorosilane, and isooctyltrichlorosilane;

Phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 2-chlorophenyltrimethoxysilane, phenyltriethoxysilane, 2-methoxyphenyltriethoxysilane, phenyldimethoxyethoxysilane, phenyldiethoxymethoxy Phenyltrialkoxysilane compounds which may have a substituent such as oxysilane;

Phenylhalogenoalkoxysilane compounds which may have a substituent such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, phenylchloromethoxyethoxysilane, phenylchlorodiethoxysilane, and phenyldichloroethoxysilane;

Phenyltri which may have a substituent such as phenyltrichlorosilane, phenyltribromosilane, 4-methoxyphenyltrichlorosilane, phenyltrichlorosilane, 2-ethoxyphenyltrichlorosilane, and 2-chlorophenyltrichlorosilane Halogenosilane compounds;

Cyanomethyltrimethoxysilane, cyanomethyltriethoxysilane, 1-cyanoethyltrimethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 2-cyano Ethyltripropoxysilane, 3-cyanopropyltrimethoxysilane, 3-cyanopropyltriethoxysilane, 3-cyanopropyltripropoxysilane, 3-cyanopropyltributoxysilane, 4-cyano Butyltrimethoxysilane, 5-cyanopentyltrimethoxysilane, 2-cyanopropyltrimethoxysilane, 2-(cyanomethoxy)ethyltrimethoxysilane, 2-(2-cyanoethoxy)ethyltri Methoxysilane, o-(cyanomethyl)phenyltripropoxysilane, m-(cyanomethyl)phenyltrimethoxysilane, p-(cyanomethyl)phenyltriethoxysilane, p-(2-cyano Cyanoalkyl trialkoxysilane compounds such as ethyl) phenyl trimethoxysilane;

Cyanomethyltrichlorosilane, cyanomethylbromodimethoxysilane, 2-cyanoethyldichloromethoxysilane, 2-cyanoethyldichloroethoxysilane, 3-cyanopropyltrichlorosilane, 3-cyanopropyl Tribromosilane, 3-cyanopropyldichloromethoxysilane, 3-cyanopropyldichloroethoxysilane, 3-cyanopropylchlorodimethoxysilane, 3-cyanopropylchlorodiethoxysilane, 4-cyanobutylchloro Diethoxysilane, 3-cyano-n-butylchlorodiethoxysilane, 2-(2-cyanoethoxy)ethyltrichlorosilane, 2-(2-cyanoethoxy)ethylbromodiethoxysilane, 2 -(2-cyanoethoxy)ethyldichloropropoxysilane, o-(2-cyanoethyl)phenyltrichlorosilane, m-(2-cyanoethyl)phenylmethoxydibromosilane, p-(2-cyano) Cyanoalkylhalogenosilane compounds such as noethyl)phenyldimethoxychlorosilane and 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 -Fluoroalkylhalogenoalkoxysilane compounds such as trifluoropropyldichloroethoxysilane;

Fluoroalkyltrihalogenosilane compounds such as 3,3,3-trifluoropropyltrichlorosilane; And the like.

The silane compound (1) can be used individually by 1 type or in combination of 2 or more types.

Among these, as the silane compound (1), since a cured product having more excellent adhesion can be easily obtained, trialkoxysilane compounds are preferable, and (i) an alkyltrialkoxysilane compound having 1 to 10 carbon atoms, (ii) ) 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 a fluoroalkyl group having 1 to 10 carbon atoms The combination of the trialkoxysilane compound having is more preferable.

When a phenyltrialkoxysilane compound and a C1-C10 cyanoalkyltrialkoxysilane compound are used in combination, the ratio of the phenyltrialkoxysilane compound and a C1-C10 cyanoalkyltrialkoxysilane compound is used in a molar ratio. , [Phenyltrialkoxysilane compound]: [Cyanoalkyltrialkoxysilane compound having 1 to 10 carbon atoms] = 95:5 to 50:50 is preferable, and 90:10 to 60:40 is more preferable.

When a C1-C10 alkyltrialkoxysilane compound and a trialkoxysilane compound having a C1-C10 fluoroalkyl group are used in combination, the C1-C10 alkyltrialkoxysilane compound and the C1-C10 fluoro. The use ratio of the trialkoxysilane compound having a roalkyl group is a molar ratio, [alkyltrialkoxysilane compound having 1 to 10 carbon atoms]: [trialkoxysilane compound having a fluoroalkyl group having 1 to 10 carbon atoms] = 95: 5 to 10:90 is preferable, 90:10 to 30:70 are more preferable, and 85:15 to 50:50 are even more preferable.

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 a solvent, and stirring the entire solution at a predetermined temperature. Can be mentioned.

The catalyst to be used may be either an acid catalyst or a base catalyst.

Further, an acid catalyst and a base catalyst may be used in combination. For example, after performing a polycondensation reaction of a silane compound in the presence of an acid catalyst, a base catalyst is added to the reaction solution to make it basic, and under basic conditions, a polycondensation reaction may be further performed.

Examples of the acid catalyst 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; And the like.

Examples of the base catalyst include ammonia (water); Trimethylamine, triethylamine, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), aniline, picoline, 1 Organic bases such as ,4-diazabicyclo[2.2.2]octane and imidazole; Organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; Metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, and potassium t-butoxide; Metal hydrides such as sodium hydride and calcium hydride; Metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; Metal carbonates such as sodium carbonate, potassium carbonate, and magnesium carbonate; Metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; And the like.

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

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, and t-butyl alcohol; And the like. These solvents can be used alone or in combination of two or more.

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

The temperature at the time of polycondensation (reaction) of the silane compound (1) is usually in the range from 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 progress of the condensation reaction may become insufficient. On the other hand, when the reaction temperature is too high, it becomes difficult to suppress gelation. The reaction is usually completed in 30 minutes to 30 hours.

Further, depending on the type of the silane compound (1) to be used, it may be difficult to achieve high molecular weight. For example, a silane compound in which R ¹ is a fluoroalkyl group tends to be inferior in reactivity to a silane compound in which R ¹ is a conventional alkyl group. In such a case, by reducing the amount of catalyst and performing the reaction for a long time under mild conditions, gelation is suppressed, and a silane compound polymer (A) having a target molecular weight is easily obtained.

After completion of the reaction, when an acid catalyst is used, an aqueous alkali solution such as sodium hydrogencarbonate is added to the reaction solution, and when a base catalyst is used, neutralization is performed by adding an acid such as hydrochloric acid to the reaction solution. The resulting salt is removed by filtration separation, washing with water, or the like, to obtain a target silane compound polymer.

When producing a silane compound polymer (A) by the above method, a portion of OR ² or X ¹ of the silane compound (1) that is not dehydrated and/or dealcoholed remains in the silane compound polymer (A). That is, when the remaining OR ² or X ¹ is 1, it remains as (R ¹ SiZO _2/2 ) in the above formula (a), and when the remaining OR ² or X ¹ is 2, the formula ( In a), it remains as (R ¹ SiZ ₂ O _1/2 ).

The silane compound polymer (A) may be a homopolymer (R ¹ is a polymer of one type) or a copolymer (R ¹ is a polymer of two or more types).

When the silane compound polymer (A) is a copolymer (R ¹ is two or more polymers), the silane compound polymer (A) may be any copolymer such as a random copolymer, a block copolymer, a graft copolymer, or an alternating copolymer. However, from the viewpoint of easiness of manufacture, a random copolymer is preferable.

In addition, the structure of the silane compound polymer (A) may be any structure of a ladder structure, a double decker structure, a basket structure, a partially cleaved basket structure, a cyclic structure, and a random structure.

The mass average molecular weight (Mw) of the silane compound polymer (A) is usually in the range of 800 to 50,000, preferably 3,000 to 30,000, and more preferably 5,000 to 15,000. By being within this range, a cured product having excellent handling properties of the composition and excellent in adhesion and heat resistance can be obtained.

The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, as standard polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent ( It is the same below).

The molecular weight distribution (Mw/Mn) of the silane compound polymer (A) is not particularly limited, but is usually 1.0 to 10.0, preferably 1.1 to 6.0. By being in the said range, a cured product excellent in adhesiveness and heat resistance is obtained.

The silane compound polymer (A) can be used alone 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.

(B) component

The curable composition of the present invention contains, as component (B), at least one metal compound selected from the group consisting of a bismuth compound, an aluminum compound, and a zirconium compound.

Since the curable composition of the present invention contains the component (B), it can be cured at a lower temperature and in a short time, and a cured product having excellent adhesiveness can be obtained.

The metal compound of the component (B) is not particularly limited as long as it is a compound containing bismuth, aluminum or zirconium, but from the viewpoint of availability, etc., a trivalent or pentavalent bismuth compound, a trivalent aluminum compound, and a tetravalent zirconium The compounds of each are preferable.

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, Carboxylate, chelate compound, etc. are mentioned.

More specifically, although the following are mentioned, it is not limited to these.

Halides such as bismuth chloride, bismuth bromide, aluminum chloride, aluminum bromide, zirconium chloride, and zirconium bromide;

Metal oxides such as bismuth oxide, bismuth oxide, aluminum oxide, and zirconium dioxide;

Metal hydroxides such as bismuth hydroxide, aluminum hydroxide, and zirconium hydroxide;

Nitrates such as bismuth nitrate, aluminum nitrate, and zirconium nitrate;

Sulfates such as bismuth sulfate, aluminum sulfate, and zirconium sulfate;

Carbonates such as bismuth carbonate, aluminum carbonate, and zirconium carbonate;

Hydrogen carbonates such as bismuth hydrogen carbonate, aluminum hydrogen carbonate, and zirconium hydrogen carbonate;

Phosphates such as bismuth phosphate, aluminum phosphate, and zirconium phosphate;

Metal alkoxides such as a bismuth compound represented by a formula: Bi(OR ⁴ ) ₃ , an aluminum compound represented by a formula: Al(OR ⁴ ) ₃ , and a zirconium compound represented by a formula: Zr(OR ⁴ ) ₄ (R ⁴ is a methyl group, 1 to 20 carbon atoms such as 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. Alkenyl groups 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; C6-C20 aromatics such as phenyl group Groups: Aralkyl groups having 7 to 20 carbon atoms such as a benzyl group and a phenethyl group; cycloalkyl groups having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group; );

Of bismuth, aluminum or zirconium, acetate, propionate, octanoate, nonanoate, dodecanoate (laurate), tetradecanoate (myrithate), hexadecanoate (palmitate), octadecanoate ( Stearate), naphthenate, octylate, neodecanoate, isostearate, and other fatty acid salts; Aromatic carboxylate salts such as benzoate; Polyvalent carboxylate salts such as succinate; Unsaturated carboxylate salts such as maleic acid salt, linolenic acid salt, linoleic acid salt, oleic acid salt, and arachidonic acid salt; Rosin acid salt; Carboxylate salts such as;

Bismuth, aluminum or zirconium, and a polydentate ligand (for example, β-diketone compounds such as acetylacetone and benzoylacetone; β-ketoesters such as methyl acetoacetate and ethyl acetoacetate; carbonato; ethylenediamine; A chelate compound of a compound having 1 to 15 carbon atoms).

In addition, the metal compound of component (B) may have a structure in which a plurality of types of ligands are bonded to bismuth, aluminum or zirconium.

As a ligand, halide ion, hydride ion (hydride), oxygen atom (oxo, peroxo), hydroxy (hydroxyl), water (aqua or aco), carbon monoxide (carbonyl), carbonate ion (carbona Inorganic ligands such as soil and CO ₃ ^2- );

Oxalic acid 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, acetylacetonate, ethylacetoacetate, cycloalkadienyl (e.g., cyclopentadienyl, dicyclopentadienyl), ether (e.g. diethyl ether), hydrocarbon group (e.g., methyl group , Alkyl groups such as ethyl groups; aryl groups such as phenyl groups and naphthyl groups);

Ammonia, nitro, knitted ritonavir (NO ₂ ^-), cyano, cyano NATO, isocyanato, alkyl amide (e.g., dimethyl amide), ethylenediamine, diethylenetriamine, nitrogen-containing amine, pyridine, and phenanthroline Ligand;

Sulfur-containing ligands such as thiocyanato and isothiocyanato; And organic ligands such as.

The following are mentioned as a preferable specific example of the metal compound of (B) component.

(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, bismuth oxysalicylate, bismuth neodecanoate, bismuth rosinate, bismuth versatate, bismuth 2-ethylhexanoate [bismuth tris (2-ethylhexanoate)], Carboxylate of bismuth such as bismuth stearate; [Carbonato(2-)-O]triphenylbismuth; Etc

(Aluminum compound)

Halides of aluminum such as aluminum chloride; Aluminum alkoxides such as aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum trisec-butyrate, and aluminum tributylate; Aluminum chelate compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), and aluminum diisopropoxyacetylacetonate;

(Zirconium compound)

Halides of zirconium, such as zirconium acid chloride; Inorganic salts of zirconium, such as zirconium sulfate and zirconium nitrate; Carboxylate of zirconium, such as zirconium acetate, zirconium octylate, and zirconium stearate; Zirconium alkoxides such as zirconium tetra n-propoxide, zirconium tetra-n-butoxide, and zirconium octoxy tridecoxide; Zirconium chelate compounds such as zirconium tetrakisacetylacetonate, zirconium tributoxy monoacetylacetonate, and zirconium tributoxy monoacetylacetonate;

Among these, bismuth halide, bismuth carboxylate, [carbonato(2-)-O]triphenylbismuth, aluminum chelate compound, and zirconium carboxylate are more preferred, and bismuth halide, bismuth The carboxylate of 6 to 20 carbon atoms, [carbonato(2-)-O] triphenylbismuth, the chelate compound of aluminum, and the carboxylate of zirconium of 6 to 20 carbon atoms are more preferable, and bismuth chloride and octylic acid Bismuth, [carbonato(2-)-O]triphenylbismuth, aluminum chelate compounds, and zirconium octylate are particularly preferred.

The lower limit of the content of the component (B) is more than 0 parts by mass, preferably 0.01 parts by mass or more, and more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the component (A). In addition, the upper limit of the content of the component (B) is 3 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less based on 100 parts by mass of the component (A).

By blending the component (B) in such a ratio, a curable composition capable of curing at a low temperature (110 to 130°C) and in a short time can be obtained.

(C) component

In the curable composition of the present invention, it is preferable to further contain (C) component: a silane coupling agent having a nitrogen atom in the molecule (hereinafter, sometimes referred to as "silane coupling agent (C)").

The curable composition containing the component (C) is excellent in workability in the application step, and provides a cured product having more excellent adhesion, peel 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. For example, a trialkoxysilane compound represented by the following formula (c-1), a dialkoxyalkylsilane compound or a dialkoxyarylsilane compound represented by the formula (c-2) may be mentioned.

[Formula 6]

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

R ^b is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group; Or an aryl group which has a substituent or does not have a substituent, such as a phenyl group, a 4-chlorophenyl group, and a 4-methylphenyl group; Represents.

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

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

In the compound represented by the above formula (c-1) or (c-2), as the compound in the case where R ^c is an organic group bonded with a group containing another silicon atom, the compound is formed with another silicon atom via an isocyanurate skeleton. Combining to constitute an isocyanurate-based silane coupling agent, or bonding with other silicon atoms via a urea skeleton to constitute a urea-based silane coupling agent may be mentioned.

Among these, as the silane coupling agent (C), an isocyanurate-based silane coupling agent and a urea-based silane coupling agent are preferable because a cured product having a higher adhesive strength is easily obtained, and further, in a molecule, It is preferable to have 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 number of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is 4 or more.

As an isocyanurate-based silane coupling agent having 4 or more alkoxy groups bonded to a silicon atom, the compound represented by the following formula (c-3) is a urea-based silane coupling agent having 4 or more alkoxy groups bonded to a silicon atom, as follows: The compound represented by formula (c-4) is mentioned.

[Formula 7]

In the formula, R ^a represents 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.

As specific examples of the compound represented by formula (c-3), 1,3,5-N-tris(3-trimethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3- Triethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-triisopropoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-tributoxy 1,3,5-N-tris [(tri(C1-C6) alkoxy)silyl (C1-C10) alkyl] isocyanurate, such as silylpropyl) isocyanurate; 1,3,5-N-tris(3-dimethoxymethylsilylpropyl)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-diethoxymethylsilylpropyl)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-diiso Propoxymethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diisopropoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diiso Propoxyisopropylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diisopropoxy n-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3 -Diisopropoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxymethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibu Toxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxyisopropylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxy n-) 1,3,5-N-tris [(di (carbon number 1 to 6), such as propylsilylpropyl) isocyanurate and 1,3,5-N-tris (3-dibutoxyphenylsilylpropyl) isocyanurate ) Alkoxy)silyl (C1-C10) alkyl] isocyanurate; And the like.

Specific examples of the compound represented by formula (c-4) include N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea, and N ,N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, N,N'-bis(2-trimethoxysilylethyl)urea, etc. N,N'-bis [(tri (carbon number 1 to 6) alkoxysilyl) (carbon number 1 to 10) alkyl] urea; N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, N,N'-bis(3-diethoxymethylsilylpropyl)urea N,N'-bis [(di (carbon number 1 to 6) alkoxy (carbon number 1 to 6) alkylsilyl (carbon number 1 to 10) alkyl) urea; N,N'-bis ((di (carbon number 1 to 6)) such as N,N'-bis(3-dimethoxyphenylsilylpropyl)urea and N,N'-bis(3-diethoxyphenylsilylpropyl)urea Alkoxy (C6-C20) arylsilyl (C1-C10) alkyl) urea; And the like.

Among these, examples of the silane coupling agent (C) include 1,3,5-N-tris(3-trimethoxysilylpropyl)isocyanurate and 1,3,5-N-tris(3-triethoxysilyl). Propyl) isocyanurate (hereinafter referred to as "isocyanurate compound"), N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilyl) It is preferable to use propyl) urea (hereinafter, referred to as "urea compound"), and a combination of the isocyanurate compound and a urea compound.

When the above isocyanurate compound and urea compound are used in combination, the ratio of both is preferably 100:1 to 100:200 in terms of the mass ratio of (isocyanurate compound) and (urea compound), 100:10-100:110 is more preferable. By using in combination with an isocyanurate compound and a urea compound in such a ratio, a curable composition providing a cured product having more excellent heat resistance and adhesion can be obtained.

The silane coupling agent (C) can be used individually by 1 type or in combination of 2 or more types.

When the curable composition of the present invention contains the component (C), the amount of component (C) is, the ratio of the component (A) and the component (C) is the mass ratio of the component (A) and the component (C) [ (A) component: (C) component], preferably 100: 0.3 to 100: 50, more preferably 100: 1 to 100: 40, still more preferably 100: 3 to 100: 35 .

By using the component (A) and the component (C) in such a ratio, the cured product of the curable composition of the present invention becomes more excellent in heat resistance and adhesiveness.

(D) component

In the curable composition of the present invention, it is preferable to contain (D) component: a silane coupling agent having an acid anhydride structure in the molecule (hereinafter, sometimes referred to as "silane coupling agent (D)").

The curable composition containing the component (D) is more excellent in workability in the application step, and provides a cured product having more excellent adhesion, peel 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).

[Formula 8]

In the formula, Q represents a group having an acid anhydride structure, R ^d represents an alkyl group having 1 to 6 carbon atoms, or a phenyl group having a substituent or no substituent, and R ^e represents an alkoxy group having 1 to 6 carbon atoms or Represents a halogen atom, i and k represents an integer of 1-3, j represents an integer of 0-2, and I+j+k=4. When j is 2, R ^{d may be the} same or different. When k is 2 or 3, a plurality of R ^{e may be the} same or different. When i is 2 or 3, a plurality of Qs may be the same or different.

Q is the following formula

[Formula 9]

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

In the formula (d), examples of the alkyl group having 1 to 6 carbon atoms for R ^d include the same groups as those exemplified as the alkyl group having 1 to 6 carbon atoms represented by R ¹ .

^Examples of 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, n-pentyl group, n -Alkyl groups, such as a hexyl group; Halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom; Alkoxy groups, such as a methoxy group and an ethoxy group; Can be mentioned.

Examples of the alkoxy group having 1 to 6 carbon atoms for R ^e include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a t-butoxy group.

^Examples of the halogen atom for R ^e include a chlorine atom and a bromine atom.

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

[Formula 10]

(In the formula, R ^e , h, i, j, k represent the same meaning as above.)

The compound represented by is preferable. In the formula, h is preferably 2 to 8, more preferably 2 or 3, and particularly preferably 3.

Specific examples of the silane coupling agent represented by the above formula (d-1) include 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, and 3-(trimethoxysilyl) Tri(C1-C6) alkoxysilyl (C2-C8) alkyl succinic anhydride, such as propyl succinic anhydride and 3-(triethoxysilyl)propyl succinic anhydride; Di (C1-C6) alkoxymethylsilyl (C2-C8) alkyl succinic anhydride, such as 2-(dimethoxymethylsilyl)ethyl succinic anhydride; (C1-C6) alkoxydimethylsilyl (C2-C8) alkyl succinic anhydride, such as 2-(methoxydimethylsilyl)ethyl succinic anhydride;

Trihalogenosilyl (carbon number 2 to 8) alkyl succinic anhydride, such as 2-(trichlorosilyl)ethyl succinic anhydride and 2-(tribromosilyl)ethyl succinic anhydride; Dihalogenomethylsilyl (carbon number 2 to 8) alkyl succinic anhydride, such as 2-(dichloromethylsilyl)ethyl succinic anhydride; Halogenodimethylsilyl (carbon number 2 to 8) alkyl succinic anhydride, such as 2-(chlorodimethylsilyl)ethyl succinic anhydride; And the like.

The silane coupling agent (D) can be used individually by 1 type or in combination of 2 or more types.

Among these, as the silane coupling agent (D), tri(C1-C6) alkoxysilyl (C2-C8) alkyl anhydride succinic acid is preferable, and 3-(trimethoxysilyl)propyl succinic anhydride, 3-(trie) Particularly preferred is oxysilyl)propyl succinic anhydride.

When the curable composition of the present invention contains the component (D), the content of the component (D) is not particularly limited, but the mass ratio of the component (A) and the component (D) [component (A): component (D) ], preferably 100:0.01 to 100:30, more preferably 100:0.1 to 100:10.

The cured product of the curable composition containing the component (A) and the component (D) in such a ratio becomes more excellent in heat resistance and adhesiveness.

(E) diluent

In the curable composition of the present invention, for the purpose of providing fluidity, a diluent may be further contained.

The diluent is not particularly limited as long as it has good compatibility with the components (A) and (B). For example, nitrogen-containing compounds such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethylimidazolidinone; Sulfur-containing compounds such as dimethyl sulfoxide; 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 monoisobutylate (texanol), γ-butyrolactone, ethyl lactate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol mono-n- Oxygen-containing compounds such as propyl ether, diacetone alcohol, and tetrahydrofurfuryl alcohol; And the like.

These diluents can be used alone 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 preferably an amount 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, and 60 to 90 The amount of mass% is more preferable, and the quantity of 70 to 85 mass% is more preferable.

(F) other ingredients

In the curable composition of the present invention, "other components" other than the components (A) to (E) may be contained within a range that does not impair the object of the present invention.

Other components include fine particles, antioxidants, ultraviolet absorbers, and light stabilizers.

When fine particles are added, a curable composition excellent in workability in the coating step may be obtained. As the material of the fine particles, silica; Resins such as acrylic and silicone; Metal oxides such as aluminum oxide and titanium oxide; Minerals, such as boehmite, etc. are mentioned.

These fine particles can be used alone or in combination of two or more. The amount of fine particles to be used is usually 10% by mass or less based on the component (A).

The antioxidant is added to prevent oxidation deterioration during heating. Examples of the antioxidant include phosphorus antioxidants, phenolic antioxidants, and sulfur antioxidants.

Phosphite, oxaphosphaphenanthrene oxide, etc. are mentioned as a phosphorus antioxidant. Examples of phenolic antioxidants include monophenols, bisphenols, and high molecular phenols. Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc. Can be mentioned.

These antioxidants can be used alone or in combination of two or more. The amount of the antioxidant to be used is usually 10% by mass or less based on the component (A).

The ultraviolet absorber is added for the purpose of improving the light resistance of the resulting cured product.

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

Ultraviolet absorbers can be used alone or in combination of two or more.

The amount of the ultraviolet absorber to be used is usually 10% by mass or less based on the component (A).

The light stabilizer is added for the purpose of improving the light resistance of the resulting cured product.

As a light stabilizer, for example, poly[{6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2 Hindered amines such as, 6,6-tetramethyl-4-piperidine)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidine)imino}]. I can.

These light stabilizers can be used alone or in combination of two or more.

The amount of the light stabilizer to be used is usually 10% by mass or less based on the component (A).

In the curable composition of the present invention, for example, the (A) component, (B) component, and, if desired, the (C) to (F) components are blended in a predetermined ratio, and mixed and removed by a known method. It can be obtained by inclusion.

The curable composition of the present invention can be cured by heating at a low temperature as compared with the conventional one, and the resulting cured product is excellent in peeling resistance and heat resistance, and has high adhesive strength.

When the curable composition of the present invention is used for an optical element device, it is not necessary to heat the curable composition at a high temperature when curing the curable composition, and therefore, damage due to heat is not imparted to members around the package.

Therefore, the curable composition of the present invention is preferably used as a raw material for an optical component or a molded article, an adhesive, a coating agent, and the like.

2) Cured product and its manufacturing method

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

As a method of curing the curable composition of the present invention, a method of curing by heating may be mentioned.

The cured product of the present invention can be obtained by curing the curable composition of the present invention by heating to usually 100°C to 150°C, preferably 110°C to 140°C, more preferably 110°C to 130°C. 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 by heating for a short time. Therefore, when used in an optical semiconductor light emitting device or the like, there is no case that damage is imparted by exposing the member around the package to a high temperature.

It can be confirmed that the cured product of the present invention is obtained by heating the curable composition of the present invention at a low temperature in a short time, for example, as follows.

In other words, using an automatic curing time measuring device (manufactured by Cyber Co., Ltd., brand name "Madoka"), a sample of the curable composition was added and stirred on a stainless steel plate heated to 120° C., and the stirring torque increased, and 0.392 N· The time until it becomes cm is measured.

It is preferable that the time until it becomes 0.392 N·cm is usually 8,000 seconds or less.

In addition, even if it is obtained by curing by low temperature heating, the fact that the cured product of the present invention has a high adhesive strength can be confirmed as follows, for example.

That is, the curable composition is applied to the mirror surface of the silicon chip, the coated surface is put on an adherend, pressed, and cured by heat treatment at a low temperature (eg, 120° C.). The adherend to which this test piece is attached is left for 30 seconds on a measurement stage of a bond tester at a predetermined temperature (e.g., 23°C) in advance, and from a position at a height of 100 μm from the adherend, horizontally with respect to the adhesive surface. A stress is applied in the direction (shear direction), and the adhesive force between the test piece and the adherend is measured.

It is preferable that it is 50 N/4 mm 2 or more, and, as for the adhesive force of the cured product measured in this way, it is more preferable that it is 70 N/4 mm 2 or more.

Here, "N/4 mm2" is the adhesive force [N] per area of 2 mm x 2 mm.

3) How to use the curable composition

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

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

<Adhesive for fixing optical elements>

The curable composition of the present invention can be preferably used as an adhesive for fixing an optical element.

As a method of using the curable composition of the present invention as an adhesive for fixing an optical element, a predetermined amount of the composition is applied to one or both adhesive surfaces of a material (optical element and its substrate, etc.) Thereafter, a method of hardening by heating and firmly bonding the materials to be bonded is exemplified.

In the present invention, as described above, since heat curing of the curable composition can be carried out at a lower temperature and in a short time compared to the conventional one, it is not necessary to expose the peripheral members of the optical semiconductor light emitting device to high temperatures, and thus the package member Does not inflict damage on.

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

<Encapsulation material for fixing optical elements>

The curable composition of the present invention can be preferably 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 containing an optical element, and then heat-cured to obtain an optical element sealing material. The method of manufacturing, etc. are mentioned.

The 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, since heat curing of the curable composition can be carried out at a lower temperature and in a short time compared to the conventional one, it is not necessary to expose the peripheral members of the optical semiconductor light emitting device to high temperatures, and thus the package member Does not inflict damage on.

The optical element encapsulation body obtained has a high adhesive force because the curable composition of the present invention is used.

Example

Next, the present invention will be described in more detail with examples and comparative examples, but the present invention is not limited to the following examples. In addition, unless otherwise specified, "%" and "part" are based on mass.

(Measurement of mass average molecular weight)

The mass average molecular weight (Mw) and number average molecular weight (Mn) of the silane compound polymer obtained in the following production examples were measured in terms of standard polystyrene, and were measured with the following apparatus and conditions.

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

Column: TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL sequentially connected

Solvent: THF

Injection volume: 80 µl

Measurement temperature: 40 ℃

Flow rate: 1 ml/min

Detector: differential refractometer

(Measurement of IR spectrum)

The IR spectrum of the silane compound polymer obtained in the production example was measured using a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer, Spectrum100).

(Production Example 1)

Into a 300 ml eggplant-shaped flask, 71.37 g (400 mmol) of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBE-13) was poured, and then 0.10 g of 35% hydrochloric acid (silane compound) was added to 21.6 ml of distilled water. With respect to the total amount of (0.25 mol%)) was added while stirring, and the total solution was heated at 30°C for 2 hours and then to 70°C and stirred for 5 hours, followed by adding 140 g of propyl acetate and stirring. Here, 0.12 g of 28% aqueous ammonia (0.5 mol% with respect to the total amount of the silane compound) was added while stirring, and the entire solution was heated to 70°C, followed by stirring for 3 hours. Purified water was added to the reaction solution, followed by separating, and this operation was repeated until the pH of the aqueous layer became 7. The organic layer was concentrated with an evaporator, and the concentrate was vacuum-dried to obtain 55.7 g of a silane compound polymer (A1). Its mass average molecular weight (MW) was 7,800, and molecular weight distribution (PDI) was 4.52.

The IR spectrum data of the silane compound polymer (A1) is shown below.

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

(Production Example 2)

To a 300 ml eggplant-shaped flask, 20.2 g (102 mmol) of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.15 g (18 mmol) of 2-cyanoethyltrimethoxysilane (manufactured by Asmax Corporation) ), and after pouring 96 ml of acetone and 24 ml of distilled water as a solvent, 0.15 g (1.5 mmol) of phosphoric acid (manufactured by Kanto Chemical Co., Ltd.) was added as a catalyst while stirring the contents, and further 16 at 25°C. Stirred for 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 neutralized with a saturated aqueous sodium hydrogencarbonate 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 separating magnesium sulfate by filtration, the filtrate was concentrated to 50 ml with an evaporator, and the obtained concentrate was dripped in 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. 13.5 g of polysilsesquioxane compounds (A2) were obtained by vacuum-drying the residue. Its mass average molecular weight (Mw) was 1,870, and molecular weight distribution (Mw/Mn) was 1.42.

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

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

(Example 1)

To 100 parts of the silane compound polymer (A1) obtained in Preparation Example 1 as a component (A), as a component (E), diethylene glycol monobutyl ether acetate (BDGAC): tripropylene glycol-n-butyl ether (TPnB) = 40 : A mixed solvent of 60 (mass ratio) was added, and it stirred. Thereafter, as component (C), 1,3,5-N-tris [3-(trimethoxysilyl) propyl] isocyanurate (Shin-Etsu Chemical Co., Ltd.: KBM-9659) 30 parts by mass, (D ) As a component, 3-(trimethoxysilyl)propylsuccinic anhydride (Shin-Etsu Chemical Industries Co., Ltd.: X-12-967C) 3 parts by mass, (B) As a component, Phucat 25 (Nihon Chemical Industries, Ltd. product) 0.25 parts by mass After addition, the entire solution was sufficiently mixed and defoamed to obtain a curable composition.

(Examples 2 to 12, Comparative Examples 1 to 4)

In Example 1, in the same manner as in Example 1, Example 2, except that the type of the component (A), the type of the component (B), and the amount used (parts) were changed as described in Table 1 below. The curable composition of -12 and the curable composition of comparative examples 1-4 were obtained.

In the following table, the kind of the following component (b) used instead of the component (B) or the component (B): B1 to B5, b1, and b2 represent the following.

In addition, in the table, the used amount [part] of the component (B) or the component (b) represents parts by mass with respect to 100 parts of the component (A).

(B) component

B1: Phucat 25 (manufactured by Nihon Chemical Industries, Ltd., bismuth octylate compound)

B2: Orgatics ZC-200 (manufactured by Matsumoto Fine Chemicals, Inc., 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: Orgatics TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis (ethylacetoacetate))

b2: Diazabicycloundecene (DBU)

About the cured product of the curable composition obtained by an Example and a comparative example, it carried out as follows, and the measurement of the adhesive strength and evaluation of curability were performed.

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 side length of 2 mm (2 mm × 2 mm = 4 mm 2) and a thickness of 350 μm, and a thickness of about 2 μm. It applied so as to be possible, and the coated surface was put on the adherend (silver plated copper plate) and pressed. Then, it heated at 120 degreeC for 2 hours to harden the curable composition, and obtained the adherend with the test piece. The adherend to which this test piece is attached is left for 30 seconds on a measurement stage of a bond tester (series 4000, manufactured by Daisy Corporation) at a predetermined temperature (23° C.) in advance, and a speed 200 from a position 100 μm high from the adherend. Stress was applied to the adhesive surface at µm/s by a horizontal method (shear direction), 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 Corporation). On the stainless steel plate heated to 120 degreeC, 0.30 ml of sample was put and stirred. The stirring torque increased over time and the time (second) until it became 0.392 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 ㎜

(Production Example 3)

In a 300 ml eggplant flask, 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Asmax Corporation) 17.0 g (77.7 mmol), and methyltriethoxysilane (manufactured by Shin-Etsu Chemical Industries, Ltd., Product name "KBE-13") After pouring 32.33 g (181.3 mmol), stirring this, 0.0675 g of 35% hydrochloric acid to 14.0 g of distilled water (the amount of HCl is 0.65 mmol, 0.25 mol with respect to the total amount of the silane compound) %) was added, and the resulting aqueous solution was added, and the total solution was heated at 30°C for 2 hours and then to 70°C, followed by stirring for 20 hours.

While continuing the stirring of the contents, a mixed solution of 28% aqueous ammonia 0.0394 g (the amount of NH ₃ is 0.65 mmol) and 46.1 g of propyl acetate was added, and the pH of the reaction solution was set to 6.9, as it was at 70° C. 40 Stir for a minute.

After the reaction solution was allowed to cool to room temperature, 50 g of propyl acetate and 100 g of water were added thereto to perform liquid separation treatment to obtain an organic layer containing a reaction product. Magnesium sulfate was added to this organic layer, and drying treatment was performed. After the magnesium sulfate was removed by filtration, the organic layer was concentrated with an evaporator, and the obtained concentrate was then dried in vacuo to obtain a polysilsesquioxane compound (A3). Its mass average molecular weight (Mw) was 5,500, and molecular weight distribution was 3.40.

IR spectrum data of the curable polysilsesquioxane compound (A3) is 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)

In Example 1, in the same manner as in Example 1, Example 13, except that the type of the component (A), the type of the component (B), and the amount used (parts) were changed as described in Table 2 below. , The curable composition of 14 and the curable composition of Comparative Example 5 were obtained.

About the cured product of the obtained curable composition, the measurement of adhesive strength and evaluation of curability were performed.

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

From Table 1 and Table 2, it is understood that in the curable composition of Examples 1 to 14, a cured product was obtained in a short time of 8,000 seconds or less in a curable evaluation test, and thus curable property was excellent.

In addition, even when cured at 120° C. for 2 hours, the obtained cured product has an adhesive strength of 50 N/4 mm 2 or more, which indicates excellent adhesive strength.

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 curable evaluation test.

In addition, when the curable compositions of Comparative Examples 1 to 5 were cured at 120° C. for 2 hours, the obtained cured product had an adhesive strength of less than 50 N/4 mm 2, and it was found that the adhesive strength was inferior.

Claims (12)

A curable composition comprising the following component (A) and component (B), wherein the content of component (B) is more than 0 parts by mass and 3 parts by mass or less based on 100 parts by mass of component (A) .
(A) component: the following formula (a)

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms having a substituent or not having a substituent group, or an aryl group having a substituent group or not having a substituent. A plurality of R ^{1s 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 represent 0 or a positive integer.)
Silane compound polymer represented by
(B) component: at least one metal compound selected from the group consisting of bismuth compounds, aluminum compounds and zirconium compounds The method of claim 1,
The curable composition, wherein the mass average molecular weight (Mw) of the silane compound polymer of the component (A) is 800 to 50,000. The method according to claim 1 or 2,
The curable composition, wherein the silane compound polymer is one or two or more polycondensation products of the silane compound represented by the following formula (1).

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms having a substituent or not having a substituent group, or an aryl group having a substituent group or not having a substituent. A plurality of R ^{1s may be the} same or different. may. R ² represents a halogen atom, and are X ¹ represents an alkyl group of carbon number 1 ~ 10, s represents an integer of 0 to 3 each other and a plurality of R ² to each other, and a plurality of X ^1, may be the same with each other , May be different. The method according to any one of claims 1 to 3,
Further, the curable composition containing the following (C) component.
(C) Component: Silane coupling agent having a nitrogen atom in the molecule The method according to any one of claims 1 to 4,
Further, the curable composition containing the following (D) component.
(D) Component: Silane coupling agent having an acid anhydride structure in the molecule The method according to any one of claims 1 to 5,
Additionally, a curable composition containing a diluent. The method of claim 6,
The curable composition, wherein the solid content concentration of the curable composition is 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 method of claim 8,
A hardened material that is an optical element fixing material. A method for producing a cured product in which the curable composition according to any one of claims 1 to 7 is heated and cured at 110°C to 130°C. A method of using the curable composition according to any one of claims 1 to 7 as an adhesive for fixing an optical element. A method of using the curable composition according to any one of claims 1 to 7 as a sealing material for fixing an optical element.