阅读说明：本技术 固化性组合物、固化物、固化物的制造方法、和固化性组合物的使用方法 (Curable composition, cured product, method for producing cured product, and method for using curable composition ) 是由 三浦迪 贱机弘宪 宫胁学 中山秀一 于 2019-03-11 设计创作，主要内容包括：本发明包含下述(A)成分和(B)成分,(B)成分的含量相对于(A)成分100质量份大于0质量份且为3质量份以下；将该组合物固化而得到的固化物；和将该组合物用作光元件固定用粘接剂或光元件固定用密封材料的方法。本发明的固化性组合物能够通过低温加热而固化,得到具有高粘接力的固化物。(A)成分：式(a)所示的硅烷化合物聚合物(R<Sup>1</Sup>表示具有取代基或不具有取代基的碳原子数1~10的烷基、或者具有取代基或不具有取代基的芳基；Z表示羟基、碳原子数1~10的烷氧基、或者卤素原子；p表示正整数；q、r表示0或正整数)(B)成分：选自铋化合物、铝化合物和锆化合物中的至少一种金属化合物。<Image he="31" wi="398" file="DEST_PATH_IMAGE002.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention comprises the following (A) component and (B) component, wherein the content of the (B) component is more than 0 part by mass and less than 3 parts by mass relative to 100 parts by mass of the (A) component; a cured product obtained by curing the composition; and a method for using the composition as an adhesive or a sealing material for fixing an optical element. The curable composition of the present invention can be cured by heating at a low temperature to obtain a cured product having high adhesion. (A) The components: a silane compound polymer (R) represented by the formula (a) 1 An alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aryl group which may or may not have a substituent; z represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; p represents a positive integer; q and r represent 0 or a positive integer) (B) component: at least one metal compound selected from the group consisting of bismuth compounds, aluminum compounds and zirconium compounds.)

1. A curable composition comprising the following component (A) and component (B), wherein the content of component (B) is more than 0 part by mass and not more than 3 parts by mass per 100 parts by mass of component (A),

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

[ solution 1]

In the formula, R¹An alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aryl group which may or may not have a substituent; plural R¹May be the same or different from each other; z represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; p represents a positive integer, q and r each independently represent 0 or a positive integer;

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

2. The curable composition according to claim 1, wherein the silane compound polymer of component (A) has a mass average molecular weight (Mw) of 800 to 50,000.

3. The curable composition according to claim 1 or 2, wherein the silane compound polymer is a polycondensation product of one or more silane compounds represented by the following formula (1),

[ solution 2]

In the formula, R¹An alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aryl group which may or may not have a substituent; plural R¹May be the same or different from each other; r²Represents an alkyl group having 1 to 10 carbon atoms, X¹Represents a halogen atom, s represents an integer of 0 to 3; plural R²Each other and a plurality of X¹May be the same or different from each other.

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

(C) the components: 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) the components: a silane coupling agent having an acid anhydride structure in a molecule.

6. The curable composition according to any one of claims 1 to 5, further comprising a diluent.

7. The curable composition according to claim 6, wherein the solid content concentration of the curable composition is 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 claims 1 to 7.

9. The cured product according to claim 8, which is an optical device-fixing material.

10. A method for producing a cured product, comprising heating the curable composition according to any one of claims 1 to 7 to 110 ℃ to 130 ℃ to cure the composition.

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

12. A method for using the curable composition according to any one of claims 1 to 7 as an optical device-fixing sealing material.

Technical Field

The present invention relates to a curable composition which gives a cured product having excellent peeling resistance and heat resistance and high adhesion, a cured product obtained by curing the composition, a method for producing the same, and a method for using the composition as an adhesive for optical element fixation or a sealing material for optical element fixation.

Background

Conventionally, curable compositions have been improved variously depending on the application, and are widely used industrially as materials, adhesives, coating agents, and the like for optical components and molded articles.

The curable composition is also attracting attention as an optical element fixing material such as an optical element fixing adhesive and an optical element fixing sealing material in the production of an optical element sealed body.

Examples of the optical element include various lasers such as a semiconductor Laser (LD), a light emitting element such as a Light Emitting Diode (LED), a light receiving element, a composite optical element, and an optical integrated circuit. In recent years, optical devices using blue light and white light having a shorter peak wavelength of light emission have been widely developed. The increase in luminance of the light-emitting element having a short peak wavelength of light emission is rapidly progressing, and the amount of heat generated by the optical element tends to further increase.

However, with the recent increase in luminance of optical devices, there has been a problem that cured products of the composition for an optical device-fixing material are exposed to light of higher energy or heat of higher temperature generated by the optical devices for a long time, and are deteriorated to cause peeling or decrease in adhesive strength.

In order to solve this problem, patent documents 1 to 3 propose compositions for optical element-fixing materials containing polysilsesquioxane compounds as a main component, and patent document 4 proposes a member for semiconductor light-emitting devices and the like using a hydrolyzed and polycondensate of a silane compound.

However, even cured products such as the compositions and members described in patent documents 1 to 4 may have difficulty in obtaining peeling resistance and heat resistance while securing sufficient adhesive strength.

In contrast, the present inventors have found a curable composition that provides a cured product having excellent peeling resistance and heat resistance and having high adhesion force (patent documents 5 and 6).

However, in order to cure these curable compositions, they need to be heated at high temperature (170 ℃ or higher) for about 2 hours. Therefore, when these curable compositions are used for optical semiconductor light-emitting devices and the like, the curable compositions may be exposed to high temperatures during curing, and the peripheral members of packages may be damaged.

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a curable composition which gives a cured product having high adhesion and can be cured by heating at a lower temperature than conventional ones, a cured product obtained by curing the composition, a method for producing the same, and a method for using the composition as an adhesive for optical element fixation and a sealing material for optical element fixation.

Means for solving the problems

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

Thus, the present invention provides the following curable compositions [1] to [7], cured products [8] and [9], a method for producing a cured product [10], a method for using the composition as an adhesive for fixing optical elements [11], and a method for using the composition as an encapsulant for fixing optical elements [12 ].

[1] A curable composition comprising the following component (A) and component (B), wherein the content of component (B) is more than 0 part by mass and not more than 3 parts by mass per 100 parts by mass of component (A),

(A) the components: the following formula (a)

[ solution 1]

(in the formula, R¹An alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aryl group which may or may not have a substituent; plural R¹May be the same or different from each other; z represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; p represents a positive integer, q and r each independently represent 0 or a positive integer)

The silane compound polymer

(B) The components: 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 a polycondensation product of one or two or more silane compounds represented by the following formula (1),

[ solution 2]

(in the formula, R¹Denotes the same meaning as described above, X¹Represents a halogen atom, s represents an integer of 0 to 3; plural R²Each other and a plurality of X¹May be the same or different from each other).

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

(C) the components: 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),

(D) the components: a silane coupling agent having an acid anhydride structure in a molecule.

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

[7] The curable composition according to [6], wherein the solid content concentration of the curable composition is 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 according to [8], which is an optical device-fixing material.

[10] A method for producing a cured product, comprising heating the curable composition according to any one of [1] to [7] to 110 ℃ to 130 ℃ and curing the composition.

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

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

ADVANTAGEOUS EFFECTS OF INVENTION

The curable composition of the present invention can be cured by heating at a lower temperature than conventional compositions. In the case where 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 a high temperature at the time of curing, and therefore the packaging member is not damaged by heat.

A 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 suitably used as an adhesive for fixing an optical element and a sealing material for fixing an optical element.

Detailed Description

The present invention will be described in detail below with respect to items 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 comprises the following component (A) and component (B), and is characterized in that the content of the component (B) is more than 0 part by mass and not more than 3 parts by mass per 100 parts by mass of the component (A),

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

[ solution 3]

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

(A) Composition (I)

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

In the above formula (a), the formula: - (R)¹SiO_3/2) -the repeating unit, formula (lb): - (R)¹SiZO_2/2) -the repeating unit shown, and formula (lb): - (R)¹SiZ₂O_1/2) The repeating units represented by (a) to (a3) can be represented by the following formulae (a1) to (a 3). In the cases (a1) to (a3), "-O-" represents an oxygen atom common to adjacent 2 Si atoms.

[ solution 4]

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

In the above formulae (a), (a1), (a2) and (a3), R¹Represents an alkyl group having 1 to 10 carbon atoms which may or may not have a substituent, or an aryl group which may or may not have a substituent.

Namely, R¹Selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and having a substituent, an unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group having a substituent, and an unsubstituted aryl group.

The number of carbon atoms of the "alkyl group having 1 to 10 carbon atoms and a substituent" means a part of the alkyl groupThe number of carbon atoms. Thus, R¹The total number of carbon atoms may be more than 10.

As R¹Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, and an n-nonyl group.

As R¹Examples of the substituent of the alkyl group having 1 to 10 carbon atoms having a substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like; a cyano group; formula (II): group shown as OG.

G represents a protecting group for a hydroxyl group. The protecting group for a hydroxyl group is not particularly limited, and known protecting groups known as protecting groups for hydroxyl groups may be mentioned. Examples thereof include protecting groups of acyl group; silyl-based protecting groups such as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl and t-butyldiphenylsilyl; acetal-based protecting groups such as methoxymethyl, methoxyethoxymethyl, 1-ethoxyethyl, tetrahydropyran-2-yl and tetrahydrofuran-2-yl; alkoxycarbonyl-based protecting groups such as tert-butoxycarbonyl; and ether-based protecting groups such as methyl, ethyl, tert-butyl, octyl, allyl, triphenylmethyl, benzyl, p-methoxybenzyl, fluorenyl, trityl, and benzhydryl.

As R¹Examples of the aryl group of (2) include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group.

As R¹Examples of the substituent of the substituted aryl group include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and an isooctyl group; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; alkoxy groups such as methoxy and ethoxy.

Among these, as R¹From the viewpoint of easily obtaining the effects of the present invention, the alkyl group having 1 to 6 carbon atoms and a substituent, the unsubstituted alkyl group having 1 to 6 carbon atoms, or the unsubstituted aryl group is preferable, and the alkyl group having a substituent is more preferableThe alkyl group having 1 to 6 carbon atoms, the unsubstituted alkyl group having 1 to 6 carbon atoms, or the phenyl group, more preferably the alkyl group having 1 to 6 carbon atoms and having a cyano group, the alkyl group having 1 to 6 carbon atoms and having a fluorine atom, the unsubstituted alkyl group having 1 to 6 carbon atoms, or the phenyl group, and particularly preferably the alkyl group having 1 to 3 carbon atoms and having a cyano group, the alkyl group having 1 to 3 carbon atoms and having a fluorine atom, the unsubstituted alkyl group having 1 to 3 carbon atoms, or the phenyl group.

Plural R¹All of which 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 of Z include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tert-butoxy group, and a pentyloxy group. Examples of the halogen atom include a chlorine atom and a bromine atom.

Among these, Z is preferably a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

p represents a positive integer, q and r each independently represent 0 or a positive integer.

Plural R¹All of which may be the same or different.

Further, all of the plurality of Z may be the same or different.

The method for producing the silane compound polymer (a) is not particularly limited.

For example, the silane compound can be produced by polycondensing one or two or more kinds of silane compounds represented by the following formula (1) (hereinafter, may be referred to as "silane compound (1)"). Here, "polycondensation" is used in a broad concept including hydrolysis and polycondensation reactions.

[ solution 5]

In the formula (1), R¹The same meanings as described above are indicated. R²Represents an alkyl group having 1 to 10 carbon atoms, X¹Represents a halogen atom, and s represents an integer of 0 to 3.

As R²The alkyl group having 1 to 10 carbon atoms of (A) may beExamples thereof are the aforementioned R¹The alkyl group having 1 to 10 carbon atoms is exemplified by the same groups.

As X¹Examples of the halogen atom of (2) include a chlorine atom and a bromine atom.

When s is 2 OR more, a plurality of OR²May be the same or different from each other. When (3-s) is 2 or more, a plurality of X' s¹May be the same or different from each other.

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

alkylhaloalkoxysilane compounds such as methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichlormethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane, n-propylchlorodimethoxysilane, n-propyldichloromethoxysilane, n-butylchlorodimethoxysilane and n-butyldichloromethoxysilane;

alkyltrihalosilane compounds such as methyltrichlorosilane, methyltrtribromosilane, ethyltrichlorosilane, ethyltribromosilane, n-propyltrichlorosilane, n-propyltribromosilane, n-butyltrichlorosilane, isobutyltrichlorosilane, n-pentyltrichlorosilane, n-hexyltrichlorosilane, and isooctyltrichlorosilane;

phenyltrialkoxysilane compounds optionally having a substituent such as phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 2-chlorophenyltrimethoxysilane, phenyltriethoxysilane, 2-methoxyphenyltriethoxysilane, phenyldimethoxyethoxysilane, and phenyldiethoxymethoxysilane;

phenylhaloalkoxysilane compounds optionally having a substituent such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, phenylchloromethoxyethoxysilane, phenylchlorodiethoxysilane, and phenyldichloroethoxysilane;

phenyltrihalosilane compounds optionally having a substituent such as phenyltrichlorosilane, phenyltribromosilane, 4-methoxyphenyltrichlorosilane, phenyltrichlorosilane, 2-ethoxyphenyltrichlorosilane, 2-chlorophenyltrichlorosilane, and the like;

cyanomethyltrimethoxysilane, cyanomethyltriethoxysilane, 1-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyltripropoxysilane, 3-cyanopropyltrimethoxysilane, 3-cyanopropyltriethoxysilane, 3-cyanopropyltripropoxysilane, 3-cyanopropyltributoxysilane, 4-cyanobutyltrimethoxysilane, 5-cyanopentyltrimethoxysilane, 2-cyanopropyltrimethoxysilane, 2- (cyanomethoxy) ethyltrimethoxysilane, 2- (2-cyanoethoxy) ethyltrimethoxysilane, o- (cyanomethyl) phenyltripropoxysilane, m- (cyanomethyl) phenyltrimethoxysilane, m-cyanomethyltrimethoxysilane, m-cyanoethyltrimethoxysilane, n-ethyltrimethoxysilane, m-ethyltrimethoxysilane, n-ethyltrimethoxysilane, Cyanoalkyltrialkoxysilane compounds such as p- (cyanomethyl) phenyltriethoxysilane and p- (2-cyanoethyl) phenyltrimethoxysilane;

cyanomethyltrichlorosilane, cyanomethylbromodimethoxysilane, 2-cyanoethyldichloromethoxysilane, 2-cyanoethyldichloroethoxysilane, 3-cyanopropyltrichlorosilane, 3-cyanopropyltribromosilane, 3-cyanopropyldichloromethoxysilane, 3-cyanopropyldichloroethoxysilane, 3-cyanopropylchlorodimethoxysilane, 3-cyanopropylchlorodiethoxysilane, 4-cyanobutyldiethoxysilane, 3-cyano-n-butylchlorodiethoxysilane, 2- (2-cyanoethoxy) ethyltrichlorosilane, 2- (2-cyanoethoxy) ethylbromodiethoxysilane, 2- (2-cyanoethoxy) ethyldichloropropoxysilane, o- (2-cyanoethyl) phenyltrichlorosilane, o- (2-cyanoethyl) dichloroethoxysilane, o- (2-cyanoethyl), Cyanoalkylhalosilane compounds such as m- (2-cyanoethyl) phenylmethoxydibromosilane, p- (2-cyanoethyl) phenyldimethoxychlorosilane and p- (2-cyanoethyl) phenyltribromosilane;

fluoroalkyl trialkoxysilane compounds such as 3,3, 3-trifluoropropyltrimethoxysilane and 3,3, 3-trifluoropropyltriethoxysilane;

fluoroalkyl halogenoalkoxysilane compounds such as 3,3, 3-trifluoropropylchlorodimethoxysilane, 3,3, 3-trifluoropropylchlorodiethoxysilane, 3,3, 3-trifluoropropyldichloromethoxysilane, and 3,3, 3-trifluoropropyldichloroethoxysilane;

fluoroalkyl trihalosilane compounds such as 3,3, 3-trifluoropropyltrichlorosilane, and the like.

The silane compound (1) may be used singly or in combination of two or more.

Among these, the silane compound (1) is preferably a trialkoxysilane compound from the viewpoint of easily obtaining a cured product having more excellent adhesiveness, and more preferably (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) a combination of an alkyltrialkoxysilane compound having 1 to 10 carbon atoms and a trialkoxysilane compound having a fluoroalkyl group having 1 to 10 carbon atoms.

When a phenyltrialkoxysilane compound and a cyanoalkyltrialkoxysilane compound having 1 to 10 carbon atoms are used in combination, the ratio of the phenyltrialkoxysilane compound to the cyanoalkyltrialkoxysilane compound having 1 to 10 carbon atoms in use is preferably [ phenyltrialkoxysilane compound ]: [ cyanoalkyltrialkoxysilane compound having 1 to 10 carbon atoms ] = 95: 5-50: 50, more preferably 90: 10-60: 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 ratio of the alkyltrialkoxysilane compound having 1 to 10 carbon atoms to the trialkoxysilane compound having a fluoroalkyl group having 1 to 10 carbon atoms is preferably [ an alkyltrialkoxysilane compound having 1 to 10 carbon atoms ]: [ trialkoxysilane compound having fluoroalkyl group having 1 to 10 carbon atoms ] = 95: 5-10: 90, more preferably 90: 10-30: 70, more preferably still 85: 15-50: 50.

the method for polycondensing the silane compound (1) is not particularly limited, and examples thereof include a method in which a predetermined amount of a catalyst is added to the silane compound (1) in a solvent or in the absence of a solvent, and the entire volume is stirred at a predetermined temperature.

The catalyst used may be either one of an acid catalyst and a base catalyst.

In addition, an acid catalyst and a base catalyst may also be used in combination. For example, after the polycondensation reaction of the silane compound is carried out in the presence of an acid catalyst, a base catalyst is added to the reaction solution to make the reaction basic, and the polycondensation reaction can be further carried out under basic conditions.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, and trifluoroacetic acid.

As the alkali catalyst, ammonia (water); organic bases such as 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, and imidazole; organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide; metal hydrides such as sodium hydride and calcium hydride; metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, and magnesium carbonate; and metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate.

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

The solvent to be used may be appropriately selected depending on the kind of the silane compound (1) and the like. Examples thereof include 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 methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol. These solvents may be used alone or in combination of two or more.

The amount of the solvent used is not particularly limited, but is usually 0.1 to 10 liters, preferably 0.1 to 2 liters, based on 1 mole 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 ℃ to the boiling point of the solvent used, and preferably in the range of 20 ℃ to 100 ℃. If the reaction temperature is too low, the condensation reaction may not proceed sufficiently. On the other hand, if the reaction temperature becomes too high, it becomes difficult to suppress gelation. The reaction is usually completed within 30 minutes to 30 hours.

Depending on the type of the silane compound (1) used, it may be difficult to increase the molecular weight. For example, the presence of R¹Silane compound being fluoroalkyl and R¹Silane compounds that are normal alkyl groups tend to be less reactive than silane compounds that are normal alkyl groups. In such a case, gelation is suppressed by reducing the amount of the catalyst and conducting the reaction under a smooth condition for a long time, and the silane compound polymer (a) having a desired molecular weight is easily obtained.

After the reaction is completed, when an acid catalyst is used, an aqueous alkali solution such as sodium hydrogencarbonate is added to the reaction solution, when an alkali catalyst is used, an acid such as hydrochloric acid is added to the reaction solution to neutralize the reaction solution, and the salt generated at that time is removed by filtration, washing with water, or the like, whereby the target silane compound polymer can be obtained.

OR of silane Compound (1) in producing silane Compound Polymer (A) by the above-described method²Or X¹Among them, a part which is not dehydrated and/or dealcoholized remains in the silane compound polymer (A). I.e. in the remaining OR²Or X¹In the case of 1, in the above formula (a), R is¹SiZO_2/2) But remain in the remaining OR²Or X¹In the formula (a), as (R) in 2 cases¹SiZ₂O_1/2) But remains.

The silane compound polymer (A) may be a homopolymer (R)¹Is a polymer of one kind), and may be a copolymer (R)¹Two or more polymers).

The silane compound polymer (A) is a copolymer (R)¹Two or more kinds of polymers), the silane compound polymer (a) may be any copolymer such as a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer, etc., and is preferably a random copolymer from the viewpoint of ease of production, etc.

The structure of the silane compound polymer (a) may be any of a ladder type structure, a double-layer type structure, a cage type structure, a partially split cage type structure, a ring type structure, and a random type 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. When the amount is within this range, a cured product having excellent handling properties of the composition and excellent adhesiveness and heat resistance can be obtained.

The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be determined as standard polystyrene values by Gel Permeation Chromatography (GPC) using Tetrahydrofuran (THF) as a solvent, for example (the same applies hereinafter).

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

The silane compound polymer (a) may 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.

(B) Composition (I)

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

Since the curable composition of the present invention contains the component (B), the curable composition can be cured at a lower temperature in a shorter 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, and from the viewpoint of availability and the like, a compound of bismuth having a valence of 3 or 5, a compound of aluminum having a valence of 3, and a compound of zirconium having a valence of 4 are each preferable.

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

More specifically, the following may be mentioned, but not limited thereto.

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

metal oxides such as bismuth oxide, bismuth oxychloride, 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;

bicarbonates such as bismuth bicarbonate, aluminum bicarbonate, zirconium bicarbonate and the like;

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

formula (II): bi (OR)⁴)₃A bismuth compound represented by the formula: al (OR)⁴)₃An aluminum compound represented by the formula: zr (OR)⁴)₄Metal alkoxide (R) of the above zirconium compound or the like⁴Represents methyl, ethyl, n-propyl, isopropyl, n-butyl, or isopropylAn alkyl group having 1 to 20 carbon atoms such as a butyl group, a sec-butyl group, a tert-butyl group, an octyl group, a 2-ethylhexyl group, a decyl group, or a dodecyl group; alkenyl groups having 2 to 20 carbon atoms such as a 1-propenyl group, a 2-propenyl isopropenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group; an aromatic group having 6 to 20 carbon atoms such as a phenyl group; aralkyl groups having 7 to 20 carbon atoms such as benzyl and phenethyl; cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl);

fatty acid salts of bismuth, aluminum or zirconium, such as acetate, propionate, octanoate, nonanoate, dodecanoate (laurate), tetradecanoate (myristate), hexadecanoate (palmitate), octadecanoate (stearate), naphthenate, octanoate, neodecanoate, and isostearate; aromatic carboxylates such as benzoate; polycarboxylic acid salts such as succinic acid salts; unsaturated carboxylates such as maleate, linolenate, linoleate, oleate, arachidonate, etc.; carboxylates such as abietate;

a chelate compound of bismuth, aluminum or zirconium with a polydentate ligand (e.g., a beta-diketone compound such as acetylacetone or benzoylacetone, a beta-ketoester such as methyl acetoacetate or ethyl acetoacetate, carbonate, or a compound having 1 to 15 carbon atoms such as ethylenediamine).

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

Examples of the ligand include halide ion, hydride ion (hydride), oxygen atom (oxo, peroxy), hydroxyl (hydroxylation), water (hydration or hydration), carbon monoxide (carbonyl), carbonate ion (carbonate, CO)₃ ^2-) And inorganic ligands;

oxalic acid ion (oxalate radical, C)₂O₄ ^2-) Alkoxy (e.g., methoxy, ethoxy), acyl (e.g., acetyl, propionyl, benzoyl), carboxylate, acetylacetonato, ethyl acetoacetate, cycloalkadienyl (e.g., cyclopentadienyl, dicyclopentadienyl), ether (e.g., diethyl ether), hydrocarbyl (e.g., alkyl such as methyl, ethyl; aryl groups such as phenyl and naphthyl);

ammonia, nitro radicalsNitrite (NO)₂ ^-) Nitrogen-containing ligands such as cyano, cyanate, isocyanate, alkylamine (e.g., dimethylamine), ethylenediamine, diethylenetriamine, pyridine, and phenanthroline;

and organic ligands such as sulfur-containing ligands such as thiocyanate groups and isothiocyanate groups.

Preferable specific examples of the metal compound of the component (B) include the following compounds.

(bismuth Compound)

Halides of bismuth such as bismuth oxychloride, bismuth chloride and bismuth bromide; inorganic salts of bismuth such as bismuth hydroxide, bismuth nitrate and bismuth sulfate; bismuth carboxylates such as bismuth acetate, bismuth benzoate, bismuth octoate, bismuth naphthenate, bismuth oxysalicylate, bismuth neodecanoate, bismuth abietate, bismuth versatate, bismuth 2-ethylhexanoate [ tris (2-ethylhexanoate) bismuth ], and bismuth stearate; [ carbonate (2-) -O ] triphenylbismuth, etc.;

(aluminum compound)

Halides of aluminum such as aluminum chloride; alkoxide of aluminum such as trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, tri-sec-butoxyaluminum, tributoxyaluminum and the like; chelate compounds of aluminum such as tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, monoacetylacetonato bis (ethylacetoacetate) aluminum, and diisopropoxylacetoacetanoaluminum;

(zirconium compound)

Zirconium halides such as zirconium oxychloride; inorganic salts of zirconium such as zirconium sulfate and zirconium nitrate; zirconium carboxylates such as zirconium acetate, zirconium octylate, and zirconium stearate; zirconium alkoxides such as tetra-n-propoxzirconium, tetra-n-butoxyzirconium, and octoxytridecyloxyzirconium; chelate compounds of zirconium such as zirconium tetraacetylacetonate, zirconium tributoxymetacetylacetonate and zirconium tributoxymetacetylacetonate;

among these, bismuth halides, bismuth carboxylates, [ carbonate (2-) -O ] triphenylbismuth, aluminum chelate compounds, and zirconium carboxylates are more preferable, bismuth halides, bismuth carboxylates having 6 to 20 carbon atoms, [ carbonate (2-) -O ] triphenylbismuth, aluminum chelate compounds, and zirconium carboxylates having 6 to 20 carbon atoms are still more preferable, and bismuth chloride, bismuth octoate, [ carbonate (2-) -O ] triphenylbismuth, aluminum chelate compounds, and zirconium octoate are particularly preferable.

(B) The lower limit of the content of the component (a) is more than 0 part by mass, preferably 0.01 part by mass or more, and more preferably 0.05 part by mass or more, relative to 100 parts by mass of the component (a). 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 part 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 which can be cured at a low temperature (110 to 130 ℃) in a short time can be obtained.

(C) Composition (I)

The curable composition of the present invention preferably further contains component (C): 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) gives a cured product having excellent workability in the coating step and further excellent 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 the molecule. Examples thereof include trialkoxysilane compounds represented by the following formula (c-1), dialkoxyalkylsilane compounds represented by the following formula (c-2), dialkoxyarylsilane compounds, and the like.

[ solution 6]

In the above formula, R^aRepresents 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, a tert-butoxy group, etc. Plural R^aMay be the same or different from each other.

R^bAn alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, etc.; or an aryl group having a substituent or having no substituent such as a phenyl group, a 4-chlorophenyl group, or a 4-methylphenyl group.

R^cDenotes a carbon atom having a nitrogen atomOrganic groups having a seed number of 1 to 10. Furthermore, R^cMay be further bonded to other silicon atom-containing groups.

As R^cSpecific examples of the organic group having 1 to 10 carbon atoms include N-2- (aminoethyl) -3-aminopropyl, N- (1, 3-dimethyl-butylidene) aminopropyl, 3-ureidopropyl, N-phenyl-aminopropyl and the like.

R is a group represented by the formula (c-1) or (c-2)^cExamples of the compound in the case of an organic group bonded to another group containing a silicon atom include compounds bonded to another silicon atom via an isocyanurate skeleton to constitute an isocyanurate-based silane coupling agent; and a urea-based silane coupling agent which is bonded to other silicon atoms through a urea skeleton.

Among these, the silane coupling agent (C) is preferably an isocyanurate-based silane coupling agent or a urea-based silane coupling agent, and more preferably a silane coupling agent having 4 or more alkoxy groups bonded to silicon atoms in the molecule, from the viewpoint of easily obtaining a cured product having a higher adhesive strength.

The alkoxy group bonded to a silicon atom having 4 or more means that the total count of the alkoxy groups bonded to the same silicon atom and the alkoxy groups bonded to different silicon atoms is 4 or more.

Examples of the isocyanurate-based silane coupling agent having 4 or more alkoxy groups bonded to silicon atoms include compounds represented by the following formula (c-3), and examples of the urea-based silane coupling agent having 4 or more alkoxy groups bonded to silicon atoms include compounds represented by the following formula (c-4).

[ solution 7]

In the formula, R^aThe same meanings as described above are indicated.

t1 to t5 each independently represent an integer of 1 to 10, preferably an integer of 1 to 6, and particularly preferably 3.

Specific examples of the compound represented by the formula (c-3) include 1,3, 5-N-tris [ (tri (C1-C6) alkoxy) silyl (C1-C10) alkyl ] isocyanurate such as 1,3, 5-N-tris (3-trimethoxysilylpropyl) isocyanurate, 1,3, 5-N-tris (3-triisopropoxysilylpropyl) isocyanurate, 1,3, 5-N-tris (3-tributoxysilylpropyl) isocyanurate and the like; 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-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-diisopropoxyesopropylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-diisopropoxyen-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 [ (di (C1-6) alkoxy) silyl (C1-10) alkyl ] isocyanurate such as 1,3, 5-N-tris (3-dibutoxy-N-propylsilylpropyl) isocyanurate, 1,3, 5-N-tris (3-dibutoxyphenylsilylpropyl) isocyanurate, and the like.

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

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

In the case where the isocyanurate compound and the urea compound are used in combination, the ratio of the both is preferably 100: 1-100: 200. more preferably 100: 10-100: 110. by using the isocyanurate compound and the urea compound in combination at such a ratio, a curable composition giving a cured product more excellent in heat resistance and adhesiveness can be obtained.

The silane coupling agent (C) may be used alone in 1 kind, or in combination with 2 or more kinds.

When the curable composition of the present invention contains component (C), the amount of component (C) used is such that the ratio of component (a) to component (C) used is such that the mass ratio of component (a) to component (C) [ (component a: (C) component ] to preferably 100: 0.3-100: 50. more preferably 100: 1-100: 40. more preferably 100: 3-100: 35, in the amount of the composition.

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

(D) Composition (I)

The curable composition of the present invention preferably contains the following component (D): 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) gives a cured product having more excellent workability in the coating step and further excellent adhesiveness, peeling resistance, and heat resistance.

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

[ solution 8]

Wherein Q represents a group having an acid anhydride structure, R^dRepresents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group, R^eRepresents an alkoxy group having 1 to 6 carbon atoms or a halogen atom, i and k represent an integer of 1 to 3, j represents an integer of 0 to 2, and i + j + k = 4. When j is 2, R^dMay be the same or different from each other. When k is 2 or 3, a plurality of R^eMay be the same or different from each other. When i is 2 or 3, Q's may be the same as or different from each other.

Q is represented by the following formula

[ solution 9]

And (wherein h represents an integer of 0 to 10), and particularly preferably (Q1).

In the formula (d), as R^dThe alkyl group having 1 to 6 carbon atoms of (A) may be mentioned as the formerR is¹Examples of the alkyl group having 1 to 6 carbon atoms include the same groups.

As R^dExamples of the substituent of the substituted phenyl group include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, and a n-hexyl group; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; alkoxy groups such as methoxy and ethoxy.

As R^eExamples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tert-butoxy group and the like.

As R^eExamples of the halogen atom of (2) include a chlorine atom and a bromine atom.

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

[ solution 10]

(in the formula, R^eH, i, j, k are as defined above)

The compounds shown. 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 formula (d-1) include tri (C1-6) alkoxysilyl (C2-8) alkyl succinic anhydrides such as 2- (trimethoxysilyl) ethyl succinic anhydride, 2- (triethoxysilyl) ethyl succinic anhydride, 3- (trimethoxysilyl) propyl succinic anhydride, and 3- (triethoxysilyl) propyl succinic anhydride; di (C1-C6) alkoxymethylsilyl (C2-C8) alkylsuccinic anhydrides such as 2- (dimethoxymethylsilyl) ethylsuccinic anhydride; (C1-C6) alkoxydimethylsilyl (C2-C8) alkyl succinic anhydride such as 2- (methoxydimethylsilyl) ethyl succinic anhydride;

trihalosilyl (C2-C8) alkyl succinic anhydrides such as 2- (trichlorosilyl) ethyl succinic anhydride and 2- (tribromosilyl) ethyl succinic anhydride; dihalogenomethylsilyl (C2-C8) alkyl succinic anhydrides such as 2- (dichloromethylsilyl) ethylsuccinic anhydride; halogenated dimethylsilyl (C2-C8) alkyl succinic anhydride such as 2- (chlorodimethylsilyl) ethyl succinic anhydride, etc.

The silane coupling agent (D) may be used alone in 1 kind, or in combination with 2 or more kinds.

Among these, the silane coupling agent (D) is preferably a tri (C1-6) alkoxysilyl (C2-8) alkyl succinic anhydride, and particularly preferably 3- (trimethoxysilyl) propyl succinic anhydride or 3- (triethoxysilyl) 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, and the ratio of the component (a) to the component (D) by mass is [ (a component: (D) component ], preferably 100: 0.01-100: 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 is more excellent in heat resistance and adhesiveness.

(E) Diluent

The curable composition of the present invention may further contain a diluent for imparting fluidity.

The diluent is not particularly limited as long as it has good compatibility with the components (A) and (B). Examples thereof include nitrogen-containing compounds such as N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethylimidazolidinone; sulfur-containing compounds such as dimethyl sulfoxide; and oxygen-containing compounds such as 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 monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol phenyl ether, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (Texanol), γ -butyrolactone, ethyl lactate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol mono-n-propyl ether, diacetone alcohol, and tetrahydrofurfuryl alcohol.

These diluents may be used singly or in combination of two or more.

When the curable composition of the present invention contains a diluent, the diluent is preferably used in an amount such that the solid content concentration of the curable composition of the present invention is 50 mass% or more and less than 100 mass%, more preferably 60 to 90 mass%, and still more preferably 70 to 85 mass%, from the viewpoint of workability.

(F) Other ingredients

The curable composition of the present invention may contain "other components" than the components (a) to (E) as long as the object of the present invention is not impaired.

Examples of the other components include fine particles, antioxidants, ultraviolet absorbers, and light stabilizers.

If fine particles are added, a curable composition having excellent workability in the coating step may be obtained. Examples of the material of the fine particles include silica; resins such as acrylic acid and silicone; metal oxides such as aluminum oxide and titanium oxide; minerals such as boehmite, and the like.

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

The antioxidant is added to prevent oxidative deterioration during heating. Examples of the antioxidant include a phosphorus antioxidant, a phenol antioxidant, and a sulfur antioxidant.

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

These antioxidants may be used singly 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 to improve the light resistance of the resulting cured product.

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

The ultraviolet absorber may be used alone or in combination of two or more.

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

The light stabilizer is added to improve the light resistance of the cured product.

Examples of the light stabilizer include hindered amines such as 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 } ].

These light stabilizers may be used singly or in combination of two or more.

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

The curable composition of the present invention can be obtained by, for example, mixing the above-mentioned component (a), component (B), and desired components (C) to (F) at a predetermined ratio, and then mixing and defoaming the mixture by a known method.

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 peeling resistance and heat resistance, and high adhesion.

When the curable composition of the present invention is used in an optical device, it is not necessary to heat the curable composition at a high temperature when curing the curable composition, and therefore, the curable composition does not cause damage to a peripheral member of a package due to heat.

Therefore, the curable composition of the present invention is suitably used as a raw material, an adhesive, a coating agent, and the like for optical parts and molded articles.

2) Cured product and method for producing same

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

The curable composition of the present invention can be cured by heating.

The cured product of the present invention can be obtained by curing the curable composition of the present invention by heating the curable composition to a temperature of usually 100 to 150 ℃, preferably 110 to 140 ℃, more preferably 110 to 130 ℃. 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 in a short time by heating. Therefore, when used in an optical semiconductor light emitting device or the like, the peripheral member of the package is not exposed to high temperature and damaged.

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

That is, a sample of the curable composition was put into stainless steel heated to 120 ℃ and stirred using an automatic curing time measuring apparatus (product name: まどか, manufactured by サイバー K.K.), and the time until the stirring torque increased to 0.392N · cm was measured.

The time required for the reaction to reach 0.392N · cm is preferably 8,000 seconds or less.

Further, even if the cured product is obtained by curing by heating at a low temperature, the cured product of the present invention has high adhesive force, and can be confirmed, for example, as described below.

That is, a curable composition is applied to the mirror surface of a silicon wafer, the applied surface is placed on an adherend and pressure-bonded, and the cured product is heat-treated at a low temperature (for example, 120 ℃). The adherend with the test piece was left on a measuring table of an adhesion tester set at a predetermined temperature (for example, 23 ℃) for 30 seconds, and stress was applied to the adhesion surface in the horizontal direction (shear direction) at a position of a height of 100 μm from the adherend to measure the adhesion between the test piece and the adherend.

The adhesion of the cured product measured in this manner is preferably 50N/4mm at 23 ℃²Above, more preferably 70N/4mm²The above.

Here, "N/4 mm²"is the adhesion force per 2mm x 2mm area [ N]。

3) Method for using 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 or a sealing material for optical element fixation.

Examples of the optical element include a light emitting element such as an LED or an LD, a light receiving element, a composite optical element, and an optical integrated circuit.

Adhesive for fixing optical element

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

As a method for using the curable composition of the present invention as an adhesive for fixing an optical element, there is a method in which a predetermined amount of the composition is applied to one or both adhesion surfaces of materials to be adhered (an optical element, a substrate thereof, or the like), and after pressure bonding, the materials to be adhered are firmly adhered to each other by heat curing.

In the present invention, as described above, since the heat curing of the curable composition can be performed at a lower temperature and in a shorter time than in the conventional case, it is not necessary to expose the peripheral members of the optical semiconductor light-emitting device to a high temperature, and the packaging member is not damaged.

Examples of the substrate material for bonding the optical element include glasses such as soda-lime glass and heat-resistant hard glass; a ceramic; sapphire; metals such as iron, copper, aluminum, gold, silver, platinum, chromium, titanium, and alloys of these metals, stainless steel (SUS302, SUS304L, SUS309, etc.); and synthetic resins such as 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, and glass epoxy resin.

Sealing material for fixing optical element

The curable composition of the present invention can be suitably used as a sealing material for sealing an optical element.

Examples of the method for using the curable composition of the present invention as a sealing material for fixing an optical element include a method for producing an optical element sealing body by molding the composition into a desired shape to obtain a molded body containing an optical element and then heating and curing the molded body.

The method for molding the curable composition of the present invention into a desired shape is not particularly limited, and a known die casting method such as a general transfer molding method or an injection molding method can be used.

In the present invention, as described above, since the heat curing of the curable composition can be performed at a lower temperature and in a shorter time than in the conventional case, it is not necessary to expose the peripheral members of the optical semiconductor light-emitting device to a high temperature, and the packaging member is not damaged.

The obtained optical element sealing body has high adhesion because the curable composition of the present invention is used.