CN115151611A

CN115151611A - Curable composition, cured product, and method for using curable composition

Info

Publication number: CN115151611A
Application number: CN202180018220.5A
Authority: CN
Inventors: 三浦迪; 宫胁学
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2020-03-23
Filing date: 2021-03-19
Publication date: 2022-10-04
Also published as: WO2021193452A1; JPWO2021193452A1; TW202142605A

Abstract

The present invention relates to a curable composition containing the following component (a) and component (B), a cured product obtained by curing the curable composition, and a method for using the curable composition as an adhesive for an optical device fixing material or a sealing material for an optical device fixing material. The present invention provides a curable composition having excellent curability and storage stabilityA curable composition, a cured product obtained by curing the curable composition, and a method for using the curable composition as an adhesive for optical element-fixing materials or a sealing material for optical element-fixing materials. Component (A): polysilsesquioxane compound [ R ] having one or more repeating units represented by the following formula (a-1) ¹ Is a group selected from an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms and a substituted aryl group having 6 to 12 carbon atoms.](B) The components: a thermal acid generator.

Description

Curable composition, cured product, and method for using curable composition

Technical Field

The present invention relates to a curable composition having excellent curability and storage stability, a cured product obtained by curing the curable composition, and a method for using the curable composition as an adhesive for an optical device fixing material or a sealing material for an optical device fixing material.

Background

Conventionally, curable compositions have been improved in various ways depending on the application, and are widely used industrially as raw materials, adhesives, coating agents, and the like for optical parts and molded articles.

The curable composition is also attracting attention as a composition for an optical element fixing material such as an adhesive for an optical element fixing material or a sealing material for an optical element fixing material.

The optical element includes various lasers such as a semiconductor Laser (LD), light-emitting elements such as a light-emitting diode (LED), light-receiving elements, composite optical elements, optical integrated circuits, and the like.

In recent years, optical devices that emit blue or white light having a shorter peak wavelength have been developed and widely used. The increase in luminance of the light-emitting element having a short peak wavelength of light emission has been dramatically advanced, and the amount of heat generated by the optical element tends to be further increased.

However, with the recent increase in luminance of optical devices, there has been a problem that the adhesive strength is reduced when a cured product of the composition for an optical device-fixing material is exposed to higher-energy light and higher-temperature heat generated from the optical device for a long time.

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

When an optical element or the like is fixed using the composition for an optical element fixing material, the composition for an optical element fixing material is usually cured by heating.

However, when a composition for an optical element-fixing material having poor curability is used, it is necessary to increase the heating time or the heating temperature, which may deteriorate the optical element or its surrounding parts or reduce the production efficiency of the product.

Therefore, studies have been made to improve the curability of a curable composition containing a polysilsesquioxane compound.

For example, patent document 4 describes a condensation reaction type silicone composition containing a specific polysilsesquioxane compound and a condensation reaction catalyst.

Patent document 4 also describes that the condensation reaction type silicone composition is excellent in various properties and excellent in curability (initial curability).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2004-359933,

patent document 2: japanese patent laid-open publication No. 2005-263869,

patent document 3: japanese patent laid-open publication No. 2006-328231,

patent document 4: WO 2017/122762.

Disclosure of Invention

Problems to be solved by the invention

As described above, the condensation reaction type silicone composition described in patent document 4 is excellent in various properties and also excellent in curability.

However, the curing conditions described in the examples of patent document 4 are such that the curable composition having more excellent curability is desired by heating at 120 ℃ for 1 hour and then heating at 150 ℃ for 3 hours.

Further, according to the study of the present inventors, it is found that when the curability of the curable composition is improved, the storage stability may be lowered.

The present invention has been made in view of the above-described circumstances of the prior art, and an object thereof is to provide a curable composition having excellent curability and storage stability, a cured product obtained by curing the curable composition, and a method for using the curable composition as an adhesive for optical device-fixing materials or a sealing material for optical device-fixing materials.

In the present invention, "excellent curability" means that when a curing reaction is performed under a predetermined condition, viscosity increases in a shorter time and the final curing is performed.

Means for solving the problems

In order to solve the above problems, the present inventors have made extensive studies on a curable composition containing a polysilsesquioxane compound.

As a result, they have found that a curable composition containing a polysilsesquioxane compound and a heat acid generator is excellent in curability and storage stability, and have completed the present invention.

Thus, the present invention provides the following curable compositions [1] to [9], the cured products [10] and [11], and the methods of using the curable compositions [12] and [13 ].

[1] A curable composition comprising the following component (A) and component (B),

(A) The components: a polysilsesquioxane compound having one or more kinds of repeating units represented by the following formula (a-1),

[ chemical formula 1]

R ¹ A group selected from an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms and a substituted aryl group having 6 to 12 carbon atoms;

(B) The components: a thermal acid generator.

[2] The curable composition according to [1], wherein the amount of the repeating unit represented by the formula (a-1) in the component (A) is 70 to 100mol% based on the total repeating units of the component (A).

[3] The curable composition according to [1] or [2], wherein the component (A) has a mass average molecular weight (Mw) of from 500 to 20,000.

[4] The curable composition according to any one of [1] to [3], wherein the content of the component (A) is 40% by mass or more and less than 100% by mass in the solid content of the curable composition.

[5] The curable composition according to any one of [1] to [4], wherein the component (B) is an onium salt thermal acid generator.

[6] The curable composition according to any one of [1] to [5], wherein the component (B) satisfies the following requirement (I):

[ essential component (I) ]

The peak temperature (acid production temperature) of the maximum endothermic peak of component (B) obtained by differential scanning calorimetry in the temperature range of 30 to 300 ℃ at a temperature rise rate of 10 ℃/min is 80 to 180 ℃.

[7] The curable composition according to any one of [1] to [6], wherein the content of the component (B) is more than 0 part by mass and not more than 5 parts by mass with respect to 100 parts by mass of the component (A).

[8] The curable composition according to any one of [1] to [7], further comprising the following component (C),

(C) The components: a silane coupling agent.

[9] The curable composition according to any one of [1] to [8], further comprising a solvent, wherein the solid content concentration is 50% by mass or more and less than 100% by mass.

[10] A cured product obtained by curing the curable composition according to any one of [1] to [9 ].

[11] The cured product according to [10], which is an optical device-fixing material.

[12] A method of using the curable composition according to any one of the above [1] to [9] as an adhesive for an optical element-fixing material.

[13] A method for using the curable composition according to any one of the above [1] to [9] as a sealing material for an optical element-fixing material.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there are provided a curable composition having excellent curability and storage stability, a cured product obtained by curing the curable composition, and a method for using the curable composition as an adhesive for an optical device fixing material or a sealing material for an optical device fixing material.

Detailed Description

The present invention will be described in detail below by dividing it into 1) a curable composition, 2) a cured product, 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),

(A) The components: a polysilsesquioxane compound having one or more than two kinds of repeating units represented by the above formula (a-1),

(B) The components: a thermal acid generator.

[ (A) component ]

The component (a) constituting the curable composition of the present invention is a polysilsesquioxane compound having one or more repeating units represented by the following formula (a-1) (hereinafter, sometimes referred to as "polysilsesquioxane compound (a)").

[ chemical formula 2]

In the formula (a-1), R ¹ Is a group selected from an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms and a substituted aryl group having 6 to 12 carbon atoms.

With R ¹ The carbon number of the "unsubstituted alkyl group having 1 to 10 carbon atoms" is preferably 1 to 6, more preferably 1 to 3.

Examples of the "unsubstituted alkyl group having 1 to 10 carbon atoms" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, and n-decyl groups.

With R ¹ The "alkyl group having 1 to 10 carbon atoms which has a substituent" represented by (A) preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The number of carbon atoms refers to the number of carbon atoms of a moiety (alkyl moiety) other than the substituent. Thus, at R ¹ In the case of "alkyl group having 1 to 10 carbon atoms and having substituent group", R ¹ The number of carbon atoms of (2) may exceed 10.

Examples of the "alkyl group having 1 to 10 carbon atoms as a substituent" include the same groups as those shown as the "unsubstituted alkyl group having 1 to 10 carbon atoms".

The number of atoms (excluding the number of hydrogen atoms) of the substituent(s) "alkyl group having 1 to 10 carbon atoms as a substituent(s)" is usually 1 to 30, preferably 1 to 20.

Examples of the substituent of the "alkyl group having 1 to 10 carbon atoms and having a substituent" include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and the like, a cyano group, represented by the formula: groups represented by OG, and the like.

Here, 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 can be mentioned. Examples thereof include an acyl-based protecting group, a silyl-based protecting group such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group or a t-butyldiphenylsilyl group, an acetal-based protecting group such as a methoxymethyl group, a methoxyethoxymethyl group, a 1-ethoxyethyl group, a tetrahydropyran-2-yl group or a tetrahydrofuran-2-yl group, an alkoxycarbonyl-based protecting group such as a t-butoxycarbonyl group, and an ether-based protecting group such as a methyl group, an ethyl group, a t-butyl group, an octyl group, an allyl group, a triphenylmethyl group, a benzyl group, a p-methoxybenzyl group, a fluorenyl group, a trityl group or a xylyl group.

With R ¹ The carbon number of the "unsubstituted aryl group having 6 to 12 carbon atoms" is preferably6。

Examples of the "unsubstituted aryl group having 6 to 12 carbon atoms" include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

With R ¹ The "aryl group having 6 to 12 carbon atoms and having a substituent" preferably has 6 carbon atoms. The number of carbon atoms refers to the number of carbon atoms of a portion (portion of an aryl group) other than the substituent. Thus, at R ¹ In the case of "aryl group having 6 to 12 carbon atoms having a substituent", R is ¹ The number of carbon atoms of (2) may exceed 12.

Examples of the "aryl group having 6 to 12 carbon atoms as a substituent" include the same groups as those shown as the "unsubstituted aryl group having 6 to 12 carbon atoms".

The number of atoms (excluding the number of hydrogen atoms) of the substituent of the "aryl group having 6 to 12 carbon atoms and having a substituent" is usually 1 to 30, preferably 1 to 20.

Examples of the "aryl group having 6 to 12 carbon atoms and having a substituent" include an alkyl group 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, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, and an alkoxy group such as a methoxy group and an ethoxy group.

Wherein, as R ¹ Preferred examples of the alkyl group include an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, an alkyl group having 1 to 10 carbon atoms and a cyano group, and an unsubstituted aryl group having 6 to 12 carbon atoms.

By using R ¹ A curable composition which can provide a cured product having more excellent heat resistance and adhesiveness can be easily obtained from a polysilsesquioxane compound (A) which is an unsubstituted alkyl group having 1 to 10 carbon atoms.

In the present specification, the "cured product having excellent adhesiveness" refers to a "cured product having high adhesive strength".

By using R ¹ The polysilsesquioxane compound (A) having an alkyl group of 1 to 10 carbon atoms and having a fluorine atom is easily obtainedA curable composition having a low refractive index and a cured product are obtained.

By using R ¹ A curable composition which provides a cured product excellent in adhesion to a highly polar adherend can be easily obtained from a polysilsesquioxane compound (A) having a cyano alkyl group having 1 to 10 carbon atoms.

By using R ¹ A curable composition and a cured product having a high refractive index can be easily obtained from a polysilsesquioxane compound (A) which is an unsubstituted aryl group having 6 to 12 carbon atoms.

The content ratio of the repeating unit represented by the formula (a-1) in the polysilsesquioxane compound (a) is preferably 70 to 100mol%, more preferably 80 to 100mol%, and still more preferably 90 to 100mol% with respect to the total repeating units.

The content ratio of the repeating unit represented by the above formula (a-1) in the polysilsesquioxane compound (A) is as follows, and can be measured ¹ H-NMR.

The repeating unit represented by the above formula (a-1) is a repeating unit represented by the following formula (a-2). In the present specification, O _1/2 It means that the oxygen atom is common to the adjacent repeating units.

[ chemical formula 3]

The polysilsesquioxane compound (A) has a structure in which 3 oxygen atoms are bonded to a silicon atom and 1 group (R) other than oxygen atoms is bonded to a silicon atom, which is generally collectively referred to as a T site, as shown in the formula (a-2) ¹ ) And forming a partial structure.

Examples of the T site contained in the polysilsesquioxane compound (A) include structures represented by the following formulae (a-3) to (a-5).

[ chemical formula 4]

In the formulae (a-3) to (a-5), R ¹ Means the same as above。R ² Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. As R ² Examples 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, a sec-butyl group, an isobutyl group, and a tert-butyl group. Plural R ² May be identical to or different from each other. In the formulae (a-3) to (a-5), a Si atom is bonded to each atom.

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

By measuring the solution state of the polysilsesquioxane compound (A) ²⁹ Si-NMR was carried out to determine the content ratio of the T3 site represented by the above formula (a-3), the T2 site represented by the formula (a-4) and the T1 site represented by the formula (a-5).

From the viewpoint of improving the adhesiveness of the cured product, the polysilsesquioxane compound (a) used in the present invention preferably contains 10 to 45mol% of T2 sites, more preferably contains 15 to 40mol%, and still more preferably contains 20 to 35mol% of T2 sites.

The polysilsesquioxane compound (a) used in the present invention preferably contains 50 to 90mol% of T3 sites, more preferably 55 to 85mol%, and still more preferably 60 to 80mol% of T3 sites, from the viewpoint of obtaining a hard and heat-resistant cured product.

The polysilsesquioxane compound (A) may have one R ¹ (homopolymer) may have two or more R ¹ (copolymer).

When the polysilsesquioxane compound (a) is a copolymer, the polysilsesquioxane compound (a) may be any of a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer, and the like, but a random copolymer is preferable from the viewpoint of ease of production and the like.

The polysilsesquioxane compound (a) may have any structure of a ladder structure, a double-layer structure, a cage structure, a partially split cage structure, a ring structure, and a random structure.

The mass average molecular weight (Mw) of the polysilsesquioxane compound (A) is usually 500 to 20,000, preferably 1,000 to 15,000, and more preferably 1,500 to 12,000. By using the polysilsesquioxane compound (a) having a mass average molecular weight (Mw) within the above range, a curable composition that provides a cured product more excellent in heat resistance and adhesiveness can be easily obtained.

The molecular weight distribution (Mw/Mn) of the polysilsesquioxane compound (A) is not particularly limited, but is usually 1.0 to 10.0, preferably 1.1 to 6.0. By using the polysilsesquioxane compound (a) having a molecular weight distribution (Mw/Mn) within the above range, a curable composition providing a cured product more excellent in heat resistance and adhesiveness can be easily obtained.

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

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

The content of the polysilsesquioxane compound (a) is preferably 40% by mass or more and less than 100% by mass, more preferably 48 to 95% by mass, and still more preferably 56 to 90% by mass, in the solid content of the curable composition.

In the present invention, "solid component" refers to a component other than a solvent in the curable composition.

The method for producing the polysilsesquioxane compound (a) is not particularly limited. The polysilsesquioxane compound (a) can be produced, for example, by polycondensation using at least one of silane compounds (1) represented by the following formula (a-6).

[ chemical formula 5]

In the formula, R ¹ The same meanings as described above are indicated. R ³ X represents an alkyl group having 1 to 10 carbon atoms ¹ Represents a halogen atom, and p represents an integer of 0 to 3. Plural R ³ And a plurality of X ¹ May be respectively the same or different from each other.

As R ³ The alkyl group having 1 to 10 carbon atoms of (A) includes ² The same groups as those shown for the alkyl group having 1 to 10 carbon atoms.

As X ¹ Examples of the halogen atom of (b) include a chlorine atom and a bromine atom.

Specific examples of the silane compound (1) include

Alkyltrialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and ethyltripropoxysilane,

alkylhaloalkoxysilane compounds such as methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichlormethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane and ethylbromodimethoxysilane,

alkyltrihalosilane compounds such as methyltrichlorosilane, methyltrtribromosilane, ethyltrichlorosilane, ethyltribromosilane and the like,

substituted alkyltrialkoxysilane compounds such as 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane and 2-cyanoethyltriethoxysilane,

substituted alkylhaloalkoxysilane compounds such as 3,3,3-trifluoropropylchlorodimethoxysilane, 3,3,3-trifluoropropylchlorodiethoxysilane, 3,3,3-trifluoropropyldichloromethoxysilane, 3,3,3-trifluoropropyldichloroethoxysilane, 2-cyanoethylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 2-cyanoethyldichloromethoxysilane and 2-cyanoethyldichloroethoxysilane,

substituted alkyltrihalosilane compounds such as 3, 3-trifluoropropyltrichlorosilane and 2-cyanoethyltrichlorosilane,

phenyltrialkoxysilane compounds having a substituent or having no substituent such as phenyltrimethoxysilane and 4-methoxyphenyltrimethoxysilane,

phenylhaloalkoxysilane compounds having or not having a substituent such as phenylchlorodimethoxysilane, phenyldichloromethoxysilane, 4-methoxyphenylchlorodimethoxysilane and 4-methoxyphenyldichloromethoxysilane,

and phenyl trihalosilane compounds having a substituent or having no substituent, such as phenyltrichlorosilane and 4-methoxyphenyltrichlorosilane.

These silane compounds (1) may be used singly or in combination of two or more.

The method for polycondensing the silane compound (1) is not particularly limited. For example, a method of adding a predetermined amount of a polycondensation catalyst to the silane compound (1) in a solvent or without a solvent and stirring at a predetermined temperature may be mentioned. More specifically, there may be mentioned: (a) A method of adding a predetermined amount of an acid catalyst to the silane compound (1) and stirring at a predetermined temperature; (b) A method in which a predetermined amount of an alkali catalyst is added to the silane compound (1) and the mixture is stirred at a predetermined temperature; (c) A method in which a predetermined amount of an acid catalyst is added to the silane compound (1), and the mixture is stirred at a predetermined temperature, and then an excess amount of a base catalyst is added to make the reaction system basic, and the mixture is stirred at a predetermined temperature. Among them, the method (a) or (c) is preferable because the target polysilsesquioxane compound (a) can be efficiently obtained.

The polycondensation catalyst used may be either an acid catalyst or a base catalyst. In addition, two or more polycondensation catalysts may be used in combination, and preferably at least an acid catalyst is used.

Examples of the acid catalyst include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid and nitric acid, and organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid. Among them, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid and methanesulfonic acid is preferable.

Examples of the base catalyst include ammonia water, organic bases such as trimethylamine, triethylamine, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, pyridine, 1, 8-diazabicyclo [5.4.0] -7-undecene, aniline, picoline, 1, 4-diazabicyclo [2.2.2] octane and imidazole, organic 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 bicarbonates such as sodium bicarbonate and potassium bicarbonate.

The amount of the polycondensation catalyst to be used is usually in the range of 0.05 to 10mol%, preferably 0.1 to 5mol%, based on the total mol amount of the silane compound (1).

When a solvent is used in the polycondensation, 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, and alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol. These solvents may be used singly or in combination of two or more. In the case of the method (c), after the polycondensation reaction is carried out in an aqueous system in the presence of an acid catalyst, an organic solvent and an excess amount of a base catalyst (ammonia water or the like) are added to the reaction solution, and the polycondensation reaction is further carried out under an alkaline condition.

The amount of the solvent used is usually 0.1 liter or more and 10 liters or less, and preferably 0.1 liter or more and 2 liters or less, based on 1mol of the total mol amount of the silane compound (1).

The temperature at which the silane compound (1) is polycondensed 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 polycondensation reaction may not be sufficiently performed. On the other hand, if the reaction temperature is too high, gelation is difficult to suppress. The reaction is usually completed within 30 minutes to 30 hours.

It should be noted that, in the following description,depending on the kind of monomer used, it may be difficult to increase the molecular weight. For example R ¹ Monomer which is an alkyl group having a fluorine atom has a reactivity ratio R ¹ Monomers which are typical alkyl groups tend to be poor. In this case, the polysilsesquioxane compound (a) having the target molecular weight is easily obtained by reducing the amount of the catalyst and conducting the reaction under mild conditions for a long period of time.

After the reaction is completed, the objective polysilsesquioxane compound (a) can be obtained by adding an aqueous alkaline solution such as sodium hydrogencarbonate to the reaction solution for neutralization in the case of using an acid catalyst, adding an acid such as hydrochloric acid to the reaction solution for neutralization in the case of using an alkaline catalyst, and removing the salt generated at that time by filtration, washing with water, or the like.

In the preparation of the polysilsesquioxane compound (A) by the above-mentioned method, at OR of the silane compound (1) ³ Or X ¹ In (b), a part in which dealcoholization has not occurred remains in the polysilsesquioxane compound (a). Therefore, the polysilsesquioxane compound (A) may contain a T site represented by the above formula (a-4) or formula (a-5) in addition to the T site represented by the above formula (a-3).

[ (B) component ]

The component (B) constituting the curable composition of the present invention is a thermal acid generator.

The thermal acid generator is a compound that generates an acid component such as a lewis acid or a bronsted acid by heating.

The curable composition of the present invention contains a thermal acid generator, and therefore, has excellent curability and storage stability.

The thermal acid generator is preferably one having a maximum endothermic peak (acid generation temperature) of 80 to 180 ℃ as measured by differential scanning calorimetry under conditions of a temperature range of 30 to 300 ℃ and a temperature rise rate of 10 ℃/min.

The curable composition containing the thermal acid generator having an acid generation temperature of 80 ℃ or higher under the above conditions is more excellent in storage stability. Further, the curable composition containing the thermal acid generator having an acid generation temperature of 180 ℃ or lower under the above conditions is more excellent in curability.

In view of easier availability of these effects, the acid production temperature under the above conditions is preferably from 90 to 170 ℃, and more preferably from 100 to 160 ℃.

As the thermal acid generator, an onium salt type thermal acid generator can be mentioned. The onium salt thermal acid generator is a thermal acid generator containing an onium cation component and an anion component.

Examples of the onium cation component include organic sulfonium ions, organic ammonium ions, organic phosphonium ions, and organic iodonium ions.

Examples of the organic sulfonium ion constituting the onium salt thermal acid generator include cations represented by the following formula (b-1).

[ chemical formula 6]

In the formula (b-1), R ⁴ 、R ⁵ 、R ⁶ Each independently is a group selected from an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms and a substituted aryl group having 6 to 12 carbon atoms.

With R ⁴ ~R ⁶ The "unsubstituted alkyl group having 1 to 10 carbon atoms" preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.

As with R ⁴ ~R ⁶ The "alkyl group having 1 to 10 carbon atoms which has a substituent" represented by (A) preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The number of carbon atoms refers to the number of carbon atoms of a moiety (alkyl moiety) other than the substituent. Thus, at R ⁴ ~R ⁶ In the case of "alkyl group having 1 to 10 carbon atoms and having substituent group", R ⁴ ~R ⁶ The number of carbon atoms of (2) may be more than 10The method is described.

The number of atoms (excluding the number of hydrogen atoms) of the substituent(s) "alkyl group having 1 to 10 carbon atoms as the substituent(s)" is usually 1 to 30, preferably 1 to 20.

Examples of the "alkyl group having 1 to 10 carbon atoms and having a substituent" include aryl groups such as a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group.

With R ⁴ ~R ⁶ The "unsubstituted aryl group having 6 to 12 carbon atoms" represented by (a) preferably has 6 carbon atoms.

With R ⁴ ~R ⁶ The "aryl group having 6 to 12 carbon atoms having a substituent" represented by (a) preferably has 6 carbon atoms. The number of carbon atoms refers to the number of carbon atoms of a portion (portion of an aryl group) other than the substituent. Thus, at R ⁴ ~R ⁶ In the case of "aryl group having 6 to 12 carbon atoms having a substituent", R is ⁴ ~R ⁶ The number of carbon atoms of (2) may exceed 12.

The number of atoms (excluding the number of hydrogen atoms) of the substituent(s) of the "aryl group having 6 to 12 carbon atoms as a substituent" is usually 1 to 30, preferably 1 to 20.

Examples of the "aryl group having 6 to 12 carbon atoms and having a substituent" include an alkyl group 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, an alkoxy group such as a methoxy group and an ethoxy group, a hydroxyl group, an acyloxy group such as an acetoxy group and a propionyloxy group, and the like.

Examples of the organic ammonium ion constituting the onium salt thermal acid generator include cations represented by the following formula (b-2).

[ chemical formula 7]

In the formula (b-2), R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ Each independently is a group selected from an unsubstituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms and an unsubstituted aryl group having 6 to 12 carbon atoms.

As R ⁷ ~R ¹⁰ May be exemplified by and represented by R ⁴ ~R ⁶ The same groups as in (1).

Examples of the organic phosphonium ion constituting the onium salt thermal acid generator include cations represented by the following formula (b-3).

[ chemical formula 8]

In the formula (b-3), R ¹¹ 、R ¹² 、R ¹³ 、R ¹⁴ Each independently is a group selected from an unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms and a substituted aryl group having 6 to 12 carbon atoms.

As R ¹¹ ~R ¹⁴ And are exemplified by and represented by R ⁴ ~R ⁶ The same groups as in (1).

Examples of the organic iodonium ion constituting the onium salt thermal acid generator include cations represented by the following formula (b-4).

[ chemical formula 9]

In the formula (b-4), R ¹⁵ 、R ¹⁶ Each independently is a group selected from an unsubstituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 12 carbon atoms and an unsubstituted aryl group having 6 to 12 carbon atoms.

As R ¹⁵ 、R ¹⁶ May be exemplified by and represented by R ⁴ ~R ⁶ The same groups as in (1).

Among them, from the viewpoint of achieving both curability and storage stability of the curable composition, the onium cation component is preferably an organic sulfonium ion or an organic ammonium ion, and more preferably an organic sulfonium ion represented by the following formula (b-5), in view of having an appropriate acid-generating temperature and easily controlling reactivity of the acid-generating reaction.

[ chemical formula 10]

In the formula (b-5), ar represents an aryl group having a substituent such as a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group or a 2-naphthyl group, or having no substituent.

Examples of the anion component of the onium salt type thermal acid generator include trifluoromethanesulfonate anion, hexafluorophosphate anion, hexafluoroantimonate anion, perfluorobutanesulfonate anion, tetrakis (pentafluorophenyl) borate anion, tetrafluoroborate anion and the like.

Among them, in view of easy availability of a cured product having excellent optical properties, the anion component is preferably a hexafluorophosphate anion, a hexafluoroantimonate anion or a tetrakis (pentafluorophenyl) borate anion, and more preferably a hexafluorophosphate anion.

The thermal acid generator may be used singly or in combination of two or more.

The content of the thermal acid generator is usually more than 0 part by mass and not more than 5 parts by mass, preferably 0.001 to 3.0 parts by mass, more preferably 0.005 to 2.0 parts by mass, still more preferably 0.010 to 1.5 parts by mass, and particularly preferably 0.015 to 1.0 part by mass, based on 100 parts by mass of the polysilsesquioxane compound (a).

If the content of the thermal acid generator is too large, the adhesiveness of the cured product may be reduced.

[ curable composition ]

The curable composition of the present invention may contain a silane coupling agent as the component (C). By using a curable composition containing a silane coupling agent, a cured product having more excellent adhesiveness can be easily obtained.

The silane coupling agent is a silane compound having a silicon atom, a functional group, and a hydrolyzable group bonded to the silicon atom.

The functional group is a group reactive with other compounds (mainly organic compounds), and examples thereof include a group having a nitrogen atom such as an amino group, a substituted amino group, an isocyanate group, a urea group, and a group having an isocyanurate skeleton, an acid anhydride group, a vinyl group, an allyl group, an epoxy group, a (meth) acryloyl group, and a mercapto group.

In the present invention, the silane coupling agent may be used singly or in combination of two or more.

When the curable composition of the present invention contains a silane coupling agent, the content thereof is not particularly limited and may be appropriately determined according to the purpose.

The content of the silane coupling agent is usually 95 parts by mass or less, preferably 65 parts by mass or less, and more preferably 35 parts by mass or less, per 100 parts by mass of the polysilsesquioxane compound (a).

The silane coupling agent is preferably a silane coupling agent having a nitrogen atom in the molecule or a silane coupling agent having an acid anhydride structure in the molecule.

Curable compositions containing a silane coupling agent having a nitrogen atom in the molecule or a silane coupling agent having an acid anhydride structure in the molecule tend to provide cured products having more excellent heat resistance and adhesiveness.

Examples of the silane coupling agent having a nitrogen atom in the molecule include trialkoxysilane compounds represented by the following formula (c-1), dialkoxyalkylsilane compounds represented by the following formula (c-2), dialkoxyarylsilane compounds, and the like.

[ chemical formula 11]

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, or a tert-butoxy group. Plural R ^a May be the same or different from each other.

R ^b And represents 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, a t-butyl group or the like, or an aryl group which may or may not have a substituent such as a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 1-naphthyl group or the like.

R ^c Represents an organic group having 1 to 10 carbon atoms and having a nitrogen atom. In addition, R ^c It may also be bonded to other groups containing silicon atoms.

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

In the compound represented by the above formula (c-1) or (c-2), R is ^c Examples of the organic group-containing compound to which other silicon atom-containing groups are bonded include a silane coupling agent having an isocyanurate skeleton (isocyanurate-based silane coupling agent) and a silane coupling agent having a urea skeleton (urea-based silane coupling agent).

Among these, as the silane coupling agent having a nitrogen atom in the molecule, an isocyanurate-based silane coupling agent and a urea-based silane coupling agent are preferable, and a compound having 4 or more alkoxy groups bonded to a silicon atom in the molecule is more preferable, in view of easy availability of a cured product having more excellent adhesiveness.

The alkoxy group having 4 or more atoms 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.

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

[ chemical formula 12]

In the formula, R ^a The 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.

Among them, as the silane coupling agent having a nitrogen atom in the molecule, 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 above-mentioned isocyanurate compound and urea compound are preferably used.

When the curable composition of the present invention contains a silane coupling agent having a nitrogen atom in the molecule, the content thereof is not particularly limited, and the amount is in a range of from 0.1 to 100, more preferably 100.

A cured product of the curable composition containing the component (a) and the silane coupling agent having a nitrogen atom in the molecule in such a ratio becomes a cured product having more excellent heat resistance and adhesiveness.

The silane coupling agent having an acid anhydride structure in a molecule is an organosilicon compound having both an acid anhydride structure-containing group and a hydrolyzable group in one molecule. Specifically, the compound represented by the following formula (c-5) may be mentioned.

[ chemical formula 13]

In the formula, Q represents a group having an acid anhydride structure, R ^d Represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group, R ^e Represents an alkoxy group having 1 to 6 carbon atoms or a halogen atom, i and k represent integers of 1 to 3, j represents an integer of 0 to 2, and i + j + k =4. When j is 2, R ^d May be the same or different from each other. When k is 2 or 3, a plurality of R ^e May 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.

Examples of Q include a group represented by the following formula, and a group represented by (Q1) is particularly preferable.

[ chemical formula 14]

In the formula, h represents an integer of 0 to 10.

Examples of the silane coupling agent having an acid anhydride structure in the molecule include tri (C1-C6) alkoxysilyl (C2-C8) alkyl succinic anhydrides such as 2- (trimethoxysilyl) ethylsuccinic anhydride, 2- (triethoxysilyl) ethylsuccinic anhydride, 3- (trimethoxysilyl) propylsuccinic anhydride, and 3- (triethoxysilyl) propylsuccinic anhydride,

a di (C1-C6) alkoxymethylsilyl (C2-C8) alkylsuccinic anhydride such as 2- (dimethoxymethylsilyl) ethylsuccinic anhydride,

an alkoxydimethylsilyl (C2-C8) alkylsuccinic anhydride such as 2- (methoxydimethylsilyl) ethylsuccinic anhydride,

trihalosilyl (C2-C8) alkyl succinic anhydrides such as 2- (trichlorosilyl) ethylsuccinic anhydride and 2- (tribromosilyl) ethylsuccinic anhydride,

dihalomethylsilyl (C2-C8) alkylsuccinic anhydrides such as 2- (dichloromethylsilyl) ethylsuccinic anhydride,

and a halogenated dimethylsilyl (C2-C8) alkylsuccinic anhydride such as 2- (chlorodimethylsilyl) ethylsuccinic anhydride.

Among them, the silane coupling agent having an acid anhydride structure in the molecule is preferably a tri (C1-C6) alkoxysilyl (C2-C8) alkylsuccinic anhydride, and particularly preferably a 3- (trimethoxysilyl) propylsuccinic anhydride or a 3- (triethoxysilyl) propylsuccinic anhydride.

When the curable composition of the present invention contains a silane coupling agent having an acid anhydride structure in the molecule, the content thereof is not particularly limited. The content of the silane coupling agent having an acid anhydride structure in a molecule is, in terms of the mass ratio of the component (a) to the silane coupling agent having an acid anhydride structure in a molecule [ (component (a): the silane coupling agent having an acid anhydride structure in a molecule ], in an amount of preferably from 100 to 30, more preferably from 0.3 to 100, more preferably from 0.5 to 100.

A cured product of the curable composition containing the component (a) and the silane coupling agent having an acid anhydride structure in the molecule at such a ratio becomes a cured product having more excellent adhesiveness.

The curable composition of the present invention may contain other components within a range not interfering with the object of the present invention.

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

When the 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 metals, metal oxides, minerals, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, metal hydroxides such as aluminum hydroxide, metal silicates such as aluminum silicate, calcium silicate and magnesium silicate, inorganic components such as silica, organic components such as silicone and acrylic polymers.

In addition, the particles used may be particles whose surfaces are modified.

These fine particles may be used singly or in combination of two or more. The content of the fine particles is not particularly limited, and is usually preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less with respect to 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 oxides, and the like. Examples of the phenolic antioxidant include monophenols, bisphenols, and high molecular weight phenols. Examples of the sulfur-based antioxidant include dilauryl 3,3' -thiodipropionate, dimyristyl 3,3' -thiodipropionate, and distearyl 3,3' -thiodipropionate.

These antioxidants may be used singly or in combination of two or more. The content of the antioxidant is not particularly limited, and is usually 10% by mass or less based on the component (A).

The ultraviolet absorber is added to improve the light resistance of the cured product obtained.

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 content of the ultraviolet absorber is not particularly limited, and 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 obtained.

As the light stabilizer, there may be mentioned, for example, poly [ {6- (1, 3-tetramethylbutyl) amino-1, 3, 5-triazine-2, 4-diyl } { (2, 6-and hindered amines such as tetramethyl-4-piperidine) imino } hexamethylene { (2, 6-tetramethyl-4-piperidine) imino } ], and the like.

These light stabilizers may be used singly or in combination of two or more. The content of the light stabilizer is usually 20% by mass or less based on the component (A).

The solvent is not particularly limited as long as it can dissolve or disperse the components of the curable composition of the present invention.

Examples of the solvent include acetic acid esters such as diethylene glycol monobutyl ether acetate and 1, 6-hexanediol diacetate, diglycidyl ethers such as tripropylene glycol n-butyl ether, glycerol diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether, cyclohexanedimethanol diglycidyl ether, alkylene diglycidyl ether, polyglycol diglycidyl ether, and polypropylene glycol diglycidyl ether, triglycidyl ethers such as trimethylolpropane triglycidyl ether and glycerol triglycidyl ether, and vinyl hexene oxides such as 4-vinyl cyclohexene oxide, vinyl cyclohexene dioxide, and methylated vinyl cyclohexene dioxide.

One kind of the solvent may be used alone, or two or more kinds may be used in combination.

When the curable composition of the present invention contains a solvent, the content thereof is such that the solid content concentration is preferably 50 mass% or more and less than 100 mass%, more preferably 60 to 90 mass%, and still more preferably 65 to 85 mass%. When the solid content concentration is within this range, a curable composition having excellent workability in the coating step can be easily obtained.

The curable composition of the present invention can be prepared, for example, by mixing the above-mentioned component (a) and component (B), and if necessary, other components at a predetermined ratio and defoaming them.

The mixing method and the defoaming method are not particularly limited, and known methods can be used.

The curable composition of the present invention contains a polysilsesquioxane compound (A) and a heat acid generator. Therefore, the curable composition of the present invention is excellent in curability and storage stability.

The curable composition of the present invention has excellent curability, and this can be confirmed by the method described in examples, for example.

That is, when a sample of the curable composition was put on a stainless steel plate heated to 150 ℃ and stirred using an automatic curing time measuring apparatus (Cyber co., ltd., product name "Madoka"), the stirring torque increased. Therefore, the curability can be quantified by measuring the time until the stirring torque reaches 0.049N cm.

The time taken for the stirring torque to reach 0.049N · cm is preferably 1000 seconds or less, more preferably 800 seconds or less, and further preferably 500 seconds or less.

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

The curable composition of the present invention has excellent storage stability, which can be confirmed by the method described in examples.

That is, a shear rate of 2s was measured at 25 ℃ by a rheometer using a cone plate having a radius of 50mm and a cone angle of 0.5 DEG ^-1 The initial viscosity was obtained from the viscosity of the sample, and then the sample was allowed to stand at 25 ℃ for 24 hours, and the viscosity was measured under the same conditions to obtain the viscosity after standing.

From the obtained measurement values, the rate of increase in viscosity was calculated based on the following formula, whereby the storage stability was quantified.

[ rate of increase in viscosity ] = [ viscosity after standing ]/[ initial viscosity ]

The rate of increase in viscosity under the above measurement conditions is preferably 1.40 or less, more preferably 1.25 or less, and still more preferably 1.10 or less.

As described above, the curable composition of the present invention has excellent storage stability. Therefore, the curable composition of the present invention can be stored for a long period of time without being subjected to freezing storage or refrigeration storage.

2) Cured product of

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

The curable composition of the present invention can be cured by heating. The heating temperature for curing is usually 80 to 140 ℃ and more preferably 90 to 120 ℃. The heating time is usually 30 minutes to 5 hours, preferably 1 to 3 hours.

The cured product of the present invention is preferably a cured product having excellent heat resistance and adhesiveness.

The heat resistance and adhesiveness of the cured product can be evaluated, for example, as follows. That is, a predetermined amount of the curable composition of the present invention is applied to the mirror surface of a silicon chip, and the applied surface is placed on an adherend, pressed, and cured by heat treatment. The sheet was left on the measuring table of an adhesion tester previously heated to a predetermined temperature (for example, 100 ℃) for 30 seconds, and stress was applied to the adhesive surface from a position 100 μm high from the adherend in the horizontal direction (shear direction), thereby measuring the adhesive strength between the test piece and the adherend.

The adhesion of the cured product of the present invention is preferably 15N/4mm under the measurement conditions described in the examples ² Above, more preferably 25N/4mm ² The above is more preferably 30N/4mm ² The above.

In this specification, "4mm ² "means" 2mm square ", that is, 2 mm. Times.2 mm (1 side is a square of 2 mm).

A cured product having excellent heat resistance and adhesiveness can be efficiently formed by, for example, curing a curable composition containing the component (C).

The cured product having excellent heat resistance and adhesiveness is more preferably used as an optical element-fixing material.

3) Method for using curable composition

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

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

< adhesive for optical element-fixing Material >

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

As a method for using the curable composition of the present invention as an adhesive for an optical element-fixing material, there is a method in which the composition is applied to one or both adhesive surfaces of materials to be adhered (an optical element, a substrate thereof, and the like), and after pressing, the composition is cured by heating to firmly adhere the materials to be adhered to each other. The amount of the curable composition of the present invention to be applied is not particularly limited, and may be an amount that can firmly bond materials to be bonded to each other by curing the curable composition. The thickness of the coating film of the curable composition is usually 0.5 to 5 μm, preferably 1 to 3 μm.

Examples of the substrate material used for the adhesive 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 (SUS 302, SUS304L, SUS 309), synthetic resins such as polyethylene glycol terephthalate, polybutylene glycol terephthalate, polyethylene glycol naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, acrylic resin, norbornene-based resin, cycloolefin resin, and glass epoxy resin.

The heating temperature for the heat curing is usually 80 to 150 ℃ and more preferably 90 to 130 ℃, although it depends on the curable composition used. The heating time is usually 30 minutes to 5 hours, preferably 1 to 3 hours.

< sealing Material for optical element-fixing Material >

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

Examples of the method for using the curable composition of the present invention as a sealing material for an optical element-fixing material include a method in which the composition is molded into a desired shape to obtain a molded body in which an optical element is enclosed, and then the molded body is cured by heating to prepare an optical element-sealed body.

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

The heating temperature during the heat curing is usually 80 to 150 ℃ and more preferably 90 to 130 ℃, although it depends on the curable composition used. The heating time is usually 30 minutes to 5 hours, preferably 1 to 3 hours.

Examples

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

(average molecular weight measurement)

The mass average molecular weight (Mw) and the number average molecular weight (Mn) of the polysilsesquioxane compound obtained in the preparation example were measured as standard polystyrene conversion values under the following apparatus and conditions.

Device name: HLC-8220GPC, manufactured by TOSOH CORPORATION;

column: a column formed by sequentially connecting TSKgelGMHXL, TSKgelGMHXL and TSKgel2000 HXL;

solvent: tetrahydrofuran;

injection amount: 80 μ l;

measuring temperature: at 40 ℃;

flow rate: 1 ml/min;

a detector: a differential refractometer.

(measurement of IR Spectrum)

The IR Spectrum of the polysilsesquioxane compound obtained in preparation example was measured using a fourier transform infrared spectrophotometer (PerkinElmer, inc., spectra 100).

( ²⁹ Si-NMR measurement)

In order to investigate the repeating units and the amounts thereof of the polysilsesquioxane compounds obtained in the preparation examples, the following conditions were carried out ²⁹ Si-NMR measurement.

The device comprises the following steps: AV-500 manufactured by Bruker BioSpin K.K.,

²⁹ Si-NMR resonance frequency: the frequency of the wave of 99.352MHz,

and (3) probe: a 5mm phi solution probe is used,

measuring temperature: at room temperature (25 ℃),

number of sample revolutions: the frequency of the light source is 20kHz,

the determination method comprises the following steps: the reverse gate-controlled decoupling method is adopted,

²⁹ the flip angle of Si: at an angle of 90 degrees,

²⁹ si 90 ° pulse width:8.0μs，

repetition time: the time of the last 5s is less than the time of the last two seconds,

and (4) accumulating times: the treatment is carried out for 9200 times,

observation width: 30kHz.

( ²⁹ Method for producing Si-NMR sample

To shorten the relaxation time, fe (acac) was added ₃ Measured as relaxation reagents.

Polysilsesquioxane compound concentration: 30 percent by mass of the reaction mixture,

Fe(acac) ₃ concentration: 0.7 percent by mass of a catalyst,

and (3) determination of a solvent: the acetone is added into the mixture of the acetone and the acetone,

internal standard: and TMS.

(analysis of waveform processing)

For each peak of the spectrum after fourier transform, a chemical shift was obtained from the position of the peak top, and integrated.

(measurement of acid production temperature of thermal acid generator)

For each thermal acid generator, differential scanning calorimetry (DSC Q2000Auto, manufactured by TA Instruments) was performed using a differential scanning calorimeter under conditions of a starting temperature of 30 ℃, a measurement temperature range of 30 to 300 ℃, and a temperature rise rate of 10 ℃/min. From the obtained DSC curve, the peak temperature (° c) of the maximum endothermic peak was calculated to obtain the acid production temperature of each thermal acid-producing agent.

Preparation example 1

71.37g (400 mmol) of methyltriethoxysilane was charged into a 300ml eggplant-shaped flask, and while stirring, an aqueous solution obtained by dissolving 0.10g (0.25 mol% relative to methyltriethoxysilane) of 35 mass% hydrochloric acid in 21.6ml of distilled water was added, and the whole was stirred at 30 ℃ for 2 hours, then heated to 70 ℃ and stirred for 5 hours.

While the contents were further stirred, 140g of propyl acetate and 0.12g of 28 mass% aqueous ammonia (0.5 mol% relative to methyltriethoxysilane) were added thereto, and the mixture was directly stirred at 70 ℃ for 3 hours.

After the reaction solution was cooled to room temperature, purified water was added thereto to conduct liquid separation treatment, and this operation was repeated until the pH of the aqueous layer reached 7. The organic layer was concentrated with an evaporator, and the concentrate was dried in vacuo, whereby polysilsesquioxane compound (A1) [ PSQ (A1) ] was obtained. PSQ (A1) had a mass average molecular weight (Mw) of 7,800 and a molecular weight distribution (Mw/Mn) of 4.52.

IR spectrum data of PSQ (A1) are shown below.

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

In addition, carry out ²⁹ Si-NMR spectroscopy showed that the ratio of peak integral values of T1, T2 and T3 was 0.

(preparation example 2)

17.0g (77.7 mmol) of 3, 3-trifluoropropyltrimethoxysilane and 32.33g (181.3 mmol) of methyltriethoxysilane were charged into a 300mL egg plant-shaped flask, and while stirring, an aqueous solution obtained by dissolving 0.0675g of 35 mass% hydrochloric acid (HCl amount 0.65mmol, 0.25mol% based on the total amount of silane compounds) in 14.0g of distilled water was added, and the whole contents were stirred at 30 ℃ for 2 hours, then, heated to 70 ℃ and stirred for 20 hours.

While continuing to stir the contents, 0.0394g of 28 mass% aqueous ammonia (NH) was added thereto ₃ In an amount of 0.65 mmol) and 46.1g of propyl acetate, the reaction solution was stirred at 70 ℃ for 40 minutes as it was so that the pH of the reaction solution was 6.9.

After the reaction mixture was cooled to room temperature, 50g of propyl acetate and 100g of water were added thereto to conduct liquid separation treatment, thereby obtaining an organic layer containing a reaction product. Magnesium sulfate was added to the organic layer to carry out drying treatment. After magnesium sulfate was removed by filtration, the organic layer was concentrated with an evaporator, and the obtained concentrate was dried in vacuo, whereby polysilsesquioxane compound (A2) [ PSQ (A2) ] was obtained. PSQ (A2) had a mass average molecular weight (Mw) of 5,500 and a molecular weight distribution of 3.40.

The IR spectrum data of PSQ (A2) are shown below.

Si-CH ₃ ：1272cm ^-1 、1409cm ^-1 ，Si-O：1132cm ^-1 ，C-F：1213cm ^-1

In addition, carry out ²⁹ Si-NMR spectroscopy revealed that the ratio of peak integral values of T1, T2 and T3 was 2.

Preparation example 3

A300 ml round bottom flask was charged with 20.2g (102 mmol) of phenyltrimethoxysilane, 3.15g (18 mmol) of 2-cyanoethyltrimethoxysilane, 96ml of acetone as a solvent and 24ml of distilled water, and then 0.15g (1.5 mmol) of phosphoric acid as a catalyst was added thereto with stirring, followed by further stirring at 25 ℃ for 16 hours.

After completion of the reaction, the reaction mixture was concentrated to 50ml with an evaporator, and 100ml of ethyl acetate was added to the concentrate to neutralize the concentrate with a saturated aqueous sodium bicarbonate solution. After standing for a while, the organic layer was separated. Subsequently, the organic layer was washed with distilled water 2 times and dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, the filtrate was concentrated to 50ml with an evaporator, the resulting concentrate was dropwise added to a large amount of n-hexane to precipitate it, 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 by an evaporator. The residue was dried in vacuo, whereby a polysilsesquioxane compound (A3) [ PSQ (A3) ] was obtained. PSQ (A3) had a mass average molecular weight (Mw) of 1,870 and a molecular weight distribution (Mw/Mn) of 1.42.

The IR spectrum data of PSQ (A3) are shown below.

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

The compounds used in examples and comparative examples are shown below.

(A component)

PSQ(A1)~(A3)。

(component B and comparative Compound)

Thermal acid generator (B1): a compound represented by the following formula (acid production temperature: 150 ℃ C.),

[ chemical formula 15]

Thermal acid generator (B2): a compound represented by the following formula (acid production temperature: 125 ℃ C.),

[ chemical formula 16]

Thermal acid generator (B3): a compound represented by the following formula (acid production temperature: 125 ℃ C.),

[ chemical formula 17]

Thermal acid generator (B4): the product name of the thermal acid generator manufactured by the company King INDUSTRIES is CXC-1612 (salt composed of hexafluoroantimonic acid anion and quaternary ammonium cation) (acid generating temperature: 115 ℃),

curing accelerator (X1): the hydrochloric acid is used for the reaction of hydrochloric acid,

curing accelerator (X2): a Ti complex.

(component C)

Silane coupling agent (C1): 1,3,5-N-tris [3- (trimethoxysilyl) propyl ] isocyanurate,

silane coupling agent (C2): 3- (trimethoxysilyl) propylsuccinic anhydride.

(example 1)

To 100 parts by mass of PSQ (A1), a mixed solvent of diethylene glycol monobutyl ether acetate tripropylene glycol n-butyl ether =40 (mass ratio), 30 parts by mass of a silane coupling agent (C1), and 3 parts by mass of a silane coupling agent (C2) were added, and the entire contents were stirred. To this, 1 part of the thermal acid generator (B1) (added as a 10 mass% ethyl acetate solution) was added, and the entire contents were thoroughly mixed to obtain a curable composition.

(examples 2 to 19 and comparative examples 1 to 7)

A curable composition was obtained in the same manner as in example 1, except that the components in example 1 were changed to those shown in table 1.

The curable compositions obtained in examples and comparative examples were used to carry out the following measurements and tests, respectively. The results are shown in table 1.

[ evaluation of curability ]

The curing time of the curable composition was measured by the following method using an automatic curing time measuring apparatus "Madoka" (Cyber co., ltd).

0.30mL of the sample was put on a stainless steel plate heated to 150 ℃ and stirred. Since the stirring torque increased with time, the time (seconds) until the stirring torque reached 0.049N · cm was measured. The stirring conditions are as follows.

Number of rotation of paddle: at a speed of 200rpm for the first time,

revolution number of paddle: 80rpm (stirring paddle made of polytetrafluoroethylene),

gap (distance between heating plate and paddle): 0.3mm.

[ evaluation of adhesive Strength ]

The curable compositions obtained in examples and comparative examples were applied to a square having a length of 2mm on one side (area 4 mm) so that the thickness became about 2 μm ² ) The coated surface of the silicon chip (2) was placed on an adherend (silver-plated copper plate) and pressed. Then, the resultant was cured by heat treatment at 100 ℃ for 2 hours to obtain an adherend with a test piece. The adherend with the test piece was left on a measuring table of a bonding tester (4000 series, manufactured by DAGE) heated to 100 ℃ in advance for 30 seconds, and stress was applied to the bonding surface at a speed of 200 μm/s in the horizontal direction (shear direction) from a position 100 μm high from the adherend to measure the bonding force (N/4 mm) between the test piece and the adherend at 100 ℃. (N/4 mm) ² )。

[ evaluation of viscosity increase rate ]

The shear rate was measured at 25 ℃ for 2s using a rheometer (MCR 301 manufactured by Anton Paar Co., ltd.) using a cone plate having a radius of 50mm and a cone angle of 0.5 DEG ^-1 Viscosity (initial viscosity) at that time.

After the sample was allowed to stand at 25 ℃ for 24 hours, the viscosity was measured under the same conditions.

From the obtained measurement value, the rate of increase in viscosity was calculated based on the following formula.

[ viscosity increase rate ] = [ viscosity after standing ]/[ initial viscosity ].

[ Table 1]

The following can be seen from the examples and comparative examples.

The curable compositions of examples 1 to 19 gave cured products in a short time of 1000 seconds or less in the curability evaluation test, and were excellent in curability.

The cured products obtained in examples 1 to 19 had a small viscosity increase rate and excellent storage stability.

On the other hand, the curable compositions of comparative examples 1 to 3 and comparative example 6 were poor in curability.

The curable compositions of comparative examples 4 and 5 had a large viscosity increase rate, and gelled, and had poor storage stability.

Claims

1. A curable composition comprising the following component (A) and component (B),

[ chemical formula 1]

R ¹ A group selected from an unsubstituted alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms and having a substituent, an unsubstituted aryl group having 6 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms and having a substituent;

(B) The components: a thermal acid generator.

2. The curable composition according to claim 1, wherein the amount of the repeating unit represented by the formula (a-1) in the component (A) is 70 to 100mol% based on the total repeating units of the component (A).

3. The curable composition according to claim 1 or 2, wherein the component (A) has a mass average molecular weight (Mw) of 500 to 20,000.

4. The curable composition according to any one of claims 1 to 3, wherein the content of the component (A) is 40% by mass or more and less than 100% by mass in the solid content of the curable composition.

5. The curable composition according to any one of claims 1 to 4, wherein the component (B) is an onium salt thermal acid generator.

6. The curable composition according to any one of claims 1 to 5, wherein the component (B) satisfies the following requirement (I):

[ essential component (I) ]

The acid production temperature, which is the peak temperature of the maximum endothermic peak obtained by differential scanning calorimetry of the component (B) at a temperature range of 30 to 300 ℃ and a temperature rise rate of 10 ℃/min, is 80 to 180 ℃.

7. The curable composition according to any one of claims 1 to 6, wherein the content of the component (B) is more than 0 part by mass and 5 parts by mass or less with respect to 100 parts by mass of the component (A).

8. The curable composition according to any one of claims 1 to 7, further comprising the following component (C),

(C) The components: a silane coupling agent.

9. The curable composition according to any one of claims 1 to 8, further comprising a solvent, wherein the solid content concentration is 50% by mass or more and less than 100% by mass.

10. A cured product obtained by curing the curable composition according to any one of claims 1 to 9.

11. The cured product according to claim 10, which is an optical device-fixing material.

12. A method for using the curable composition according to any one of claims 1 to 9 as an adhesive for an optical element-fixing material.

13. A method for using the curable composition according to any one of claims 1 to 9 as a sealing material for an optical component-fixing material.