Curable composition, cured material, and method of using a curable composition

Abstract

The present invention relates to a curable composition containing the following components (A) and (C), a cured product formed by curing the curable composition, and a method of using the curable composition as an adhesive for an optical device fixing material or as an encapsulant for an optical device fixing material. The curable composition of the present invention has a high refractive index and is preferably used in the field of optics. (A) Component: Formula (a-1) A repeating unit [repeating unit (1)] represented by [R1 represents an unsubstituted aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms with a substituent], and the following formula (a-2) A polysilsesquioxane compound having a repeating unit [repeating unit (2)] represented by [R2 represents an unsubstituted alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms with a substituent], characterized by satisfying specific requirements regarding molecular structure. (C) Ingredient: Silane coupling agent

Description

Technology Field

[0001] The present invention relates to a curable composition having a high refractive index and preferably used in the field of optics, a cured product formed by curing the curable composition, and a method of using the curable composition as an adhesive for a fixing material for an optical device or as a sealing material for a fixing material for an optical device. Background Technology

[0002] Conventionally, curable compositions have been modified in various ways depending on their application and are widely used industrially as raw materials for optical components or molded bodies, adhesives, coating agents, etc.

[0003] In addition, curable compositions are also attracting attention as compositions for optical device fixing materials, such as adhesives for optical device fixing materials or encapsulating materials for optical device fixing materials.

[0004] Optical devices include various lasers such as semiconductor lasers (LDs), light-emitting devices such as light-emitting diodes (LEDs), light-receiving devices, composite optical devices, and optical integrated circuits.

[0005] Recently, light-emitting devices with shorter peak wavelengths of emission, such as blue or white light, have been developed and widely used. The brightness of such light-emitting devices with short peak wavelengths has increased dramatically, and along with this, there is a tendency for the amount of heat generated by the light-emitting devices to increase further.

[0006] However, with the recent increase in the brightness of optical devices, a problem has arisen in which the adhesive strength of the cured product of the composition for fixing optical devices decreases when exposed for a long time to higher energy light or heat generated from the optical device.

[0007] To solve this problem, patent documents 1 to 3 propose a composition for a fixing material for optical devices having a polysilsesquioxane compound as the main component.

[0008] However, when fixing optical elements using a curable composition, a curable composition with an appropriate refractive index is selected to match the refractive index of surrounding materials in order to increase light extraction efficiency.

[0009] For example, in order to suppress reflection at the interface between the encapsulant and the fixing material and to increase light extraction efficiency, it is desirable that the difference between the refractive index of the encapsulant and the refractive index of the fixing material be small.

[0010] Therefore, when using a sealant with a relatively high refractive index, it becomes necessary to form a fixative using a curable composition with an equally high refractive index. Prior art literature

[0011] Japanese Published Patent Application No. 2004-359933, Japanese Published Patent Application No. 2005-263869, Japanese Published Patent Application No. 2006-328231 The problem to be solved

[0012] The present invention is made in consideration of the actual conditions of the prior art described above, and aims to provide a curable composition having a high refractive index and preferably used in the optical field, a cured product formed by curing the curable composition, and a method of using the curable composition as an adhesive for an optical device fixing material or as an encapsulant for an optical device fixing material. means of solving the problem

[0013] In order to solve the above problem, the inventors have repeatedly examined curable compositions containing polysilsesquioxane compounds.

[0014] in result,

[0015] (i) As a polysilsesquioxane compound, a curable composition with a high refractive index is obtained by using a polysilsesquioxane compound containing many aryl groups,

[0016] (ii) In the cured product of a curable composition containing a polysilsesquioxane compound containing a large amount of aryl groups, there is a risk of cracking occurring,

[0017] (iii) A cured product of a curable composition containing a polysilsesquioxane compound containing a large amount of aryl groups tends to have poor adhesion,

[0018] (iv) The problem of (ii) and (iii) can be solved by controlling the amount of aryl groups in the polysilsesquioxane compound, introducing a specific molecular structure into the polysilsesquioxane compound, and adding a silane coupling agent to the curable composition.

[0019] By discovering [this], we came to complete the present invention.

[0020] Thus, according to the present invention, a method of using the curable compositions of [1] to [7], the cured products of [8] and [9], and the curable compositions of

[10] and

[11] is provided.

[0021] [1] A curable composition containing the following components (A) and (C).

[0022] (A) Component: Formula (a-1)

[0023] [Chemical Formula 1]

[0024]

[0025] [R 1 ... represents an unsubstituted aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms with a substituent.

[0026] A repetition unit represented by [repetition unit (1)] and the following expression (a-2)

[0027] [Chemical Formula 2]

[0028]

[0029] [R 2represents an unsubstituted alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having a substituent.

[0030] A polysilsesquioxane compound having a repeating unit [repeating unit (2)] represented by, and characterized by satisfying the following requirements 1 and 2.

[0031] [Requirement 1]

[0032] With respect to the total amount of the repeating unit (1) and the repeating unit (2), the amount of the repeating unit (1) is 40 mol% or more and less than 80 mol%.

[0033] [Requirement 2]

[0034] With respect to the total amount of T site (T1 site) represented by the following formula (a-3), T site (T2 site) represented by the following formula (a-4), and T site (T3 site) represented by the following formula (a-5), the amount of T2 site is 20 to 70 mol%.

[0035] [Chemical Formula 3]

[0036]

[0037] [G is, R 1 or R 2 Represents the group represented by . R 3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. A silicon atom is bonded to *.

[0038] (C) Ingredient: Silane coupling agent

[0039] [2] (A) A curable composition described in [1] having a mass average molecular weight (Mw) of the component of 500 to 25,000.

[0040] [3] A curable composition described in [1] or [2], wherein the total amount of repeating unit (1) and repeating unit (2) in component (A) is 90 to 100 mol% of the total repeating unit of component (A).

[0041] [4] A curable composition described in any one of [1] to [3], wherein the content of component (C) is 0.1 to 70 parts by mass per 100 parts by mass of component (A).

[0042] [5] A curable composition described in any one of [1] to [4], wherein the total amount of component (A) and component (C) is 50 to 100 mass% of the solid content of the curable composition.

[0043] [6] A curable composition described in any one of [1] to [5], additionally containing a diluent and having a solid content concentration of 60 mass% or more and less than 100 mass%.

[0044] [7] A curable composition described in any one of [1] to [6], having a refractive index (nD) at 25 ℃ of 1.46 to 1.56.

[0045] A cured product obtained by curing a curable composition described in any one of [8] [1] to [7].

[0046] [9] A cured material described in [8], which is a fixing material for optical elements.

[0047] A method of using a curable composition described in any one of

[10] [1] to [7] as an adhesive for fixing optical devices.

[0048] A method of using a curable composition described in any one of

[11] [1] to [7] as an encapsulant for fixing optical devices. Effects of the invention

[0049] According to the present invention, a curable composition having a high refractive index and preferably used in the field of optics, a cured product formed by curing the curable composition, and a method of using the curable composition as an adhesive for a fixing material for an optical device or as a sealing material for a fixing material for an optical device are provided. Specific details for implementing the invention

[0050] Hereinafter, the present invention will be described in detail by classifying it into 1) a curable composition, 2) a cured product, and 3) a method of using the curable composition.

[0051] 1) Curable composition

[0052] The curable composition of the present invention contains the following components (A) and (C).

[0053] (A) Component: A polysilsesquioxane compound having a repeating unit represented by the above formula (a-1) and a repeating unit represented by the above formula (a-2), characterized by satisfying requirements 1 and 2 [Hereinafter, it may be referred to as "polysilsesquioxane compound (A)".]

[0054] (C) Ingredient: Silane coupling agent

[0055] [(A) Component]

[0056] The polysilsesquioxane compound (A) constituting the curable composition of the present invention has a repeating unit [repeating unit (1)] represented by the following formula (a-1).

[0057] [Chemical Formula 4]

[0058]

[0059] [R 1 ... represents an unsubstituted aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms with a substituent.

[0060] The repetition unit (1) is R 1 Because it has repeating units (1), the polysilsesquioxane compound has a high refractive index. For this reason, the curable composition of the present invention has a high refractive index.

[0061] R 1 Examples of “unsubstituted aryl groups having 6 to 12 carbon atoms” include phenyl groups, 1-naphthyl groups, 2-naphthyl groups, etc.

[0062] R 1The carbon number of the “unsubstituted aryl group having 6 to 12 carbon atoms” is preferably 6.

[0063] R 1 The carbon number of the "6 to 12 C-type aryl group having a substituent" is preferably 6. Furthermore, this carbon number refers to the carbon number of the portion excluding the substituent (the aryl group portion). Therefore, R 1 In the case where this is a “6 to 12 C-aryl group having a substituent,” R 1 The number of carbon atoms may exceed 12.

[0064] R 1 As for the aryl group of “6 to 12 carbon atoms having a substituent,” the same as that shown as “6 to 12 carbon atoms unsubstituted aryl group” can be cited.

[0065] R 1 The number of atoms of the substituents of the “6 to 12 carbon atom aryl group having substituents” (excluding the number of hydrogen atoms) is typically 1 to 30, preferably 1 to 20.

[0066] R 1 Examples of substituents for the “6- to 12 carbon atom aryl group having a substituent” include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and isooctyl groups; halogen atoms such as chlorine and bromine atoms; and alkoxy groups such as methoxy and ethoxy groups.

[0067] Among these, in terms of the ability to efficiently prepare a curable composition with a high refractive index, R 1 As for the group, an unsubstituted aryl group having 6 to 12 carbon atoms is preferred, and a phenyl group is more preferred.

[0068] Polysilsesquioxane compound (A) is of type 1 R 1 Even if it has 2 or more types of R 1 It is also acceptable to have.

[0069] The polysilsesquioxane compound (A) also has a repeating unit [repeating unit (2)] represented by the following formula (a-2).

[0070] [Chemical Formula 5]

[0071]

[0072] [R 2 represents an unsubstituted alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having a substituent.

[0073] The polysilsesquioxane compound (A) has a repeating unit (2), thereby increasing the molecular weight and improving the flexibility of the molecular chain. Because of this, cracks are less likely to occur in the cured product of the curable composition of the present invention, and the curable composition of the present invention has excellent adhesion.

[0074] R 2 The number of carbon atoms of the “unsubstituted alkyl group having 1 to 10 carbon atoms” is preferably 1 to 6, and more preferably 1 to 3.

[0075] R 2 Examples of “unsubstituted alkyl groups having 1 to 10 carbon atoms” include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, s-butyl groups, t-butyl groups, n-pentyl groups, n-hexyl groups, n-octyl groups, n-nonyl groups, n-decyl groups, etc.

[0076] R 2 The number of carbon atoms in the “alkyl group having 1 to 10 carbon atoms having a substituent” is preferably 1 to 6, and more preferably 1 to 3. Furthermore, this number of carbon atoms refers to the number of carbon atoms in the portion excluding the substituent (the alkyl group portion). Therefore, R 2 If is a “1 to 10 C-alkyl group having a substituent,” R 2 The number of carbon atoms may exceed 10.

[0077] R 2As for the alkyl group of the “alkyl group having 1 to 10 carbon atoms having a substituent,” the same as that shown as the “unsubstituted alkyl group having 1 to 10 carbon atoms” can be cited.

[0078] The number of atoms of the substituents of the “alkyl group having 1 to 10 carbon atoms having substituents” (excluding the number of hydrogen atoms) is typically 1 to 30, preferably 1 to 20.

[0079] Examples of substituents for “alkyl groups having 1 to 10 carbon atoms with substituents” include halogen atoms such as chlorine atoms and bromine atoms; cyano groups; etc.

[0080] Among these, R 2 In the case of the alkyl group, an unsubstituted alkyl group having 1 to 10 carbon atoms is preferred, an unsubstituted alkyl group having 1 to 6 carbon atoms is more preferred, and an unsubstituted alkyl group having 1 to 3 carbon atoms is even more preferred.

[0081] R 2 a. By using a polysilsesquioxane compound (A) which is an unsubstituted alkyl group having 1 to 10 carbon atoms, the molecular weight of the polysilsesquioxane compound (A) can be efficiently controlled.

[0082] Polysilsesquioxane compound (A) is of type 1 R 2 Even if it has , 2 or more types of R 2 It is also acceptable to have .

[0083] The polysilsesquioxane compound (A) may be any of the following: random copolymer, block copolymer, graft copolymer, alternating copolymer, etc., but a random copolymer is preferred from the perspective of ease of manufacturing, etc.

[0084] In addition, the structure of the polysilsesquioxane compound (A) may be any of the following: a ladder structure, a double-decker structure, a basket structure, a partially cleaved basket structure, a ring structure, or a random structure.

[0085] The repetition unit (1) or the repetition unit (2) is represented by the following formula (a-6).

[0086] [Chemical Formula 6]

[0087]

[0088] [G is, R 1 or R 2 Represents the group represented by . R 1 , R 2 Each represents the same meaning as above. O 1 / 2 [This indicates that an oxygen atom is shared with an adjacent repeating unit.]

[0089] As shown in formula (a-6), the polysilsesquioxane compound (A) has a partial structure in which three oxygen atoms are bonded to a silicon atom, which is generally collectively called the T site, and one other group (represented by G) is bonded thereto.

[0090] Examples of T sites included in the polysilsesquioxane compound (A) include the T site represented by the following formula (a-3) (T1 site), the T site represented by the following formula (a-4) (T2 site), and the T site represented by the following formula (a-5) (T3 site).

[0091] [Chemical Formula 7]

[0092]

[0093] Among equations (a-3), (a-4), and (a-5), G represents the same meaning as above. R 3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 3 Examples of the "alkyl group having 1 to 10 carbon atoms" include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, s-butyl groups, isobutyl groups, t-butyl groups, etc. Multiple R 3All of them may be identical or different. Also, among the above formulas (a-3) to (a-5), * contains silicon atoms.

[0094] When synthesizing polysilsesquioxane compound (A), immediately after the reaction starts, the product contains a large amount of T1 sites or T2 sites, but as the reaction proceeds, the amount of these sites decreases and the amount of T3 sites gradually increases.

[0095] Therefore, while polysilsesquioxane compounds with a high proportion of T1 or T2 sites are relatively low-molecular-weight compounds, polysilsesquioxane compounds with a high proportion of T3 sites are relatively high-molecular-weight compounds, and the movement of molecular chains is restricted.

[0096] Also, residual reactive groups (-OR 3 As indicated by the number of T1 or T2 sites, polysilsesquioxane compounds with a high content of T1 or T2 sites have sufficient reactivity, whereas polysilsesquioxane compounds with a high content of T3 sites tend to have lower reactivity.

[0097] Polysilsesquioxane compound (A) satisfies the above requirement 1.

[0098] That is, the polysilsesquioxane compound (A) has an amount of repeating unit (1) of 40 mol% or more and less than 80 mol% with respect to the total amount of repeating unit (1) and repeating unit (2).

[0099] The curable composition of the present invention has a high refractive index because it contains a polysilsesquioxane compound that satisfies requirement 1. In addition, as the curable composition satisfies requirement 1, the cured product is less likely to crack and its adhesion is improved.

[0100] In order to obtain these effects in better balance, the amount of the repeating unit (1) is preferably 45 to 77 mol% with respect to the total amount of the repeating unit (1) and the repeating unit (2), more preferably 50 to 74 mol%, and even more preferably 55 to 71 mol%.

[0101] The ratio of repeating units (1) or repeating units (2) in the polysilsesquioxane compound (A) is, for example, of the polysilsesquioxane compound (A). 29 It can be obtained by measuring Si-NMR.

[0102] Polysilsesquioxane compound (A) is soluble in various organic solvents such as ketone-based solvents such as acetone; aromatic hydrocarbon-based solvents such as benzene; sulfur-containing solvents such as dimethyl sulfoxide; ether-based solvents such as tetrahydrofuran; ester-based solvents such as ethyl acetate; halogen-containing solvents such as chloroform; and mixed solvents composed of two or more of these. Therefore, using these solvents, in the solution state of polysilsesquioxane compound (A) 29 Si-NMR can be measured.

[0103] Polysilsesquioxane compound (A) satisfies requirement 2 above.

[0104] That is, the polysilsesquioxane compound (A) contains a relatively large amount of T2 sites, with respect to the total amount of T1 sites, T2 sites, and T3 sites, wherein the amount of T2 sites is 20 to 70 mol%.

[0105] By satisfying requirement 2 in addition to requirement 1 above, the curable composition of the present invention becomes less prone to cracking, and its adhesion is further improved.

[0106] In other words, when a curable composition containing a polysilsesquioxane compound with a large number of T1 sites is cured, excessive hydrolysis or condensation reactions occur, and due to curing shrinkage, cracks are prone to develop in the cured product.

[0107] Furthermore, since polysilsesquioxane compounds containing a large number of T3 sites are relatively high-molecular-weight compounds with low mobility, the cured product of a curable composition containing such polysilsesquioxane compounds is prone to residual stress and cracking.

[0108] On the other hand, since a curable composition containing a polysilsesquioxane compound with a high content of T2 sites can be cured without causing excessive hydrolysis or condensation reactions, it is difficult for cracks to occur in the cured product.

[0109] In addition, since polysilsesquioxane compounds containing a large number of T2 sites do not have a very high molecular weight and possess moderate mobility, the cured product of a curable composition containing polysilsesquioxane compounds containing a large number of T2 sites is less prone to residual stress and less prone to cracking.

[0110] Since the above effect is easily obtained, the amount of T2 site relative to the total amount of T1 site, T2 site and T3 site is 20 to 70 mol%, preferably 22 to 60 mol%, more preferably 24 to 55 mol%, and even more preferably 26 to 50 mol%.

[0111] In addition, the amount of T1 site relative to the total amount of T1 site, T2 site and T3 site is preferably 0 to 40 mol%, more preferably 0 to 30 mol%, even more preferably 0 to 20 mol%, and even more preferably 0 to 10 mol%.

[0112] By appropriately including the T1 site in the polysilsesquioxane compound (A), a curable composition with better curability can be obtained.

[0113] In addition, the amount of T3 sites relative to the total amount of T1 sites, T2 sites, and T3 sites is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 30 to 50 mol%.

[0114] By appropriately including T3 sites in the polysilsesquioxane compound (A), the generation of by-products caused by the condensation reaction during curing can be suppressed.

[0115] The content ratio of T1 sites, T2 sites and T3 sites is in the solution state of polysilsesquioxane compound (A). 29 It can be obtained by measuring Si-NMR.

[0116] For example, when acetone is used as the measurement solvent and TMS (tetramethylsilane) is used as the internal standard, in formulas (a-3) to (a-6), the signal originating from the silicon atom of G in the T-site of the phenyl group is observed at -65 to -58 ppm at the T1 site, -74 to -65 ppm at the T2 site, and -82 to -75 ppm at the T3 site, and in formulas (a-3) to (a-6), the signal originating from the silicon atom of G in the T-site of the methyl group is observed at -50 to -46 ppm at the T1 site, -61 to -52 ppm at the T2 site, and -70 to -61 ppm at the T3 site.

[0117] The mass average molecular weight (Mw) of the polysilsesquioxane compound (A) is preferably 500 to 25,000, more preferably 700 to 20,000, even more preferably 1,000 to 15,000, and even more preferably 2,000 to 10,000. By using a polysilsesquioxane compound (A) having a mass average molecular weight (Mw) within the above range, it becomes easier to obtain a curable composition that is less likely to crack after curing.

[0118] The molecular weight distribution (Mw / Mn) of the polysilsesquioxane compound (A) is not particularly limited, but is typically 1.0 to 10.0, preferably 1.1 to 6.0, and more preferably 1.1 to 4.0. By using a polysilsesquioxane compound (A) having a molecular weight distribution (Mw / Mn) within the above range, it becomes easier to obtain a curable composition that imparts a cured product with better heat resistance and adhesion.

[0119] Mass average molecular weight (Mw) and number average molecular weight (Mn) can be obtained as standard polystyrene equivalents by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, for example.

[0120] The total amount of repeating unit (1) and repeating unit (2) in the polysilsesquioxane compound (A) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and even more preferably 98 to 100 mol% of the total repeating unit of the polysilsesquioxane compound (A).

[0121] The refractive index (nD) of the polysilsesquioxane compound (A) at 25°C is preferably 1.46 to 1.56, more preferably 1.48 to 1.55, and even more preferably 1.50 to 1.55.

[0122] Since the refractive index (nD) of the polysilsesquioxane compound (A) at 25°C is within the range of 1.46 to 1.56, it becomes easier to obtain a curable composition or cured product with a high refractive index.

[0123] The refractive index (nD) of polysilsesquioxane compound (A) can be measured using an Abbe refractometer.

[0124] In the present invention, the polysilsesquioxane compound (A) may be used alone or in combination of two or more types.

[0125] The method of synthesizing the polysilsesquioxane compound (A) is not particularly limited. For example, the polysilsesquioxane compound (A) can be synthesized by polycondensing at least one type of silane compound (1) represented by the following formula (a-7) and at least one type of silane compound (2) represented by the following formula (a-8).

[0126] [Chemical Formula 8]

[0127]

[0128] (during food, R 1 represents the same meaning as above. R 4 represents an alkyl group having 1 to 10 carbon atoms, and X 1 represents a halogen atom, and p represents an integer from 0 to 3. Multiple R 4 and multiple X 1 Each may be identical or different from one another.

[0129] [Chemical Formula 9]

[0130]

[0131] (during food, R 2 represents the same meaning as above. R 5 represents an alkyl group having 1 to 10 carbon atoms, and X 2 represents a halogen atom, and q represents an integer from 0 to 3. Multiple R 5and multiple X 2 They may each be identical or different from one another.)

[0132] R 4 , R 5 As for the "alkyl group having 1 to 10 carbon atoms," R 3 Examples include those identical to those represented as “alkyl groups having 1 to 10 carbon atoms.”

[0133] X 1 , X 2 Examples of halogen atoms include chlorine atoms and bromine atoms.

[0134] Specific examples of silane compounds (1) include,

[0135] Unsubstituted aryltrialkoxysilane compounds such as phenyltrimethoxysilane and phenyltriethoxysilane;

[0136] Unsubstituted arylhalogenoalkoxysilane compounds such as phenylchlorodimethoxysilane, phenylchlorodiethoxysilane, phenyldichloromethoxysilane, and phenyldichloroethoxysilane;

[0137] Unsubstituted aryl trihalogenosilane compounds such as phenyltrichlorosilane;

[0138] Aryltrialkoxysilane compounds having substituents such as 4-methylphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 4-methylphenyltriethoxysilane, 4-methoxyphenyltriethoxysilane, 4-chlorophenyltriethoxysilane;

[0139] Arylhalogenoalkoxysilane compounds having substituents such as 4-methylphenylchlorodimethoxysilane, 4-methoxyphenylchlorodimethoxysilane, 4-chlorophenylchlorodimethoxysilane, 4-methylphenyldichloromethoxysilane, 4-methoxyphenyldichloromethoxysilane, 4-chlorophenyldichloromethoxysilane;

[0140] Examples include aryl trihalogenosilane compounds having substituents such as 4-methylphenyltrichlorosilane, 4-methoxyphenyltrichlorosilane, and 4-chlorophenyltrichlorosilane.

[0141] These silane compounds (1) can be used as a single type or in combination of two or more types.

[0142] Specific examples of silane compounds (2) include,

[0143] Unsubstituted alkyltrialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, etc.;

[0144] Unsubstituted alkylhalogenalkoxysilane compounds such as methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethoxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane, etc.

[0145] Unsubstituted alkyltrihalogenosilane compounds such as methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, and ethyltribromosilane;

[0146] Alkyltrialkoxysilane compounds having substituents such as 2-cyanoethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 2-cyanoethyltriethoxysilane, and 3-chloropropyltriethoxysilane;

[0147] Alkylhalogenoalkoxysilane compounds having substituents such as 2-cyanoethylchlorodimethoxysilane, 3-chloropropylchlorodimethoxysilane, 2-cyanoethylchlorodiethoxysilane, 3-chloropropylchlorodiethoxysilane, 2-cyanoethyldichloromethoxysilane, 3-chloropropyldichloromethoxysilane, 2-cyanoethyldichloroethoxysilane, 3-chloropropyldichloroethoxysilane, etc.;

[0148] Examples include alkyltrihalogenosilane compounds having substituents such as 2-cyanoethyltrichlorosilane, 3-chloropropyltrichlorosilane, etc.

[0149] These silane compounds (2) can be used as a single type or in combination of two or more types.

[0150] The method of polycondensing the above silane compound is not particularly limited. For example, a method may be used in which a predetermined amount of a polycondensation catalyst is added to the silane compound in a solvent or in a solvent-free manner and stirred at a predetermined temperature. More specifically, the following methods may be used: (a) a method of adding a predetermined amount of an acid catalyst to the silane compound and stirring at a predetermined temperature; (b) a method of adding a predetermined amount of a base catalyst to the silane compound and stirring at a predetermined temperature; (c) a method of adding a predetermined amount of an acid catalyst to the silane compound, stirring at a predetermined temperature, then adding an excess amount of a base catalyst to make the reaction system basic, and stirring at a predetermined temperature.

[0151] Among these, the method of (a) is preferred in that it can efficiently obtain the target polysilsesquioxane compound (A).

[0152] The polycondensation catalyst used may be either an acid catalyst or a base catalyst. Additionally, a combination of two or more polycondensation catalysts may be used, but it is preferable to use at least an acid catalyst.

[0153] Examples of acid catalysts include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, and nitric acid; organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; etc. Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid is preferred.

[0154] Examples of base catalysts include: water ammonia; 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, imidazole; organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide and potassium t-butoxide; metal hydrides such as sodium hydride and calcium hydride; metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate and magnesium carbonate; metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; etc.

[0155] The amount of polycondensation catalyst used is typically in the range of 0.05 to 10 mol%, preferably 0.1 to 5 mol%, with respect to the total molar amount of the silane compound.

[0156] When a solvent is used during polycondensation, the solvent used can be appropriately selected depending on the type of silane compound, etc. Examples 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 methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, and t-butyl alcohol. These solvents may be used individually or in combination of two or more types.

[0157] The amount of solvent used is 0.1 liters or more and 10 liters or less per 1 mole of the total molar amount of the silane compound, preferably 0.1 liters or more and 2 liters or less.

[0158] The temperature for polycondensing a silane compound is typically in the range from 0°C to the boiling point of the solvent used, preferably in the range of 20°C to 100°C. If the reaction temperature is excessively low, the polycondensation reaction may proceed insufficiently. On the other hand, if the reaction temperature is excessively high, it becomes difficult to inhibit gelation. The reaction is typically completed in 30 minutes to 30 hours.

[0159] When synthesizing a polysilsesquioxane compound (A) by the above method, the OR of the silane compound (1) 4 or X 1 Or, OR of silane compound (2) 5 or X 2 The portions in which de-alcoholization, etc., did not occur remain in the polysilsesquioxane compound (A). For this reason, in addition to the repeating unit represented by formula (a-5) above, the polysilsesquioxane compound (A) may contain repeating units represented by formulas (a-3) and (a-4) above.

[0160] [(C) Component]

[0161] The component (C) constituting the curable composition of the present invention is a silane coupling agent.

[0162] Since the curable composition of the present invention contains component (C), the cured product of the curable composition of the present invention has even better adhesion at room temperature or at high temperature.

[0163] A silane coupling agent refers to a silane compound having a silicon atom, a functional group, and a hydrolyzable group bonded to the silicon atom.

[0164] A functional group refers to a group that is reactive with other compounds (mainly organic compounds), and examples include groups having a nitrogen atom such as amino groups, substituted amino groups, isocyanate groups, ureido groups, and groups having an isocyanurate backbone; acid anhydride groups (groups having an acid anhydride structure); vinyl groups; allyl groups; epoxy groups; (meth)acrylic groups; mercapto groups; etc.

[0165] In the present invention, the silane coupling agent may be used as a single type or in combination of two or more types.

[0166] The content of the silane coupling agent is, with respect to 100 parts by mass of polysilsesquioxane compound (A), preferably 0.1 to 70 parts by mass, more preferably 1 to 60 parts by mass, even more preferably 5 to 55 parts by mass, even more preferably 10 to 50 parts by mass, and particularly preferably 15 to 45 parts by mass.

[0167] By using a curable composition in which the content of the silane coupling agent is within the above range, a cured product with superior adhesion at room temperature or high temperature can be formed.

[0168] As for the silane coupling agent, a silane coupling agent having a nitrogen atom in the molecule or a silane coupling agent having an acid anhydride structure in the molecule is preferred, and a silane coupling agent having an isocyanurate structure in the molecule or a silane coupling agent having a succinic anhydride structure in the molecule is more preferred.

[0169] Examples of silane coupling agents having a nitrogen atom within the molecule include, for instance, a trialkoxysilane compound represented by the following formula (c-1), a dialkoxyalkylsilane compound represented by the formula (c-2), or a dialkoxyarylsilane compound.

[0170] [Chemical Formula 10]

[0171]

[0172] Among the above formulas, Ra represents an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, etc. Multiple R a They may be the same or different.

[0173] R b 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, etc.; or an aryl group having a substituent or not having a substituent, such as a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 1-naphthyl group, etc.

[0174] R c represents an organic group having 1 to 10 carbon atoms and containing a nitrogen atom. Also, R c It may additionally be combined with a group containing other silicon atoms.

[0175] R c Specific examples of organic groups having 1 to 10 carbon atoms include N-2-(aminoethyl)-3-aminopropyl groups, 3-aminopropyl groups, N-(1,3-dimethyl-butylidene)aminopropyl groups, 3-ureidopropyl groups, N-phenyl-aminopropyl groups, etc.

[0176] Among the compounds represented by the above formula (c-1) or (c-2), R c a. Compounds in which the organic group is combined with a group containing another silicon atom include those that form an isocyanurate-based silane coupling agent by combining with another silicon atom via an isocyanurate backbone, or those that form a urea-based silane coupling agent by combining with another silicon atom via a urea backbone.

[0177] Among these, as silane coupling agents having nitrogen atoms in the molecule, isocyanurate-based silane coupling agents and urea-based silane coupling agents are preferred because they make it easier to obtain a cured product with better adhesion, and it is also preferable to have four or more alkoxy groups bonded to silicon atoms in the molecule.

[0178] Having 4 or more alkoxy groups bonded to silicon atoms means that the total coefficient of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is 4 or more.

[0179] Examples of isocyanurate-based silane coupling agents having 4 or more alkoxy groups bonded to silicon atoms include compounds represented by the following formula (c-3). Examples of urea-based silane coupling agents having 4 or more alkoxy groups bonded to silicon atoms include compounds represented by the following formula (c-4).

[0180] [Chemical Formula 11]

[0181]

[0182] During the meal, R a represents the same meaning as above. t1 to t5 each independently represent an integer from 1 to 10, preferably an integer from 1 to 6, and particularly preferably 3.

[0183] Among these, as silane coupling agents having a nitrogen atom in the molecule, it is preferable to use 1,3,5-N-tris(3-trimethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-triethoxysilylpropyl)isocyanurate (hereinafter referred to as "isocyanurate compound"), N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea (hereinafter referred to as "urea compound"), and a combination of the isocyanurate compound and the urea compound.

[0184] When the curable composition of the present invention contains a silane coupling agent having a nitrogen atom in its molecule, the content thereof is not particularly limited, but the amount thereof is an amount such that the mass ratio of the component (A) and the silane coupling agent having a nitrogen atom in its molecule [component (A) : silane coupling agent having a nitrogen atom in its molecule] is preferably 100 : 0.1 to 100 : 65, more preferably 100 : 0.3 to 100 : 60, more preferably 100 : 1 to 100 : 50, even more preferably 100 : 3 to 100 : 40, and particularly preferably 100 : 5 to 100 : 35.

[0185] A cured product of a curable composition containing (A) component and a silane coupling agent having nitrogen atoms within the molecule in such a ratio has superior heat resistance and adhesion.

[0186] A silane coupling agent having an acid anhydride structure within the molecule is an organosilicon compound that possesses both an acid anhydride group and a hydrolyzable group within a single molecule. Specifically, examples include compounds represented by the following formula (c-5).

[0187] [Chemical Formula 12]

[0188]

[0189] In the formula, Q represents a group having an acid anhydride structure, and R d represents an alkyl group having 1 to 6 carbon atoms, or a phenyl group having a substituent or not having a substituent, and R e represents an alkoxy group or halogen atom having 1 to 6 carbon atoms, i and k represent integers from 1 to 3, j represents an integer from 0 to 2, and i + j + k = 4. When j is 2, R d They may be identical or different. When k is 2 or 3, multiple R eQs may be identical or different. When i is 2 or 3, multiple Qs may be identical or different.

[0190] For Q, the following formula

[0191] [Chemical Formula 13]

[0192]

[0193] Examples include the group represented by (where h represents an integer from 0 to 10), and the group represented by (Q1) is particularly preferred.

[0194] Silane coupling agents having an acid anhydride structure within the molecule include tri(C1-6)alkoxysilyl(C2-8)alkyl anhydride succinic acids, such as 2-(trimethoxysilyl)ethyl anhydride succinic acid, 2-(triethoxysilyl)ethyl anhydride succinic acid, 3-(trimethoxysilyl)propyl anhydride succinic acid, and 3-(triethoxysilyl)propyl anhydride succinic acid;

[0195] 2-(dimethoxymethylsilyl)ethyl anhydride succinic acid, etc., di (carbon 1-6) alkoxymethylsilyl (carbon 2-8) alkyl anhydride succinic acid;

[0196] 2-(methoxydimethylsilyl)ethyl anhydride succinic acid, etc., (carbon 1 to 6) alkoxydimethylsilyl (carbon 2 to 8) alkyl anhydride succinic acid;

[0197] Trihalogenosilyl (carbon 2 to 8) alkyl succinic acids, such as 2-(trichlorosilyl)ethyl anhydride succinic acid, 2-(tribromosilyl)ethyl anhydride succinic acid, etc.;

[0198] Dihalogenomethylsilyl (carbon 2 to 8) alkyl succinic anhydride, such as 2-(dichloromethylsilyl)ethyl anhydride succinic acid;

[0199] Examples include halogenodimethylsilyl (carbon number 2 to 8) alkyl succinic acids such as 2-(chlorodimethylsilyl)ethyl anhydride succinic acid; etc.

[0200] Among these, as a silane coupling agent having an acid anhydride structure within the molecule, tri(1-6)alkoxysilyl(2-8)alkyl anhydride succinic acid is preferred, and 3-(trimethoxysilyl)propyl anhydride succinic acid or 3-(triethoxysilyl)propyl anhydride succinic acid is particularly preferred.

[0201] When the curable composition of the present invention contains a silane coupling agent having an acid anhydride structure within the molecule, the content thereof is not particularly limited, but the amount thereof is an amount such that the mass ratio of the component (A) and the silane coupling agent having an acid anhydride structure within the molecule [(A) component : silane coupling agent having an acid anhydride structure within the molecule] is preferably 100:0.1 to 100:30, more preferably 100:0.3 to 100:20, more preferably 100:0.5 to 100:15, and even more preferably 100:1 to 100:10.

[0202] The cured product of a curable composition containing (A) component and a silane coupling agent having an acid anhydride structure within the molecule in this ratio has superior adhesion.

[0203] [Curable composition]

[0204] In the curable composition of the present invention, the total amount of component (A) and component (C) is preferably 50 to 100 mass% of the solid content of the curable composition, and more preferably 70 to 100 mass%.

[0205] In the present invention, "solid content" refers to a component other than the solvent in the curable composition.

[0206] The curable composition of the present invention may contain, as component (B), fine particles having an average primary particle size of 5 nm or more and 40 nm or less (hereinafter referred to as “fine particles (B)”).

[0207] A curable composition containing fine particles (B) has excellent workability in the coating process.

[0208] Because this effect is more easily obtained, the average primary particle size of the fine particles (B) is preferably 5 to 30 nm, more preferably 5 to 20 nm.

[0209] The average first-order particle size of the microparticle (B) is obtained by observing the shape of the microparticle using a transmission electron microscope.

[0210] The materials of the fine particles (B) 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; silicon; organic components such as acrylic polymers; etc.

[0211] Also, the microparticle (B) used may have a modified surface.

[0212] The fine particles (B) can be used as a single type or in combination of two or more types.

[0213] When the curable composition of the present invention contains fine particles (B) [component (B)], the content of component (B) is not particularly limited, but the amount is such that the mass ratio of component (A) and component (B) [component (A) : component (B)] is preferably 100 : 0.1 to 100 : 90, more preferably 100 : 0.2 to 100 : 60, more preferably 100 : 0.3 to 100 : 50, more preferably 100 : 0.5 to 100 : 40, and more preferably 100 : 0.8 to 100 : 30. By using component (B) within the above range, the effect of adding component (B) can be further expressed.

[0214] The curable composition of the present invention may contain other components to the extent that it does not impede the purpose of the present invention.

[0215] Other ingredients include antioxidants, UV absorbers, light stabilizers, etc.

[0216] Antioxidants are added to prevent oxidative degradation during heating. Examples of antioxidants include phosphorus-based antioxidants, phenolic-based antioxidants, and sulfur-based antioxidants.

[0217] Phosphorus-based antioxidants include phosphites and oxaphosphaphenanthrene oxides. Phenol-based antioxidants include monophenols, bisphenols, and high molecular weight phenols. Sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.

[0218] These antioxidants may be used as a single type or in combination of two or more types. The content of the antioxidant is not particularly limited, but is typically 10 mass% or less with respect to component (A).

[0219] UV absorbers are added for the purpose of improving the light resistance of the resulting cured product.

[0220] Examples of ultraviolet absorbers include salicylic acids, benzophenones, benzotriazoles, hindered amines, etc.

[0221] One type of UV absorber may be used alone or in combination of two or more types. The content of the UV absorber is not particularly limited, but is typically 10 mass% or less with respect to component (A).

[0222] Light stabilizers are added to improve the light resistance of the resulting cured product.

[0223] Examples of light stabilizers 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}].

[0224] These light stabilizers may be used as a single type or in combination of two or more types. The content of the light stabilizer is typically 20 mass% or less with respect to component (A).

[0225] The curable composition of the present invention may contain a diluent. The diluent is not particularly limited as long as it is capable of dissolving or dispersing the components of the curable composition of the present invention. One type of diluent may be used, or two or more types may be used in combination.

[0226] When the curable composition of the present invention contains a diluent, the amount is such that the solid content concentration is preferably 60 mass% or more and less than 100 mass%, more preferably 65 to 98 mass%, and even more preferably 70 to 95 mass%.

[0227] The polysilsesquioxane compound (A) used in the present invention often has a relatively small molecular weight. A curable composition containing such a polysilsesquioxane compound (A) has good coating properties even without containing a large amount of diluent (i.e., even with a high solid content concentration).

[0228] When using a curable composition with a high solid content, even without strictly controlling the drying or curing conditions of the coating film, a cured product with consistent characteristics can be stably formed because the cured product contains almost no solvent.

[0229] Because the curable composition of the present invention contains a polysilsesquioxane compound (A), the refractive index is high.

[0230] The refractive index (nD) of the curable composition of the present invention at 25°C is typically 1.46 or higher, preferably 1.46 to 1.56, more preferably 1.46 to 1.54, and even more preferably 1.47 to 1.53.

[0231] The refractive index (nD) of the curable composition can be measured using the method described in the example.

[0232] The curable composition of the present invention can be prepared, for example, by mixing the above-mentioned component (A) and component (C) and, if desired, other components in a predetermined ratio, and by degassing.

[0233] The mixing method and the degassing method are not particularly limited, and known methods may be used.

[0234] 2) Cured material

[0235] The cured product of the present invention is obtained by curing the curable composition of the present invention.

[0236] Heat curing can be used as a method for curing the curable composition of the present invention. The heating temperature for curing is typically 100 to 200°C, and the heating time is typically 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

[0237] The cured product of the present invention has excellent heat resistance and adhesion.

[0238] It can be confirmed, for example, that the cured product of the present invention has these characteristics 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, the coated surface is placed on a substrate, pressed, and cured by heat treatment. This is then placed on the measurement stage of a bond tester heated to a predetermined temperature (e.g., 23°C, 100°C) for 30 seconds, and stress is applied in a horizontal direction (shear direction) to the adhesive surface from a position 50 μm high from the substrate to measure the adhesion strength between the test specimen and the substrate.

[0239] The adhesive strength of the cured product of the present invention is preferably 100 N / 4 mm² or more at 23 ℃, and more preferably 120 N / 4 mm² or more.

[0240] The adhesive strength of the cured product of the present invention is preferably 40 N / 4 mm² or more at 100 ℃, and more preferably 45 N / 4 mm² or more.

[0241] In this specification, "4 mm²" means "2 mm square," that is, 2 mm × 2 mm (a square with sides of 2 mm).

[0242] The cured product of the present invention has a high refractive index and also possesses excellent adhesion. Therefore, the cured product of the present invention is preferably used as an adhesive layer with a high refractive index.

[0243] The refractive index (nD) of the cured product of the present invention at 25°C is typically 1.46 or higher, preferably 1.46 to 1.56, more preferably 1.46 to 1.54, and even more preferably 1.47 to 1.53.

[0244] The refractive index (nD) of the cured material can be measured using an Abbe refractometer.

[0245] In having the above characteristics, the cured material of the present invention is preferably used as a fixing material for optical devices.

[0246] 3) Method of using the curable composition

[0247] The method of the present invention is a method of using the curable composition of the present invention as an adhesive for an optical device fixing material or as an encapsulant for an optical device fixing material.

[0248] Examples of optical devices include light-emitting devices such as LEDs and LDs, light-receiving devices, composite optical devices, and optical integrated circuits.

[0249] <Adhesive for Optical Device Fixing Materials>

[0250] The curable composition of the present invention can preferably be used as an adhesive for fixing optical devices.

[0251] A method of using the curable composition of the present invention as an adhesive for fixing optical devices includes applying a predetermined amount of the composition to one or both bonding surfaces of materials to be bonded (such as an optical device and its substrate), pressing them together, and then heating and curing them to firmly bond the materials to be bonded together. The amount of curable composition applied according to the present invention is not particularly limited and is sufficient as long as it is an amount that allows the materials to be bonded together to be firmly bonded by curing. Typically, it is an amount such that the thickness of the coating film of the curable composition is 0.5 to 5 μm, preferably 1 to 3 μm.

[0252] Examples of substrate materials for bonding optical elements include: glasses such as soda-lime glass and heat-resistant hard glass; ceramics; sapphire; metals such as iron, copper, aluminum, gold, silver, platinum, chromium, titanium and alloys of these metals, and stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); 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, glass epoxy resin, etc.

[0253] The heating temperature during heat curing varies depending on the curable composition used, but is typically 100 to 200°C. The heating time is typically 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

[0254] <Encapsulating material for optical device fixing>

[0255] The curable composition of the present invention can be suitably used as an encapsulating material for fixing optical devices.

[0256] Methods for using the curable composition of the present invention as an encapsulant for fixing optical elements include, for example, a method of manufacturing an optical element encapsulant by molding the composition into a desired shape to obtain a molded body containing an optical element, and then heat-curing the molded body.

[0257] The method for molding the curable composition of the present invention into a desired shape is not particularly limited, and known mold methods such as conventional transfer molding or molding methods may be employed.

[0258] The heating temperature during heat curing varies depending on the curable composition used, but is typically 100 to 200°C. The heating time is typically 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

[0259] The resulting optical device encapsulator has excellent heat resistance and adhesion because it uses the curable composition of the present invention.

[0260] Examples

[0261] The present invention will be explained in more detail below with reference to examples. However, the present invention is not limited in any way to the following examples.

[0262] (Measurement of average molecular weight)

[0263] The mass average molecular weight (Mw) and number average molecular weight (Mn) of the polysilsesquioxane compound were converted to standard polystyrene values ​​and measured under the following apparatus and conditions.

[0264] Device Name: HLC-8220GPC, Manufactured by Tosoh Corporation

[0265] Column: TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL connected in sequence

[0266] Solvent: Tetrahydrofuran

[0267] Injection volume: 20 μl

[0268] Measured temperature: 40 ℃

[0269] Flow rate: 0.6 ml / min

[0270] Detector: Parallax Refractometer

[0271] ( 29 Si-NMR measurement)

[0272] To investigate the repeating units and amounts of polysilsesquioxane compounds, under the following conditions 29 Si-NMR measurements were performed.

[0273] Device: AV-500 manufactured by Bruker Biospin

[0274] 29 Si-NMR Resonance Frequency: 99.352 MHz

[0275] Probe: 5 mmφ solution probe

[0276] Measurement temperature: Room temperature (25 ℃)

[0277] Sample rotation speed: 20 kHz

[0278] Measurement method: Inverse gate decoupling method

[0279] 29 Si flip angle: 90°

[0280] 29 Si 90° pulse width: 8.0 μs

[0281] Repeat time: 5 s

[0282] Accumulated count: 9,200 times

[0283] Observation width: 30 kHz

[0284] ( 29 Si-NMR Sample Preparation Method)

[0285] To shorten the relaxation time, Fe(acac)3 was added as a relaxation reagent and measured.

[0286] Polysilsesquioxane compound concentration: 15 mass%

[0287] Fe(acac)3 concentration: 0.6 mass%

[0288] Measurement solvent: Acetone

[0289] Internal Standard: TMS

[0290] (Waveform processing analysis)

[0291] For each peak of the spectrum after Fourier transform, the chemical shift was determined based on the position of the peak top, and integration of each peak was performed within the following range. Based on the obtained values, the ratios of the T1 site, T2 site, and T3 site were calculated.

[0292] T sites having a phenyl group (T1: -65 to -58 ppm, T2: -74 to -65 ppm, T3: -82 to -75 ppm)

[0293] T sites with methyl groups (T1: -50 to -46 ppm, T2: -61 to -52 ppm, T3: -70 to -61 ppm)

[0294] (Refractive index)

[0295] The refractive index (nD) of a polysilsesquioxane compound was measured at 25°C using a multi-wavelength Abbe refractometer (manufactured by Atago Co., Ltd., DR-M2).

[0296] (Preparation Example 1)

[0297] 9.34 g (47.1 mmol) of phenyltrimethoxysilane and 8.40 g (47.1 mmol) of methyltriethoxysilane were added to a 300 ml branched flask, and while stirring, an aqueous solution of 0.025 g of 35 mass% hydrochloric acid (0.25 mol% of HCl relative to the total amount of silane compounds) dissolved in 5.09 g of distilled water was added, and the entire mixture was stirred at 30 ℃ for 2 hours, then raised to 80 ℃ and stirred for 20 hours.

[0298] After cooling the reaction solution to room temperature, 50 g of propyl acetate and 100 g of water were added thereto to perform a liquid-liquid treatment, thereby obtaining an organic layer containing the reaction product. Magnesium sulfate was added to this organic layer to perform a drying treatment. After removing the magnesium sulfate through filtration, the organic layer was concentrated using an evaporator, and then the obtained concentrate was vacuum dried to obtain a polysilsesquioxane compound (A1).

[0299] (Preparation Example 2)

[0300] 12.55 g (63.3 mmol) of phenyltrimethoxysilane and 4.83 g (27.1 mmol) of methyltriethoxysilane were added to a 300 ml branched flask, and while stirring, an aqueous solution of 0.024 g of 35 mass% hydrochloric acid (0.25 mol% of HCl relative to the total amount of silane compounds) dissolved in 4.88 g of distilled water was added, and the entire mixture was stirred at 30 ℃ for 2 hours, then raised to 80 ℃ and stirred for 20 hours.

[0301] While continuing to stir the contents, 17 g of propyl acetate and 0.149 g of 28 mass% ammonia water (2.5 mol% relative to phenyltriethoxysilane) were added, the temperature was raised to 80 ℃, and the mixture was stirred for 20 hours.

[0302] After cooling the reaction solution to room temperature, polysilsesquioxane compound (A2) was obtained by performing separation, drying, etc., in the same manner as in Preparation Example 1.

[0303] (Preparation Example 3)

[0304] 9.34 g (47.1 mmol) of phenyltrimethoxysilane and 8.40 g (47.1 mmol) of methyltriethoxysilane were added to a 300 ml branched flask, and while stirring, an aqueous solution of 0.294 g of 35 mass% hydrochloric acid (3.00 mol% of HCl relative to the total amount of silane compounds) dissolved in 5.09 g of distilled water was added, and the entire mixture was stirred at 30 ℃ for 2 hours, then raised to 80 ℃ and stirred for 20 hours.

[0305] After cooling the reaction solution to room temperature, 50 g of propyl acetate and 100 g of water were added thereto to perform a liquid-liquid treatment, thereby obtaining an organic layer containing the reaction product. Magnesium sulfate was added to this organic layer to perform a drying treatment. After removing the magnesium sulfate by filtration, the organic layer was concentrated in an evaporator, and then the obtained concentrate was vacuum dried to obtain a polysilsesquioxane compound (A3).

[0306] (Comparative Manufacturing Example 1)

[0307] 14.455 g (72.9 mmol) of phenyltrimethoxysilane was added to a 300 ml branched flask, and while stirring, an aqueous solution of 0.0188 g of 35 mass% hydrochloric acid (0.25 mol% of HCl relative to phenyltrimethoxysilane) dissolved in 3.937 g of distilled water was added, and the entire mixture was stirred at 30 ℃ for 2 hours, then raised to 70 ℃ and stirred for 22 hours.

[0308] While continuing to stir the contents, 15 g of propyl acetate and 0.0109 g of 28 mass% ammonia water (0.25 mol% relative to phenyltriethoxysilane) were added, the temperature was raised to 80 ℃, and the mixture was stirred for 20 hours.

[0309] After cooling the reaction solution to room temperature, a polysilsesquioxane compound (A4) was obtained by performing separation, drying, etc., in the same manner as in Preparation Example 1.

[0310] (Comparative Manufacturing Example 2)

[0311] 28.77 g (145.1 mmol) of phenyltrimethoxysilane and 0.2675 g (1.5 mmol) of methyltriethoxysilane were added to a 300 ml branched flask, and while stirring, an aqueous solution of 0.477 g of 35 mass% hydrochloric acid (3 mol% of HCl relative to the total amount of silane compounds) dissolved in 8.24 g of distilled water was added, and the entire mixture was stirred at 30 ℃ for 2 hours, then raised to 80 ℃ and stirred for 20 hours.

[0312] After cooling the reaction solution to room temperature, a polysilsesquioxane compound (A5) was obtained by performing separation, drying, etc., in the same manner as in Preparation Example 1.

[0313] Details of the obtained polysilsesquioxane compound (PSQ) are shown in Table 1.

[0314]

[0315] The compounds used in the examples, comparative examples, and reference examples are shown below.

[0316] (Silanic coupling agent)

[0317] Silane coupling agent (C1): 1,3,5-N-tris[3-(trimethoxysilyl)propyl]isocyanurate

[0318] Silane coupling agent (C2): 3-(trimethoxysilyl)propylsuccinic acid anhydride

[0319] (Filler)

[0320] Silica fine particles: (Manufactured by Nippon Aerosil Co., Ltd., Product name "AEROSIL RX300", Average primary particle size: 7 nm, Specific surface area: 210 m² / g)

[0321] (Example 1)

[0322] 5 parts by mass of silica fine particles were added to 100 parts by mass of a polysilsesquioxane compound (A1), and a mixed solvent of diethylene glycol monobutyl ether acetate : tripropylene glycol-n-butyl ether = 40 : 60 (mass ratio) was additionally added and the entire mixture was stirred. 3. After dispersion treatment by a roll mill, 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 mixture was thoroughly mixed and degassed to obtain a curable composition having a solid content concentration of 80 mass%.

[0323] (Example 2)

[0324] A curable composition having a solid content of 80 mass% was obtained by making the same as in Example 1, except that polysilsesquioxane compound (A2) was used instead of polysilsesquioxane compound (A1), the content of silica fine particles was changed to 20 mass parts, and the amount of mixed solvent was also changed.

[0325] (Example 3)

[0326] A curable composition having a solid content of 80 mass% was obtained in the same manner as in Example 1, except that a polysilsesquioxane compound (A3) was used instead of a polysilsesquioxane compound (A1).

[0327] (Comparative Example 1)

[0328] A curable composition having a solid content of 80 mass% was obtained by doing the same as in Example 1, except that a polysilsesquioxane compound (A4) was used instead of a polysilsesquioxane compound (A1), the content of silica fine particles was changed to 20 mass parts, and the amount of mixed solvent was changed.

[0329] (Comparative Example 2)

[0330] A curable composition having a solid content of 78 mass% was obtained by making the same as in Example 1, except that a polysilsesquioxane compound (A5) was used instead of a polysilsesquioxane compound (A1), a silane coupling agent (C1) and a silane coupling agent (C2) were not used, and the amount of mixed solvent was changed.

[0331] (Comparative Example 3)

[0332] A curable composition having a solid content of 75 mass% was obtained by making the same as in Example 1, except that the silane coupling agent (C1) and the silane coupling agent (C2) were not used and the amount of mixed solvent was changed.

[0333] Using the curable compositions obtained in the examples, comparative examples, and reference examples, the following measurements and tests were performed, respectively.

[0334] [Refractive Index Measurement]

[0335] The refractive index (nD) of the curable composition was measured at 25°C using a multi-wavelength Abbe refractometer (manufactured by Atago Co., Ltd., DR-M2).

[0336] [Crack Resistance Evaluation]

[0337] The curable compositions obtained in the examples and comparative examples were each applied to the mirror surface of a square glass chip with a side length of 0.5 mm to a thickness of about 2 μm, and the coated surface was placed on a substrate (silver-plated copper plate) and pressed. Afterward, the mixture was heat-treated at 170°C for 2 hours and cured to obtain a test specimen attached substrate. In addition, 20 test specimen attached substrates were prepared for one type of curable composition. Using a scanning electron microscope (KEYENCE VE-9800S), the resin portion (fillet portion) protruding from the glass chip was observed, and the number of samples with cracks was counted. The crack occurrence rate was evaluated as "A" for 0% or more and less than 25%, "B" for 25% or more and less than 50%, and "C" for 50% or more and 100% or less.

[0338] [Adhesion Strength Evaluation]

[0339] The curable compositions obtained in the examples and comparative examples were each applied to the mirror surface of a square silicon chip (area 4 mm²) with a side length of 2 mm, to a thickness of about 2 μm, and the coated surface was placed on a substrate (silver-plated copper plate) and pressed. Afterward, the substrate was heat-treated at 170°C for 2 hours and cured to obtain a test specimen attached substrate. This test specimen attached substrate was placed on the measurement stage of a bond tester (manufactured by Daisy, Series 4000) that had been preheated to a predetermined temperature (23°C, 100°C) for 30 seconds, and stress was applied in the horizontal direction (shear direction) to the bonding surface at a speed of 200 μm / s from a position 50 μm high from the substrate to measure the adhesion strength (N / 4 mm²) between the test specimen and the substrate at 23°C and 100°C.

[0340] The measurement results and evaluation results are shown in Table 2.

[0341]

[0342] From the above examples, comparative examples, and reference examples, the following can be seen.

[0343] The curable compositions of Examples 1 to 3 contain polysilsesquioxane compounds (PSQ (A1), PSQ (A2), PSQ (A3)) having repeating units (1), so the refractive index is suitably high.

[0344] In addition, the curable compositions of Examples 1 to 3 contain a silane coupling agent. Also, PSQ (A1), PSQ (A2), and PSQ (A3) all have repeating units (2) and appropriately contain T2 sites. Because of this, the cured products of Examples 1 to 3 have excellent crack resistance and adhesion.

[0345] Meanwhile, the curable composition of Comparative Example 1 also has a high refractive index because it contains a polysilsesquioxane compound (PSQ (A4)) with a high content of repeating units (1).

[0346] However, since PSQ (A4) does not have repeating units (2) and the proportion of T2 sites is not high, the cured product of Comparative Example 1 has inferior crack resistance.

[0347] Meanwhile, since the curable compositions obtained in Comparative Examples 2 and 3 do not contain a silane coupling agent, the cured product does not have sufficient adhesive strength.

Claims

Claim 1 A curable composition containing the following components (A) and (C). (A) Component: Formula (a-1) [R 1 ...represents an unsubstituted aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms with a substituent.] A repeating unit [repeating unit (1)] and the following formula (a-2) [R 2 [represents an unsubstituted alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms with a substituent.] A polysilsesquioxane compound having a repeating unit [repeating unit (2)] represented by, wherein the total amount of repeating unit (1) and repeating unit (2) in component (A) is 90 to 100 mol% of the total repeating unit of component (A), and satisfying the following requirements 1 and 2: [Requirement 1] With respect to the total amount of repeating unit (1) and repeating unit (2), the amount of repeating unit (1) is 40 mol% or more and less than 80 mol%. [Requirement 2] With respect to the total amount of T site (T1 site) represented by the following formula (a-3), T site (T2 site) represented by the following formula (a-4), and T site (T3 site) represented by the following formula (a-5) Regarding this, the amount of the above T2 site is 20 to 70 mol%. [G is, R 1 or R 2 Represents the group represented by . R 3 ... represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. A silicon atom is bonded to *.〕(C) Component: Silane coupling agent Claim 2 In claim 1, (A) a curable composition having a mass average molecular weight (Mw) of 500 to 25,000. Claim 3 A curable composition according to claim 1, wherein the content of component (C) is 0.1 to 70 parts by mass per 100 parts by mass of component (A). Claim 4 A curable composition according to claim 1, wherein the total amount of component (A) and component (C) is 50 to 100 mass% of the solid content of the curable composition. Claim 5 A curable composition according to claim 1, further containing a diluent and having a solid content concentration of 60 mass% or more and less than 100 mass%. Claim 6 A curable composition according to claim 1, wherein the refractive index (nD) at 25°C is 1.488 to 1.

56. Claim 7 A cured product obtained by curing a curable composition described in any one of claims 1 to 6. Claim 8 In claim 7, a cured material that is a fixing material for an optical element. Claim 9 A method of using a curable composition described in any one of claims 1 to 6 as an adhesive for fixing optical devices. Claim 10 A method of using a curable composition described in any one of claims 1 to 6 as an encapsulant for fixing optical devices. Claim 11 delete

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