TW202031739A - Curable polysilsesquioxane compound, curable composition, cured product, and, method for using curable composition - Google Patents

Abstract

The present invention is: a curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1), wherein said curable polysilsesquioxane compound is characterized by fulfilling a specified requirement relating to 29Si-NMR and having a mass-average molecular weight (Mw) in a specified range; a curable composition containing said curable polysilsesquioxane compound; a cured product made by curing the curable composition; and, a method for using the curable composition as an adhesive for an optical element fixing material or as a sealing material for an optical element fixing material. The curable composition according to the present invention has excellent curing properties and a low refractive index. In formula (a-1), R1 represents a fluoroalkyl group represented by a compositional formula CmH(2m-n+1)Fn. m represents an integer from 1-10, and n represents an integer of at least 2 and no more than (2m+1). D represents a connecting group (except for an alkylene group) which joins the R1 and Si, or represents a single bond.

Description

Curable polysilsesquioxane compound, curable composition, cured product, and use method of curable composition

The present invention relates to a curable polysilsesquioxane compound, a curable composition containing the aforementioned curable polysilsesquioxane compound having excellent curability and a low refractive index, and the aforementioned curable composition A cured product with high adhesive strength after curing, and a method of using the curable composition as an adhesive for an optical element fixing material or a sealing agent for an optical element fixing material.

Previously, curable compositions were modified in various ways according to applications, and were widely used industrially as raw materials, adhesives, coating agents, and the like for optical parts or molded articles. In addition, 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 and a sealant for an optical element fixing material.

Optical components include various lasers such as semiconductor lasers (LD), light-emitting components such as light-emitting diodes (LED), light-receiving components, composite optical components, optical integrated circuits, and the like. In recent years, optical elements with blue light or white light whose emission peak wavelength is a shorter wavelength have been developed and widely used. The high-brightness system of such a light-emitting element with a short emission peak wavelength is advancing drastically, and with this situation, the calorific value of the optical element tends to increase further.

However, with the recent increase in brightness of optical elements, the hardened material of the composition for fixing optical elements has been exposed to high-energy light and high-temperature heat generated from optical elements for a long time, resulting in a decrease in adhesive strength. problem.

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. However, even in the cured product of the composition described in Patent Documents 1 to 3, it may be difficult to obtain heat resistance while maintaining sufficient adhesive force.

In addition, when using a curable composition to fix an optical element, etc., it is important to form a cured product having a refractive index for the purpose in most cases. In particular, since most of the conventional curable compositions or their cured products have higher refractive indices, curable compositions with lower refractive index are required.

Patent Document 4 describes a curable composition containing a curable polysilsesquioxane compound having a fluoroalkyl group as a curable composition that provides a curable product with a lower refractive index. However, as shown in the examples of Patent Document 4, when a curable composition containing a curable polysilsesquioxane compound with a higher ratio of repeating units having a fluoroalkyl group is used, it is difficult to obtain a curable composition with higher adhesive strength. Things. In this way, the cured product of the curable composition described in Patent Document 4 has a trade-off relationship between higher adhesive strength and lower refractive index. Therefore, when the curable composition described in Patent Document 4 is used, it is difficult to obtain a cured product having the characteristics of both high adhesive strength and low refractive index.

Moreover, it is known to improve workability etc. by adding filler etc. to a curable composition. However, usually curable compositions containing fillers and the like or their cured products tend to have a higher refractive index. Therefore, even if fillers are added, a curable composition with a lower refractive index is desired. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2004-359933 A [Patent Document 2] Japanese Patent Application Publication No. 2005-263869 [Patent Document 3] Japanese Patent Application Publication No. 2006-328231 [Patent Document 4] WO2017/110948 (US2018/0355111 A1)

Problems to be solved by the invention The present invention was made in view of the actual situation of the above-mentioned prior art, and its object is to provide a curable composition having excellent curability and a low refractive index, and curable polysilsesquioxane useful as a component of the curable composition An oxane compound, a cured product with a high adhesive strength obtained by curing the curable composition, and a method of using the curable composition as an adhesive for an optical element fixing material or a sealing agent for an optical element fixing material. In the present invention, the "curable composition" refers to a composition that changes into a cured product by satisfying predetermined conditions such as heating. In the present invention, the "curable polysilsesquioxane compound" refers to a polysilsesquioxane compound that is individually changed into a cured product by satisfying predetermined conditions such as heating, or is achieved in the aforementioned curable composition A polysilsesquioxane compound that functions as a curable component. Means to solve the problem

In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive studies on curable polysilsesquioxane compounds having a fluoroalkyl group. As a result, (1) The adhesive strength of the cured product is low due to the introduction of fluoroalkyl groups into the curable polysilsesquioxane compound. It is possible to use specific repeating units and meet the requirements of the molecular structure (described later) The necessary condition 1) and the necessary condition related to the molecular weight (required condition 2 described later) are cured polysilsesquioxane compound (hereinafter referred to as "curable polysilsesquioxane compound (A)"). ;and (2) The curable composition containing the curable polysilsesquioxane compound (A) has excellent curability characteristics, so it also has the advantage of being able to undergo a curing reaction without excessive heating. Furthermore, it has been found that a curable composition containing a curable polysilsesquioxane compound (A) and a solvent having a boiling point of 254°C or higher has little change in viscosity even after it is left for a long time after coating, so it has the advantages of Same workability immediately after coating. The present invention has been completed based on these findings.

Thus, according to the present invention, the following curable polysilsesquioxane compounds [1] to [5], curable compositions of [6] to [9], and curing of [10] and [11] can be provided物, and the use method of the curable composition of [12] and [13].

[1] A curable polysilsesquioxane compound, which is a curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1), characterized in that it satisfies the following requirement 1 And necessary conditions 2.

[R ¹ represents the composition formula: C _m H _(2m-n+1) fluoroalkyl group represented by F _n , m represents an integer from 1 to 10, and n represents an integer from 2 to (2m+1), D represents the linking group (except the alkylene group) or the single bond that connects R ¹ to Si. [Requirement 1] When measuring ²⁹ Si-NMR of the curable polysilsesquioxane compound, it can be -62ppm 1 or more peaks are observed in the region above and below -52ppm [region (2)], and can be in the region above -52ppm and below -45ppm [region (1)] and region above -73ppm but below -62ppm [Area (3)] At least one area has 1 or 2 sharp peaks observed, and Z2 derived from the following formula is 20-40%,

P1: Integral value in area (1) P2: Integral value in area (2) P3: Integral value in area (3) [Required Condition 2] The mass average molecular weight (Mw) of the curable polysilsesquioxane compound is 4,000 to 11,000.

[2] The curable polysilsesquioxane compound as described in [1], wherein the ratio of the repeating unit represented by the formula (a-1) is 25 mol% or more with respect to the total repeating unit. [3] The curable polysilsesquioxane compound as described in [1] or [2], which further has a repeating unit represented by the following formula (a-2).

[R ² represents an unsubstituted alkyl group having 1 to 10 carbons, or a substituted or unsubstituted aryl group having 6 to 12 carbons]. [4] The curable polysilsesquioxane compound according to [3], wherein the ratio of the repeating unit represented by the formula (a-2) is greater than 0 mol% and 75 mol% or less with respect to the total repeating units. [5] The curable polysilsesquioxane compound described in any one of [1] to [3], wherein when ²⁹ Si-NMR is measured, 1 or 2 or more can be observed in the region (3) Z3 derived from the following formula is 60 to 80%.

[6] A curable composition characterized by containing the following (A) component and a solvent having a boiling point of 254°C or higher. (A) Component: the curable polysilsesquioxane compound as described in any one of [1] to [5] [7] The curable composition as described in [6], which further contains the following component (B). (B) Component: Silane coupling agent with nitrogen atom in the molecule [8] The curable composition as described in [6] or [7], which further contains the following (C) component. (C)Component: Silane coupling agent with acid anhydride structure in the molecule [9] The curable composition according to any one of [6] to [8], which further contains the following (D). (D)Component: Fine particles with an average primary particle size of 5-40nm [10] A cured product obtained by curing the curable composition described in any one of [6] to [9]. [11] The cured product described in [10] is an optical element fixing material. [12] A method of using the curable composition as described in any one of [6] to [9] as an adhesive for fixing an optical element. [13] A method of using the curable composition as described in any one of [6] to [9] as a sealant for fixing an optical element. Invention effect

According to the present invention, it is possible to provide a curable composition having excellent curability and a low refractive index, a curable polysilsesquioxane compound useful as a component of the curable composition, and curing the aforementioned curable composition The resulting cured product with high adhesive strength and the method of using the curable composition as an adhesive for an optical element fixing material or a sealing agent for an optical element fixing material.

The form used to implement the invention Hereinafter, the method of using the present invention divided into 1) curable polysilsesquioxane compound, 2) curable composition, 3) curable product, and 4) curable composition will be described in detail.

1) Curing polysilsesquioxane compound The curable polysilsesquioxane compound of the present invention [curable polysilsesquioxane compound (A)] is a curable polysilsesquioxane having a repeating unit represented by the following formula (a-1) The compound is characterized by satisfying the above-mentioned requirement 1 and requirement 2.

[R ¹ represents a fluoroalkyl group represented by the composition formula C _m H _(2m-n+1) F _n . m is an integer of 1-10, and n represents an integer of 2 or more and (2m+1) or less. D represents a linking group (except for the alkylene group) or a single bond connecting R ¹ and Si.

In the formula (a-1), R ¹ represents the composition formula: a fluoroalkyl group represented by C _m H _(2m-n+1) F _n . m is an integer of 1-10, and n represents an integer of 2 or more and (2m+1) or less. m is preferably an integer of 1 to 5, more preferably an integer of 1 to 3. By using a curable polysilsesquioxane compound having R ¹ , a curable composition with a low refractive index can be obtained.

As the composition formula: fluoroalkyl represented by C _m H _(2m-n+1) F _n , CF ₃ , CF ₃ CF ₂ , CF ₃ (CF ₂ ) ₂ , CF ₃ (CF ₂ ) ₃ , CF ₃ (CF ₂ ) ₄ , CF ₃ (CF ₂ ) ₅ , CF ₃ (CF ₂ ) ₆ , CF ₃ (CF ₂ ) ₇ , CF ₃ (CF ₂ ) ₈ , CF ₃ (CF ₂ ) _9, etc. Fluoroalkyl; CF ₃ CH ₂ CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ and other hydrofluorine alkyl.

In the formula (a-1), D represents a linking group (except for the alkylene group) or a single bond that bonds R ¹ to Si. Examples of the linking group of D include 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, and other carbon atoms with 6-20 carbon atoms. base.

The curable polysilsesquioxane compound (A) may have one type of (R ¹ -D) (homopolymer), or may have two or more types of (R ¹ -D) (copolymerization).物). When the curable polysilsesquioxane compound (A) is a copolymer, the curable polysilsesquioxane compound (A) can be a random copolymer, block copolymer, graft copolymer, alternating copolymer, etc. From the viewpoint of ease of manufacture and the like, random copolymers are preferred. In addition, the structure of the sclerosing polysilsesquioxane compound (A) may be a ladder type structure, a double-decker structure, a cage structure, a partially cracked cage structure, and a cyclic structure. , Any structure of random structure.

The ratio of the repeating unit represented by the formula (a-1) contained in the curable polysilsesquioxane compound (A) is preferably 25 mol% or more, preferably 25 to 90 mol%, relative to the total repeating units , More preferably 25~85mol%. By using the curable polysilsesquioxane compound (A) whose repeating unit ratio represented by the formula (a-1) is 25 mol% or more with respect to the total repeating units, a curable composition with a lower refractive index can be obtained .

The curable polysilsesquioxane compound (A) may further have a repeating unit represented by the following formula (a-2) (copolymer).

In formula (a-2), R ² represents an unsubstituted alkyl group having 1 to 10 carbons, or a substituted group, or an unsubstituted aryl group having 6 to 12 carbons.

Examples of the unsubstituted alkyl group having 1 to 10 carbon atoms in R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. , N-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, etc.

Examples of the unsubstituted aryl group having 6 to 12 carbon atoms for R ² include phenyl, 1-naphthyl, 2-naphthyl and the like. Examples of the substituent of the substituted aryl group having 6 to 12 carbon atoms in R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, Alkyl groups such as tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and isooctyl groups; halogen atoms such as fluorine atom, chlorine atom, bromine atom, etc.; methoxy group, ethoxy group, etc. Alkoxy.

Among these, as R ² , it is easy to obtain a hardened product with higher bonding strength and better heat resistance. It is preferably an unsubstituted alkyl group with 1-10 carbon atoms, and an unsubstituted carbon number An alkyl group of 1 to 6 is preferred, and an unsubstituted alkyl group of 1 to 3 carbons is particularly preferred.

When the curable polysilsesquioxane compound (A) has a repeating unit represented by formula (a-2), the curable polysilsesquioxane compound (A) may have one type of R ² or It may have two or more types of R ² .

When the curable polysilsesquioxane compound (A) has a repeating unit represented by the formula (a-2), the ratio is preferably more than 0 mol% and 75 mol% or less with respect to the total repeating units, preferably 10 ~75mol%, more preferably 15~75mol%. By using the curable polysilsesquioxane compound (A) whose repeating unit ratio represented by formula (a-2) is within the above range, it is easy to obtain a cured product with higher bonding strength and better heat resistance .

The ratio of the repeating unit represented by formula (a-1) or formula (a-2) in the curable polysilsesquioxane compound (A) can be measured, for example, by measuring the curable polysilsesquioxane compound ( A) is determined by ²⁹ Si-NMR.

Because the curable polysilsesquioxane compound (A) is a ketone-based solvent such as acetone; an aromatic hydrocarbon-based solvent such as benzene; a sulfur-containing solvent such as dimethyl sulfoxide; an ether-based solvent such as tetrahydrofuran; Ester solvents such as ethyl acetate; halogen-containing solvents such as chloroform; and various organic solvents such as mixed solvents composed of these two or more kinds are soluble, so it is possible to use these solvents to measure the curable polymer ²⁹ Si-NMR of the semisiloxane compound (A) in a solution state.

The repeating unit represented by the formula (a-1) and the repeating unit represented by the formula (a-2) are those represented by the following formula (a-3).

[G represents (R ¹ -D) or R ² . R ¹ , D, and R ² each have the same meaning as above. The so-called O _1/2 means that it shares an oxygen atom with the adjacent repeating unit].

As shown in formula (a-3), the curable polysilsesquioxane compound (A) has three oxygen atoms commonly referred to as T-sites (T-site) bonded to silicon atoms and the other 1 A part of the structure formed by a group (group represented by G) bonded to a silicon atom. Examples of the T-position contained in the curable polysilsesquioxane compound (A) include those represented by the following formulas (a-4) to (a-6).

In formulas (a-4), (a-5) and (a-6), G represents the same meaning as above. R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms in R ³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, and tertiary butyl. The plurality of R ³ may all be the same or different. In addition, in the above formulas (a-4) to (a-6), * is a silicon atom.

The T-position shown in formula (a-4) and formula (a-5) contains a group (R ³ -O) that can contribute to the polycondensation reaction. Therefore, polysilsesquioxane compounds containing a plurality of these T-positions have excellent reactivity. In addition, a composition containing such a polysilsesquioxane compound has excellent curability. On the other hand, the T-position represented by the formula (a-5) and the formula (a-6) is bonded to two or more silicon atoms (silicon atoms in adjacent T-positions). Therefore, polysilsesquioxane compounds containing a plurality of these T-positions tend to have larger molecular weights.

Therefore, the polysilsesquioxane compound containing a plurality of T-positions represented by the formula (a-5) has a relatively large molecular weight and sufficient reactivity. The present invention was made based on this knowledge. That is, the curable polysilsesquioxane compound (A) of the present invention satisfies the following requirement 1.

(Requirement 1) When measuring ²⁹ Si-NMR of a curable polysilsesquioxane compound, one or more sharp peaks can be observed in the region of -62ppm or more and less than -52ppm [region (2)] , And more than one or two peaks and below can be observed in at least one of the region above -52ppm and below -45ppm [region (1)] and region above -73ppm but below -62ppm [region (3)] The Z2 derived from the formula is 20-40%. In addition, the so-called "peaks that can be observed in the area (1)" refers to the range where the peak position is in the area (1). The same applies to "spikes that can be observed in area (2)" and "spikes that can be observed in area (3)".

P1: Integral value in area (1) P2: Integral value in area (2) P3: Integral value in area (3)

In this manual, the so-called "integrated value in area (1)", "integrated value in area (2)", and "integrated value in area (3)" refer to -52ppm~-45ppm and -62ppm respectively ~-52ppm, -73ppm~-62ppm are set as integral range and calculated value.

The peaks that can be observed in area (1), area (2), and area (3) are derived from the T shown in formula (a-4), formula (a-5), and formula (a-6) respectively -The silicon atom in the location.

Therefore, the curable polysilsesquioxane compound that satisfies requirement 1 contains 20-40% of the T-position represented by the formula (a-5) with respect to the entire T-position. The curable polysilsesquioxane compound has a relatively large molecular weight and has sufficient reactivity as described above, and is useful as a curable component of a curable composition.

In the necessary condition 1, the value of Z2 is preferably 24 to 36%, more preferably 27 to 32%. When Z2 is too small, the reactivity is insufficient, and when Z2 is too large, the storage stability will decrease.

The curable polysilsesquioxane compound (A) can observe 1 or more peaks in the region (3) when ²⁹ Si-NMR is measured. The Z3 system derived from the following formula is 60~80% Better.

Z3 is 60-80% curable polysilsesquioxane compound (A), which contains 60-80% of the T-position represented by the formula (a-6) with respect to the entire T-position. The curable polysilsesquioxane compound (A) whose value of Z3 is in the range of 60 to 80% has a more excellent balance between molecular weight and reactivity. Because this effect is easier to obtain, the value of Z3 is preferably 64~76%, and 68~73% is more preferred.

The value of Z2 or Z3 can be calculated by measuring ²⁹ Si-NMR under the conditions described in the examples to obtain P1 to P3 and calculating according to the above formula.

The curable polysilsesquioxane compound (A) satisfies the requirement 2 above. That is, the mass average molecular weight (Mw) of the curable polysilsesquioxane compound (A) is 4,000 to 11,000, preferably 4,000 to 8,000, and more preferably 6,000 to 7,000.

As described above, the curable polysilsesquioxane compound that satisfies the requirement 1 tends to have a larger molecular weight. Requirement 2 is to clarify the molecular weight range. By using a curable polysilsesquioxane compound (A) having a mass average molecular weight (Mw) within the above range as a curable component, it is possible to obtain a cured product with high adhesive strength and excellent heat resistance. Hardening composition.

The molecular weight distribution (Mw/Mn) of the curable polysilsesquioxane compound (A) is not particularly limited, and it is usually 1.0 to 10.0, preferably 1.1 to 6.0. By using a curable polysilsesquioxane compound (A) having a molecular weight distribution (Mw/Mn) within the above range as a curable component, it is possible to obtain a cured product that provides a cured product with excellent adhesion and heat resistance Sexual composition. The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent and in terms of standard polystyrene conversion values.

The curable polysilsesquioxane compound (A) can be, for example, a compound represented by the following formula (a-7) (hereinafter referred to as "silane compound (1)"), or a silane compound (1) ) And a compound represented by the following formula (a-8) (hereinafter referred to as "silane compound (2)") in the presence of a polycondensation catalyst to produce it by polycondensation.

In formulas (a-7) and (a-8), R ¹ , R ² , and D have the same meanings as above. R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 10 carbon atoms, X ¹ and X ² each independently represent a halogen atom, and p and q each independently represent an integer of 0 to 3. The plurality of R ⁴ , R ⁵ , and the plurality of X ¹ , X ² systems may be the same or different from each other.

Examples of the alkyl group having 1 to 10 carbon atoms of R ⁴ and R ⁵ include the same ones as those already shown as the alkyl group having 1 to 10 carbon atoms of R ² . Examples of the halogen atom of X ¹ and X ² include a chlorine atom and a bromine atom.

As the silane compound (1), CF ₃ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ Si(OCH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ (C ₆ H ₄ )Si( OCH ₃ ) ₃ (4-(trifluoromethyl)phenyltrimethoxysilane), CF ₃ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ (C ₆ H ₄ )Si(OCH ₂ CH ₃ ) ₃ , 4-(trifluoromethyl)phenyl triethoxysilane, etc. Fluoroalkyl trialkoxysilane compounds; CF ₃ SiCl(OCH ₃ ) ₂ , CF ₃ CF ₂ SiCl(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ SiCl(OCH ₃ ) ₂ , CF ₃ SiBr(OCH ₃ ) ₂ , CF ₃ CF ₂ SiBr(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ SiBr(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ SiCl(OCH ₃ ) ₂ , CF ₃ CH ₂ CH ₂ SiCl (OCH ₃ ) ₂ 、CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₃ ) ₂ , CF ₃ (C ₆ H ₄ ) SiCl(OCH ₃ ) ₂ , 4-(trifluoromethyl)phenylchlorodimethoxysilane, CF ₃ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ SiCl(OCH ₂ CH ₃ ) ₂ 、CF ₃ CH ₂ CH ₂ SiCl(OCH ₂ CH ₃ ) ₂ 、CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₂ CH ₃ ) ₂ 、CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ (C ₆ H ₄ ) SiCl (OCH ₂ CH ₃ ) ₂ , 4-(trifluoromethyl)phenylchlorodiethoxysilane and other fluoroalkyl halide dialkoxysilane compounds; CF ₃ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ CF ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ SiCl ₂ (OCH ₃ ), CF ₃ CH ₂ CH ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₃ ), CF ₃ (C ₆ H ₄ ) SiCl ₂ (OCH ₃ ), 4-(trifluoromethyl)phenyldichloromethoxysilane , CF ₃ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CF ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CF ₂ CF ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CH ₂ CH ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ (C ₆ H ₄ ) SiCl ₂ (OCH ₂ CH ₃ ), 4-(trifluoromethyl)phenyldichloroethoxysilane and other fluoroalkyl dihalo alkoxysilane compounds; CF ₃ SiCl ₃ , CF ₃ CF ₂ SiCl ₃ , CF ₃ SiBr ₃ , CF ₃ CF ₂ SiBr ₃ , CF ₃ CF ₂ CF ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ SiCl ₃ , CF ₃ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ (C ₆ H ₄ ) SiCl ₃ , 4-trifluoromethyl phenyl trichlorosilane, CF ₃ SiCl ₃ , CF ₃ CF ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ SiCl ₃ , CF ₃ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ (C ₆ H ₄ ) SiCl _3. Fluoroalkyl trihalosilane compounds such as 4-(trifluoromethyl)phenyltrichlorosilane. The silane compound (1) can be used individually by 1 type or in combination of 2 or more types. Among these, as the silane compound (1), what is contained in the fluoroalkyltrialkoxysilane compound is preferable.

Examples of the silane compound (2) include methyl trimethoxy silane, methyl triethoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, ethyl tripropoxy silane, n-propyl Trimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n- Alkyl trialkoxysilane compounds such as pentyltrimethoxysilane, n-hexyltrimethoxysilane, and isooctyltriethoxysilane;

Methylchlorodimethoxysilane, methylchlorodiethoxysilane, methyldichloromethoxysilane, methylbromodimethoxysilane, ethylchlorodimethoxysilane, ethylchlorodiethyl Oxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane, n-propylchlorodimethoxysilane, n-propyldichloromethoxysilane, n-butylchlorodimethoxysilane Alkyl halide alkoxy silane compounds such as silane and n-butyl dichloromethoxy silane;

Methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, ethyltribromosilane, n-propyltrichlorosilane, n-propyltribromosilane, n-butyltrichlorosilane, isobutyltrichlorosilane Alkyl trihalosilane compounds such as chlorosilane, n-pentyl trichlorosilane, n-hexyl trichlorosilane, isooctyl trichlorosilane, etc. Silane compounds (series 21 can be used alone or in combination of two or more. Among these, as the silane compound (2), what is contained in alkyltrialkoxysilane compounds is preferable.

The method of polycondensing the silane compound is not particularly limited, and a conventional method can be used. However, since the production system of the curable polysilsesquioxane compound (A) has the following problems, it is necessary to study the reaction conditions in particular.

One of the problems in the production of the curable polysilsesquioxane compound (A) is disclosed in Patent Document 4 mentioned above. That is, when looking at Table 1 of Patent Document 4, it is found that as the use ratio of the fluoroalkyl group-containing silane compound increases, the resulting polymer tends to have a lower molecular weight. As such, because the reactivity of the silane compound (1) is greatly different from the reactivity of the silane compound (2), it is difficult to directly use the previous knowledge about the polycondensation reaction of the silane compound (2) to satisfy the necessary conditions 1 And the curable polysilsesquioxane compound of necessary condition 2.

In the examples of Patent Document 4, a polycondensation reaction is actually performed using a compound having a fluoroalkyl silane to produce a polymer. However, as described above, in the production method described in this document, the mixing ratio of the silane compound used in the reaction greatly affects the reaction, so the molecular weight of the polymer cannot be controlled. In addition, as described later, although the reaction conditions described in the Examples of Patent Document 4 can be used as monomers with poor reactivity (silane compounds having a fluoroalkyl group), even if the reaction conditions are used, It was also difficult to obtain a curable polysilsesquioxane compound that satisfies requirement 1 and requirement 2 (Comparative Examples 1 to 3).

The inventors of the present invention conducted studies on the polycondensation reaction using the silane compound (1), and found that by taking time to carry out the polycondensation reaction under milder conditions, it is possible to obtain those that satisfy the requirements 1 and 2 Curing polysilsesquioxane compound. Specifically, after the polycondensation reaction of the silane compound is carried out in a solvent or without a solvent and an appropriate amount of acid catalyst is used at a predetermined temperature to obtain a reaction solution containing a production intermediate, an alkali is added to neutralize the reaction solution, and The curable polysilsesquioxane compound (A) can be produced by performing a polycondensation reaction.

Examples of solvents include water; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; acetone, methyl Ketones such as ethyl ketone, methyl isobutyl ketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, tertiary butanol, etc. The alcohols and so on. These solvent systems can be used individually by 1 type or in combination of 2 or more types. When the solvent is used, the amount used is usually 0.001 to 10.000 liters per 1 mol of the total mol of the silane compound, preferably 0.010 to 0.9 liters.

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 them, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid is preferred. The usage amount of the acid catalyst is relative to the total mol amount of the silane compound, usually 0.01 to 2.00 mol%, preferably 0.05 to 1.00 mol%, and more preferably in the range of 0.10 to 0.30.

The reaction temperature of the reaction in the presence of an acid catalyst is usually 20 to 90°C, preferably 25 to 80°C. The reaction time of the reaction in the presence of an acid catalyst is usually 1 to 48 hours, preferably 3 to 24 hours.

The mass average molecular weight (Mw) of the production intermediate obtained by the reaction in the presence of an acid catalyst is usually 800 to 5,000, preferably 1,200 to 4,000.

The base used when neutralizing the reaction solution includes ammonia; trimethylamine, triethylamine, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, aniline, picoline , 1,4-diazabicyclo[2.2.2]octane, imidazole and other organic bases; tetramethylammonium hydroxide, tetraethylammonium hydroxide and other organic salt hydroxides; sodium methoxide, ethoxylation Metal alkoxides such as sodium, 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; carbonic acid Metal carbonates such as sodium, potassium carbonate and magnesium carbonate; metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, etc.

The amount of the alkali used in the reaction solution is usually 0.01 to 2.00 mol%, preferably 0.05 to 1.00 mol%, and more preferably in the range of 0.10 to 0.70 relative to the total mol of the silane compound. In addition, the amount (mol) of the alkali used in the reaction solution is preferably 0.5 to 5.0 times the amount (mol) of the acid catalyst used in step 1, and preferably 0.8 to 3.0 times, More preferably, it is 1.0 to 2.0 times. The pH of the neutralized reaction liquid is usually 6.0 to 8.0, preferably 6.2 to 7.0, and more preferably 6.4 to 6.9.

The reaction temperature of the reaction after neutralization is usually 40 to 90°C, preferably 50 to 80°C. The reaction time of the reaction after neutralization is usually 20 to 200 minutes, preferably 30 to 150 minutes.

In the above-mentioned production method, the main purpose of the reaction in the presence of an acid catalyst is hydrolysis, and the main purpose of the reaction system after neutralization is dehydration and condensation. By proceeding the polycondensation reaction of the silane compound in this way, the target curable polysilsesquioxane compound (A) can be produced efficiently.

After the reaction is completed, a conventional refining treatment can be performed to isolate the curable polysilsesquioxane compound (A).

The curable polysilsesquioxane compound of the present invention has a repeating unit having a fluoroalkyl group, has sufficient reactivity, and has a relatively large molecular weight. Such a curable polysilsesquioxane compound is useful as a curable component of a curable composition having excellent curability and a low refractive index.

2) Hardening composition The curable composition of the present invention is characterized by containing the following (A) component and a solvent having a boiling point of 254°C or higher (hereinafter, it may be described as "solvent (S1)"). (A) Component: The curable polysilsesquioxane compound of the present invention (curable polysilsesquioxane compound (A))

In the curable composition of the present invention, the curable polysilsesquioxane compound (A) can be used alone or in combination of two or more types.

The content of the curable polysilsesquioxane compound (A) in the curable composition of the present invention is based on the total solid content of the curable composition, usually 40 to 80% by mass, preferably 50 to 70 quality%.

The boiling point of the solvent (S1) is above 254°C, preferably 254~300°C. Here, the boiling point refers to the boiling point at 1013 hPa (the same in this specification).

The solvent (S1) is not particularly limited as long as it has a boiling point of 254°C or higher and can dissolve the curable polysilsesquioxane compound (A). This solvent (S1) has a slower volatilization rate. Therefore, even if the curable composition containing the solvent (S1) is left for a long time after application, the viscosity change is small, and therefore optical elements and the like can be assembled well just after application.

As the solvent (S1), specifically, tripropylene glycol n-butyl ether (boiling point 274°C), 1,6-hexanediol diacrylate (boiling point 260°C), diethylene glycol dibutyl ether (boiling point 256 ℃), triethylene glycol butyl methyl ether (boiling point 261℃), polyethylene glycol dimethyl ether (boiling point 264~294℃), tetraethylene glycol dimethyl ether (boiling point 275℃), polyethylene glycol monomethyl ether (Boiling point, 290~310℃) etc. Among these, as the solvent (S1), from the viewpoint of obtaining the effects of the present invention more easily, tripropylene glycol n-butyl ether and 1,6-hexanediol diacrylate are preferred. The solvent (S1) can be used individually by 1 type or in combination of 2 or more types.

The curable composition of the present invention may contain a solvent other than the solvent (S1). As a solvent other than the solvent (S1), a solvent having a boiling point of 200° C. or higher and less than 254° C. (hereinafter referred to as "solvent (S2)") is preferred. The solvent (S2) is not particularly limited as long as it has a boiling point of 200°C or higher and less than 254°C and can dissolve the curable polysilsesquioxane compound (A). By using the solvent (S1) and the solvent (S2) together, the curability of the curable composition is improved.

Specific examples of the solvent (S2) include diethylene glycol monobutyl ether acetate (boiling point 247°C), dipropylene glycol n-butyl ether (boiling point 229°C), benzyl alcohol (boiling point 204.9°C), and dipropylene glycol methyl ether. Ether acetate (boiling point 209℃), diethylene glycol butyl methyl ether (boiling point 212℃), dipropylene glycol n-propyl ether (boiling point 212℃), tripropylene glycol dimethyl ether (boiling point 215℃), triethylene glycol two Methyl ether (boiling point 216°C), diethylene glycol monoethyl ether acetate (boiling point 217.4°C), diethylene glycol n-butyl ether (boiling point 230°C), ethylene glycol monophenyl ether (boiling point 245°C), tripropylene glycol Methyl ether (boiling point 242°C), propylene glycol phenyl ether (boiling point, 243°C), triethylene glycol monomethyl ether (boiling point 249°C), etc. Among them, as the solvent (S2), because it is easy to obtain its effect, the glycol-based solvent is preferred, diethylene glycol monobutyl ether acetate and dipropylene glycol n-butyl ether are preferred, and diethylene glycol Alcohol monobutyl ether acetate is preferred.

When solvent (S1) and solvent (S2) are used together, specifically, it is a combination of tripropylene glycol n-butyl ether (solvent (S1)) and diethylene glycol monobutyl ether acetate (solvent (S2)), 1, Combination of 6-hexanediol diacrylate (solvent (S1)) and diethylene glycol monobutyl ether acetate (solvent (S2)), tripropylene glycol n-butyl ether (solvent (S1)) and dipropylene glycol n-butyl The combination of ether (solvent (S2)), 1,6-hexanediol diacrylate (solvent (S1)) and dipropylene glycol n-butyl ether (organic solvent (S2)) are preferred.

The curable composition of the present invention contains a solvent having a solid content concentration of preferably 50 to 95% by mass, more preferably 60 to 85% by mass. When the solid content concentration is within this range, the effect of the solvent (S1) or the solvent (S2) can be sufficiently exhibited.

The total amount of solvent (S1) and solvent (S2) contained in the curable composition of the present invention is usually 50-100% by mass, preferably 70-100% by mass, more preferably 90% relative to the total solvent. ~100% by mass. The content of the solvent (S1) contained in the curable composition of the present invention is relative to the total amount of the solvent (S1) and the solvent (S2), usually 20-100% by mass, preferably 30-85% by mass, More preferably, it is 50 to 80% by mass. The curable composition containing the solvent (S1) or the solvent (S2) at such a ratio is a thing that can appropriately balance the adhesiveness and the wetness expandability (characteristics related to the expansion of droplets described later).

The curable composition of the present invention may also contain a silane coupling agent having a nitrogen atom in the molecule (hereinafter, it may be described as "silane coupling agent (B)") as the (B) component.

The curable composition containing the silane coupling agent (B) has excellent workability in the coating step and provides a cured product with more excellent adhesion, peel resistance, and heat resistance. Here, the excellent workability in the coating step refers to a situation in which the amount of wire drawing is small or is immediately interrupted when the curable composition is discharged from the discharge tube in the coating step and then the discharge tube is raised. By using a curable composition with this property, it is possible to prevent the pollution of the surroundings caused by resin splashing and droplet expansion.

The silane coupling agent (B) is not particularly limited as long as it has a nitrogen atom in the molecule. For example, a trialkoxysilane compound represented by the following formula (b-1), a dialkoxyalkylsilane compound or a dialkoxyarylsilane compound represented by the formula (b-2), etc. can be mentioned.

In the above formulas, R ^a represents methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy and other alkoxy having 1 to 6. Plural R ^a may be identical or different from each other. R ^b represents a C1-C6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, etc.; or phenyl, 4-chlorophenyl, 4-methylbenzene Substituent or unsubstituted aryl groups, such as phenyl group and 1-naphthyl group.

R ^c represents an organic group having 1 to 10 carbon atoms with a nitrogen atom. In addition, R ^c may be further bonded to groups containing other silicon atoms. Specific examples of the organic group having 1 to 10 carbon atoms in R ^c include N-2-(aminoethyl)-3-aminopropyl, 3-aminopropyl, N-(1,3-dimethyl -Butylene) aminopropyl, 3-ureapropyl, N-phenyl-aminopropyl, etc.

Among the compounds represented by the above formula (b-1) or (b-2), when R ^c is an organic group formed by bonding with a group containing other silicon atoms, examples include heterocyanuric cyanide An acid ester skeleton is bonded with other silicon atoms to form an isocyanurate-based silane coupling agent, or through a urea skeleton to bond with other silicon atoms to form a urea-based silane coupling agent.

Among them, as the silane coupling agent (B), since it is easy to obtain a cured product with higher bonding strength, the isocyanurate-based silane coupling agent and the urea-based silane coupling agent are preferred. It is preferable to have 4 or more alkoxy groups bonded to silicon atoms. The so-called having 4 or more alkoxy groups bonded to silicon atoms means that the total count of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is 4 or more .

As an isocyanurate-based silane coupling agent having 4 or more alkoxy groups bonded to a silicon atom, a compound represented by the following formula (b-3) can be mentioned; as having 4 or more bonds The urea-based silane coupling agent of the alkoxy group bound to the silicon atom includes a compound represented by the following formula (b-4).

Wherein, R ^a represents the same meaning as described above. t1 to t5 each independently represent an integer of 1 to 10, preferably an integer of 1 to 6, and particularly preferably 3.

As specific examples of the compound represented by the formula (b-3), 1,3,5-N-para(3-trimethoxysilylpropyl) isocyanurate, 1,3,5, -N-ginseng (3-triethoxysilylpropyl) isocyanurate, 1,3,5,-N-ginseng (3-triisopropyloxysilylpropyl) isocyanurate , 1,3,5,-N-parameter (3-tributoxysilylpropyl) isocyanurate and other 1,3,5-N-parameter [(three (carbon number 1~6) alkane (Oxy) silyl group (carbon number 1~10) alkyl] isocyanurate; 1,3,5,-N-parameter (3-dioxymethylsilylpropyl) isocyanuric acid Esters, 1,3,5,-N-ginseng (3-dimethoxyethylsilylpropyl) isocyanurate, 1,3,5,-N-ginseng (3-dimethoxy Isopropylsilylpropyl) isocyanurate, 1,3,5,-N-ginseng (3-dimethoxy n-propylsilylpropyl) isocyanurate, 1,3 ,5,-N-(3-Dimethoxyphenylsilylpropyl) isocyanurate, 1,3,5,-N-(3-diethoxymethylsilylpropyl) Group) isocyanurate, 1,3,5,-N-parameter (3-diethoxyethylsilylpropyl) isocyanurate, 1,3,5,-N-parameter (3-diethoxy isopropylsilyl propyl) isocyanurate, 1,3,5,-N-ginseng (3-diethoxy n-propylsilyl propyl) isotrimer Cyanate ester, 1,3,5,-N-parameter (3-diethoxyphenylsilylpropyl) isocyanurate, 1,3,5,-N-parameter (3-diisocyanate Propoxymethylsilylpropyl) isocyanurate, 1,3,5,-N-ginseng (3-diisopropoxyethylsilylpropyl) isocyanurate, 1 ,3,5,-N-ginseng (3-diisopropoxyisopropylsilylpropyl) isocyanurate, 1,3,5,-N-ginseng (3-diisopropoxy N-Propylsilylpropyl) isocyanurate, 1,3,5,-N-ginseng (3-diisopropoxyphenylsilylpropyl) isocyanurate, 1,3 ,5,-N-(3-dibutoxymethylsilylpropyl) isocyanurate, 1,3,5,-N-(3-dibutoxyethylsilylpropyl) Group) isocyanurate, 1,3,5,-N-ginseng (3-dibutoxyisopropylsilylpropyl) isocyanurate, 1,3,5,-N- Ginseng (3-dibutoxy n-propylsilylpropyl) isocyanurate, 1,3,5,-N-ginseng (3-dibutoxyphenyl silyl propyl) isotrimer 1,3,5-N-parameter [(bis(carbon number 1~6)alkoxy)silyl group (carbon number 1~10)alkyl]isocyanurate etc. such as cyanate ester.

As specific examples of the compound represented by formula (b-4), N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilyl) Propyl)urea, N,N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, N,N'-bis( N,N'-bis[(tris(carbon number 1~6)alkoxysilyl)(carbon number 1~10)alkyl]urea such as 2-trimethoxysilylethyl)urea; N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, N,N'-bis (3-diethoxymethylsilylpropyl)urea and other N,N'-bis((bis(carbon number 1~6) alkoxy (carbon number 1~6) alkylsilyl group (carbon number 1~10) Alkyl) urea; N,N'-bis(3-dimethoxyphenylsilylpropyl)urea, N,N'-bis(3-diethoxyphenylsilylpropyl)urea and other N,N'- Bis[(Di(C1~6)alkoxy(C6~20)arylsilyl(C1~10)alkyl)urea etc. The silane coupling agent (B) can be used individually by 1 type or in combination of 2 or more types.

Among them, as the silane coupling agent (B), 1,3,5-N-(3-trimethoxysilylpropyl) isocyanurate, 1,3,5-N- Ginseng (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 above isocyanurate compound and urea compound are preferred.

When the above isocyanurate compound and urea compound are used in combination, the use ratio of the two is the mass ratio of (isocyanurate compound) and (urea compound), 100:1~100:200 Best, preferably 100:10~100:110. By using this ratio in combination with the isocyanurate compound and the urea compound, it is possible to obtain a curable composition that provides a cured product with higher adhesive strength and better heat resistance.

When the curable composition of the present invention contains the silane coupling agent (B) [(B) component], the content of (B) component is not particularly limited, and the amount is the mass ratio of the above-mentioned (A) component and (B) component [(A) component: (B) component], good is 100:0.1~100:90, preferably 100:0.3~100:60, preferably 100:1~100:50, more preferably 100:3 ~100:40, it is particularly good to be 100:5~100:30. The cured product of the curable composition containing the (A) component and the (B) component at such a ratio becomes a product with higher adhesive strength and better heat resistance.

The curable composition of the present invention may also contain a silane coupling agent having an acid anhydride structure in the molecule (hereinafter, it may be described as "silane coupling agent (C)") as the (C) component. The curable composition containing the silane coupling agent (C) has excellent workability in the coating step and provides a cured product with higher adhesion strength and better peel resistance and heat resistance.

Examples of the silane coupling agent (C) include 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, and 3-(trimethoxysilyl)propyl succinic anhydride. Acid anhydride, 3-(triethoxysilyl) propyl succinic anhydride, etc. Tris (carbon number 1~6) alkoxysilyl (carbon number 2~8) alkyl succinic anhydride; 2-(dimethoxymethyl Di (carbon number 1~6) alkoxymethylsilyl group (carbon number 2~8) alkyl succinic anhydride; 2-(methoxydimethylsilyl) ethyl (Carbon number 1~6) alkoxy dimethylsilyl group (carbon number 2~8) alkyl succinic anhydride such as succinic anhydride;

2-(Trichlorosilyl) ethyl succinic anhydride, 2-(tribromosilyl) ethyl succinic anhydride, etc. Trihalosilyl (carbon number 2~8) alkyl succinic anhydride; 2-(Dichloromethane Dihalomethylsilyl (carbon number 2~8) alkyl succinic anhydride such as ethyl silyl) ethyl succinic anhydride; halo dimethyl such as 2-(chlorodimethylsilyl) ethyl succinic anhydride Silyl group (carbon number 2-8) alkyl succinic anhydride, etc. The silane coupling agent (C) can be used individually by 1 type or in combination of 2 or more types.

Among them, as the silane coupling agent (C), tris(carbon number 1~6) alkoxysilyl (carbon number 2~8) alkyl succinic anhydride is preferred, and 3-(trimethoxysilyl) Propyl succinic anhydride or 3-(triethoxysilyl) propyl succinic anhydride is particularly preferred.

When the curable composition of the present invention contains a silane coupling agent (C) [(C) component], the content of (C) component is not particularly limited, and the amount is the mass ratio of the above-mentioned (A) component to (C) component [(A) component: (C) component], good is 100:0.1~100:30, preferably 100:0.3~100:20, preferably 100:0.5~100:15, more preferably 100: 1~100: 10 amount. The cured product of the curable composition containing the component (C) in such a ratio has a higher adhesive strength.

The curable composition of the present invention may contain fine particles having an average primary particle diameter of 5 to 40 nm (in the following, they may be described as "fine particles (D)") as the (D) component. The curable composition containing fine particles (D) has excellent workability in the coating step. Because this effect is easier to obtain, the average primary particle size of the fine particles (D) is preferably 5-30 nm, more preferably 5-20 nm.

The average primary particle size of the particles (D) can be obtained by observing the shape of the particles using a transmission electron microscope.

The specific surface area of the fine particles (D) is preferably 10 to 500 m ² /g, more preferably 20 to 300 m ² /g. When the specific surface area is in the above range, it is easy to obtain a curable composition having more excellent workability in the coating step. The specific surface area can be obtained using the BET multipoint method.

The shape of the particles (D) may be any of spherical, chain-like, needle-like, plate-like, sheet-like, rod-like, and fiber-like shapes, and a spherical shape is preferred. Here, the term “spherical shape” means that in addition to a true spherical shape, it can also include a polyhedral shape that can approximate a spherical shape, such as a spheroid, an oval shape, a sugar spherical shape, and a cocoon shape.

The constituent components of the fine particles (D) are not particularly limited, and examples include metals; metal oxides; minerals; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; aluminum hydroxide Metal hydroxides such as aluminum silicate, calcium silicate, and magnesium silicate; inorganic components such as silicon oxide; polysiloxane; organic components such as acrylic polymers. In addition, the microparticles (D) used may be those whose surface has been modified.

The so-called metal refers to the periodic table in Group 1 (except H), 2-11, 12 (except Hg), 13 (except B), 14 (except C and Si), Group 15 (except N, P, As, and Sb), or group 16 (except O, S, Se, Te, and Po) elements.

Examples of metal oxides include titanium oxide, aluminum oxide, boehmite, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, zinc oxide, and these composite oxides. . The fine particles of metal oxides also include sol particles composed of the metal oxides.

Examples of minerals include smectite and bentonite. As the bentonite, for example, montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, zinc montmorillonite Sauconite and so on. Examples of silica include dry silica, wet silica, and surface-modified silica (silicon oxide with a modified surface).

The fine particle (D) system can be used individually by 1 type or in combination of 2 or more types. Among them, since it is easy to obtain a cured product with excellent transparency, as the fine particles (D), silicon oxide, metal oxide, and mineral are preferred, and silicon oxide is preferred.

Among silica, since it is easy to obtain a curable composition having better workability in the coating step, surface-modified silica is preferred, and hydrophobic surface-modified silica is preferred. Examples of hydrophobic surface-modified silica include three trialkylsilyl groups with 1-20 carbon atoms, such as trimethylsilyl group, and two alkylsilane groups with 1-20 carbon atoms, such as dimethylsilyl group. Group; Silicon oxide formed by bonding alkylsilyl groups with 1-20 carbon atoms such as octylsilyl group on the surface; and silicon oxide formed by treating the surface with polysiloxane oil. The hydrophobic surface-modified silica system can be used, for example, by using three trialkylsilyl groups with 1 to 20 carbons, two alkylsilyl groups with 1 to 20 carbons, and alkylsilanes with 1 to 20 carbons. It can be obtained by surface modification of silica particles with silane coupling agent such as base, or treatment of silica particles with silicone oil. In addition, it is also possible to directly use commercially available surface-modified silica.

When the curable composition of the present invention contains fine particles (D) [(D) component], the content of (D) component is not particularly limited, and the amount is the mass ratio of the above-mentioned (A) component to (D) component [( A) component: (D) component], good is 100:0.1~100:90, preferably 100:0.2~100:60, preferably 100:0.3~100:50, preferably 100:0.5~100 : 40, preferably 100:0.8~100:30. By using the component (D) in the above range, the effect of adding the component (D) can be further expressed.

The curable composition of the present invention may contain fine particles having an average primary particle diameter of more than 0.04 μm and 8 μm or less (hereinafter, described as "fine particles (E)") as the (E) component. By using a curable composition containing fine particles (E), a cured product with excellent peel resistance can be formed. Since this effect is easier to obtain, the average primary particle size of the fine particles (E) is preferably 0.06-7 μm, preferably 0.3-6 μm, and more preferably 0.5-4 μm.

The average primary particle size of the particles (E) can be determined by using a laser diffraction and scattering particle size distribution measuring device (for example, manufactured by Horiba Co., Ltd., product name "LA-920"), etc., by laser scattering It is determined by measuring the particle size distribution.

The shape of the fine particles (E) may be any of spherical, chain-like, needle-like, plate-like, sheet-like, rod-like, and fiber-like shapes, and a spherical shape is preferred. Here, the term “spherical shape” means that in addition to a true spherical shape, it can also include a polyhedral shape that can approximate a spherical shape, such as a spheroid, an oval shape, a sugar spherical shape, and a cocoon shape.

As the structural component of the microparticle (E), the same thing as exemplified as the structural component of the microparticle (D) can be mentioned. The microparticle (E) system can be used individually by 1 type or in combination of 2 or more types. Among them, because the above-mentioned effects are easily obtained, as the particles (E), at least one kind of particles selected from the group consisting of metal oxides, silicon oxides and polysiloxanes coated on the surface of polysiloxy is preferably used. Silicon oxide and polysiloxane are preferred.

When the curable composition of the present invention contains fine particles (E) [(E) component], the content of (E) component is not particularly limited, and the amount is the mass ratio of (A) component to (E) component [(A) ) Ingredient: (E) Ingredient], good is 100:0.1~100:40, preferably 100:0.2~100:30, preferably 100:0.3~100:20, preferably 100:0.5~100: 15. It is better to be 100:0.8~100:12. By using the component (E) in the above range, the effect of adding the component (E) can be further expressed.

The curable composition of the present invention may contain other components ((F) component) other than the above-mentioned (A) to (E) components within a range that does not hinder the purpose of the present invention. As (F) component, antioxidant, ultraviolet absorber, light stabilizer, etc. are mentioned.

The antioxidant is added in order to prevent oxidative deterioration during heating. Examples of antioxidants include phosphorus-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

Examples of phosphorus-based antioxidants include phosphites, oxa phosphaphenanthrene oxides, and the like. Examples of phenolic antioxidants include monophenols, bisphenols, and polymer phenols. Examples of sulfur-based antioxidants include 3,3'-thiodipropionate dilauryl ester, 3,3'-thiodipropionate dimyristate, 3,3'-thiodipropionate distearate Fatty acid esters and so on.

These antioxidants can be used individually by 1 type or in combination of 2 or more types. The amount of antioxidant used is usually 10% by mass or less with respect to (A) component.

The ultraviolet absorber is added in order to improve the light resistance of the obtained cured product. Examples of ultraviolet absorbers include salicylic acids, diphenylketones, benzotriazoles, hindered amines, and the like. The ultraviolet absorber system can be used individually by 1 type or in combination of 2 or more types. The amount of the ultraviolet absorber used is usually 10% by mass or less with respect to the component (A).

The light stabilizer is added for the purpose of improving the light resistance of the obtained cured product. As the light stabilizer, for example, poly[{6-(1,1,3,3,-tetramethylbutyl)amine-1,3,5-triazine-2,4-diyl}{( 2,2,6,6-Tetramethyl-4-piperidine)imine}hexamethylene{(2,2,6,6-tetramethyl-4-piperidine)imine}] etc. are hindered Amines, etc. These light stabilizers can be used individually by 1 type or in combination of 2 or more types. The total usage amount of (F) component is usually 20% by mass or less with respect to (A) component.

The curable composition of the present invention can be prepared, for example, by mixing the above-mentioned (A) component, the solvent (S1), and components other than these as necessary at a predetermined ratio and degassing. The mixing method and degassing method are not particularly limited, and conventional methods can be used.

The curable composition of the present invention contains a curable polysilsesquioxane compound (A). Therefore, the curable composition system of the present invention has excellent curability and a low refractive index. In addition, the curable composition system of the present invention is useful as a material for forming a cured product with high adhesive strength.

The refractive index (nD) of the curable composition of the present invention at 25°C is usually 1.380 to 1.434, preferably 1.380 to 1.430, preferably 1.380 to 1.428, and more preferably 1.380 to 1.425. The refractive index (nD) of the curable composition can be measured using the method described in the examples.

Furthermore, the curable composition system of this invention contains a solvent (S1). Therefore, even after the curable composition system of the present invention is left to stand for a long time after application, operations such as assembly of optical elements can be performed in the same manner as immediately after application. For example, after the curable composition system of the present invention is applied, even after 20 minutes or more, preferably 30 minutes or more, and more preferably 60 minutes or more, the same operation as immediately after the application can be performed.

3) Hardening The cured product of the present invention is obtained by curing the curable composition of the present invention. As a method of curing the curable composition of the present invention, heat curing can be cited. The heating temperature for curing is usually 100~200°C, and the heating time is usually from 10 minutes to 20 hours, preferably from 30 minutes to 10 hours.

The cured product of the present invention is a product with high adhesive strength and excellent heat resistance. The cured product of the present invention has these characteristics, for example, it can be confirmed as follows. That is, the curable composition of the present invention is coated on the mirror surface of the silicon wafer in a predetermined amount, the coated surface is placed on the adherend, and pressure bonding and heat treatment are performed to harden it. Place it on the measuring stage of a bond tester (bond tester) preheated to a predetermined temperature (for example, 23°C, 100°C) for 30 seconds, at a height of 50μm from the object to be bonded, facing the adhesive surface Stress is applied in the horizontal direction (shear direction) to measure the adhesion between the test piece and the substrate.

The adhesive force of the cured product of the present invention is preferably 60N/4mm ² or more at 23°C, preferably 80N/4mm ² or more, and particularly preferably 100N/4mm ² or more. In addition, the adhesive force of the cured product at 100°C is preferably 30N/4mm ² or more, preferably 40N/4mm ² or more, more preferably 50N/4mm ² or more, and particularly preferably 60N/4mm ² or more. In this specification, "4mm ² "means 2mm×2mm (one side is a square of 2mm).

Because of the above-mentioned characteristics, the cured product system of the present invention can be suitably used as an optical element fixing material.

4) How to use the 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 agent for an optical element fixing material. Examples of optical elements include light-emitting elements such as LEDs and LDs, light-receiving elements, composite optical elements, and optical integrated circuits.

>Adhesives for optical element fixing materials> The curable composition system of this invention can be used suitably as an adhesive agent for optical element fixing materials. As a method of using the curable composition of the present invention as an adhesive for an optical element fixing material, the composition is applied to one or both of the adhesive surfaces of the material (optical element and its substrate, etc.) to be adhered. After pressure bonding, it is a method to heat and harden the materials to be bonded to each other firmly. The coating amount of the curable composition of the present invention is not particularly limited, and it is sufficient to harden the materials to be bonded to each other firmly. Generally, the thickness of the coating film of the curable composition is 0.5 to 5 μm, preferably 1 to 3 μm.

As the substrate material for bonding optical elements, glass such as soda lime glass and heat-resistant hard glass; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium and such metals Alloys, stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.) and other metals; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate Copolymer, polystyrene, polycarbonate, polymethylpentene, polyether, polyetheretherketone, polyetherether, polyphenylene sulfide, polyetherimine, polyimide, polyimide Synthetic resins such as amide, acrylic resin, norbornene resin, cycloolefin resin, glass epoxy resin, etc.

The heating temperature when heat-curing is also dependent on the curable composition used, and is usually 100 to 200°C. The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

>Sealant for optical element fixing material> The curable composition system of the present invention can be suitably used as a sealant for an optical element fixing material. As a method of using the curable composition of the present invention as a sealant for an optical element fixing material, for example, after molding the composition into a desired shape to obtain a molded body encapsulating an optical element, by making the composition The material is heated and hardened to manufacture the optical element sealing body. The method for molding the curable composition of the present invention into a desired shape is not particularly limited, and conventional molding methods such as a general transfer molding method and a casting method can be used.

The heating temperature during heat curing also depends on the curable composition used, etc., and is usually 100 to 200°C. The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

Since the obtained optical element sealing system uses the curable composition of the present invention, it has excellent heat resistance and high adhesive strength. [Example]

Hereinafter, the present invention will be explained in more detail with examples. However, the present invention is not limited by the following examples at all. The parts and% in each example are quality standards unless notified in advance.

(Example 1) After adding 17.0 g (77.7 mmol) of 3,3,3-trifluoropropyltrimethoxysilane and 32.33 g (181.3 mmol) of methyltriethoxysilane to a 300 mL eggplant type flask, An aqueous solution obtained by dissolving 0.0675 g of 35% hydrochloric acid (the amount of HCl is 0.65 mmol and the total amount of the silane compound is 0.25 mol%) in 14.0 g of distilled water was added while stirring, and the whole content was stirred at 30°C. It was heated to 70°C and stirred for 20 hours. While continuing to stir the contents, a mixed solution of 0.0394 g of 28% ammonia water (amount of NH ₃ 0.65 mmol) and 46.1 g of propyl acetate was added here to make the pH of the reaction liquid 6.9, and the mixture was stirred at 70° C. for 60 minutes. After the reaction liquid was allowed to cool to room temperature, 50 g of propyl acetate and 100 g of water were added here to perform liquid separation treatment to obtain an organic layer containing the reaction product. Magnesium sulfate was added to the organic layer to perform drying treatment. After the magnesium sulfate was separated by filtration and removed, the organic layer was concentrated using an evaporator, and then, the obtained concentrate was vacuum dried to obtain a curable polysilsesquioxane compound (1).

To 100 parts of the curable polysilsesquioxane compound (1), 20 parts of a silica filler having an average primary particle diameter of 7 nm and 10 parts of a polysiloxane filler having an average primary particle diameter of 0.8 μm were added. Furthermore, after adding 30 parts of a mixed solvent of diethylene glycol monobutyl ether acetate:tripropylene glycol n-butyl ether=40:60 (mass ratio) as a solvent, the entire contents were stirred. After dispersing treatment using a three-roll mill, add 30 parts of 1,3,5-N-parameter [3-(trimethoxysilyl)propyl] isocyanurate and 3-(trimethoxysilyl) propyl 3 parts of base succinic anhydride, and a mixed solvent of diethylene glycol monobutyl ether acetate:tripropylene glycol n-butyl ether=40:60 (mass ratio) as a solvent, and by fully mixing all the contents to remove To obtain a curable composition (1) having a solid content concentration of 82%.

(Example 2) Except that the stirring time after adding the mixed solution of 28% ammonia and propyl acetate was changed to 120 minutes, the same procedure as in Example 1 was carried out to obtain a curable polysilsesquioxane compound (2) and a curable combination物(2).

(Example 3) Except that the stirring time after adding the mixed solution of 28% ammonia and propyl acetate was changed to 90 minutes, the same procedure as in Example 1 was carried out to obtain a curable polysilsesquioxane compound (3) and a curable combination物(3).

(Example 4) A curable polysilsesquioxane compound (4) and curable combination were obtained in the same manner as in Example 1, except that the stirring time after adding the mixed solution of 28% ammonia and propyl acetate was changed to 50 minutes物(4).

(Example 5) A curable polysilsesquioxane compound (5) and curable combination were obtained in the same manner as in Example 1, except that the stirring time after adding the mixed solution of 28% ammonia and propyl acetate was changed to 40 minutes物(5).

(Comparative Example 1) The curable polysilsesquioxane compound (6) was obtained in accordance with the method of Example 8 of WO2017/110948. Next, to 100 parts of the curable polysilsesquioxane compound (6), 20 parts of a silica filler having an average primary particle size of 7 nm and 10 parts of a polysiloxane filler having an average primary particle size of 0.8 μm were added. And after adding 30 parts of diethylene glycol monobutyl ether acetate as a solvent, the whole content was stirred. After dispersing treatment using a three-roll mill, add 10 parts of 1,3,5-N-parameter [3-(trimethoxysilyl)propyl] isocyanurate and 3-(trimethoxysilyl) propyl 3 parts of base succinic anhydride, and the viscosity when measured under the conditions of 25°C and 200s ^-1 with an E-type viscometer becomes 4.5 Pa‧s of diethylene glycol monobutyl ether acetate, and the entire content is The hardenable composition (6) was obtained by thoroughly mixing and degassing. In addition, in the paragraph (0115) of WO2017/110948, the amount of hydrochloric acid used is described as "0.25 mol% relative to the total amount of the silane compound", but when calculated from the added amount, it is correct as "relative to the silane compound The total amount of is about 1.6mol%". The same applies to Comparative Examples 2 and 3 below.

(Comparative example 2) The curable polysilsesquioxane compound (7) was obtained according to the method of Example 9 of WO2017/110948. Next, the same method as in Comparative Example 1 was used to obtain a curable composition (7).

(Comparative example 3) The curable polysilsesquioxane compound (8) was obtained according to the method of Example 10 of WO2017/110948. Next, the same method as in Comparative Example 1 was used to obtain a curable composition (8).

(Comparative Example 4) After adding 71.37 g (400 mmol) of methyltriethoxysilane to a 300 mL eggplant-type flask, adding 0.1 g of 35% hydrochloric acid (relative to the total amount of the silane compound is 0.25 mol%) while stirring. ) An aqueous solution obtained by dissolving 21.6 g of distilled water, and stirring the entire content at 30°C for 2 hours, and then raising the temperature to 70°C and stirring for 5 hours. While continuing to stir the contents, 140 g of propyl acetate and 0.12 g of 28% ammonia water (with respect to the total amount of the silane compound, NH ₃ is 0.5 mol%) were added here, and the mixture was stirred at 70° C. for 3 hours. After cooling the reaction liquid to room temperature, the organic layer was washed with purified water until the pH of the water layer reached 7. The organic layer was concentrated using an evaporator and the concentrate was vacuum dried to obtain a curable polysilsesquioxane compound (9). Next, the same procedure as in Example 1 was used to obtain a curable composition (9).

(Comparative Example 5) A curable polysilsesquioxane compound (10) and curable combination were obtained in the same manner as in Example 1, except that the stirring time after adding the mixed solution of 28% ammonia and propyl acetate was changed to 240 minutes物(10).

Using the curable polysilsesquioxane compounds (1) to (10) and curable compositions (1) to (10) obtained in the examples and comparative examples, the following measurements and tests were performed, respectively. The results are shown in Table 1.

[Determination of mass average molecular weight] The mass average molecular weight (Mw) of the curable polysilsesquioxane compound is measured under the following equipment and conditions. Device name: HLC-8220GPC, TOSOH Corporation Column: Connect TSKgel GMHXL, TSKgelGMHXL, and TSKgel2000HXL in sequence Solvent: Tetrahydrofuran Standard material: Polystyrene Injection volume: 20μl Measuring temperature: 40℃ Flow rate: 0.6ml/min Detector: differential refractometer

[ ²⁹ Si-NMR measurement] Apparatus: AV-500 ²⁹ Si-NMR manufactured by Bruker BioSpin Co., Ltd. Resonance frequency: 99.352MHz Detector: 5mmϕ solution detector Measuring temperature: Room temperature (25°C) Sample revolution: 20kHz Measuring method: reverse Inverse gated decoupling method ²⁹ Si Flip angle: 90° ²⁹ Si 90° Pulse width: 8.0μs Repetition time: 5s Cumulative times: 9200 times Observation width: 30kHz

> ²⁹ Si-NMR sample manufacturing method> In order to shorten the relaxation time, Fe(acac) _{3 was added} as a relaxation reagent and measured. Polysilsesquioxane concentration: 15% Fe(acac) ₃ concentration: 0.6% Measurement solvent: Acetone Internal standard: TMS

>Waveform processing analysis> For each peak of the spectrum after Fourier transformation, the chemical shift is obtained and integrated according to the position of the peak top.

[Measurement of refractive index] The curable composition was discharged on a horizontal surface, and the refractive index (nD) was measured by pressing the measurement surface of a pen-type refractometer (manufactured by ATAGO, PEN-RI) at 25°C.

[Sclerosis Evaluation] Using a rheometer (manufactured by Anton Paar, MCR302) and using a 20 mm parallel plate, the shear stress was measured under the conditions of a test starting temperature of 80°C, a heating rate of 5°C/min, a shear strain of 1%, and a frequency of 1 Hz. The temperature at which the shear stress becomes 2000 Pa is the hardening temperature.

[Viscosity evaluation] A rheometer (manufactured by Anton Paar, MCR301) was used, and a cone and plate with a radius of 50 mm and a cone angle of 0.5° were used, and each was measured at 25° C., a shear rate of 2 s ^-1 , and The shear rate is 200s ^-1 viscosity. The thixotropy index (viscosity at a shear rate of 2 s ^-1 /viscosity at a shear rate of 200 s ^-1 ) was calculated from the obtained measured values.

[Measurement of Adhesive Strength] The curable composition was applied to the mirror surface of a square (4mm ² ) silicon wafer with a side of 2mm in thickness of about 2μm, and the coated surface was placed on the substrate ( Silver-plated copper plate) and pressure-bonded. Subsequently, heat treatment was performed at 170° C. for 2 hours and cured to obtain a substrate with a test piece. The substrate with the test piece was placed on the measuring stage of a bonding strength tester (manufactured by Dage Corporation, Series 4000) heated in advance at a predetermined temperature (23°C, 100°C) for 30 seconds, and the substrate Then, at a height of 100μm from the object, apply stress to the adhesive surface in a horizontal method (shear direction) at a speed of 200um/s to measure the adhesive strength between the test piece and the substrate at 23℃ and 100℃ (N/4mm ² ).

[Crack resistance evaluation] The curable composition was applied to the mirror surface of a square (area of 0.25 mm ² ) silicon wafer with a thickness of about 2 μm each with a thickness of 0.5 mm, and the coated surface was placed on On the substrate (silver-plated copper plate) and pressure-bonded. Subsequently, heat treatment was performed at 170° C. for 2 hours and cured to obtain a substrate with a test piece. Use a digital microscope (VHX-1000, manufactured by KEYENCE) to observe the resin part (fillet part) extruded from the glass wafer, and calculate the number of samples with cracks, and the crack generation rate is 0% or more And less than 25% is evaluated as "A", 25% and less than 50% are evaluated as "B", and 50% to 100% is evaluated as "C".

[Evaluation of resistance to peeling] The curable composition was coated on an LED lead frame (made by ENOMOTO, 5050D/G PKG LEADFRAME) at a thickness of about 0.4mmϕ, and pressure-bonded to a 0.5mm square ( A sapphire wafer with an area of 0.25mm ² ). Then, after heat treatment at 170°C for 2 hours to harden, a sealant (manufactured by Shin-Etsu Chemical Co., Ltd., LPS-3419) was poured into the cup and heated at 120°C for 1 hour and at 150°C for 1 hour to obtain a test piece. After exposing the test piece to an environment of 85°C and 85% RH for 168 hours, it was preheated at 160°C and the maximum temperature was 260°C with a heating time of 1 minute IR reflow (reflow oven: manufactured by Sagami Riko Co., product name " WL-15-20DNX type") for processing. Subsequently, a thermal cycle tester was used to set the test at -40°C and +100°C for 30 minutes each as 1 cycle and implement 500 cycles. Subsequently, the sealant removal operation was performed and it was investigated whether the components were peeled off together at this time. This test was performed 100 times for each curable composition. Count the number of times that the components peel off together. If the peel generation rate is less than 25%, it is evaluated as "A", if it is greater than 25% and less than 50%, it is evaluated as "B", and if it is greater than 50%, it is evaluated as "C".

[Table 1] Curing polysilsesquioxane compound Hardening composition Hardening Ratio of monomers containing F atoms [addition amount] Mass average molecular weight [Mw] ²⁹ Si-NMR measurement Refractive index Hardening [hardening temperature] Viscosity evaluation [thixotropy index] Adhesion strength (N/4mm ² ) Crack resistance Peel resistance Z2 value Z3 value 23℃ 100℃ Example 1 30mol% 5900 28% 70% 1.425 186°C 4.2 140.2 72.5 A A Example 2 30mol% 7100 25% 73% 1.424 189°C 3.8 143.7 74.3 A A Example 3 30mol% 6500 28% 71% 1.425 186°C 4.3 135.0 66.2 A A Example 4 30mol% 5800 27% 71% 1.424 191°C 4.3 127.4 70.9 A A Example 5 30mol% 5500 27% 71% 1.424 193°C 4.7 134.1 72.5 A A Comparative example 1 30mol% 3500 16% 84% 1.416 204°C 4.5 115 85 A A Comparative example 2 20mol% 4600 16% 84% 1.421 203°C 5.1 110 86 A A Comparative example 3 10mol% 5300 17% 83% 1.423 203°C 4.2 118 88 A A Comparative example 4 0mol% 9500 17% 83% 1.435 202°C 5.1 136 90 A A Comparative example 5 30mol% 13000 20% 79% 1.423 200°C 3.8 88.8 55.9 A A

From Table 1, the following situations are known. It was found that the curable polysilsesquioxane compounds (1) to (5) obtained in Examples 1 to 5 were measured by ²⁹ Si-NMR and the value of Z2 was in the range of 20 to 40%. In addition, any of the mass average molecular weights of the curable polysilsesquioxane compounds (1) to (5) is in the range of 4000 to 11000. The curable compositions (1) to (5) containing these curable polysilsesquioxane compounds have a low refractive index (nD) and are fully cured at a relatively low temperature. In addition, the adhesive strength of the cured products of the curable compositions (1) to (5) is relatively high.

On the other hand, Comparative Examples 1 to 3 use the curable polysilsesquioxane compounds of Examples 8 to 10 in Patent Document 4 (curable polysilsesquioxane compounds (6) to (8)). . In the example of Patent Document 4, a large amount of acid catalyst is used in order to supplement the low reactivity of the silane compound having a fluoroalkyl group. However, in this method, only curable polysilsesquioxane compounds with a small Z2 value can be obtained. Furthermore, as the addition amount of 3,3,3-trifluoropropyltrimethoxysilane increases, the mass average molecular weight of the curable polysilsesquioxane compound decreases. For these reasons, compared with the curable compositions (1) to (5) of Examples 1 to 5, the curable compositions (6) to (8) of Comparative Examples 1 to 3 are based on curable and hardened compositions. The bonding strength is poor.

The curable polysilsesquioxane compound (9) obtained in Comparative Example 4 does not have a repeating unit derived from 3,3,3-trifluoropropyltrimethoxysilane. Therefore, the refractive index (nD) of the curable composition (9) becomes a large value. In addition, since the Z2 value of the curable polysilsesquioxane compound (9) is small, the curable composition (9) has insufficient curability.

The curable polysilsesquioxane compound (10) obtained in Comparative Example 5 has a too large molecular weight. As a result, compared with the curable compositions (1) to (5) of Examples 1 to 5, the curable composition (10) is inferior in curability and adhesive strength of the cured product.

no.

no.

Claims (13)

A curable polysilsesquioxane compound, a curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1), characterized in that it satisfies the following requirements 1 and requirements 2,

[R ¹ represents the composition formula: C _m H _(2m-n+1) fluoroalkyl group represented by F _n , m represents an integer from 1 to 10, and n represents an integer from 2 to (2m+1), D represents the linking group (except the alkylene group) or the single bond that connects R ¹ to Si. [Requirement 1] When measuring ²⁹ Si-NMR of the curable polysilsesquioxane compound, it can be -62ppm 1 or more peaks are observed in the region above and below -52ppm [region (2)], and can be in the region above -52ppm and below -45ppm [region (1)] and region above -73ppm but below -62ppm [Area (3)] At least one area has 1 or 2 sharp peaks observed, and Z2 derived from the following formula is 20-40%,

P1: Integral value in area (1) P2: Integral value in area (2) P3: Integral value in area (3) [Required Condition 2] Mass average molecular weight of curable polysilsesquioxane compound (Mw ) Is 4,000~11,000. The curable polysilsesquioxane compound according to claim 1, wherein the ratio of the repeating unit represented by the formula (a-1) is 25 mol% or more with respect to the total repeating unit. The curable polysilsesquioxane compound according to claim 1, which further has a repeating unit represented by the following formula (a-2),

[R ² represents an unsubstituted alkyl group having 1 to 10 carbons, or a substituted or unsubstituted aryl group having 6 to 12 carbons]. The curable polysilsesquioxane compound according to claim 3, wherein the ratio of the repeating unit represented by the formula (a-2) is greater than 0 mol% and 75 mol% or less with respect to the total repeating units. The curable polysilsesquioxane compound described in claim 1, wherein when ²⁹ Si-NMR is measured, 1 or more peaks can be observed in the region (3) and Z3 derived from the following formula is 60 ~80%,

. A curable composition characterized by containing the following (A) component and a solvent having a boiling point of 254°C or higher, (A) Component: The curable polysilsesquioxane compound according to any one of claims 1 to 5. The curable composition according to claim 6, which further contains the following (B) component, (B) Component: Silane coupling agent with nitrogen atom in the molecule. The curable composition according to claim 6, which further contains the following (C) component, (C) Component: Silane coupling agent with acid anhydride structure in the molecule. The curable composition according to claim 6, which further contains the following (D), (D) Component: Fine particles with an average primary particle size of 5-40 nm. A hardened product obtained by hardening the hardenable composition according to any one of claims 6 to 9. The cured product described in claim 10 is an optical element fixing material. A method is to use the curable composition according to any one of claims 6 to 9 as an adhesive for fixing an optical element. A method is to use the curable composition according to any one of claims 6 to 9 as a sealant for an optical element fixing material.