KR20210066800A - Curable polysilsesquioxane compound, curable composition, cured product, and method of 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), ^{satisfying specific requirements for 29} Si-NMR and having a mass average molecular weight (Mw) in a specific range A curable polysilsesquioxane compound comprising: a curable polysilsesquioxane compound, a curable composition containing the curable polysilsesquioxane compound, a cured product obtained by curing the curable composition, and an adhesive for an optical device fixing material or an optical device fixing material How to use it as a sealing material. The curable composition of this invention is excellent in sclerosis|hardenability, and a thing with a low refractive index. In formula (a-1), R ¹ represents a fluoroalkyl group represented by the composition formula: C _m H _(2m-n+1) F _{n .} m represents the integer of 1-10, n represents the integer of 2 or more and (2m+1) or less. D represents a linking group (however, except for an alkylene group) or a single bond which bonds ^{R 1 and Si.} R ¹ -D-SiO _3/2 (a-1)

Description

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

The present invention relates to a curable polysilsesquioxane compound, a curable composition containing the curable polysilsesquioxane compound having excellent curability and a low refractive index, a cured product having high adhesive strength formed 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 material for an optical element fixing material.

Conventionally, various improvements are made according to the use of a curable composition, and it has been widely used industrially as a raw material of an optical component or a molded object, an adhesive agent, a coating agent, etc.

Moreover, a curable composition attracts attention also as a composition for optical element fixing materials, such as an adhesive for optical element fixing materials and a sealing material for optical element fixing materials.

The optical element includes various lasers such as a semiconductor laser (LD), a light emitting element such as a light emitting diode (LED), a light receiving element, a composite optical element, an optical integrated circuit, and the like.

In recent years, optical elements of blue light or white light whose peak wavelength of light emission has a shorter wavelength have been developed and are widely used. The high luminance of the light emitting device having such a short peak wavelength of light emission progresses rapidly, and the amount of heat generated by the optical device tends to increase with this.

However, with the recent increase in luminance of optical devices, the cured product of the optical device fixing material composition is exposed to high energy light or high temperature heat generated from the optical device for a long period of time, resulting in a decrease in adhesive strength. occurred

In order to solve this problem, the composition for optical element fixing materials which has a polysilsesquioxane compound as a main component is proposed by patent documents 1-3.

However, even if it was the hardened|cured material of the composition of patent documents 1-3, it may be difficult to acquire heat resistance, maintaining sufficient adhesive force.

Moreover, when fixing an optical element etc. using a curable composition, it becomes important to form the hardened|cured material which has the refractive index suitable for the objective in many cases. In particular, since the conventional curable composition and its hardened|cured material have many things with a high refractive index, the curable composition with a lower refractive index was calculated|required.

Patent Document 4 describes a curable composition containing a curable polysilsesquioxane compound having a fluoroalkyl group as a curable composition that provides a cured product having a low refractive index.

However, as shown in the Example of Patent Document 4, when a curable composition containing a curable polysilsesquioxane compound having a high proportion of repeating units having a fluoroalkyl group is used, it is difficult to obtain a cured product having high adhesive strength. did. Thus, in the hardened|cured material of the curable composition of patent document 4, there existed a trade-off relationship between high adhesive strength and low refractive index. For this reason, when the curable composition of patent document 4 was used, it was difficult to obtain the hardened|cured material which has the characteristic of both high adhesive strength and low refractive index.

Moreover, it is known that workability|operativity etc. are improved by adding a filler etc. to a curable composition.

However, in general, since the refractive index of a curable composition containing a filler etc. and its hardened|cured material tends to become high, even if it added a filler etc., the curable composition with a low refractive index was desperate.

Japanese Patent Laid-Open No. 2004-359933 Japanese Laid-Open Patent Publication No. 2005-263869 Japanese Laid-Open Patent Publication No. 2006-328231 WO2017/110948 (US2018/0355111 A1)

The present invention has been made in view of the circumstances of the prior art described above, a curable composition having excellent curability and a low refractive index, a curable polysilsesquioxane compound useful as a component of the curable composition, a curable composition obtained by curing the curable composition, It aims at providing the hardened|cured material with high adhesive strength, and the method of using the said curable composition as an adhesive agent for optical element fixing materials or a sealing material for optical element fixing materials.

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 changes independently into a cured product by satisfying predetermined conditions such as heating, or functions as a curable component in the curable composition polysilsesquioxane compound.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors repeated earnest examination about the curable polysilsesquioxane compound which has a fluoroalkyl group.

As a result,

(1) The problem that the adhesive strength of the cured product is lowered by introducing a fluoroalkyl group into the curable polysilsesquioxane compound has a specific repeating unit, and a requirement regarding molecular structure (requirement 1 to be described later) and molecular weight What can be solved by using a curable polysilsesquioxane compound (hereinafter sometimes referred to as "curable polysilsesquioxane compound (A)") that both satisfy the requirements (requirement 2 to be described later), and

(2) Since the curable composition containing the curable polysilsesquioxane compound (A) has excellent curability, it also has an advantage that it can be cured without excessive heating;

found out

Moreover, since the curable composition containing a curable polysilsesquioxane compound (A) and the solvent which has a boiling point of 254 degreeC or more has a small change in viscosity even if it is left to stand for a long time after application|coating, it discovered that it has the same workability as immediately after application|coating.

The present invention has been completed based on these findings.

In this way, according to the present invention, the curable polysilsesquioxane compound of the following [1] to [5], the curable composition of [6] to [9], the cured product of [10] and [11], and [12] , a method of using the curable composition of [13] is provided.

[1] A curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1), wherein the following requirements 1 and 2 are satisfied.

[Formula 1]

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

[Requirement 1]

^{When 29} Si-NMR of the curable polysilsesquioxane compound is measured, one or two or more peaks are observed in the region [region (2)] of -62 ppm or more and less than -52 ppm, -52 ppm or more -45 ppm 1 or 2 or more peaks are observed in at least one of the region of less than [region (1)] and the region of -73 ppm or more and less than -62 ppm [region (3)], and Z2 derived by the following formula is 20 to 40%.

P1: integral value in region (1)

P2: integral value in region (2)

P3: integral value in region (3)

[Requirement 2]

The mass average molecular weights (Mw) of sclerosing|hardenable polysilsesquioxane compound are 4,000-11,000.

[2] The curable polysilsesquioxane compound according to [1], wherein the proportion of the repeating unit represented by the formula (a-1) is 25 mol% or more with respect to all the repeating units.

[3] The curable polysilsesquioxane compound according to [1] or [2], further having a repeating unit represented by the following formula (a-2).

[Formula 2]

[R ² is an alkyl group has a carbon number of 1 to 10 non-substituted, or substituted or non-substituted, or represents a group of a carbon number of 6 to 12 aryl group.]

[4] The curable polysilsesquioxane compound according to [3], wherein the proportion of the repeating unit represented by the formula (a-2) is more than 0 mol% and 75 mol% or less with respect to all repeating units.

[5] Any one of [1] to [4], wherein 1 or 2 or more peaks are observed in the region (3) when ^{29 Si-NMR is measured, and Z3 derived by the following formula is 60 to 80%} The curable polysilsesquioxane compound described in.

[6] A curable composition comprising the following component (A) and a solvent having a boiling point of 254°C or higher.

(A) component: curable polysilsesquioxane compound according to any one of [1] to [5]

[7] The curable composition according to [6], further comprising the following component (B).

(B) component: a silane coupling agent having a nitrogen atom in the molecule

[8] The curable composition according to [6] or [7], further comprising the following component (C).

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

[9] The curable composition according to any one of [6] to [8], further comprising the following component (D).

(D) component: fine particles having an average primary particle diameter of 5 to 40 nm

[10] A cured product obtained by curing the curable composition according to any one of [6] to [9].

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

[12] A method in which the curable composition according to any one of [6] to [9] is used as an adhesive for an optical element fixing material.

[13] A method in which the curable composition according to any one of [6] to [9] is used as a sealing material for an optical element fixing material.

According to the present invention, a curable composition having excellent curability and a low refractive index, a curable polysilsesquioxane compound useful as a component of the curable composition, a cured product having high adhesive strength obtained by curing the curable composition, and the curable composition A method of using the composition as an adhesive for an optical element fixing material or an encapsulant for an optical element fixing material is provided.

Hereinafter, the present invention will be described in detail by classifying the items into 1) a curable polysilsesquioxane compound, 2) a curable composition, 3) a cured product, and 4) a method of using the curable composition.

1) Curable polysilsesquioxane compound

The curable polysilsesquioxane compound of the present invention [curable polysilsesquioxane compound (A)] is a curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1), It is characterized in that the requirement 2 is satisfied.

[Formula 3]

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

In formula (a-1), R ¹ represents a fluoroalkyl group represented by the composition formula: C _m H _(2m-n+1) F _{n .} m represents the integer of 1-10, n represents the integer of 2 or more and (2m+1) or less. m becomes like this. Preferably it is an integer of 1-5, More preferably, it is an integer of 1-3.

A curable composition with a low refractive index can be obtained by using the curable polysilsesquioxane compound which has R<^1>.

Compositional formula: C _m H _{(2m-n+1) As} the fluoroalkyl group represented by F _{n , CF 3} , CF ₃ CF ₂ , CF ₃ (CF ₂ ) ₂ , CF ₃ (CF ₂ ) ₃ , CF ₃ (CF ₂ ) a perfluoroalkyl group such as 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 ;} a hydrofluoroalkyl group such as 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 ;} can be heard

In formula (a-1), D represents the coupling group (however, the alkylene group is excluded) or a single bond which couple|bonds ^{R<1> and Si.}

Examples of the linking group for D include arylene groups having 6 to 20 carbon atoms, such as a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, and a 1,5-naphthylene group.

The curable polysilsesquioxane compound (A) may be one ^{having one type of (R 1} -D) (homopolymer), or may be ^{one having two or more types of (R 1} -D) (copolymer).

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

Moreover, the structure of a sclerosing|hardenable polysilsesquioxane compound (A) is any structure among a ladder structure, a double decker type|mold structure, a cage structure, a partial cleavage cage structure, a cyclic structure, and a random structure. may be

Preferably the ratio of the repeating unit represented by Formula (a-1) contained in curable polysilsesquioxane compound (A) is 25 mol% or more with respect to all the repeating units, More preferably, 25-90 mol%, More preferably, it is 25-85 mol%.

When the ratio of the repeating unit represented by Formula (a-1) uses the curable polysilsesquioxane compound (A) which is 25 mol% or more with respect to all the repeating units, the 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).

[Formula 4]

In formula (a-2), R<^2> has an unsubstituted C1-C10 alkyl group or a substituent, or represents an unsubstituted C6-C12 aryl group.

Examples of the unsubstituted alkyl group having 1 to 10 carbon atoms for R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pene tyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned.

As an unsubstituted C6-C12 aryl group of R<^2> , a phenyl group, 1-naphthyl group, 2-naphthyl group, etc. are mentioned.

Examples of the substituent of the aryl group having 6 to 12 carbon atoms having a substituent for R ² include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, alkyl groups such as n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and isooctyl group; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; Alkoxy groups, such as a methoxy group and an ethoxy group; can be heard

Among these, as R ² , an unsubstituted C1-C10 alkyl group is preferable, and an unsubstituted C1-C6 alkyl group is more preferable at the point which adhesive strength is higher and it is easy to obtain the hardened|cured material excellent in heat resistance. and an unsubstituted C1-C3 alkyl group is especially preferable.

When the curable polysilsesquioxane compound (A) has a repeating unit represented by the formula (a-2), the curable polysilsesquioxane compound (A) may have one type of R ² , What has 2 or more types of R<^2> may be sufficient.

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 all repeating units, more Preferably it is 10-75 mol%, More preferably, it is 15-75 mol%.

When the ratio of the repeating unit represented by Formula (a-2) uses the curable polysilsesquioxane compound (A) within the said range, adhesive strength becomes higher and it becomes easy to obtain the hardened|cured material excellent in heat resistance.

The ratio of the repeating unit represented by Formula (a-1) or Formula (a-2) in a curable polysilsesquioxane compound (A) is ²⁹ Si- of a curable polysilsesquioxane compound (A), for example. It can obtain|require by measuring NMR.

The curable polysilsesquioxane compound (A) is a ketone solvent such as acetone; aromatic hydrocarbon-based solvents such as benzene; sulfur-containing solvents such as dimethyl sulfoxide; ether solvents such as tetrahydrofuran; ester solvents such as ethyl acetate; halogen-containing solvents such as chloroform; and a mixed solvent composed of two or more thereof; ^{Since it is soluble in various organic solvents, such as, 29} Si-NMR in the solution state of a sclerosing|hardenable polysilsesquioxane compound (A) can be measured using these solvents.

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

[Formula 5]

[G represents (R ¹ -D) or R ² . R ¹ , D and R ² each have the same meaning as described above. O _{1/2 indicates} that an oxygen atom is shared with an adjacent repeating unit.]

As represented by the formula (a-3), in the curable polysilsesquioxane compound (A), three oxygen atoms are bonded to a silicon atom generally referred to as a T site, and other groups (groups represented by G) ) has a partial structure formed by bonding one.

Examples of the T site contained in the curable polysilsesquioxane compound (A) include those represented by the following formulas (a-4) to (a-6).

[Formula 6]

In formulas (a-4), (a-5) and (a-6), G has the same meaning as above. R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. As a C1-C10 alkyl group of R<^3> , a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, etc. are mentioned. A plurality of R ^{3 s may} all be the same or different. Moreover, the silicon atom is couple|bonded with * in said Formula (a-4) - (a-6).

The T site represented by the formulas (a-4) and (a-5) contains a group (R ³ -O) capable of contributing to the polycondensation reaction. Therefore, the polysilsesquioxane compound containing many of these T sites is excellent in reactivity. Moreover, the composition containing such a polysilsesquioxane compound is excellent in sclerosis|hardenability.

On the other hand, the T sites represented by the formulas (a-5) and (a-6) are bonded to two or more silicon atoms (silicon atoms in the adjacent T sites). Therefore, the polysilsesquioxane compound containing many of these T sites tends to have a large molecular weight.

Therefore, the polysilsesquioxane compound containing many T sites represented by Formula (a-5) has a comparatively large molecular weight, and has sufficient reactivity.

The present invention has been made based on this knowledge.

That is, the sclerosing|hardenable polysilsesquioxane compound (A) of this invention satisfy|fills the following requirements 1.

[Requirement 1]

^{When 29} Si-NMR of the curable polysilsesquioxane compound is measured, one or two or more peaks are observed in the region [region (2)] of -62 ppm or more and less than -52 ppm, -52 ppm or more -45 ppm 1 or 2 or more peaks are observed in at least one of the region of less than [region (1)] and the region of -73 ppm or more and less than -62 ppm [region (3)], and Z2 derived by the following formula is 20 to 40%.

In addition, "a peak observed in the area|region (1)" means that a peak top exists in the range of the area|region (1). The same applies to "a peak observed in the region (2)" and "a peak observed in the region (3)".

P1: integral value in region (1)

P2: integral value in region (2)

P3: integral value in region (3)

In the present specification, "integral value in region (1)", "integral value in region (2)", and "integral value in region 3" are -52 ppm to -45 ppm, respectively. The values obtained by calculating ppm, -62 ppm to -52 ppm, and -73 ppm to -62 ppm as the integral range are referred to.

The peaks observed in the region (1), region (2), and region (3) are, respectively, from silicon atoms in the T sites represented by formulas (a-4), (a-5), and (a-6). it comes from

Therefore, the sclerosing|hardenable polysilsesquioxane compound which satisfy|fills the requirement 1 contains 20 to 40% of T sites represented by Formula (a-5) with respect to the whole T site.

As mentioned above, this curable polysilsesquioxane compound has a comparatively large molecular weight, and has sufficient reactivity, and is useful as a sclerosing|hardenable component of a curable composition.

Among the requirements 1, the value of Z2 is preferably 24 to 36%, more preferably 27 to 32%. When Z2 is too small, the reactivity is not enough, and when Z2 is too large, the storage stability will fall.

As for the curable polysilsesquioxane compound (A), when ²⁹ Si-NMR is measured, one or two or more peaks are observed in the region (3), and Z3 derived by the following formula is 60 to 80% desirable.

The sclerosing|hardenable polysilsesquioxane compound (A) whose Z3 is 60 to 80% contains 60 to 80% of T sites represented by Formula (a-6) with respect to the whole T site.

The curable polysilsesquioxane compound (A) in the range whose value of Z3 is 60 to 80 % is more excellent in molecular weight and reactivity balance.

From the point where this effect is more easily acquired, 64 to 76 % is more preferable, and, as for the value of Z3, 68 to 73 % is still more preferable.

The values of Z2 and Z3 can be calculated, for example, ^{by measuring 29} Si-NMR under the conditions described in Examples to obtain P1 to P3, and according to the above formula.

The curable polysilsesquioxane compound (A) satisfies the above requirement 2 .

That is, the mass average molecular weights (Mw) of a sclerosing|hardenable polysilsesquioxane compound (A) are 4,000-11,000, Preferably it is 4,000-8,000, More preferably, it is 6,000-7,000.

As described above, the curable polysilsesquioxane compound satisfying the requirement 1 tends to have a relatively large molecular weight. Requirement 2 is to clarify the range of the molecular weight.

By using the curable polysilsesquioxane compound (A) having a mass average molecular weight (Mw) within the above range as a curable component, a curable composition providing a cured product having high adhesive strength and excellent heat resistance can be obtained.

Although the molecular weight distribution (Mw/Mn) in particular of a sclerosing|hardenable polysilsesquioxane compound (A) is not restrict|limited, Usually, it is 1.0-10.0, Preferably it is the range of 1.1-6.0. By using the curable polysilsesquioxane compound (A) having a molecular weight distribution (Mw/Mn) within the above range as the curable component, it is possible to obtain a curable composition that provides a cured product having more excellent adhesion and heat resistance.

A mass average molecular weight (Mw) and a number average molecular weight (Mn) can be calculated|required as a standard polystyrene conversion value by gel permeation chromatography (GPC) which uses tetrahydrofuran (THF) as a solvent, for example.

The curable polysilsesquioxane compound (A) is, for example, a compound represented by the following formula (a-7) (hereinafter, sometimes referred to as “silane compound (1)”), or a silane compound (1) and a compound represented by the following formula (a-8) (hereinafter sometimes referred to as “silane compound (2)”) can be produced by polycondensing in the presence of a polycondensation catalyst.

[Formula 7]

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

Examples of the alkyl group having 1 to 10 carbon atoms for R ⁴ and R ⁵ include the same groups as those shown for the alkyl group having 1 to 10 carbon atoms for ^{R 2 .}

Examples ^{of the halogen atom for X 1} and X ² include a chlorine atom and a bromine atom.

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

Among these, as a silane compound (1), what is contained in the fluoroalkyl trialkoxysilane compounds is preferable.

Examples of the silane compound (2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane, and n-propyltriethane. Toxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, alkyltrialkoxysilane compounds such as isooctyltriethoxysilane;

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

Methyltrichlorosilane, methyltribromosilane, ethyltritrichlorosilane, ethyltribromosilane, n-propyltrichlorosilane, n-propyltribromosilane, n-butyltrichlorosilane, isobutyltrichlorosilane, n- Alkyl trihalogenosilane compounds, such as pentyl trichlorosilane, n-hexyl trichlorosilane, and isooctyl trichlorosilane; and the like.

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

Among these, as a silane compound (2), what is contained in alkyl trialkoxysilane compounds is preferable.

The method of polycondensing the said silane compound is not specifically limited, A well-known method can be used. However, in manufacture of a sclerosing|hardenable polysilsesquioxane compound (A), since there exists a problem shown below, it is necessary to examine reaction conditions in particular.

One of the problems at the time of manufacturing a sclerosing|hardenable polysilsesquioxane compound (A) is shown in the said patent document 4. That is, referring to Table 1 of Patent Document 4, it can be seen that as the usage ratio of the silane compound having a fluoroalkyl group increases, the resulting polymer tends to have a lower molecular weight.

As described above, since the reactivity of the silane compound (1) and the reactivity of the silane compound (2) are significantly different, the requirements 1 and 2 are satisfied using the conventional knowledge regarding the polycondensation reaction of the silane compound (2) as it is. It is difficult to obtain a curable polysilsesquioxane compound.

In the Example of patent document 4, the polycondensation reaction is actually performed using the silane compound which has a fluoroalkyl group, and the polymer is manufactured. However, as described above, in the production method described in this document, since the mixing ratio of the silane compound used for the reaction greatly affects the reaction, the molecular weight of the polymer cannot be controlled.

In addition, as described later, by using the reaction conditions described in the Examples of Patent Document 4, a silane compound with poor reactivity (a silane compound having a fluoroalkyl group) can be used as a monomer, but even if this reaction condition is used, the requirements It is difficult to obtain the curable polysilsesquioxane compound which satisfy|fills 1 and requirement 2 (Comparative Examples 1-3).

As a result of the present inventors examining the polycondensation reaction using a silane compound (1), curable polysilsesquioxane which satisfies the requirement 1 and the requirement 2 by performing polycondensation reaction over time on comparatively mild conditions. It was found that the compound could be obtained.

Specifically, in a solvent or without a solvent, using an appropriate amount of an acid catalyst, polycondensation reaction of a silane compound is performed at a predetermined temperature to obtain a reaction solution containing a production intermediate, and then a base is added to prepare the reaction solution. A sclerosing|hardenable polysilsesquioxane compound (A) can be manufactured by making it neutralize and also performing a polycondensation reaction.

As a solvent, Water; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol and t-butyl alcohol; and the like. These solvents can be used individually by 1 type or in combination of 2 or more type.

When using a solvent, the usage-amount is 0.001-10.000 liters normally, Preferably it is 0.010-0.9 liters per 1 mol of total moles of a silane compound.

Examples of the acid catalyst 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; and the like. Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid, and methanesulfonic acid is preferable.

The usage-amount of an acid catalyst is 0.01-2.00 mol% normally with respect to the total mol of a silane compound, Preferably it is 0.05-1.00 mol%, More preferably, it is the range of 0.10-0.30.

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 from 1 to 48 hours, preferably from 3 to 24 hours.

The mass average molecular weight (Mw) of the manufacturing intermediate obtained by reaction in acid catalyst presence is 800-5,000 normally, Preferably it is 1,200-4,000.

As a base used when neutralizing a reaction liquid, Ammonia water; Trimethylamine, triethylamine, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, aniline, picoline, 1,4-diazabicyclo[2.2.2]octane, imidazole, etc. organic base; organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide and potassium t-butoxide; metal hydrides such as sodium hydride and calcium hydride; metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, and magnesium carbonate; metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; and the like.

The amount of the base used for neutralization of the reaction solution is usually in the range of 0.01 to 2.00 mol%, preferably 0.05 to 1.00 mol%, and more preferably 0.10 to 0.70, based on the total mol of the silane compound.

Moreover, the amount (mol) of the base used for neutralization of the reaction solution is preferably 0.5 to 5.0 times the amount (mol) of the acid catalyst used before step 1, more preferably 0.8 to 3.0 times, still more preferably 1.0 to 2.0 times.

The pH of the reaction solution after neutralization 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 reaction after neutralization is 40-90 degreeC normally, Preferably it is 50-80 degreeC.

The reaction time of reaction after neutralization is 20 to 200 minutes normally, Preferably it is 30 to 150 minutes.

In the above production method, in the reaction in the presence of an acid catalyst, hydrolysis is the main purpose, and in the reaction after neutralization, dehydration condensation is the main purpose.

In this way, by performing polycondensation reaction of a silane compound, the target curable polysilsesquioxane compound (A) can be manufactured efficiently.

After completion of the reaction, a known purification 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 sclerosing|hardenable polysilsesquioxane compound is excellent in sclerosis|hardenability and is useful as a sclerosing|hardenable component of a curable composition with a low refractive index.

2) curable composition

The curable composition of the present invention is characterized by containing the following component (A) and a solvent having a boiling point of 254°C or higher (hereinafter, may be referred to as “solvent (S1)”).

(A) component: curable polysilsesquioxane compound (curable polysilsesquioxane compound (A)) of the present invention

Curable composition of this invention WHEREIN: A sclerosing|hardenable polysilsesquioxane compound (A) can be used individually by 1 type or in combination of 2 or more type.

Content of the curable polysilsesquioxane compound (A) in the curable composition of this invention is 40-80 mass % normally on the basis of the whole solid content of a curable composition, Preferably it is 50-70 mass %.

The boiling point of a solvent (S1) is 254 degreeC or more, and 254-300 degreeC is preferable.

Here, the boiling point means the boiling point in 1013 hPa (the same in this specification.)

As a solvent (S1), if a boiling point is 254 degreeC or more and can melt|dissolve a curable polysilsesquioxane compound (A), it will not restrict|limit in particular.

Such a solvent (S1) has a relatively slow volatilization rate. Therefore, since the curable composition containing the solvent (S1) has a small change in viscosity even if it is left to stand for a long time after application, it becomes possible to favorably mount an optical element or the like in the same manner as immediately after application.

Specifically, as the solvent (S1), tripropylene glycol-n-butyl ether (boiling point 274°C), 1,6-hexanediol diacrylate (boiling point 260°C), diethylene glycol dibutyl ether (boiling point 256°C) , triethylene glycol butyl methyl ether (boiling point 261 ° C.), polyethylene glycol dimethyl ether (boiling point 264 to 294 ° C.), tetraethylene glycol dimethyl ether (boiling point 275 ° C.), polyethylene glycol monomethyl ether (boiling point 290 to 310 ° C.), etc. can be heard

Among these, as the solvent (S1), tripropylene glycol-n-butyl ether and 1,6-hexanediol diacrylate are preferable from the viewpoint that the effect of the present invention can be obtained more easily.

A solvent (S1) can be used individually by 1 type or in combination of 2 or more type.

The curable composition of this invention may contain solvents other than a solvent (S1).

As the solvent other than the solvent (S1), a solvent having a boiling point of 200°C or higher and lower than 254°C (hereinafter, may be referred to as “solvent (S2)”) is preferable.

As a solvent (S2), if a boiling point is 200 degreeC or more and less than 254 degreeC, and can melt|dissolve a curable polysilsesquioxane compound (A), it will not restrict|limit in particular.

By using a solvent (S1) and a solvent (S2) together, sclerosis|hardenability of a curable composition improves.

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. Acetate (boiling point 209 ° C.), diethylene glycol butylmethyl ether (boiling point 212 ° C.), dipropylene glycol-n-propyl ether (boiling point 212 ° C.), tripropylene glycol dimethyl ether (boiling point 215 ° C.), triethylene glycol dimethyl 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 deg. C), propylene glycol phenyl ether (boiling point 243 deg. C), triethylene glycol monomethyl ether (boiling point 249 deg. C), and the like.

Among these, as a solvent (S2), since the effect is easy to acquire, a glycol-type solvent is preferable, diethylene glycol monobutyl ether acetate and dipropylene glycol-n-butyl ether are preferable, and diethylene glycol monobutyl ether. Acetate is more preferable.

When the solvent (S1) and the solvent (S2) are used together, specifically, 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 A combination of -n-butyl ether (solvent (S2)) and a combination of 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 mass%, more preferably 60 to 85 mass%. When solid content concentration is in this range, the effect of a solvent (S1) and a solvent (S2) is fully exhibited.

The total amount of solvent (S1) and solvent (S2) contained in the curable composition of this invention is 50-100 mass % normally with respect to all solvents, Preferably it is 70-100 mass %, More preferably, 90-100 mass % to be.

Content of the solvent (S1) contained in the curable composition of this invention is 20-100 mass % normally with respect to the total amount of solvent (S1) and solvent (S2), Preferably it is 30-85 mass %, More preferably It is 50-80 mass %.

The curable composition containing the solvent (S1) and the solvent (S2) in such a ratio is suitably balanced in adhesiveness and wet diffusivity (characteristics regarding the diffusion of a droplet mentioned later).

The curable composition of this invention may contain the silane coupling agent (Hereinafter, it may describe as "silane coupling agent (B)") which has a nitrogen atom in a molecule|numerator as (B) component.

The curable composition containing a silane coupling agent (B) provides the hardened|cured material excellent in the workability|operativity in an application|coating process, and more excellent in adhesiveness, peeling resistance, and heat resistance.

Here, excellent workability in the coating step means that the amount of thread drag is small or immediately interrupted when the curable composition is discharged from the discharge pipe and then the discharge pipe is pulled up in the coating step. By using the curable composition having this property, it is possible to prevent contamination of the surroundings due to scattering of resin or diffusion of droplets.

As a silane coupling agent (B), if it is a silane coupling agent which has a nitrogen atom in a molecule|numerator, there will be no restriction|limiting in particular. For example, the trialkoxysilane compound represented by a following formula (b-1), the dialkoxy alkylsilane compound represented by a formula (b-2), a dialkoxy arylsilane compound, etc. are mentioned.

[Formula 8]

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

R ^b is an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group; or an aryl group having a substituent such as a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, and a 1-naphthyl group, or having no substituent; indicates

R ^c represents an organic group having 1 to 10 carbon atoms and having a nitrogen atom. Moreover, R ^c may further couple|bond with the group containing another silicon atom.

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

Among the compounds represented by the formula (b-1) or (b-2), the compound in the case where R ^c is an organic group bonded to a group containing another silicon atom is a compound represented by an isocyanurate skeleton with another silicon atom Examples thereof include bonding to form an isocyanurate-based silane coupling agent, and bonding to other silicon atoms via a urea skeleton to form a urea-based silane coupling agent.

Among these, as the silane coupling agent (B), an isocyanurate-based silane coupling agent and a urea-based silane coupling agent are preferable from the viewpoint of easily obtaining a cured product having higher adhesive strength, and furthermore, in the molecule, It is preferable to have 4 or more alkoxy groups which couple|bonded.

Having 4 or more alkoxy groups bonded to silicon atoms means that the sum total of the 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) is a urea-based silane coupling agent having 4 or more alkoxy groups bonded to a silicon atom, The compound represented by Formula (b-4) is mentioned.

[Formula 9]

In formula, R ^a represents the same meaning as the above. Each of t1 to t5 independently represents an integer of 1 to 10, preferably an integer of 1 to 6, particularly preferably 3, respectively.

Specific examples of the compound represented by the formula (b-3) include 1,3,5-N-tris(3-trimethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3- Triethoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-trii-propoxysilylpropyl)isocyanurate, 1,3,5-N-tris(3-tribu 1,3,5-N-tris[(tri(C1-6)alkoxy)silyl(C1-10)alkyl]isocyanurate, such as oxysilylpropyl)isocyanurate;

1,3,5-N-tris(3-dimethoxymethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dimethoxyethylsilylpropyl)isocyanurate, 1,3, 5-N-tris(3-dimethoxyi-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dimethoxyn-propylsilylpropyl)isocyanurate, 1,3, 5-N-tris(3-dimethoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diethoxymethylsilylpropyl)isocyanurate, 1,3,5-N- Tris(3-diethoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diethoxyi-propylsilylpropyl)isocyanurate, 1,3,5-N-tris( 3-diethoxyn-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-diethoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-tris(3- Dii-propoxymethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dii-propoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris( 3-dii-propoxyi-propylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dii-propoxyn-propylsilylpropyl)isocyanurate, 1,3, 5-N-tris(3-dii-propoxyphenylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxymethylsilylpropyl)isocyanurate, 1,3,5 -N-tris(3-dibutoxyethylsilylpropyl)isocyanurate, 1,3,5-N-tris(3-dibutoxyi-propylsilylpropyl)isocyanurate, 1,3,5-N 1,3,5-N-, such as tris(3-dibutoxyn-propylsilylpropyl)isocyanurate and 1,3,5-N-tris(3-dibutoxyphenylsilylpropyl)isocyanurate tris[(di(C1 to C6)alkoxy)silyl(C1 to C10)alkyl]isocyanurate; and the like.

Specific examples of the compound represented by the formula (b-4) include N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilylpropyl)urea, N ,N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, N,N'-bis(2-trimethoxysilylethyl)urea, etc. N,N'-bis[(tri(C1-C6) alkoxysilyl)(C1-C10)alkyl]urea;

N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, N,N'-bis(3-diethoxymethylsilylpropyl)urea N,N'-bis[(di(C1-C6)alkoxy(C1-C6)alkylsilyl(C1-C10)alkyl)urea, such as;

N,N'-bis[(di(C1-6), such as N,N'-bis(3-dimethoxyphenylsilylpropyl)urea, N,N'-bis(3-diethoxyphenylsilylpropyl)urea, etc. Alkoxy (C6-C20) arylsilyl (C1-C10) alkyl) urea; and the like.

A silane coupling agent (B) can be used individually by 1 type or in combination of 2 or more type.

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

When the isocyanurate compound and the urea compound are used in combination, the ratio of both is preferably 100:1 to 100:200 by mass ratio of (isocyanurate compound) to (urea compound), 100:10 - 100:110 are more preferable. By using a combination of an isocyanurate compound and a urea compound in such a ratio, it is possible to obtain a curable composition that provides a cured product having higher adhesive strength and better heat resistance.

When the curable composition of the present invention contains the silane coupling agent (B) [component (B)], the content of the component (B) is not particularly limited, but the amount is the mass ratio of the component (A) and the component (B). [Component (A): component (B)], preferably 100:0.1 to 100:90, more preferably 100:0.3 to 100:60, more preferably 100:1 to 100:50, still more preferably Preferably, the amount is 100:3 to 100:40, particularly preferably 100:5 to 100:30.

The cured product of the curable composition containing the component (A) and the component (B) in such a ratio has higher adhesive strength and more excellent heat resistance.

The curable composition of this invention may contain the silane coupling agent (Hereinafter, it may describe as "silane coupling agent (C)") which has an acid-anhydride structure in a molecule|numerator as (C)component.

The curable composition containing a silane coupling agent (C) provides the hardened|cured material which is excellent in workability|operativity in an application|coating process, adhesive strength is higher, and is more excellent in peeling resistance and heat resistance.

As the silane coupling agent (C), 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, 3-(trimethoxysilyl)propyl succinic anhydride, 3-(triethoxy tri(C1-C6) alkoxysilyl(C2-C8) alkyl succinic anhydride, such as silyl) propyl succinic anhydride;

di(C1-C6) alkoxymethylsilyl (C2-C8) alkyl succinic anhydride, such as 2-(dimethoxymethylsilyl)ethyl succinic anhydride;

(C1-C6) alkoxy dimethylsilyl (C2-C8) alkyl succinic anhydride, such as 2-(methoxydimethylsilyl) ethyl succinic anhydride;

trihalogenosilyl (C2-8)alkyl succinic anhydride, such as 2-(trichlorosilyl)ethyl succinic anhydride and 2-(tribromosilyl)ethyl succinic anhydride;

dihalogenomethylsilyl (C2-8)alkyl succinic anhydride, such as 2-(dichloromethylsilyl)ethyl succinic anhydride;

halogenodimethylsilyl (C2-8)alkyl succinic anhydride, such as 2-(chlorodimethylsilyl)ethyl succinic anhydride; and the like.

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

Among these, as a silane coupling agent (C), tri(C1-C6) alkoxysilyl (C2-C8) alkyl succinic anhydride is preferable, 3-(trimethoxysilyl)propyl succinic anhydride, or 3-(trie Particular preference is given to oxysilyl)propyl succinic anhydride.

When the curable composition of the present invention contains the silane coupling agent (C) [component (C)], the content of the component (C) is not particularly limited, but the amount is the mass ratio of the component (A) and the component (C). [Component (A): component (C)], preferably 100:0.1 to 100:30, more preferably 100:0.3 to 100:20, more preferably 100:0.5 to 100:15, still more preferably Usually, the amount is 100: 1 to 100: 10.

The hardened|cured material of the curable composition containing (C)component in such a ratio becomes a thing with higher adhesive strength.

The curable composition of the present invention may contain, as component (D), fine particles having an average primary particle diameter of 5 to 40 nm (hereinafter, may be referred to as “fine particles (D)”).

The curable composition containing microparticles|fine-particles (D) is excellent in the workability|operativity in an application|coating process.

Since this effect is more easily acquired, the average primary particle diameter of microparticles|fine-particles (D) becomes like this. Preferably it is 5-30 nm, More preferably, it is 5-20 nm.

The average primary particle diameter of microparticles|fine-particles (D) can be calculated|required by observing the shape of microparticles|fine-particles using a transmission electron microscope.

The specific surface area of the microparticles|fine-particles (D) becomes like this. Preferably it is 10-500 m<2>/g, More preferably, it is 20-300 m<2>/g. When a specific surface area is in the said range, it becomes easy to obtain the more excellent curable composition in the workability|operativity in a coating process.

The specific surface area can be calculated|required by the BET multipoint method.

The shape of the fine particles (D) may be any of a spherical shape, a chain shape, a needle shape, a plate shape, a flaky shape, a rod shape, and a fibrous shape, but is preferably a spherical shape. Here, the spherical shape means a substantially spherical shape including a polyhedral shape that can be approximated to a sphere, such as a spheroid, an oval, a confetti, and a cocoon, in addition to a true spherical shape.

There is no restriction|limiting in particular as a structural component of microparticles|fine-particles (D), A metal; metal oxides; Mineral ; 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 an aluminum silicate, a calcium silicate, and a magnesium silicate; inorganic components such as silica; silicon ; organic components such as acrylic polymers; and the like.

In addition, the microparticles|fine-particles (D) to be used may be the thing by which the surface was modified.

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

Examples of the metal oxide include titanium oxide, alumina, boehmite, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, zinc oxide, and complex oxides thereof. The microparticles|fine-particles of a metal oxide also contain the sol particle which consists of these metal oxides.

As a mineral, smectite, bentonite, etc. are mentioned.

Examples of smectite include montmorillonite, weidellite, hectorite, saponite, stevensite, nontronite, and soconite.

Examples of the silica include fumed silica, wet silica, and surface-modified silica (surface-modified silica).

Microparticles|fine-particles (D) can be used individually by 1 type or in combination of 2 or more type.

Among these, since it is easy to obtain the hardened|cured material excellent in transparency, as microparticles|fine-particles (D), a silica, a metal oxide, and a mineral are preferable and silica is more preferable.

Among silica, surface-modified silica is preferable, and hydrophobic surface-modified silica is more preferable from the viewpoint of easy to obtain a curable composition having more excellent workability in the coating step.

Examples of the hydrophobic surface-modified silica include a trialkylsilyl group having 1 to 20 carbon atoms on the surface, such as a trimethylsilyl group; an alkylsilyl group having 1 to 20 carbon atoms such as a dimethylsilyl group; C1-C20 alkylsilyl groups, such as an octylsilyl group; Silica bound to; Silica surface-treated with silicone oil; and the like.

The hydrophobic surface-modified silica is, for example, a silane coupling agent having a trialkylsilyl group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms in the silica particles. It can be obtained by surface modification using , or by treating silica particles with silicone oil. Moreover, what is marketed as a surface-modified silica can also be used as it is.

When the curable composition of the present invention contains fine particles (D) [component (D)], the content of the component (D) is not particularly limited, but the amount is the mass ratio of the component (A) to the component (D) [( A) component: (D) component], Preferably it is 100:0.1-100:90, More preferably, 100:0.2-100:60, More preferably, 100:0.3-100:50, More preferably, 100:0.5 - 100:40, More preferably, it is an amount used as 100:0.8 - 100:30. (D) By using component in the said range, the effect of adding (D)component can be expressed more.

The curable composition of the present invention may contain, as component (E), fine particles having an average primary particle size of more than 0.04 µm and 8 µm or less (hereinafter, referred to as “fine particles (E)”).

By using the curable composition containing microparticles|fine-particles (E), the hardened|cured material excellent in peeling resistance can be formed.

Since this effect is more easily acquired, the average primary particle diameter of microparticles|fine-particles (E) becomes like this. Preferably it is 0.06-7 micrometers, More preferably, it is 0.3-6 micrometers, More preferably, it is 0.5-4 micrometers.

The average primary particle diameter of the fine particles (E) is measured by a laser scattering method using a laser diffraction/scattering particle size distribution analyzer (for example, manufactured by Horiba Corporation, product name “LA-920”) or the like. It can be obtained by performing

The shape of the fine particles (E) may be any of a spherical shape, a chain shape, a needle shape, a plate shape, a flaky shape, a rod shape, and a fibrous shape, but is preferably a spherical shape. Here, the spherical shape means a substantially spherical shape including a polyhedral shape that can be approximated to a sphere, such as a spheroid, an oval, a confetti, and a cocoon, in addition to a true spherical shape.

As a structural component of microparticles|fine-particles (E), the thing similar to what was illustrated as a structural component of microparticles|fine-particles (D) is mentioned.

Microparticles|fine-particles (E) can be used individually by 1 type or in combination of 2 or more type.

Among these, from the viewpoint of ease of obtaining the above effects, the fine particles (E) are preferably at least one type of fine particles selected from the group consisting of metal oxides, silica and silicon whose surface is coated with silicon, more preferably silica and silicon. Do.

When the curable composition of the present invention contains fine particles (E) [component (E)], the content of the component (E) is not particularly limited, but the amount is the mass ratio of the component (A) to the component (E) [(A) ) component: (E) component], Preferably it is 100:0.1-100:40, More preferably, 100:0.2-100:30, More preferably, 100:0.3-100:20, More preferably, 100 : 0.5-100:15, More preferably, it is an amount used as 100:0.8 - 100:12. (E) By using component in the said range, the effect of adding (E) component can be expressed more.

The curable composition of this invention may contain other components ((F) component) other than the said (A)-(E) component in the range which does not impair the objective of this invention.

(F) As a component, antioxidant, a ultraviolet absorber, an optical stabilizer, etc. are mentioned.

An antioxidant is added in order to prevent oxidative deterioration at the time of heating. As antioxidant, a phosphorus antioxidant, a phenol-type antioxidant, a sulfur-type antioxidant, etc. are mentioned.

Phosphites, oxaphosphaphenanthrene oxides, etc. are mentioned as phosphorus antioxidant. Monophenols, bisphenols, polymer type phenols, etc. are mentioned as a phenolic antioxidant. As the sulfur-based antioxidant, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc. can be heard

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

A ultraviolet absorber is added in order to improve the light resistance of the hardened|cured material obtained.

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

A ultraviolet absorber can be used individually by 1 type or in combination of 2 or more type.

The usage-amount of a ultraviolet absorber is 10 mass % or less normally with respect to (A) component.

An optical stabilizer is added in order to improve the light resistance of the hardened|cured material obtained.

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

These light stabilizers can be used individually by 1 type or in combination of 2 or more type.

(F) The total usage amount of component is 20 mass % or less normally with respect to (A) component.

The curable composition of the present invention can be prepared by, for example, mixing the component (A) with the solvent (S1), and components other than these in a predetermined ratio as desired, followed by defoaming.

A mixing method and a defoaming method are not specifically limited, A well-known method can be used.

The curable composition of this invention contains a sclerosing|hardenable polysilsesquioxane compound (A). Therefore, the curable composition of this invention is excellent in sclerosis|hardenability and has a low refractive index. Moreover, the curable composition of this invention is useful as a forming material of hardened|cured material with high adhesive strength.

Refractive index (nD) at 25 degreeC of curable composition of this invention is 1.380-1.434 normally, Preferably it is 1.380-1.430, More preferably, it is 1.380-1.428, More preferably, it is 1.380-1.425.

The refractive index (nD) of a curable composition can be measured by the method as described in an Example.

Moreover, the curable composition of this invention contains a solvent (S1). Therefore, even after the curable composition of the present invention is left to stand for a long time after application, an operation such as mounting of an optical element can be performed in the same manner as immediately after application.

For example, in the curable composition of the present invention, after application, usually 20 minutes or more, preferably 30 minutes or more, and more preferably 60 minutes or more, the same operation as immediately after application can be performed.

3) cured product

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

Heat curing is mentioned as a method of hardening the curable composition of this invention. The heating temperature at the time of hardening is 100-200 degreeC normally, and the heating time is 10 minutes - 20 hours normally, Preferably it is 30 minutes - 10 hours.

The hardened|cured material of this invention has high adhesive strength and is excellent in heat resistance.

It can be confirmed that the hardened|cured material of this invention has these characteristics as follows, for example. That is, a predetermined amount of the curable composition of the present invention is applied to a mirror surface of a silicon chip, the coated surface is placed on an adherend, pressed, and cured by heat treatment. This is left on the measurement stage of the bond tester heated in advance to a predetermined temperature (eg, 23° C., 100° C.) for 30 seconds, and at a height of 50 μm from the adherend, in the horizontal direction (shearing) with respect to the adhesive surface. direction) to measure the adhesive force between the test piece and the adherend.

It is preferable that it is 60 N/4 mm<2> or more in 23 degreeC, as for the adhesive force of the hardened|cured material of this invention, it is more preferable that it is 80 N/4 mm<2> or more, It is especially preferable that it is 100 N/4 mm<2> or more. Moreover, it is preferable that the adhesive force of hardened|cured material is 30 N/4 mm<2> or more in 100 degreeC, It is more preferable that it is 40 N/4 mm<2> or more, It is still more preferable that it is 50 N/4 mm<2> or more, It is especially 60 N/4 mm<2> or more desirable.

In this specification, "4 mm2" means 2 mm x 2 mm (square with one side of 2 mm).

Since it has the said characteristic, the hardened|cured material of this invention is used suitably 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 material for an optical element fixing material.

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

<Adhesive for Optical Device Fixing Material>

The curable composition 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 device fixing material, the composition is applied to one or both bonding surfaces of a material to be bonded (optical device and its substrate, etc.), and after compression, A method of making it heat-hardened and making the materials used as the bonding object adhere|attach firmly is mentioned. The application amount of the curable composition of the present invention is not particularly limited, and by curing it, the amount of materials to be adhered can be firmly adhered to each other. Usually, the thickness of the coating film of a curable composition is 0.5-5 micrometers, Preferably it is an amount used as 1-3 micrometers.

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

Although the heating temperature at the time of heat-hardening changes with the curable composition etc. to be used, it is 100-200 degreeC normally. Heating time is 10 minutes - 20 hours normally, Preferably they are 30 minutes - 10 hours.

<Encapsulant for optical element fixing material>

The curable composition of this invention can be used suitably as a sealing material for optical element fixing materials.

As a method of using the curable composition of the present invention as an encapsulant for an optical element fixing material, for example, the composition is molded into a desired shape to obtain a molded article encapsulating an optical element, and then heat-cured to cure the optical element rod. The method of manufacturing a body member, etc. are mentioned.

It does not specifically limit as a method of shape|molding the curable composition of this invention into a desired shape, A well-known molding method, such as a normal transfer molding method and a casting method, is employable.

Although the heating temperature at the time of heat-hardening changes with the curable composition etc. to be used, it is 100-200 degreeC normally. Heating time is 10 minutes - 20 hours normally, Preferably they are 30 minutes - 10 hours.

Since the optical element sealing body obtained uses the curable composition of this invention, it is excellent in heat resistance and has high adhesive strength.

Example

Hereinafter, the present invention will be described in more detail by way of Examples. However, the present invention is not limited to the following examples at all.

Unless otherwise noted, parts and % in each example are based on mass.

(Example 1)

After injecting 17.0 g (77.7 mmol) of 3,3,3-trifluoropropyltrimethoxysilane and 32.33 g (181.3 mmol) of methyltriethoxysilane into a 300 ml eggplant-type flask, this is stirred While adding an aqueous solution obtained by dissolving 0.0675 g of 35% hydrochloric acid (the amount of HCl is 0.65 mmol, 0.25 mol% with respect to the total amount of the silane compound) in 14.0 g of distilled water, the solution is added, and the whole is mixed at 30°C for 2 hours Then, the temperature was raised to 70 °C and stirred for 20 hours.

While continuing stirring the contents, a mixed solution of 0.0394 g of 28% aqueous ammonia ( _{the amount of NH 3} is 0.65 mmol) and 46.1 g of propyl acetate is added thereto, the pH of the reaction solution is set to 6.9, and the pH of the reaction solution is set to 60 at 70°C as it is. stirred for minutes.

After standing to cool a reaction liquid to room temperature, 50 g of propyl acetate and 100 g of water were added there, liquid separation processing was performed, and the organic layer containing a reaction product was obtained. Magnesium sulfate was added to this organic layer, and the drying process was performed. Curable polysilsesquioxane compound (1) was obtained by concentrating the organic layer with an evaporator, then vacuum-drying the obtained concentrate after filtration separation removal of magnesium sulfate.

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 silicone filler having an average primary particle diameter of 0.8 µm were added. Moreover, after adding 30 parts of mixed solvents of diethylene glycol monobutyl ether acetate:tripropylene glycol-n-butyl ether =40:60 (mass ratio) as a solvent, the exclusive use was stirred.

After dispersing with a three roll mill, 30 parts of 1,3,5-N-tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-(trimethoxysilyl)propylsuccinic anhydride 3 parts, further, as a solvent, a mixed solvent of diethylene glycol monobutyl ether acetate: tripropylene glycol-n-butyl ether = 40: 60 (mass ratio) is added, and the mixture is thoroughly mixed and defoamed to obtain a solid content concentration of 82%. of the curable composition (1) was obtained.

(Example 2)

Curable polysilsesquioxane compound (2) and curable composition (2) in the same manner as in Example 1 except that the stirring time after adding a mixed solution of 28% aqueous ammonia and propyl acetate was changed to 120 minutes. got

(Example 3)

Curable polysilsesquioxane compound (3) and curable composition (3) in the same manner as in Example 1 except that the stirring time after adding a mixed solution of 28% aqueous ammonia and propyl acetate was changed to 90 minutes. got

(Example 4)

Curable polysilsesquioxane compound (4) and curable composition (4) in the same manner as in Example 1 except that the stirring time after adding a mixed solution of 28% aqueous ammonia and propyl acetate was changed to 50 minutes. got

(Example 5)

Curable polysilsesquioxane compound (5) and curable composition (5) in the same manner as in Example 1 except that the stirring time after adding a mixed solution of 28% aqueous ammonia and propyl acetate was changed to 40 minutes. got

(Comparative Example 1)

According to the method of Example 8 of WO2017/110948, a curable polysilsesquioxane compound (6) was obtained.

Next, 20 parts of silica fillers having an average primary particle diameter of 7 nm and 10 parts of silicone fillers having an average primary particle diameter of 0.8 µm were added to 100 parts of the curable polysilsesquioxane compound (6). Moreover, after adding 30 parts of diethylene glycol monobutyl ether acetate as a solvent, the exclusive use was stirred.

After dispersing treatment with a three-roll mill, 10 parts of 1,3,5-N-tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-(trimethoxysilyl)propylsuccinic anhydride 3 parts, diethylene glycol monobutyl ether acetate is added so that the viscosity when measured under the conditions of 25 ° C. and 200 s ^{-1 using an E-type viscometer is 4.5 Pa.s, and then thoroughly mix and desorb the product} By inclusion, the curable composition (6) was obtained.

Further, in paragraph (0115) of WO2017/110948, the amount of hydrochloric acid to be used is described as "0.25 mol% with respect to the total amount of the silane compound", but when calculated from the injection amount, it is precisely "about 1.6 mol% with respect to the total amount of the silane compound" " to be. It is the same also in the following comparative examples 2 and 3.

(Comparative Example 2)

According to the method of Example 9 of WO2017/110948, a curable polysilsesquioxane compound (7) was obtained.

Next, the curable composition (7) was obtained by the method similar to the comparative example 1.

(Comparative Example 3)

According to the method of Example 10 of WO2017/110948, a curable polysilsesquioxane compound (8) was obtained.

Next, the curable composition (8) was obtained by the method similar to the comparative example 1.

(Comparative Example 4)

After injecting 71.37 g (400 mmol) of methyltriethoxysilane into a 300 mL eggplant flask, and stirring this, 0.1 g of 35% hydrochloric acid to 21.6 g of distilled water (0.25 mol% with respect to the total amount of the silane compound) An aqueous solution in which was dissolved was added, and the mixture was heated at 30°C for 2 hours, then at 70°C, and stirred for 5 hours.

Continuing stirring of the contents, 140 g of propyl acetate and 0.12 g of 28% aqueous ammonia (NH ₃ is 0.5 mol% with respect to the total amount of the silane compound) were added thereto, and the mixture was stirred at 70°C for 3 hours.

After cooling the reaction solution to room temperature, purified water was used to wash the organic layer until the pH of the aqueous layer became 7.

Curable polysilsesquioxane compound (9) was obtained by concentrating an organic layer with an evaporator and vacuum-drying a concentrate.

Next, the curable composition (9) was obtained by the method similar to Example 1.

(Comparative Example 5)

A curable polysilsesquioxane compound (10) and a curable composition (10) were carried out in the same manner as in Example 1 except that the stirring time after adding a mixed solution of 28% aqueous ammonia and propyl acetate was changed to 240 minutes. got

The following measurements and tests were performed using the curable polysilsesquioxane compounds (1)-(10) obtained by the Example and the comparative example, and curable composition (1)-(10), respectively. The results are shown in Table 1.

[Measurement of mass average molecular weight]

The mass average molecular weight (Mw) of the curable polysilsesquioxane compound was measured with the following apparatus and conditions.

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

Column: sequentially connected TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL

Solvent: tetrahydrofuran

Standard material: polystyrene

Injection volume: 20 μl

Measuring temperature: 40℃

Flow rate: 0.6 ml/min

Detector: Differential Refractometer

[ ²⁹ Si-NMR measurement]

Apparatus: AV-500 manufactured by Bruker Biospin

²⁹ Si-NMR resonance frequency: 99.352 MHz

Probe: 5 mmφ solution probe

Measurement temperature: room temperature (25℃)

Sample rotation speed: 20 kHz

Measurement method: Inverse gate decoupling method

²⁹ Si flip angle: 90˚

²⁹ Si 90˚ Pulse width: 8.0 ㎲

Repetition time: 5 s

Integration count: 9200 times

Observation width: 30 ㎑

< ²⁹ Si-NMR sample preparation method>

To shorten the relaxation time, Fe(acac) ₃ was added as a relaxation reagent.

Polysilsesquioxane concentration: 15%

Fe(acac) ₃ concentration: 0.6%

Measuring solvent: acetone

Internal standard: TMS

<Waveform processing analysis>

For each peak of the spectrum after Fourier transform, a chemical shift was calculated|required by the position of a peak top, and integration was performed.

[Refractive Index Measurement]

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

[Curability evaluation]

With a rheometer (manufactured by Anton Paar, MCR302), a 20 mm parallel plate was used to measure the shear stress at a test start temperature of 80°C, a temperature increase rate of 5°C/min, a shear strain of 1%, and a frequency of 1 Hz. The temperature at which a shear stress was set to 2000 Pa was made into hardening temperature.

[Viscosity evaluation]

Using a rheometer (manufactured by Anton Paar, MCR301), using a cone plate with a radius of 50 mm and a cone angle of 0.5°, at 25° C., a shear rate of 2 s ⁻¹ and a shear rate of 200 s ⁻¹ were measured. Each was measured. A thixotropic index (viscosity at a shear rate of 2 s ⁻¹ / viscosity at a shear rate of 200 s ⁻¹ ) was determined from the obtained measured values.

[Measurement of adhesion strength]

The curable composition was applied to the mirror surface of a square (area 4 mm 2 ) silicon chip having a side of 2 mm, each having a thickness of about 2 µm, and the coated surface was placed on an adherend (silver-plated copper plate) and pressed. . Then, it heat-processed at 170 degreeC for 2 hours, and it hardened|cured, and obtained the to-be-adhered body with a test piece. The adherend to which this test piece was attached was left for 30 seconds on a measurement stage of a bond tester (manufactured by Daisy, series 4000) heated in advance to a predetermined temperature (23°C, 100°C), At the position, stress was applied in the horizontal direction (shear direction) to the adhesive surface at a speed of 200 µm/s, and the adhesive strength (N/4 mm 2 ) of the test piece and the adherend at 23° C. and 100° C. was measured.

[Evaluation of Crack Resistance]

The curable composition was applied to the mirror surface of a square (area 0.25 mm 2 ) glass chip having a side of 0.5 mm so that the thickness was about 2 µm, and the coated surface was placed on an adherend (silver-plated copper plate) and pressed. Then, it heat-processed and hardened at 170 degreeC for 2 hours, and the to-be-adhered body with a test piece was obtained. Using a digital microscope (VHX-1000, manufactured by Keyence), the resin part (fillet part) protruding from the glass chip is observed, the number of samples having cracks is counted, and the crack occurrence rate is 0% or more and less than 25%. A", 25% or more and less than 50% were evaluated as "B", and 50% or more and 100% were evaluated as "C".

[Evaluation of peel resistance]

About 0.4 mmφ of the curable composition was applied to an LED lead frame (manufactured by Enomoto Co., Ltd., 5050 D/G PKG LEADFRAME), and then a square sapphire chip with a side of 0.5 mm (area 0.25 mm 2 ) was pressed. Then, after heat-processing and hardening at 170 degreeC for 2 hours, the sealing material (Shin-Etsu Chemical Co., Ltd. make, LPS-3419) was poured into a cup, and it heated at 120 degreeC for 1 hour, and 150 degreeC for 1 hour, and obtained the test piece. .

After exposing this test piece to an environment of 85°C and 85% RH for 168 hours, preheat 160°C and IR reflow for 1 minute with a maximum temperature of 260°C (reflow furnace: manufactured by Sagami Engineering Co., Ltd., Product name "WL-15-20DNX type")). Thereafter, with a thermal cycle tester, a test left at -40°C and +100°C for 30 minutes each was set as 1 cycle, and 500 cycles were performed. Then, the operation which removes the sealing material was performed, and it was investigated whether the element peeled together at that time. This test was performed 100 times for each curable composition, respectively.

The number of times the elements peeled together was counted, and if the peeling incidence rate was 25% or less, it was evaluated as "A", if it was larger than 25% and 50% or less, "B" was evaluated, and if it was larger than 50%, it was evaluated as "C".

From Table 1, the following can be seen.

As for the curable polysilsesquioxane compounds (1)-(5) obtained in Examples 1-5, as ^{a result of 29} Si-NMR measurement, it turned out that the value of Z2 exists in 20 to 40% of range. Moreover, all of the mass average molecular weights of sclerosing|hardenable polysilsesquioxane compounds (1)-(5) exist in the range of 4000-11000.

Curable compositions (1)-(5) containing these sclerosing|hardenable polysilsesquioxane compounds have a low refractive index (nD), and are fully hardened|cured at comparatively low temperature.

Moreover, the hardened|cured material of curable composition (1)-(5) has high adhesive strength.

On the other hand, Comparative Examples 1-3 use the curable polysilsesquioxane compounds [curable polysilsesquioxane compounds (6)-(8)] of Examples 8-10 of patent document 4, respectively.

In the Example of Patent Document 4, in order to compensate for the low reactivity of the silane compound having a fluoroalkyl group, a large amount of the acid catalyst is used. However, by this method, only the sclerosing|hardenable polysilsesquioxane compound with a small Z2 value could be obtained. Moreover, as the injection amount of 3,3,3-trifluoropropyl trimethoxysilane increases, the mass average molecular weight of curable polysilsesquioxane compound is falling.

This is the cause, and the curable compositions (6)-(8) of Comparative Examples 1-3 are inferior to the curable compositions (1)-(5) of Examples 1-5 in sclerosis|hardenability and the adhesive strength of hardened|cured material. .

The curable polysilsesquioxane compound (9) obtained in Comparative Example 4 does not have a repeating unit derived from 3,3,3-trifluoropropyltrimethoxysilane. For this reason, the refractive index (nD) of the curable composition 9 is a large value.

Moreover, since the curable polysilsesquioxane compound (9) has a small Z2 value, sclerosis|hardenability of the curable composition (9) is not enough.

The curable polysilsesquioxane compound (10) obtained in Comparative Example 5 has an excessively large molecular weight. As a result, curable composition 10 is inferior to curable composition (1)-(5) of Examples 1-5 in sclerosis|hardenability and adhesive strength of hardened|cured material.

Claims (13)

A curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1), wherein the following requirements 1 and 2 are satisfied.

[R ¹ represents a fluoroalkyl group represented by the composition formula: C _m H _(2m-n+1) F _{n .} m represents the integer of 1-10, n represents the integer of 2 or more and (2m+1) or less. D represents ^{a linking group for bonding R 1} and Si (however, except for an alkylene group) or a single bond.]
[Requirement 1]
^{When 29} Si-NMR of the curable polysilsesquioxane compound is measured, one or two or more peaks are observed in the region [region (2)] of -62 ppm or more and less than -52 ppm, -52 ppm or more -45 ppm 1 or 2 or more peaks are observed in at least one of the region of less than [region (1)] and the region of -73 ppm or more and less than -62 ppm [region (3)], and Z2 derived by the following formula is 20 to 40%.

P1: integral value in region (1)
P2: integral value in region (2)
P3: integral value in region (3)
[Requirement 2]
The mass average molecular weights (Mw) of sclerosing|hardenable polysilsesquioxane compound are 4,000-11,000. The method of claim 1,
The curable polysilsesquioxane compound whose ratio of the repeating unit represented by Formula (a-1) is 25 mol% or more with respect to all the repeating units. 3. The method according to claim 1 or 2,
Furthermore, the curable polysilsesquioxane compound which has a repeating unit represented by following formula (a-2).

[R ² is an alkyl group has a carbon number of 1 to 10 non-substituted, or substituted or non-substituted, or represents a group of a carbon number of 6 to 12 aryl group.] 4. The method of claim 3,
The curable polysilsesquioxane compound whose ratio of the repeating unit represented by Formula (a-2) is more than 0 mol% and 75 mol% or less with respect to all repeating units. 5. The method according to any one of claims 1 to 4,
^{When 29} Si-NMR is measured, 1 or 2 or more peaks are observed in the area|region (3), The curable polysilsesquioxane compound whose Z3 derived|guided|derived by the following formula is 60 to 80%.

The curable composition characterized by containing the following (A) component and the solvent which has a boiling point of 254 degreeC or more.
(A) Component: The curable polysilsesquioxane compound in any one of Claims 1-5 7. The method of claim 6,
Furthermore, the curable composition containing the following (B) component.
(B) component: a silane coupling agent having a nitrogen atom in the molecule 8. The method according to claim 6 or 7,
Furthermore, the curable composition containing the following (C)component.
(C) component: a silane coupling agent having an acid anhydride structure in the molecule 9. The method according to any one of claims 6 to 8,
Furthermore, the curable composition containing the following (D) component.
(D) component: fine particles having an average primary particle diameter of 5 to 40 nm Hardened|cured material obtained by hardening|curing the curable composition in any one of Claims 6-9. 11. The method of claim 10,
A cured product that is an optical device fixing material. The method of using the curable composition in any one of Claims 6-9 as an adhesive agent for optical element fixing materials. The method of using the curable composition in any one of Claims 6-9 as a sealing material for optical element fixing materials.