TW201522516A - Silane compound polymer, curable composition, cured product, and method for using cured composition - Google Patents

Abstract

A silane compound copolymer represented by formula (a-1) [In the formula, R1 represents a hydrogen atom or a C1-6 alkyl group; X0 represents a sulfur atom-containing functional group; D represents a C1-20 bivalent organic group having a single bond, or an unsubstituted or substituted group; R2 represents a C1-20 alkyl group having an unsubstituted or substituted group (excluding a sulfur atom-containing functional group), or a phenyl group having an unsubstituted or substituted group; Z1 represents a hydroxyl group or a C1-10 alkoxy group; Z2 represents a hydroxyl group, a C1-10 alkoxy group, or a halogen atom; m represents a positive integer; and n, o, p, q, and r each independently represents a 0 or a positive integer.]; a curable composition containing the aforementioned silane compound polymer; a cured product obtained by curing said composition; and a method for using said composition as an adhesive agent for an optical element or a sealing agent for an optical element. Formula (a-1) is (CHR1X0-D-SiO3/2)m(R2SiO3/2)n(CHR1X0-D-SiZ1O2/2)o(R2SiZ2O2/2)p(CHR1X0-D-SiZ1 2O1/2)q(R2SiZ2 2O1/2)r.

Description

Method for using decane compound polymer, curable composition, cured product, and curable composition

The present invention relates to a decane compound polymer having a sulfur-containing functional group as a main component of a curable composition, a curable composition containing the decane compound polymer, and a cured product obtained by curing the composition. And a method of using the above composition as an adhesive for an optical element or an encapsulant for an optical element.

In the production of the optical element package, the curable composition is used as a composition for an optical element fixing material such as an adhesive for an optical element or an encapsulant for an optical element.

The optical element includes a light-emitting element such as a semiconductor laser (LD), a light-emitting element such as a light-emitting diode (LED), a light-receiving element, a composite optical element, and an optical unit circuit. In recent years, blue light and white light light elements having shorter wavelengths of light-emitting peak wavelengths have been developed and are gradually being widely used. The high luminance of such a light-emitting element having a short light-emitting peak wavelength is progressing violently, and in this case, the heat generation amount of the optical element tends to be further increased.

In recent years, with the increase in the brightness of the optical element, the cured product of the composition for the optical element fixing material is exposed to higher-energy light and higher-temperature heat generated by the optical element for a long period of time, causing deterioration and producing a turtle. Crack, or Then the problem of low power.

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

However, in the cured product of the composition for an optical element fixing material containing a polysilsesquioxane compound as a main component described in Patent Documents 1 to 3, it is difficult to maintain a sufficient adhesion.

Therefore, it has been desired to develop a curable composition capable of obtaining a cured product having more excellent adhesion.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-359933

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-263869

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2006-328231

The present invention has been made in view of the actual circumstances of the prior art, and is provided with a decane compound polymer having a sulfur-containing functional group as a main component of a curable composition, and a polymer containing the decane compound can be obtained excellent. A curable composition of a cured product, a cured product obtained by curing the composition, and a method of using the composition as an adhesive for an optical element or an encapsulant for an optical element are problems.

In order to solve the above problems, the inventors of the present invention have repeatedly studied intensively. As a result, as described below, it has been found that a curable composition containing a specific decane compound polymer having a functional group containing a sulfur atom can be a cured product having extremely excellent adhesion without containing other additives. The present invention has been completed.

Therefore, according to the present invention, the following decane compound polymers of [1] to [10], the curable composition of [11] to [12], the cured products of [13], [14], and [15] can be provided. The method of using the curable composition of [16].

[1] a decane compound polymer represented by the following formula (a-1)

(CHR ¹ X ⁰ -D-SiO _3/2 ) _m (R ² SiO _3/2 ) _n (CHR ¹ X ⁰ -D-SiZ ¹ O _2/2 ) _o (R ² SiZ ² O _2/2 ) _p (CHR ¹ X ⁰ -D-SiZ ¹ ₂ O _1/2 ) _q (R ² SiZ ² ₂ O _1/2 ) _r . . . (a-1)

[wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X ⁰ represents a functional group containing a sulfur atom, and D represents a single bond or a carbon number of an unsubstituted or substituted group 1~ a divalent organic group of 20, and R ² represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or has a substituent (but does not include a functional group containing a sulfur atom), or an unsubstituted or substituted phenyl group. Z ¹ represents a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, Z ² represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms or a halogen atom, and m represents a positive integer, n, o, p, q, r Each independently represents 0 or a positive integer].

[2] The decane compound polymer according to [1], wherein the sulfur atom-containing functional group of X ^{0 is} a group represented by the following formula (i) or formula (ii), or a group-derived group-SH (i)

-S-CO-R’ (ii)

[In the formula, R' represents a one-valent organic group having 1 to 20 carbon atoms].

[3] The decane compound polymer according to [1], wherein n is a positive integer.

[4] The decane compound polymer according to [1], wherein the ratio of (m+o+q) to (n+p+r) [(m+o+q):(n+p+r)] It is 5:95~80:20.

[5] The decane compound polymer according to [1], wherein the weight average molecular weight is from 1,000 to 30,000.

[6] A decane compound polymer which uses at least one of the decane compound (1) represented by the formula (1): R ¹ -CH(X ⁰ )-D-Si(OR ³ ) ₃ as a monomer and It is obtained by a condensation reaction, wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X ⁰ represents a functional group containing a sulfur atom, and D represents a single bond, or is unsubstituted or substituted. The divalent hydrocarbon group having a carbon number of 1 to 20, and the R ³ group is an alkyl group having 1 to 10 carbon atoms.

[7] The decane compound polymer according to [6], wherein the sulfur atom-containing functional group of X ^{0 is} a group represented by the following formula (i) or formula (ii), -SH (i)

-S-CO-R’ (ii)

[In the formula, R' represents a one-valent organic group having 1 to 20 carbon atoms].

[8] The decane compound polymer according to [6], which comprises at least one of the aforementioned decane compound (1) and a formula (2): R ² Si(OR ⁴ ) _v (X ¹ ) _3-v A mixture obtained by condensing a mixture of at least one of the decane compounds of the decane compound (2), wherein R ² represents a carbon number of 1 to 1 which is unsubstituted or has a substituent (but does not include a sulfur atom-containing functional group). An alkyl group of 20 or an unsubstituted or substituted phenyl group, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, X ¹ represents a halogen atom, and v represents an integer of 0 to 3].

[9] The decane compound polymer according to [8], wherein the molar ratio of the decane compound (1) to the decane compound (2) contained in the mixture of the aforementioned decane compounds [the decane compound (1): decane compound ( 2)] is 5:95~80:20.

[10] The decane compound polymer according to [6], which has a weight average molecular weight of 1,000 to 30,000.

[11] A curable composition comprising the decane compound polymer according to any one of the above [1] to [10].

[12] The curable composition according to [11], which is a composition for an optical element fixing material.

[13] A cured product obtained by curing the curable composition according to the above [11].

[14] The cured product according to [13], which is a light element fixing material.

[15] A method of using the curable composition according to [11] as an adhesive for an optical element fixing material.

[16] A method of using the curable composition according to the above [11] as an encapsulant for an optical element fixing material.

The decane compound polymer of the present invention is useful as a main component of a curable composition such as an adhesive for an optical element or an encapsulant for an optical element.

By using the curable composition of the present invention, a cured product having extremely excellent adhesion can be obtained.

When the curable composition of the present invention can be used for forming an optical element fixing material, it can be suitably used as an adhesive for an optical element and an encapsulant for an optical element.

Form for implementing the invention

Hereinafter, the method of using the present invention as 1) a decane compound polymer, 2) a curable composition, 3) a cured product, and 4) a curable composition will be described in detail.

1) decane compound polymer

The decane compound polymer of the present invention is a decane compound polymer represented by the above formula (a-1) (hereinafter referred to as "decane compound polymer (A)"), or by the above formula (1). A decane compound polymer (hereinafter referred to as "decane compound polymer (A')") obtained by a condensation reaction using at least one of the decane compound (1) as a monomer.

[Chane Compound Polymer (A)]

The decane compound polymer (A) is a decane compound polymer represented by the following formula (a-1).

(CHR ¹ X ⁰ -D-SiO _3/2 ) _m (R ² SiO _3/2 ) _n (CHR ¹ X ⁰ -D-SiZ ¹ O _2/2 ) _o (R ² SiZ ² O _2/2 ) _p (CHR ¹ X ⁰ -D-SiZ ¹ ₂ O _1/2 ) _q (R ² SiZ ² ₂ O _1/2 ) _r . . . (a-1)

In the above formula (a-1), a repeating unit represented by the formula: -(CHR ¹ X ⁰ -D-SiO _3/2 )-, a repeating unit represented by the formula: -(R ² SiO _3/2 )-, A repeating unit represented by the formula: -(CHR ¹ X ⁰ -D-SiZ ¹ O _2/2 )-, a repeating unit represented by the formula: -(R ² SiZ ² O _2/2 )-, with the formula: -( CHR ¹ X ⁰ -D-SiZ ¹ ₂ O _1/2 )- represents a repeating unit, and a repeating unit represented by the formula: -(R ² SiZ ² ₂ O _1/2 )-, each of which can be as follows (a11 )~(a16) indicates. Further, in (a11) to (a16), "-O-" means an oxygen atom shared by two adjacent Si atoms.

In the decane compound copolymer (A) used in the present invention, in the above formula (a-1), when each of m, n, o, p, q, and r is two or more, the above formula (a11) to (a) Each of the repeating units indicated by a16) may be the same or different.

In the formula (a-1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms of R ¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a t-butyl group, and a n-pentyl group. Base, n-hexyl, etc.

Among these, as R ¹ , a hydrogen atom is preferred.

X ⁰ represents a functional group containing a sulfur atom.

The functional group containing a sulfur atom is not particularly limited as long as it contains an organic group of a sulfur atom. For example, a group represented by the following formula (i) or formula (ii) or a group derived from these groups may be mentioned. The term "base derived from these groups" means a reaction represented by the formula (i) or formula (ii) by a side reaction generated when a decane compound polymer is produced.

-SH (i)

-S-CO-R’ (ii)

In the formula, R' represents a one-valent organic group having 1 to 20 carbon atoms. The one-valent organic group having 1 to 20 carbon atoms is not particularly limited as long as -CO-R' has a function as a protective group. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl An alkyl group such as a fluorenyl group, a n-decyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group; an unsubstituted or substituted phenyl group;

Examples of the substituent of the unsubstituted or substituted phenyl group of R' include an alkyl group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a n-butyl group; and a fluorine atom, a chlorine atom or a bromine atom; Or a halogen atom; an alkoxy group such as a methoxy group or an ethoxy group.

R' is preferably an alkyl group having 1 to 20 carbon atoms and an alkyl group having 1 to 10 carbon atoms. The base is preferred.

In the present invention, the functional group containing a sulfur atom of X ⁰ is particularly preferably a group represented by the formula (i).

D represents a single bond or an unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms, an extended alkenyl group having 2 to 20 carbon atoms, an extended alkynyl group having 2 to 20 carbon atoms, and a carbon number of 6 to 20; An aryl group, a divalent group having 7 to 20 carbon atoms, or the like, which is composed of a combination of an alkyl group, an alkenyl group or an alkynyl group and an extended aryl group.

Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an exoethyl group, a propyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

Examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, a propylene group, a butenyl group, and a pentenyl group.

Examples of the alkynyl group having 2 to 20 carbon atoms include an exetylene group and a propargylene group.

Examples of the extended aryl group having 6 to 20 carbon atoms include an ortho-phenyl group, an exophenyl group, a para-phenyl group, and a 2,6-anthranyl group.

Examples of the substituent of the alkylene group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, and the alkynyl group having 2 to 20 carbon atoms include halogens such as fluorine atoms and chlorine atoms. An alkoxy group such as a methoxy group or an ethoxy group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; and the like.

Examples of the substituent of the aryl group having 6 to 20 carbon atoms include a nitro group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkyl group such as a methyl group or an ethyl group; and a methoxy group and an ethoxy group. An alkoxy group such as a methyl group; an alkylthio group such as a methylthio group or an ethylthio group; and the like.

These substituents may be bonded to any of the groups of an alkyl group, an alkenyl group, an alkynyl group, and an extended aryl group, and may be bonded in the same or different numbers.

The divalent group consisting of a combination of an unsubstituted or substituted (alkyl, alkenyl, or alkynyl group) and an unsubstituted or substituted aryl group may be exemplified by the aforementioned unsubstituted or At least one of a substituent (alkylene group, an alkenyl group, or an alkynylene group) having at least one of the above-mentioned unsubstituted or substituted aryl groups, and the like. Specifically, a base represented by the following formula and the like can be given.

Among these, as D, since a cured product having a higher adhesion can be obtained, an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 1 to 6 carbon atoms is preferred, and The base or the ethyl group is particularly preferred.

R ² represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or has a substituent (but does not include a functional group containing a sulfur atom), or an unsubstituted or substituted phenyl group.

The alkyl group having 1 to 20 carbon atoms of R ² may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group or a n-pentyl group. , n-hexyl, n-octyl, isooctyl, n-decyl, n-decyl, n-decyl and the like.

Examples of the substituent of the alkyl group having 1 to 20 carbon atoms which has a substituent of R ² include alkoxy groups having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; and a phenyl group and a 4-methylphenyl group; , an aryl group having an unsubstituted or substituted group such as a 3-methoxyphenyl group, a 2,4-dichlorophenyl group, a 1-naphthyl group or a 2-naphthyl group; a halogen atom such as a fluorine atom or a chlorine atom; and a cyano group; A group represented by the formula OG, such as an ethoxycarbonyl group or a benzamidine group (wherein G represents a protective group of a hydroxyl group).

Examples of the substituent of the phenyl group having a substituent of R ² include an alkyl group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a n-butyl group; and an alkoxy group such as a methoxy group or an ethoxy group. A halogen atom such as a fluorine atom or a chlorine atom.

Among these, R ² an alkyl group having 1 to 20 carbon atoms or an unsubstituted or substituted phenyl group of the preferred, an alkyl group having 1 to 6 carbon atoms or unsubstituted or substituted phenyl group of Preferably, it is particularly preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.

Z ¹ represents a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

Examples of the alkoxy group having 1 to 10 carbon atoms of Z ¹ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a third butoxy group, a pentyloxy group, and a hexyloxy group. Base, octyloxy, etc.

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

Z ² represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms or a halogen atom.

The alkoxy group having 1 to 10 carbon atoms of Z ² may be the same as the alkoxy group having a carbon number of 1 to 10 which is disclosed as Z ¹ .

Examples of the halogen atom of Z ² include a chlorine atom and a bromine atom.

Among these, Z ² is preferably a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

The m system represents a positive integer.

n, o, p, q, and r are each independent and represent 0 or a positive integer. Especially n It is better to use a positive integer. By hardening the curable composition containing the decane compound polymer (A) in which n is a positive integer, a cured product having more excellent adhesion can be obtained.

The ratio of (m+o+q) to (n+p+r) [(m+o+q):(n+p+r)] is preferably 5:95~80:20, 10:90 ~70:30 is better, 20:80~65:35 is better, and 30:70~60:40 is especially good. By curing a curable composition containing a ratio of (m+o+q) to (n+p+r) to the decane compound polymer (A) in such a range, it is possible to obtain a more excellent adhesion property. Hardened material.

Moreover, for the same reason, the ratio of m to n (m:n) is preferably 5:95 to 80:20, preferably 10:90 to 70:30, and 20:80 to 65:35. Better, 30:70~60:40 is especially good.

The equivalent value can be determined, for example, by measuring the nuclear magnetic resonance spectrum (NMR spectrum) of the decane compound polymer (A).

When the decane compound polymer (A) is a copolymer, the decane compound polymer (A) may be any copolymer of a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer or the like. Among these, a random copolymer is preferred, and the structure of the decane compound polymer (A) may be a ladder type structure, a double-decker type structure, a cage structure, Any of the structures of a partially cleft-cage structure, a ring-shaped structure, and a random structure.

The weight average molecular weight (Mw) of the decane compound polymer (A) is preferably in the range of 400 to 30,000, preferably 600 to 10,000, particularly preferably in the range of 800 to 3,000. By curing the curable composition containing the decane compound polymer (A) having a weight average molecular weight within such a range, a cured product having more excellent adhesion can be obtained.

The weight average molecular weight (Mw) can be determined, for example, by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, in terms of standard polystyrene (the same applies hereinafter).

The molecular weight distribution (Mw/Mn) of the decane compound polymer (A) is not particularly limited, and is usually in the range of 1.0 to 3.0, preferably 1.1 to 2.0. By hardening the curable composition containing the decane compound polymer (A) having the molecular weight distribution within such a range, a cured product having more excellent adhesion can be obtained.

The decane compound (A) of the present invention can be produced, for example, by condensing a decane compound (1) or the like in a method for producing a decane compound (A') as described later.

When the decane compound polymer (A) is obtained by condensation (reaction) in the manner of a method for producing a decane compound polymer (A') to be described later, the OR ³ of the decane compound (1) is not dehydrated and/or The dealcoholated portion remains in the decane compound polymer (A). In other words, when there is one residual OR ³ , the above formula (a-1) is retained as (CHR ¹ X ⁰ -D-SiZ ¹ O _2/2 ), and when the remaining OR ³ is two In the above formula (a-1), it is retained as (CHR ¹ X ⁰ -D-SiZ ¹ ₂ O _1/2 ).

Similarly to the decane compound (2), among the OR ⁴ or X ¹ , the undehydrated and/or dealcoholated portion remains in the decane compound polymer (A). In other words, when there is one residual OR ⁴ or X ¹ , the formula (a-1) remains as (R ² SiZ ² O _2/2 ), and when the remaining OR ⁴ or X ¹ is two, In the formula (a-1), it remains as (R ² SiZ ² ₂ O _1/2 ).

[decane compound polymer (A')]

The decane compound polymer (A') is a condensation which is used as a monomer by at least one of the decane compound (1) represented by the formula (1): R ¹ -CH(X ⁰ )-D-Si(OR ³ ) ₃ The decane compound polymer obtained by the reaction.

[decane compound (1)]

The decane compound (1) is a compound represented by the formula (1): R ¹ -CH(X ⁰ )-D-Si(OR ³ ) ₃ . By using the decane compound (1), a decane compound polymer having good transparency and adhesion after curing can be obtained.

In the formula (1), R ¹ , X ⁰ and D represent the same meaning as described above. R ³ represents an alkyl group having 1 to 10 carbon atoms. OR ³ may be the same or different from each other.

Examples of the alkyl group having 1 to 10 carbon atoms of R ³ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, and a n-pentyl group. Base, and hexyl group, etc.

Among the decane compounds (1), examples of the decane compound represented by the above formula (i) as X ⁰ include thiomethylmethyltrimethoxydecane, thiomethylmethyltriethoxydecane, and hydrogen. Thiomethyltripropoxydecane, 2-hydrothioethyltrimethoxydecane, 2-hydrothioethyltriethoxydecane, 2-hydrothioethyltripropoxydecane, 3- A thiolalkyltrialkalkoxynonane such as hydrogenthiopropyltrimethoxydecane, 3-hydrothiopropyltriethoxydecane or 3-hydrothiopropyltripropoxydecane.

Among the decane compounds (1), examples of the decane compound represented by the above formula (ii) as X ⁰ include 2-hexylthioethyltrimethoxydecane and 2-hexylsulfanylethyl three. Ethoxy decane, 2-octyl thioethyl trimethoxy decane, 2-octyl thioethyl triethoxy decane, 2-decyl thioethyl trimethoxy decane, 2- sulfonium sulphide Base ethyl triethoxy decane, 3-hexyl thiopropyl trimethoxy decane, 3-hexyl thiopropyl triethoxy decane, 3-octyl thiopropyl trimethoxy decane, 3 - alkyl sulfonyl trialkoxy decane such as octyl thiopropyltriethoxy decane, 3-decyl propyl trimethoxy decane, 3-decyl propyl propyl triethoxy decane Compound class.

These decane compounds (1) can be used singly or in combination of two or more.

Among these, as the decane compound (1), since a cured product having more excellent adhesion can be obtained, a decane compound having a group represented by the above formula (i) as X ⁰ is preferable.

As the decane compound polymer (A'), at least one of the aforementioned decane compound (1) and a decane compound represented by the formula (2): R ² Si(OR ⁴ ) _v (X ¹ ) _3-v (2) It is preferred that a mixture of at least one of the decane compounds is condensed. By curing the curable composition containing the decane compound polymer (A') obtained by condensing such a mixture, a cured product having more excellent adhesion can be obtained. Here, "condensation" is used in a broad concept including hydrolysis and polycondensation reaction.

[decane compound (2)]

The decane compound (2) is a compound represented by the formula (2): R ² Si(OR ⁴ ) _v (X ¹ ) _3-v .

In the formula (2), R ² has the same meaning as defined above. R ⁴ represents an alkyl group having 1 to 10 carbon atoms similar to the above R ³ , X ¹ represents a halogen atom such as a chlorine atom or a bromine atom, and v represents an integer of 0 to 3.

When v is 2 or more, OR ⁴ may be the same or different from each other. Further, when (3-v) is 2 or more, X ¹ may be the same or different from each other.

Specific examples of the decane compound (2) include methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, and ethyltriethoxylate. Baseline, n-propyltrimethoxydecane, n-butyltriethoxydecane, isobutyltrimethoxydecane, n-pentyltriethoxydecane, n-hexyltrimethoxydecane, isooctyltriethoxy Base decane, dodecyltrimethoxy decane, methyl dimethoxyethoxy decane, methyl diethoxy methoxy decane, chloromethyl trimethoxy decane, bromomethyl triethoxy decane, 2 -chloroethyltripropoxydecane, 2-bromoethyltributoxydecane, 3-chloropropyltrimethoxydecane, 3-chloropropyltriethoxydecane, 3-ethyloxypropyl An alkyltrialkoxy alkane compound of an unsubstituted or substituted group such as trimethoxydecane, 3-ethoxymethoxypropyltriethoxydecane or 3-ethoxymethoxypropyltripropoxydecane; Methylchlorodimethoxydecane, methylchlorodiethoxydecane, ethylchlorodimethoxydecane, n-propylchlorodimethoxydecane, bromomethylbromodimethoxydecane, 3-B An unsubstituted or substituted alkyl halo dialkoxy decane compound such as methoxypropyl chlorodimethoxy decane; methyl dichloromethoxy decane, methyl dichloro methoxy decane , ethyl dichloromethoxy decane, n-propyl dichloromethoxy decane, 2-chloroethyl dichloromethoxy decane, 2-bromoethyl dichloroethoxy decane, 3-chloropropyl An unsubstituted or substituted alkyl dihaloalkoxy group such as chloromethoxy decane, 3-ethoxymethoxypropyl dichloromethoxy decane, 3-ethoxypropyl propyl dichloroethoxy decane Decane compounds; methyltrichlorodecane, methyltribromodecane, ethyltrichlorodecane, ethyltribromodecane, n-propyltrichlorodecane, chloromethyltrichlorodecane, 3-chloropropyltrichloromethane An unsubstituted or substituted alkyl trihalodecane compound such as 3-chloropropyltribromodecane, 3-ethyloxypropyltrichlorodecane or 3-ethoxymethoxypropyltribromodecane; benzene Trimethoxy decane, 4-methoxyphenyl trimethoxy decane, 2-chlorophenyltrimethoxydecane, phenyltriethoxydecane, 2-methoxyphenyltriethoxydecane, phenyldimethoxyethoxynonane, phenyldiethoxymethoxy An unsubstituted or substituted phenyltrialkoxydecane compound such as decane; unsubstituted or phenylchlorodimethoxydecane, phenylchloromethoxyethoxydecane, phenylchlorodiethoxydecane, or the like a phenyl haloalkoxy decane compound having a substituent; an unsubstituted or substituted phenyl dihalo alkoxy decane compound such as phenyldichloromethoxy decane or phenyldichloroethoxy decane; Phenyltrichloromethane, phenyltribromonane, 4-methoxyphenyltrichlorodecane, phenyltrichlorodecane, 2-ethoxyphenyltrichlorodecane, 2-chlorophenyltrichlorodecane, etc. A phenyl trihalodecane compound which is unsubstituted or has a substituent.

These decane compounds (2) can be used singly or in combination of two or more.

Among these, as the decane compound (2), an unsubstituted or substituted alkyltrialkoxydecane compound having 1 to 6 carbon atoms, an unsubstituted or substituted phenyltrialkoxy group Decanated compounds are preferred.

[condensation reaction]

In the production of the decane compound polymer (A'), the condensation reaction may be carried out using only the decane compound (1), or a mixture of the decane compound (1) and the decane compound (2) may be used for the condensation reaction. Further, other decane compounds may be further used without departing from the object of the present invention, but it is preferred to use a decane compound other than the decane compound (1) and the decane compound (2).

The molar ratio of the decane compound (1) to the decane compound (2) contained in the mixture of the decane compound (1) and the decane compound (2) [decane] The compound (1): the decane compound (2) is preferably from 5:95 to 80:20 and preferably from 10:90 to 70:30 from the viewpoint of obtaining a cured product having more excellent adhesion. It is better to use 20:80~65:35, and 30:70~60:40 is especially good.

By curing the curable composition containing the decane compound polymer (A') obtained by the reaction in this range, a cured product having more excellent adhesion can be obtained.

The method of condensing the decane compound (1) or the like is not particularly limited, and a method in which a decane compound such as a decane compound (1) is dissolved in a solvent, and a predetermined amount of a catalyst is added and stirred at a predetermined temperature is mentioned.

The catalyst to be used may be either an acid catalyst or an alkali catalyst.

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

Examples of the base catalyst include trimethylamine, triethylamine, lithium diisopropyl decylamine, lithium bis(trimethyldecyl) guanamine, pyridine, and 1,8-diazabicyclo [5.4.0]. -7-undecene, aniline, pyridyl, 1,4-diazabicyclo[2.2.2]octane, organic base such as imidazole; organic salt hydrogen such as tetramethylammonium hydroxide or tetraethylammonium hydroxide Oxide; metal alkoxide such as sodium methoxide, sodium ethoxide, sodium butoxide or potassium t-butoxide; metal hydride such as sodium hydride or calcium hydride; sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. Metal hydroxide; metal carbonate such as sodium carbonate, potassium carbonate or magnesium carbonate; metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate.

The amount of the catalyst used is usually from 0.1 mol% to 10 mol%, preferably from 1 mol% to 5 mol%, based on the total moles of the decane compound.

The solvent to be used can be appropriately selected depending on the type of the decane compound and the like. For example, water, aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, and methyl propionate; acetone, methyl ethyl ketone, and methyl alcohol A ketone such as isobutyl ketone or cyclohexanone; an alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol or third butanol. These solvents can be used singly or in combination of two or more.

The amount of the solvent used is usually from 0.1 mol to 10 mol, preferably from 0.5 mol to 10 mol, per 1 liter of the solvent.

The temperature at which the decane compound is condensed (reacted) is usually in the range of from 0 ° C to the boiling point of the solvent to be used, and preferably in the range of from 20 ° C to 100 ° C. When the reaction temperature is too low, the progress of the condensation reaction may become insufficient. On the other hand, when the reaction temperature is too high, it is difficult to suppress gelation. The reaction system is usually completed in 30 minutes to 20 hours.

When an acid catalyst is used, when an alkali aqueous solution such as sodium hydrogencarbonate or the like is added to the reaction solution, and an alkali catalyst is used, neutralization is carried out by adding an acid such as hydrochloric acid to the reaction solution, and filtration is used at this time. The target decane compound polymer can be obtained by separating or washing with water or the like to remove the salt.

The weight average molecular weight (Mw) of the decane compound polymer (A') is preferably in the range of 400 to 30,000, preferably 600 to 10,000, from the viewpoint of obtaining a cured product having more excellent adhesion, and particularly preferably Range of 800~3,000.

The molecular weight distribution (Mw/Mn) of the decane compound polymer (A') is not particularly limited, and is usually in the range of 1.0 to 3.0, preferably 1.1 to 2.0, from the viewpoint of obtaining a cured product having more excellent adhesion. .

When the above decane compound polymer (A) and the decane compound polymer (A') are ladder-type polymers, the decane compound polymer (A) and the decane compound polymer (A') are intramolecular, and the following formula Among the repeating units indicated in (i), (ii) and (iii), having (i) and (ii), (i) and (iii), (ii) and (iii), or (i), The decane compound polymer of the repeating unit of ii) and (iii) is preferred.

(wherein R ¹ , R ² , D, and X ^{0 have the} same meanings as defined above).

In this case, the ^{formula: R 1 -CH (X 0)} -D- represents the group is present in an amount ^{([R 1 -CH (X 0} ) -D]) and R ² is present in an amount ([R ^2]) based In terms of molar ratio, [R ¹ -CH(X ⁰ )-D]:[R ² ]=5:95~80:20 is preferred, and 10:90~70:30 is preferred, 20:80 ~65:35 is better, with 30:70~60:40 as the best. By using a curable composition containing a decane compound polymer in this range, a cured product having more excellent adhesion can be obtained.

The decane compound polymer (A) and the decane compound polymer (A') may each have one type of repeating unit represented by (i), (ii), or (iii), or may have two or more types.

2) Sturdy composition

The second aspect of the present invention is a curable composition containing the decane compound polymer of the present invention.

The curable composition of the present invention preferably contains a decane compound polymer of the present invention as a main component. The term "containing as a main component" means one or two or more kinds of the decane compound polymers of the present invention containing 50% by mass or more of the entire curable composition. The content of the decane compound polymer of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more based on the entire curable composition. The content of the decane compound polymer of the present invention is not particularly limited, and the curable composition of the present invention may be composed of the decane compound polymer of the present invention (the content of the decane compound polymer of the present invention is 100% by mass).

When the curable composition of the present invention contains other additional components, examples of the other additive component include an antioxidant, an ultraviolet absorber, a photostabilizer, and a diluent.

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

Examples of the phosphorus-based antioxidant include phosphites and oxaphosphorus oxides.

Examples of the phenolic antioxidant include monophenols, bisphenols, and polymeric phenols.

Examples of the sulfur-based antioxidant include dilauryl-3,3'-thiopropionate, dimyristyl-3,3'-thiopropionate, distearyl-3,3'-sulfur Propionate and the like.

These antioxidants can be used singly or in combination of two or more. The amount of the antioxidant to be used is usually 10% by mass or less based on the component (A) (or the component (A').

The ultraviolet absorber is added for the purpose of light resistance of the obtained cured product.

Examples of the ultraviolet absorber include salicylic acid, diphenylketone, benzotriazole, and hindered amine.

The ultraviolet absorbers can be used singly or in combination of two or more.

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

The light stabilizer is added for the purpose of improving the light resistance of the obtained cured product.

As the photostabilizer, for example, poly[{6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{ (2,2,6,6-tetramethyl-4-piperidine)imido}hexamethylene {(2,2,6,6-tetramethyl-4-piperidine)imido}] Hindered amines, etc.

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

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

The diluent is added to adjust the viscosity of the curable composition.

As a diluent, for example, glycerol diepoxypropyl ether, butanediol diepoxypropyl ether, diepoxypropyl aniline, neopentyl alcohol epoxy propyl ether, cyclohexane dimethanol diepoxypropyl Ether, alkyl diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, glycine Oil triepoxypropyl ether, 4-vinylcyclohexene oxide, 4-vinylcyclohexene dioxide, methylated vinylcyclohexene, and the like.

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

The curable composition of the present invention can be obtained, for example, by blending the above (A) (or (A') component) and other components as needed, in a predetermined ratio, and mixing and defoaming according to a conventional method.

When the curable composition of the present invention obtained as described above is used, it is possible to obtain a cured product having a high adhesion force over a long period of time even when it is irradiated with high-energy light and when it is placed at a high temperature.

The curable composition containing a decane compound polymer obtained by using 2-cyanoethyltrimethoxydecane or the like as a raw material can provide a cured product having excellent adhesion. However, since 2-cyanoethyltrimethoxydecane or the like is designated as a low toxicity poison, its use is limited. Although the curable composition of the present invention does not use such a decane compound polymer obtained as a raw material designated as a poison, it is possible to provide a cured product having excellent excellent adhesion.

Therefore, the curable composition of the present invention can be suitably used as a raw material, an adhesive, a coating agent, or the like as an optical member and a molded body. In particular, since the problem of deterioration of the optical element fixing material due to the increase in luminance of the optical element can be solved, the curable composition of the present invention can be suitably used as the optical element fixing composition.

3) Hardened material

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

As a method of hardening the hardening composition of the invention, heat hardening is mentioned. The heating temperature at the time of hardening is usually from 100 to 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 has excellent adhesion. In particular, even when the cured product of the present invention is cured by using a curable composition containing no additive such as a decane coupling agent, it has excellent adhesion. Therefore, when the cured product is produced by using the decane compound polymer of the present invention, since the step of adding the additive to the decane compound polymer can be omitted, it is possible to efficiently obtain a cured product having excellent adhesion.

The cured product obtained by curing the curable composition of the present invention has a high adhesion, and can be confirmed, for example, by measuring the adhesion force as follows. That is, the curable composition is applied to the mirror surface of the tantalum wafer, and the coated surface is placed on the object to be pressed, pressed and heat treated to be hardened. It is placed on a measuring stage of a bond tester which has been previously heated to a predetermined temperature (for example, 23 ° C, 100 ° C) for 30 seconds, and is at a height of 50 μm from the object to be pressed, Next, stress was applied in the horizontal direction (shear direction) and the adhesion between the test piece and the object to be pressed was measured.

The adhesion of the cured product is preferably 50 N/2 mm □ or more at 23 ° C, and preferably 100 N / 2 mm □ or more. Further, the adhesion of the cured product is preferably 50 N/2 mm □ or more at 100 ° C, and preferably 70 N / 2 mm □ or more.

The cured product of the present invention can solve the problem of deterioration of the optical element fixing material due to the high luminance of the optical element, and thus can be suitably used as the optical element fixing material. For example, a raw material, an adhesive, a coating agent, a sealing material, or the like, which is an optical member and a molded body, can be suitably used.

4) How to use the hardenable composition

In the fourth aspect of the invention, the curable composition of the present invention is used as a composition for an optical element fixing material such as an adhesive for an optical element or an encapsulant for an optical element.

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

<Battery for optical element>

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

As a method of using the curable composition of the present invention as an adhesive for an optical element, the composition is applied to one or both of the materials (optical elements, substrates, and the like) of the target material and is pressure-bonded. Thereafter, the method is such that the heat is hardened and the materials of the following objects are firmly adhered to each other.

Examples of the main substrate material to be used for the optical element include glass such as soda lime glass and heat-resistant hard glass; ceramics; iron, copper, aluminum, gold, silver, platinum, chromium, titanium, and the like. Metals such as alloys, stainless steels (SUS302, SUS304, SUS304L, SUS309, etc.); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, Polystyrene, polycarbonate, polymethylpentene, polyfluorene, polyetheretherketone, polyether oxime, polyphenylene sulfide, polyether oximine, polyimine, polyamine, acrylic A synthetic resin such as a resin, a decene-based resin, a cycloolefin resin, or a glass epoxy resin.

The heating temperature at the time of heat curing depends on the curable composition to be 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.

<Packaging agent for optical components>

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

As a method of using the curable composition of the present invention as an encapsulant for an optical element, for example, a shape in which the composition is formed into a shape and a molded body in which the optical element is contained is obtained, and then the object is heated. A method of hardening to manufacture an optical element package or the like.

The method of forming the shape required for the curable composition of the present invention is not particularly limited, and a conventional molding method such as a normal transfer molding method or a casting method can be employed.

The heating temperature at the time of heat curing is usually 100 to 200 ° C depending on the curable composition to be used and the like. The heating time is usually from 10 minutes to 20 hours, preferably from 30 minutes to 10 hours.

Since the obtained optical element package uses the curable composition of the present invention, even when the light-emitting element uses a light-emitting peak wavelength such as a white or blue light-emitting LED of 400 to 490 nm in a short wavelength, it is not easy to be heated and light. Causes a low level of adhesion.

[Examples]

Next, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited by the examples described below.

(weight average molecular weight determination)

The weight average molecular weight (Mw) of the decane compound polymer obtained in the following production example is set to a standard polystyrene equivalent value and the following apparatus and conditions Determined below.

Device name: HLC-8220GPC, made by TOSOH

Column: Connect TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL in sequence

Solvent: tetrahydrofuran

Injection volume: 80μl

Measuring temperature: 40 ° C

Flow rate: 1ml/min

Detector: Differential Refractometer

(Measurement of IR spectrum)

The IR spectrum of the decane compound polymer obtained in the production example was measured using the following apparatus.

Fourier transformation infrared spectrophotometer (Spectrum100, manufactured by Perkinelmer)

(Example 1)

In a 500 ml eggplant type flask, 26.77 g (135 mmol) and 3-hydrothiopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., product name) were added to phenyltrimethoxydecane (manufactured by Tokyo Chemical Industry Co., Ltd., the same). "KBM-803", the same as the following) 2.95 g (15 mmol), and 120 g of acetone and 30 g of distilled water were used as a solvent, and 0.15 g (1.5 mmol) of phosphoric acid (manufactured by Kanto Chemical Co., Ltd.) was added as a catalyst while stirring the contents. Further stirring was continued at 25 ° C for 16 hours with stirring.

After completion of the reaction, 100 ml of ethyl acetate was added to the reaction mixture, and the mixture was neutralized with a saturated aqueous sodium hydrogencarbonate solution, and the mixture was allowed to stand for a while, and then separated. Machine layer. Next, the organic layer was washed twice with distilled water, and then dried using anhydrous magnesium sulfate. After separating the magnesium sulfate by filtration, the filtrate was concentrated to 50 ml using an evaporator, and the obtained concentrate was dropped into a large amount of n-hexane to precipitate it, and the precipitate was separated by decantation. The obtained precipitate was dissolved in methyl ethyl ketone (MEK), recovered, and the solvent was distilled off under reduced pressure using an evaporator. The decane compound polymer (A1) was obtained by vacuum drying the residue.

The weight average molecular weight (Mw) of the decane compound polymer (A1) was 1,200.

The IR spectrum data of the decane compound polymer (A1) is shown below.

^{Si-Ph: 698cm -1, 740cm} -1, Si-O: 1132cm -1, SH :( repeating units as derived from a small amount of 3- mercapto propyl trimethoxy Silane it, it is impossible to detect)

(Example 2)

In Example 1, except that the amount of phenyltrimethoxydecane used was 22.31 g (112.5 mmol), and the amount of 3-hydrothiopropyltrimethoxydecane used was 7.36 g (37.5 mmol). The decane compound polymer (A2) was obtained in the same manner as in Example 1.

The weight average molecular weight (Mw) of the decane compound polymer (A2) was 2,700.

The IR spectrum data of the decane compound polymer (A2) is shown below.

Si-Ph: 698 cm ^-1 , 740 cm ^-1 , Si-O: 1132 cm ^-1 , SH: 2567 cm ^-1

(Example 3)

In Example 1, except that the amount of use of phenyltrimethoxydecane was 14.87 g (75.0 mmol), and the amount of 3-hydrothiopropyltrimethoxydecane used was 14.72 g (75.0 mmol). The decane compound polymer (A3) was obtained in the same manner as in Example 1.

The weight average molecular weight (Mw) of the decane compound polymer (A3) was 1,700.

Further, the IR spectrum data of the decane compound polymer (A3) is shown below.

Si-Ph: 699 cm ^-1 , 741 cm ^-1 , Si-O: 1132 cm ^-1 , SH: 2567 cm ^-1

(Example 4)

In Example 1, except that the amount of use of phenyltrimethoxydecane was 29.45 g (148.5 mmol), and the amount of 3-hydrothiopropyltrimethoxydecane used was set to 0.29 g (1.5 mmol). The decane compound polymer (A4) was obtained in the same manner as in Example 1.

The weight average molecular weight (Mw) of the decane compound polymer (A4) is 900.

Further, the IR spectrum data of the decane compound polymer (A4) is shown below.

Si-Ph: 699 cm ^-1 , 741 cm ^-1 , Si-O: 1132 cm ^-1 , SH: (Because the amount of repeating units derived from 3-hydrothiopropyltrimethoxydecane is small, it cannot be detected)

(Example 5)

In Example 1, except that the amount of use of phenyltrimethoxydecane was 28.26 g (142.5 mmol), and the amount of 3-hydrothiopropyltrimethoxydecane used was 1.47 g (7.5 mmol). The decane compound polymer (A5) was obtained in the same manner as in Example 1.

The weight average molecular weight (Mw) of the decane compound polymer (A5) is 900.

Further, IR spectrum data of the decane compound polymer (A5) is shown below.

Si-Ph: 699 cm ^-1 , 741 cm ^-1 , Si-O: 1132 cm ^-1 , SH: (Because the amount of repeating units derived from 3-hydrothiopropyltrimethoxydecane is small, it cannot be detected)

(Example 6)

In the same manner as in Example 1, except that phenyltrimethoxydecane was not used and 29.45 g (150.0 mmol) of 3-hydrothiopropyltrimethoxydecane was used, a decane compound polymer was obtained ( A6).

The weight average molecular weight (Mw) of the decane compound polymer (A6) is 1800.

Further, the IR spectrum data of the decane compound polymer (A6) is shown below.

Si-O: 1132cm ^-1 , SH: 2567cm ^-1

(Example 7)

In Example 1, except that the amount of use of phenyltrimethoxydecane was 7.43 g (37.5 mmol), and the amount of 3-hydrothiopropyltrimethoxydecane used was 22.09 g (112.5 mmol). The decane compound polymer (A7) was obtained in the same manner as in Example 1.

The weight average molecular weight (Mw) of the decane compound polymer (A7) was 1,100.

Further, IR spectrum data of the decane compound polymer (A7) is shown below.

Si-Ph: 699 cm ^-1 , 741 cm ^-1 , Si-O: 1132 cm ^-1 , SH: 2567 cm ^-1

(Comparative Example 1)

In a 300 ml eggplant type flask, 20.2 g (102 mmol) of phenyltrimethoxydecane, 3.15 g (18 mmol) of 2-cyanoethyltrimethoxydecane (manufactured by AZMAX Co., Ltd.), and 96 ml of acetone and 24 ml of distilled water were added. After the solvent, 0.15 g (1.5 mmol) of phosphoric acid was added as a catalyst while stirring the contents, and further stirring was continued at 25 ° C for 16 hours.

After completion of the reaction, the reaction mixture was concentrated to 50 ml using an evaporator, and ethyl acetate (100 ml) was added to the concentrate and neutralized using a saturated aqueous sodium hydrogen carbonate solution. After standing for a while, the organic layer was separated. Next, the organic layer was washed twice with distilled water, and then dried using anhydrous magnesium sulfate. After separating the magnesium sulfate by filtration, the filtrate was concentrated to 50 ml using an evaporator, and the obtained concentrate was dropped into a large amount of n-hexane to precipitate it, and the precipitate was separated by decantation. The resulting precipitate is dissolved in methyl ethyl ketone (MEK) and returned The solvent was distilled off under reduced pressure using an evaporator. The decane compound polymer (A8) was obtained by vacuum drying the residue.

The weight average molecular weight (Mw) of the decane compound polymer (A8) was 1,900.

The IR spectrum data of the decane compound polymer (A8) is shown below.

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

(Comparative Example 2)

In a 300 ml eggplant type flask, 20.2 g (102 mmol) of phenyltrimethoxydecane, 4.0 g (18 mmol) of 3-ethoxymethoxypropyltrimethoxydecane (manufactured by AZMAX Co., Ltd.), 60 ml of toluene, and 30 ml of distilled water were added. After the solvent, 0.15 g (1.5 mmol) of phosphoric acid was added as a catalyst while stirring the contents, and further stirring was continued at 25 ° C for 16 hours.

After completion of the reaction, 100 ml of ethyl acetate was added to the reaction mixture, and the mixture was neutralized with a saturated aqueous sodium hydrogencarbonate solution, and the mixture was allowed to stand for a while, and then the organic layer was separated. Next, the organic layer was washed twice with distilled water, and then dried using anhydrous magnesium sulfate. After separating the magnesium sulfate by filtration, the filtrate was concentrated to 50 ml using an evaporator, and the obtained concentrate was dropped into a large amount of n-hexane to precipitate it, and the precipitate was separated by decantation. The obtained precipitate was dissolved in methyl ethyl ketone (MEK), recovered, and the solvent was distilled off under reduced pressure using an evaporator. 14.7 g of a decane compound polymer (A9) was obtained by vacuum drying the residue.

The weight average molecular weight (Mw) of the decane compound polymer (A9) was 2,700.

Further, the IR spectrum data of the decane compound polymer (A9) is shown below.

Si-Ph: 699 cm ^-1 , 741 cm ^-1 , Si-O: 1132 cm ^-1 , -CO: 1738 cm ^-1

(Comparative Example 3)

In a 300 ml eggplant flask, phenyltrimethoxydecane was added. After adding 20.2 g (102 mmol), 3-chloropropyltrimethoxydecane (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.58 g (18 mmol), and 60 ml of toluene and 30 ml of distilled water as a solvent, 0.15 g (1.5 mmol) of phosphoric acid was added while stirring the contents. As a catalyst, stirring was further continued at 25 ° C for 16 hours.

After the reaction was completed, the reaction mixture was neutralized with a saturated aqueous sodium hydrogencarbonate solution. Here, 100 ml of ethyl acetate was added and stirred, and after allowing to stand still, the organic layer was separated and obtained. Next, the organic layer was washed twice with distilled water, and then dried using anhydrous magnesium sulfate. After separating the magnesium sulfate by filtration, the filtrate was dropped into a large amount of n-hexane to precipitate it, and the precipitate was separated by decantation. The obtained precipitate was dissolved in methyl ethyl ketone (MEK) and recovered, and the solvent was distilled off under reduced pressure using an evaporator. The decane compound polymer (A10) was obtained by vacuum drying the residue.

The weight average molecular weight (Mw) of the decane compound polymer (A10) is 3,000.

Further, IR spectrum data of the decane compound polymer (A10) is shown below.

Si-Ph: 700 cm ^-1 , 741 cm ^-1 , Si-O: 1132 cm ^-1 , -Cl: 648 cm ^-1

The decane compound polymers (A1) to (A10) obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were used as they are, and the adhesion was measured by the following method. The measurement results are shown in the first table below.

(Continue force test)

The decane compound polymers obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were coated on the mirror surface of a 2 mm square tantalum wafer so as to have a thickness of about 2 μm, and the coated surface was placed and pressed. Above the substrate (silver plated copper plate). Subsequently, it was heat-treated at 170 ° C for 2 hours to be hardened to obtain an adherend to which a test piece was attached. The substrate to which the test piece is attached is placed in the preheated to pre The bonding strength tester (Series 4000, manufactured by Dage Co., Ltd.) at a constant temperature (23 ° C, 100 ° C) was placed on the stage for 30 seconds, and the height was 50 μm from the substrate, followed by a speed of 200 μm/s. The surface was subjected to stress in a horizontal method (shear direction) to measure the adhesion force (N/2 mm□) between the test piece and the substrate to be tested at 23 ° C and 100 ° C.

From the first table, the following cases are known.

The cured product obtained by using the decane compound polymers of Examples 1 to 7 had excellent adhesion at any of 23 ° C and 100 ° C.

On the other hand, the cured product obtained by using the polymer of Comparative Example 1 to 3 decane compound was inferior in both of 23 ° C and 100 ° C.

Claims (16)

A decane compound polymer represented by the following formula (a-1) (CHR ¹ X ⁰ -D-SiO _3/2 ) _m (R ² SiO _3/2 ) _n (CHR ¹ X ⁰ -D-SiZ ¹ O _{2 / 2} ) _o ( R ² SiZ ² O _2/2 ) _p (CHR ¹ X ⁰ -D-SiZ ¹ ₂ O _1/2 ) _q (R ² SiZ ² ₂ O _1/2 ) _r . . . (a-1) [the formula, R ¹ is a hydrogen atom or a carbon-based alkyl group having 1 to 6, X ⁰ represents a sulfur atom-based functional group, D represents a single bond system, or an unsubstituted or substituted a divalent organic group having 1 to 20 carbon atoms, and R ² represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or has a substituent (but does not include a functional group containing a sulfur atom), or is unsubstituted or substituted. a phenyl group, Z ¹ represents a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms, Z ² represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms or a halogen atom, and m represents a positive integer, n, o, p, q, and r each independently represent 0 or a positive integer]. The decane compound polymer according to claim 1, wherein the sulfur atom-containing functional group of X ^{0 is} a group represented by the following formula (i) or formula (ii), or a group derived from the group -SH ( i) -S-CO-R' (ii) [wherein R' represents a one-carbon organic group having 1 to 20 carbon atoms]. The decane compound polymer of claim 1, wherein n is a positive integer. The decane compound polymer as described in claim 1, wherein the ratio of (m+o+q) to (n+p+r) [(m+o+q):(n+p+r)] It is 5:95~80:20. The decane compound polymer as described in claim 1 has a weight average molecular weight of 1,000 to 30,000. A decane compound polymer obtained by using at least one of the decane compound (1) represented by the following formula (1) as a monomer, and having a condensation reaction to obtain a formula (1): R ¹ -CH(X ⁰ )-D -Si(OR ³ ) ₃ [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X ⁰ represents a functional group containing a sulfur atom, and D represents a single bond, or is unsubstituted or has The substituent has a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ³ represents an alkyl group having 1 to 10 carbon atoms. The decane compound polymer according to claim 6, wherein the sulfur atom-containing functional group of X ^{0 is} a group represented by the following formula (i) or formula (ii), -SH (i) -S-CO -R' (ii) [wherein R' represents a one-carbon organic group having 1 to 20 carbon atoms]. The decane compound polymer according to claim 6, wherein the mixture of at least one of the decane compound (1) and at least one decane compound of the decane compound (2) represented by the following formula (2) is condensed. The formula (2): R ² Si(OR ⁴ ) _v (X ¹ ) _3-v [wherein R ² represents a carbon which is unsubstituted or has a substituent (but does not include a functional group containing a sulfur atom) alkyl having 1 to 20, or an unsubstituted or substituted phenyl group of, R ⁴ represents alkyl having lines 1 to 10, X ¹ represents a halogen atom based, v represents an integer of 0 to 3. Department of]. The decane compound polymer according to the invention of claim 8, wherein the molar ratio of the decane compound (1) to the decane compound (2) contained in the mixture of the aforementioned decane compounds is a decane compound (1): a decane compound ( 2)] is 5:95~80:20. The decane compound polymer as described in claim 6 has a weight average molecular weight of 1,000 to 30,000. A sclerosing composition containing a decane compound polymer as described in any one of claims 1 to 10. The curable composition according to claim 11, which is a composition for a fixing member for an optical element. A cured product obtained by hardening a curable composition according to claim 11 of the patent application. A cured product according to claim 13 which is a fixing member for an optical element. A method of using the curable composition according to Item 11 of the patent application as an adhesive for an optical element fixing material. A method of using the curable composition described in claim 11 as a sealing agent for an optical element fixing material.