JP5623761B2 - Photochromic organopolysiloxane composition - Google Patents

Description

  The present invention relates to a photochromic organopolysiloxane composition useful for a light control glass or a light control lens.

  Photochromism refers to a phenomenon in which optical properties (color, fluorescence, etc.) reversibly change due to the action of light. A compound exhibiting photochromism (hereinafter also referred to as a photochromic compound or a photochromic material) undergoes a reversible structural change due to the action of light, and changes its absorption spectrum and other characteristics. Photochromism is roughly classified into two types: P-type photochromism that changes its color by absorbing light of a certain wavelength, and returns to its original state by absorption of light of another wavelength, and T-type photochromism that returns to its original state by heat.

  A compound that exhibits T-type photochromism that quickly returns to normal at room temperature, that is, a photochromic compound that is colored by absorption of UV light (ultraviolet light) (absorption of light in the visible light region) and fades when irradiation is stopped, As optical glass and lenses (hereinafter, lenses having photochromic properties are referred to as light control lenses), they have been suitably used for building windows, vehicle windows, building openings, partitions, glasses, and the like.

  Photochromic compounds for light control glasses and light control lenses have low initial coloration (coloration in the visible light region before UV irradiation), high color density (coloration when irradiated with UV light), color development High sensitivity (speed from the start of UV light irradiation until the color density reaches saturation), high fading sensitivity (speed from UV light irradiation to return to the original state), repeated this reversible action Characteristics such as good durability are required.

  In the light control glass for the windshield of the car and the light control lens for the sunglasses, when the sunlight is irradiated, the light is quickly colored to block the sunlight, and conversely, when entering a dark place (for example, a tunnel) suddenly In order to improve the visibility, it is necessary to quickly fade from the colored state. That is, a photochromic compound used for a light control glass for a windshield or a light control lens for sunglasses is required to have high color development sensitivity and fading sensitivity.

  Photochromic compounds generally have a fading sensitivity lower than the color development sensitivity, but it is known that when a photochromic compound is kneaded into a synthetic resin, the fading sensitivity is further reduced as compared to a solution. When photochromic compounds are kneaded into synthetic resins, the fading sensitivity decreases because the free space in the matrix is overwhelmingly smaller than in solution, and structural changes are constrained. In particular, the tendency is remarkable when kneaded into a synthetic resin having high hardness and heat resistance (see, for example, Patent Document 1).

  For this reason, the loss of fading sensitivity is reduced by curing a monomer that yields a resin with high hardness when homopolymerized, a monomer that yields a resin with low hardness when homopolymerized, and a curable composition containing a photochromic compound. Although it is known that a small amount of a cross-linked reaction product can be obtained (see, for example, Patent Documents 1 and 2), it is not sufficient to suppress a decrease in fading sensitivity, and physical properties such as hardness and water absorption of the resulting cross-linked reaction product are not sufficient. There was also a disadvantage that it was lowered.

  Organopolysiloxane is known as a matrix that has a large free volume compared to a carbon-based polymer and has little influence on the photochromic properties of a photochromic compound (see, for example, Patent Document 3). Due to the poor properties, there is a problem that when a photochromic compound that can be used as a light control glass or a light control lens is dissolved, the photochromic compound is precipitated with time.

  There is no problem of precipitation of the photochromic compound. A polymer in which the main chain introduces a group exhibiting photochromism into a carbon-based polymer (see, for example, Patent Document 4) or an alkoxysilane having a group exhibiting photochromism is reacted on the surface. Although there is silica glass (see, for example, Patent Document 5), it has not been sufficient in terms of suppressing a decrease in fading sensitivity.

Japanese Patent Laid-Open No. 2006-239887 Reissue WO01 / 005854 Japanese Patent Application Laid-Open No. 64-039744 JP-A-6-256758 JP-A-6-301142

  An object of the present invention is to provide a photochromic material in which no photochromic compound is precipitated and the degradation of photochromic performance is small.

  As a result of intensive studies, the present inventors have cross-linked a photochromic organopolysiloxane having a group exhibiting photochromism with a specific compound, so that the photochromic group has little influence on reversible structural changes due to the action of light, and photochromic The present inventors have found that a cross-linked reaction product with little deterioration in performance can be obtained, and the present invention has been completed.

That is, this invention contains the following (A) component and the following (B) component, and this (A) component and this (B) component are photochromic organopolysiloxane compositions which have crosslinking reactivity ,
The present invention provides a photochromic organopolysiloxane composition in which the crosslinking reaction is a crosslinking reaction by hydrosilylation reaction or ene-thiol reaction .
(A) Photochromic organopolysiloxane having a group exhibiting photochromism (B) Siloxane compound

  Further, the present invention is a photochromic organopolysiloxane in which the component (A) has at least three Si-H groups in one molecule, and the carbon component in which the component (B) has reactivity to Si-H groups. The photochromic organopolysiloxane composition is a siloxane compound having at least two carbon double bonds in one molecule.

  Further, the present invention is a photochromic organopolysiloxane in which the component (A) has at least three carbon-carbon double bonds having reactivity to Si-H groups in one molecule, and the component (B) is The photochromic organopolysiloxane composition is a siloxane compound having at least two Si—H groups in one molecule, and the crosslinking reaction is a hydrosilylation reaction.

  In the present invention, the photochromic group is selected from the group consisting of a group having a spiropyran structure, a group having a spirooxazine structure, a group having a naphthopyran structure, a group having a spirocyclohexadiene structure and a hexaarylbisimidazole structure. The above-mentioned photochromic organopolysiloxane composition is provided.

The present invention also provides the photochromic organopolysiloxane composition, wherein the ratio of the number of moles of the reactive group of the component (B) to the number of moles of the reactive group of the component (A) is 0.2-10. It is.

  The present invention also provides a photochromic organopolysiloxane crosslinking reaction product obtained by crosslinking the photochromic organopolysiloxane composition.

  Moreover, this invention provides the laminated glass which uses the said crosslinking reaction product as an intermediate | middle layer.

  Moreover, this invention provides the light control glass which has the layer of the said crosslinking reaction material.

  ADVANTAGE OF THE INVENTION According to this invention, compared with a solution state, there is little deterioration of a fading sensitivity, and the photochromic material without the deterioration of the photochromic performance by precipitation can be provided.

  Hereinafter, the photochromic organopolysiloxane composition of the present invention will be described in detail based on preferred embodiments.

<Crosslinking reactivity>
The component (A) and the component (B) of the present invention have crosslinking reactivity. As the crosslinking reaction, a known method can be applied and is not particularly limited. For example, a radical polymerization reaction of a carbon-carbon double bond, a ring-opening polymerization reaction of an epoxy group, a ring-opening reaction between an epoxy group and a group having active hydrogen. Urethane reaction of isocyanate group and group having active hydrogen, esterification reaction of hydroxyl group and carboxyl group, hydrosilylation reaction of Si—H group and carbon-carbon double bond, thiol group (—SH) and carbon -Enthiol reaction with a carbon double bond, etc. are mentioned.

  Among the cross-linking reactions, since the fading sensitivity of the cross-linked reaction product obtained from the photochromic organopolysiloxane composition of the present invention is good, the hydrosilylation reaction between a Si-H group and a carbon-carbon double bond, a thiol group An enethiol reaction between a carbon-carbon double bond and a hydrosilylation reaction between a Si-H group and a carbon-carbon double bond is more preferable.

When the crosslinking reaction is performed by a hydrosilylation reaction or an enethiol reaction, the number of reactive groups in either component (A) or component (B) is at least 3, and the number of reactive groups in the other is at least 2. preferable. The preferred combination when the crosslinking reaction is carried out by hydrosilylation reaction or enethiol reaction is preferably such that the number of reactive groups in component (A) is larger than the number of reactive groups in component (B). The number of reactive groups in the component) is more preferably 3 to 500, still more preferably 4 to 100, and the number of reactive groups in the component (B) is preferably 2 to 10, preferably 2 to 5. More preferably.
Hereinafter, the component (A) will be described.

<(A) component>
The component (A) of the present invention is a photochromic organopolysiloxane having a group exhibiting photochromism and having crosslinking reactivity with the component (B), specifically, a group exhibiting photochromism, It is comprised from the group which has the crosslinking reactivity of, and a principal chain.

<Main chain>
The structure of the organopolysiloxane serving as the main chain of the component (A) is not particularly limited, and may be cyclic or linear (including linear and branched). For example, examples of the cyclic organopolysiloxane include cyclic organopolysiloxanes having 3 to 8 silicon atoms in the ring, and examples of the linear organopolysiloxane include linear or branched linear chains. And organopolysiloxane.

  Further, the organopolysiloxane that is the main chain of the component (A) may have a structure in which the cyclic and / or chain organopolysiloxane is crosslinked, and a ladder-like (ladder-like) structure is formed by the crosslinked structure. ), A cage shape, a random shape, or the like. The cross-linking may be cross-linking by Si—O—Si group, cross-linking by organic group such as alkylene group, (poly) ether group, ester group, amide group, thioether group, etc., or a combination thereof.

  When the structure of the organopolysiloxane that is the main chain of the component (A) has a structure in which the cyclic and / or chain organopolysiloxane is crosslinked, the flexibility of the crosslinking reaction product of the present invention decreases. The hardness of the crosslinking reaction product of the present invention is improved. In particular, when the crosslinking is crosslinking by Si—O—Si groups, the hardness of the crosslinking reaction product of the present invention is further improved. Therefore, since a material having high flexibility is required for the intermediate layer of the laminated glass and a material having high hardness is required for the light control lens, a structure in which cyclic and / or chain organopolysiloxane is cross-linked depending on the application. What is necessary is just to change the content.

<Group showing photochromism>
Examples of the group exhibiting photochromism include a group having a spiropyran structure, a group having a spirooxazine structure, a group having a naphthopyran structure, a group having a spirocyclohexadiene structure, a group having a hexaarylbisimidazole structure, a group having an azobenzene structure, Examples thereof include a group having a fulgide structure, a group having a fulgimide structure, a group having a diarylethene structure, and a group having a spiroperimidine structure.

  Among the groups exhibiting photochromism, examples of the group exhibiting P-type photochromism include a group having a fulgide structure which is a bismethylene succinic anhydride derivative, a group having a diarylethene structure having a hetero ring in the aryl group, and the like. The crosslinking reaction product of the present invention having a group exhibiting type photochromism is preferably used for an optical recording medium, an optical display medium and the like.

Among the groups exhibiting photochromism, the group exhibiting T-type photochromism includes a group having a spiropyran structure, a group having a spirooxazine structure, a group having a naphthopyran structure, a group having a spirocyclohexadiene structure, a hexaarylbisimidazole structure Group having a spiropyran structure, a group having a spirooxazine structure, and a group having a naphthopyran structure are preferred, and the spiropyran structure has a low durability and a decrease in fading sensitivity. A group having an oxazine structure and a group having a naphthopyran structure are more preferable. The crosslinking reaction product of the present invention having a group exhibiting T-type photochromism is preferably used for a light control glass, a light control lens and the like.
In the following description, the case where the component (A) has a group exhibiting T-type photochromism among the groups exhibiting photochromism will be described, but the present invention is not limited thereto.

  Examples of the group having a spiropyran structure that is a group exhibiting T-type photochromism include a group represented by the following general formula (1).

（式中、Ｒ¹〜Ｒ¹⁰は、各々独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、シアノ基、ホルミル基、カルボキシル基、アミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシル基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換の炭素環、置換若しくは無置換の複素環、又はアルキレン鎖を有する連結基を表わし、Ｘ¹〜Ｘ³は、各々独立して、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアラルキル基、又はアルキレン鎖を有する連結基を表わし、Ｗ¹は酸素原子又は硫黄原子を表わす。Ｒ¹〜Ｒ¹⁰は、架橋して炭素環又は複素環を形成してもよい。但し、Ｒ¹〜Ｒ¹⁰及びＸ¹〜Ｘ³の少なくとも１つは、アルキレン鎖を有する連結基である。）

Wherein R ^{1 to} R ¹⁰ are each independently a hydrogen atom, halogen atom, nitro group, hydroxy group, cyano group, formyl group, carboxyl group, amino group, substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted alkoxyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle, or a linking group having an alkylene chain, X ¹ to X ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a linking group having an alkylene chain, W ¹ represents an oxygen atom or a sulfur atom. R ¹ to R ¹⁰ are bridged to may form a carbocyclic or heterocyclic ring. However, at least one of R ¹ to R ¹⁰ and X ¹ to X ³ have the alkylene chain It is a binding group.)

  As group which has the said spirooxazine structure, group represented by following General formula (2) is mentioned, for example.

（式中、Ｒ¹¹〜Ｒ¹⁹は、各々独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、シアノ基、ホルミル基、カルボキシル基、アミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシル基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換の炭素環、置換若しくは無置換の複素環、又はアルキレン鎖を有する連結基を表わし、Ｘ⁴〜Ｘ⁶は、各々独立して、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアラルキル基、又はアルキレン鎖を有する連結基を表わし、Ｗ²は酸素原子又は硫黄原子を表わす。Ｒ¹¹〜Ｒ¹⁹は、架橋して炭素環又は複素環を形成してもよい。但し、Ｒ¹¹〜Ｒ¹⁹及びＸ⁴〜Ｘ⁶の少なくとも１つは、アルキレン鎖を有する連結基である。）

(Wherein R ^{11 to} R ¹⁹ are each independently a hydrogen atom, halogen atom, nitro group, hydroxy group, cyano group, formyl group, carboxyl group, amino group, substituted or unsubstituted alkyl group, substituted or X ⁴ represents an unsubstituted alkoxyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle, or a linking group having an alkylene chain; to X ⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a linking group having an alkylene chain, W ² represents an oxygen atom or a sulfur atom. R ¹¹ to R ¹⁹ are bridged to may form a carbocyclic or heterocyclic ring. However, at least one of R ¹¹ to R ¹⁹ and X ⁴ to X ⁶ is having a alkylene chain A linking group.)

  Examples of the group having a naphthopyran structure include a group represented by the following general formula (3) or general formula (4).

（式中、Ｒ²⁰〜Ｒ²⁵は、各々独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、シアノ基、ホルミル基、カルボキシル基、アミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシル基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換の炭素環、置換若しくは無置換の複素環、又はアルキレン鎖を有する連結基を表わし、Ｘ⁷は置換若しくは無置換のアリール基、又はアルキレン鎖を有する連結基を表わし、Ｘ⁸は置換若しくは無置換のアルキル基、無置換のアリール基、又はアルキレン鎖を有する連結基を表わす。Ｒ²⁰〜Ｒ²⁵は、架橋して炭素環又は複素環を形成してもよい。但し、Ｒ²⁰〜Ｒ²⁵、Ｘ⁷及びＸ⁸の少なくとも１つは、アルキレン鎖を有する連結基である。）

(Wherein R ^{20 to} R ²⁵ are each independently a hydrogen atom, halogen atom, nitro group, hydroxy group, cyano group, formyl group, carboxyl group, amino group, substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted alkoxyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle, or a linking group having an alkylene chain, X ⁷ Represents a substituted or unsubstituted aryl group or a linking group having an alkylene chain, and X ⁸ represents a substituted or unsubstituted alkyl group, an unsubstituted aryl group or a linking group having an alkylene chain, R ²⁰ to R. communication ^25, which cross-linked may form a carbocyclic or heterocyclic ring. However, at least one of R ²⁰ to R ^25, X ⁷ and X ^8, having an alkylene chain A group.)

（式中、Ｒ²⁶〜Ｒ³¹は、各々独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、シアノ基、ホルミル基、カルボキシル基、アミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシル基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換の炭素環、置換若しくは無置換の複素環、又はアルキレン鎖を有する連結基を表わし、Ｘ⁹は置換若しくは無置換のアリール基、又はアルキレン鎖を有する連結基を表わし、Ｘ¹⁰は置換若しくは無置換のアルキル基、無置換のアリール基、又はアルキレン鎖を有する連結基を表わす。Ｒ²⁶〜Ｒ³¹は、架橋して炭素環又は複素環を形成してもよい。但し、Ｒ²⁶〜Ｒ³¹、Ｘ⁹及びＸ¹⁰の少なくとも１つは、アルキレン鎖を有する連結基である。）

(Wherein R ^{26 to} R ³¹ are each independently a hydrogen atom, halogen atom, nitro group, hydroxy group, cyano group, formyl group, carboxyl group, amino group, substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted alkoxyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle, or a linking group having an alkylene chain, X ⁹ Represents a substituted or unsubstituted aryl group or a linking group having an alkylene chain, and X ¹⁰ represents a substituted or unsubstituted alkyl group, an unsubstituted aryl group or a linking group having an alkylene chain, R ²⁶ to R. ^31, cross-linked may form a carbocyclic or heterocyclic ring. However, at least one of R ²⁶ to R ^31, X ⁹ and X ¹⁰ have the alkylene chain It is a binding group.)

  Examples of the spirocyclohexadiene structure include a group represented by the following general formula (5).

（式中、Ｒ³²〜Ｒ³⁶は、各々独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、シアノ基、ホルミル基、カルボキシル基、アミノ基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルコキシル基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換の炭素環、置換若しくは無置換の複素環、又はアルキレン鎖を有する連結基を表わし、Ｗ³は酸素原子又は硫黄原子を表わす。Ｒ³²とＲ³³とは、架橋して炭素環又は複素環を形成してもよい。但し、Ｒ³²〜Ｒ³⁶の少なくとも１つは、アルキレン鎖を有する連結基である。）

(Wherein R ^{32 to} R ³⁶ are each independently a hydrogen atom, halogen atom, nitro group, hydroxy group, cyano group, formyl group, carboxyl group, amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted carbocyclic ring, substituted or unsubstituted heterocyclic, or a linking group having an alkylene chain, W ³ Represents an oxygen atom or a sulfur atom, and R ³² and R ³³ may be bridged to form a carbocycle or a heterocycle, provided that at least one of R ^{32 to} R ³⁶ is a linkage having an alkylene chain. Group.)

  Examples of the hexaarylbisimidazole structure include a group represented by the following general formula (6).

（式中、Ｒ³⁷〜Ｒ⁴²は置換若しくは無置換のアリール基を表わす。但し、Ｒ³⁷〜Ｒ⁴²の少なくとも１つは、アルキレン鎖を有する連結基を置換基とするアリール基である。）

(In the formula, R ^{37 to} R ^{42 each} represents a substituted or unsubstituted aryl group, provided that at least one of R ^{37 to} R ⁴² is an aryl group having a linking group having an alkylene chain as a substituent.)

<Linking group having an alkylene chain>
In the above general formulas (1) to (6), the linking group having an alkylene chain is a group that bonds a photochromic group as a side chain and an organopolysiloxane as a main chain. The linking group having an alkylene chain is not particularly limited as long as the portion bonded to the main chain organopolysiloxane is a linking group having 2 or more carbon atoms, and is a linking group consisting of only an alkylene chain. Alternatively, it may be a linking group composed of an alkylene chain having a substituent, or a linking group composed of an alkylene chain in which a part of the alkylene chain is substituted with another element.

Examples of the linking group having an alkylene chain that can be preferably used for the organopolysiloxane that is the main chain include, for example, groups represented by the following formulas (7-1) to (7-18), and -Si Examples include groups in which groups such as (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ — and —S—CH ₂ CH ₂ — are linked.

In the following formulas (7-1) to (7-18), wherein the right side, a portion that binds to the organopolysiloxane which is the main chain, these groups _{-S-CH 2 CH 2 -,} - Si When a group such as (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ — is linked, it may be a group linked to the right side of the formulas (7-1) to (7-18). preferable. In Formula (7-8), m represents a number of 2 to 16, a number of 4 to 12 is preferable, a number of 6 to 10 is more preferable, and a number of 9 is most preferable. In formula (7-11), n represents a number of 1 to 15, preferably 3 to 11, more preferably 5 to 19, and most preferably 8.

The linking group having an alkylene chain is easy to produce and has high chemical stability. Therefore, the following formulas (7-1), (7-2), (7-5), (7-6) , (7-8), (7-2) or formula (7-5), a group in which —Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ — is linked, formula (7-2) or A group in which —S—CH ₂ CH ₂ — is linked to (7-5) and formula (7-11) are preferred, and formulas (7-2), (7-5), (7-8) and (7 −11) is more preferable, and formulas (7-2) and (7-5) are most preferable.

  Among the groups exhibiting the above-described photochromism described above, preferable groups as the side chain of the organopolysiloxane of the present invention include, for example, the following formulas (8) to (12) and (15).

<Content of group showing photochromism>
The content of the group exhibiting photochromism is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass in the component (A) of the present invention, Most preferably, it is 20%. When the content of the group exhibiting photochromism is less than 0.01% by mass, the amount of the component (A) for exhibiting sufficient light control property is increased, and the physical properties of the composition of the present invention may be lowered. In addition, when the content of the group exhibiting photochromism is more than 30% by mass, the fading sensitivity may be lower than that in the solution.

<Group having reactivity with component (B)>
Although it does not restrict | limit especially as group which has the reactivity with the said (B) component, Since the fading sensitivity of the photochromic organopolysiloxane crosslinking reaction material of this invention is favorable, Si-H group and carbon-carbon double A group capable of hydrosilylation reaction with a bond or enethiol reaction between a thiol group and a carbon-carbon double bond is preferred.

  Examples of the group having a carbon-carbon double bond having reactivity with a Si-H group or the group having a carbon-carbon double bond having reactivity with a thiol group include vinyl, allyl, and 4-vinylphenyl. , 2-cyclohexenylethyl, 3-methacryloxypropyl, 3-acryloxypropyl, norbornenyl, 2-norbornenylethyl, and in terms of reactivity and ease of industrial production, vinyl, 2-cyclo Hexenylethyl is preferred and vinyl is more preferred.

  Examples of the group having a thiol group include 3-mercaptopropyl, 1,2-dimercaptoethyl, 2-mercaptomethyl-3-mercaptopropyl, and 1-mercaptomethyl-3-mercaptopropyl. From the viewpoint of easy production, 3-mercaptopropyl is preferable.

<Other organic groups>
The organopolysiloxane serving as the main chain of the component (A) may have other organic groups in addition to the group exhibiting photochromism and the group having reactivity with the component (B). The other organic group is not particularly limited, and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle. Any of a ring and the like may be used, but an alkyl group having 1 to 6 carbon atoms, phenyl, and cyclohexyl are preferable, and methyl and phenyl are more preferable because they are easily industrially available and easy to produce.

  The mass average molecular weight of the component (A) of the present invention is preferably 2000 to 500,000, more preferably 3000 to 100,000, since the fading sensitivity of the photochromic organopolysiloxane crosslinking reaction product is increased. Most preferably, it is 30000. In the present invention, the mass average molecular weight refers to a polystyrene equivalent mass average molecular weight when GPC analysis is performed using tetrahydrofuran (hereinafter referred to as THF) as a solvent.

<Production method of component (A)>
Although it does not restrict | limit especially as a manufacturing method of (A) component of this invention,
(A) a hydrosilylation reaction between an organopolysiloxane having an Si—H group and a photochromic compound having a carbon-carbon double bond having reactivity with the Si—H group; and (b) an Si—H group. A hydrosilylation reaction between an organopolysiloxane having a carbon-carbon double bond having a reactivity of 5 and a photochromic compound having a Si-H group,
(C) a method of hydrolyzing and condensing a photochromic compound having an alkoxysilyl group and an alkoxysilane compound having a reactive group with the component (B),
(D) An thiol-reactive method of an organopolysiloxane having a thiol group and a photochromic compound having a carbon-carbon double bond having reactivity with a thiol group can be mentioned. In the component (A) of the present invention The method (b) is preferred because it is easy to increase the content of the group exhibiting photochromism.
Hereinafter, the methods (a) to (d) will be described in order.

<Method (a)>
First, a method for hydrosilylating (a) an organopolysiloxane having a Si—H group and a photochromic compound having a carbon-carbon double bond having reactivity with the Si—H group will be described.

  The structure of the organopolysiloxane having a Si—H group in the method (a) is determined in accordance with the above-described organopolysiloxane serving as the main chain. The reaction ratio of the organopolysiloxane having a Si—H group and the photochromic compound having a carbon-carbon double bond having a reactivity with the Si—H group is as follows. The reaction ratio is preferably such that the number of Si—H groups is at least two. The organopolysiloxane having a Si—H group can be produced by a known method.

  As the carbon-carbon double bond having reactivity with the Si-H group of the photochromic compound having a carbon-carbon double bond having reactivity with the Si-H group, for example, the following formula (7-1a): To (7-18a). Formulas (7-1a) to (7-18a) are groups corresponding to Formulas (7-1) to (7-18), respectively, and m in Formula (7-8a) is Formula (7-8). And n in the formula (7-11a) is synonymous with the formula (7-11). Since the production is easy and the reactivity with the Si—H group is high, the formulas (7-1a), (7-2a), (7-5a), (7-6a), (7-8a) and (7-11a) is preferred, formulas (7-2a), (7-6a), (7-8a) and (7-11a) are more preferred, and formulas (7-2a) and (7-6a) are most preferred. preferable.

  Formulas (7-8a) and (7-11a) are more difficult to produce than formulas (7-2a) and (7-6a), but the steric hindrance of the carbon-carbon double bond moiety is small. When the mass average molecular weight of the organopolysiloxane having a Si-H group is 5000 or more, it is more preferably used than the formulas (7-2a) and (7-6a).

  Specific examples of preferable compounds as the photochromic compound having a carbon-carbon double bond having reactivity with the Si-H group include the following compounds (8a) to (12a) and (15a). it can. The compounds (8a) to (12a) and (15a) are compounds corresponding to the groups of the above formulas (8) to (12) and (15).

  For example, the compound (8a) is formed by reacting 2,7-dihydroxynaphthalene and 1,1-diphenylpropargyl alcohol in the presence of an acid catalyst to form a naphthopyran structure as shown in the following reaction formula. The hydroxyl group can be obtained by allyl etherification by a known method.

  The compound (9a) is obtained, for example, by reacting 2,3,3-trimethyl-3H-indolenine with methyl iodide and then desorbing hydrogen iodide with alkali as shown in the following reaction formula. This compound can be reacted with 1-nitroso-2,7-dihydroxynaphthalene to form a spironaphthoxazine structure, and the hydroxyl group at the 7-position of the naphthalene moiety can be allyl etherified by a known method. 1-nitroso-2,7-dihydroxynaphthalene can be obtained by nitrosating 2,7-dihydroxynaphthalene with sodium nitrite or the like.

  The above compound (10a) was prepared by the same method as the above compound (9a) except that 1-nitroso-2,6-dihydroxynaphthalene was used instead of 1-nitroso-2,7-dihydroxynaphthalene. It can be obtained by doing. 1-nitroso-2,6-dihydroxynaphthalene can be obtained by nitrosating 2,6-dihydroxynaphthalene with sodium nitrite and sulfuric acid.

  For example, the compound (11a) is obtained by reacting 2,3,3-trimethyl-3H-indolenin with 3-iodo-1-propene as shown in the following reaction formula, and then removing hydrogen iodide with an alkali. The compound obtained by separation can be obtained by reacting 2-hydroxy-5-nitrobenzaldehyde to form a spironaphthoxazine structure.

  The compound (12a) is, for example, a process for producing the compound (11a), in which 1-nitroso-2-hydroxynaphthalene is used instead of 2-hydroxy-1-nitrobenzaldehyde as shown in the following reaction formula. Can be obtained by carrying out a similar reaction.

  In the compound (15a), for example, as shown in the following reaction formula, 3,3-diphenyl-9-hydroxy-3H-naphtho [2,1-b] pyran and 6-bromo-1-hexene are present in the presence of a base. It can obtain by making it react under.

  When hydrosilylation reaction of the organopolysiloxane having the Si-H group and the photochromic compound having a carbon-carbon double bond having reactivity with the Si-H group, in the presence of a hydrosilylation catalyst, What is necessary is just to react by a well-known method.

  Examples of the hydrosilylation catalyst include platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, and the like.

Examples of the platinum-based catalyst include chloroplatinic acid, complexes of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetramethyldisiloxane. Complex (Karstedt catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (for example, Pt [P (C ₆ H ₅ ) ₃ ] ₄ , PtCl [P (C ₆ H ₅ ) ₃ ] ₃ , Pt [P (C ₄ H ₉ ) ₃ ) ₄ ]), platinum-phosphite complexes (eg, Pt [P (OC ₆ H ₅ ) ₃ ] ₄ , Pt [P (OC ₄ H ₉ ) ₃ ]) ₄ ), dicarbonyldichloroplatinum and the like.

  Examples of the palladium catalyst or rhodium catalyst include compounds containing a palladium atom or a rhodium atom instead of the platinum atom of the platinum catalyst. These may be used alone or in combination of two or more.

  The hydrosilylation catalyst is preferably a platinum-based catalyst from the viewpoint of reactivity, more preferably a platinum-divinyltetramethyldisiloxane complex and a platinum-carbonylvinylmethyl complex, and most preferably a platinum-carbonylvinylmethyl complex.

  Moreover, the usage-amount of a catalyst is the photochromic compound which has the carbon-carbon double bond which has the reactivity from said organopolysiloxane which has said Si-H group, and said Si-H group from the point of reactivity. 5 mass% or less of the total amount of is preferable, 0.0001-1.0 mass% is still more preferable, 0.001-0.1 mass% is the most preferable.

  The reaction conditions for hydrosilylation are not particularly limited, and may be performed under the conditions known in the art using the above catalyst, but from the viewpoint of the reaction rate, it is preferably performed at room temperature to 130 ° C. During the reaction, toluene, hexane, isopropanol A conventionally known solvent such as methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used. By such a hydrosilylation reaction, the organopolysiloxane which is the component (A) of the present invention can be obtained. However, if necessary, decatalyst, desolvation and the like may be performed.

<Method (b)>
Next, (b) a method for hydrosilylation reaction of an organopolysiloxane having a carbon-carbon double bond having reactivity with a Si—H group and a photochromic compound having a Si—H group will be described.

  The structure of the organopolysiloxane having a carbon-carbon double bond having reactivity with the Si—H group in the method (b) is determined in accordance with the aforementioned organopolysiloxane serving as the main chain.

  Examples of the group having a carbon-carbon double bond having reactivity with the Si-H group include vinyl, allyl, 4-vinylphenyl, 2-cyclohexenylethyl, 3-methacryloxypropyl, 3-acrylic. Roxypropyl, norbornenyl, and 2-norbornenylethyl are exemplified, and vinyl and 2-cyclohexenylethyl are preferable and vinyl is more preferable from the viewpoint of reactivity and ease of industrial production.

  The reaction ratio between the organopolysiloxane having a carbon-carbon double bond having reactivity with the Si-H group and the photochromic compound having the Si-H group is obtained by reacting the component (A). The reaction ratio is preferably such that the number of carbon-carbon double bonds having reactivity with Si—H groups per molecule is at least two. The organopolysiloxane having a carbon-carbon double bond having reactivity with the Si—H group can be produced by a known method.

  The photochromic compound having a Si—H group in the method (b) is, for example, a carbon-carbon double bond of a photochromic compound having a carbon-carbon double bond having reactivity with the Si—H group. It can be obtained by hydrosilylation reaction of a silicon compound having at least two Si—H groups in the molecule. As a silicon compound having at least two Si—H groups in the molecule, the reactivity is good and the reaction 1,1,3,3-tetramethyldisiloxane is preferred because it can be easily purified later.

  The hydrosilylation reaction between the photochromic compound having a carbon-carbon double bond having reactivity with the Si-H group and the silicon compound having at least two Si-H groups in the molecule is the above (a ) In the same manner as the hydrosilylation reaction described in the method. The reaction molar ratio of the silicon compound having at least two Si—H groups in the molecule to the photochromic compound having a carbon-carbon double bond having reactivity with the Si—H group is preferably 2 to 100, More preferably, it is 5-30, and most preferably 10-15. Examples of the reaction conditions and catalyst for hydrosilylation in the method (b) include the same reaction conditions and catalyst as in the method (a).

  The groups represented by the above formulas (7-1a) to (7-18a) are obtained by subjecting a carbon-carbon double bond to a hydrosilylation reaction with 1,1,3,3-tetramethyldisiloxane. 7-1b) to (7-18b).

For example, when the photochromic compound having the formula (7-2b) is reacted with the organopolysiloxane having a vinyl group, the linking group is —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ). ₂ CH ₂ CH ₂ -, and the linking group when reacted with photochromic compound having the formula (7-9b), a organopolysiloxane having a vinyl _{group, -OC (= O) CH 2} CH 2 Si ( _{CH 3) 2 OSi (CH 3} ) 2 CH 2 CH 2 - and becomes.

<Method (c)>
Next, a method for hydrolyzing and condensing (c) a photochromic compound having an alkoxysilyl group and an alkoxysilane compound having a reactive group with the component (B) will be described.

  The photochromic compound having an alkoxysilyl group is, for example, an alkoxysilane compound having a Si-H group in a carbon-carbon double bond of a photochromic compound having a carbon-carbon double bond having reactivity with the Si-H group. As an alkoxysilane compound having a Si—H group, an alkoxysilane compound represented by the following general formula (13) is preferable.

（式中、Ｚは炭素数１〜４のアルキル基を表し、Ｒ⁴³は炭素数１〜６のアルキル基又はフェニル基を表し、ｙは２又は３の数を表す。）

(In the formula, Z represents an alkyl group having 1 to 4 carbon atoms, R ⁴³ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and y represents a number of 2 or 3.)

In the general formula (13), Z is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl, and R ⁴³ is an alkyl group or aralkyl group having 1 to 6 carbon atoms, methyl, ethyl, propyl Butyl is preferred, methyl or ethyl is more preferred, and methyl is most preferred. y is a number of 2 or 3, and the number of 2 is preferable.

  Specific examples of preferable alkoxysilane compounds having the Si-H group include dimethoxymethylsilane, dimethoxyethylsilane, dimethoxypropylsilane, dimethoxybutylsilane, diethoxymethylsilane, diethoxyethylsilane, and diethoxypropyl. Silane, diethoxybutylsilane, triethoxysilane, etc. are mentioned.

  The hydrosilylation reaction between the photochromic compound having a carbon-carbon double bond having reactivity with the Si-H group and the alkoxysilane compound having the Si-H group is described in the method (a) above. It can be performed by the same method as the hydrosilylation reaction. The groups represented by the formulas (7-1a) to (7-18a) are reacted with the alkoxysilane compound represented by the general formula (13) to thereby form the following formulas (7-1c) to (7-18c). Can be converted into a group represented by:

  The following compound (11c) obtained by reacting the alkoxysilane compound represented by the above general formula (13) with the above compound (11a) is the 3-iodo-1-propene used in the production method of the above compound (11a). Instead, it can also be obtained by using an alkoxysilane compound represented by the following general formula (14).

（式中、Ｚ、Ｒ⁴³及びｙは上記一般式（１３）と同義である。）

(In the formula, Z, R ⁴³ and y have the same meaning as in the general formula (13).)

（式中、Ｚ、Ｒ⁴³及びｙは上記一般式（１３）と同義であり、Ｙはハロゲン原子を表す。）

(In the formula, Z, R ⁴³ and y have the same meaning as in the general formula (13), and Y represents a halogen atom.)

  Similarly, the following compound (12c) obtained by reacting the alkoxysilane compound represented by the general formula (13) with the compound (12a) is 3-iodo-1 used in the production method of the compound (12a). -It can obtain by using the alkoxysilane compound represented by the said General formula (14) instead of a propene.

（式中、Ｚ、Ｒ⁴³及びｙは上記一般式（１３）と同義である。）

(In the formula, Z, R ⁴³ and y have the same meaning as in the general formula (13).)

  In the general formula (14), the halogen atom represented by Y is preferably chlorine, bromine and iodine, more preferably bromine and iodine, and most preferably iodine.

  The alkoxysilane compound represented by the general formula (14) includes allyl halide compounds such as 3-chloro-1-propene, 3-bromo-1-propene, and 3-iodo-1-propene, and the general formula (13). It can obtain by carrying out hydrosilylation reaction with the alkoxysilane compound represented by these. The hydrosilylation reaction between the allyl halide compound and the alkoxysilane compound represented by the general formula (13) can be performed by the same method as the hydrosilylation reaction described in the method (a).

  When a compound having a linking group (7-2c) on the nitrogen atom of the indoline portion of the spiropyran structure and the spirooxazine structure, such as the compound (11c) or the compound (12c), the yield is good. Therefore, a method using the alkoxysilane compound represented by the general formula (14) is preferable.

  As the alkoxysilane compound having a reactive group with the component (B), the photochromic organopolysiloxane crosslinking reaction product of the present invention has good fading sensitivity, so that the alkoxysilane compound having an Si-H group, Si-H An alkoxysilane compound having a carbon-carbon double bond having reactivity with a group, an alkoxysilane compound having a carbon-carbon double bond having reactivity with a thiol group, and an alkoxysilane compound having a thiol group are preferred. As these alkoxysilane compounds, dialkoxysilane compounds or trialkoxysilane compounds are preferred.

  Examples of the alkoxysilane compound having the Si-H group include dimethoxysilane, trimethoxysilane, triethoxysilane, dimethoxymethylsilane, dimethoxyphenylsilane, diethoxymethylsilane, diethoxyphenylsilane, and the like. From the viewpoint of good reactivity, trimethoxysilane, triethoxysilane, and dimethoxymethylsilane are preferable, and trimethoxysilane and dimethoxymethylsilane are more preferable.

  Examples of the alkoxysilane compound having a carbon-carbon double bond having reactivity with the Si-H group or the alkoxysilane compound having a carbon-carbon double bond having reactivity with the thiol group include: Trimethoxyvinylsilane, triethoxyvinylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, allyltrimethoxysilane, allyltriethoxysilane, allyldimethoxymethylsilane, allyldiethoxymethylsilane, trimethoxy-4-vinylphenylsilane, triethoxy-4- Vinylphenylsilane, dimethoxymethyl-4-vinylphenylsilane, diethoxymethyl-4-vinylphenylsilane, 2-cyclohexenylethyltrimethoxysilane, 2-cyclohexenylethyltriethoxysila 2-cyclohexenylethyldimethoxymethylsilane, 2-cyclohexenylethyldiethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacrylate Examples include loxypropyltriethoxysilane, trimethoxynorbornenylsilane, triethoxynorbornenylsilane, trimethoxy-2-norbornenylethylsilane, triethoxy-2-norbornenylethylsilane, etc., and good reactivity. Therefore, trimethoxyvinylsilane, triethoxyvinylsilane, dimethoxymethylvinylsilane, and diethoxymethylvinylsilane are preferable.

  Examples of the alkoxysilane compound having a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyldiethoxymethylsilane, 1,4-dimercapto- 2- (trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2-dimercaptoethyltriethoxysilane, etc. are mentioned, and since the reactivity is good, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Triethoxysilane, 3-mercaptopropyl dimethoxymethyl silane, 3-mercaptopropyl diethoxy methylsilane is preferred, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl dimethoxy methylsilane more preferred.

  The method for hydrolyzing and condensing the photochromic compound having an alkoxysilyl group and the alkoxysilane compound having a reactive group with the component (B) may be carried out by performing a so-called sol-gel reaction. The method of performing a hydrolysis and a condensation reaction using catalysts, such as a base, is mentioned.

  The solvent used at this time is not particularly limited, and specific examples include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran and the like.

  The hydrolysis / condensation reaction proceeds when the alkoxysilane is hydrolyzed with water to generate a silanol group (Si—OH), and the generated silanol groups or silanol groups and alkoxyl groups are condensed.

  In order to rapidly advance this hydrolysis reaction, it is preferable to add an appropriate amount of water, and the catalyst may be dissolved in water and added. In addition, the hydrolysis reaction proceeds even with a small amount of water contained in air or in a solvent other than water.

  The catalyst such as acid and base used in the hydrolysis / condensation reaction may be any catalyst that promotes the hydrolysis / condensation reaction. Specifically, inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; Organic acids such as acid, methanesulfonic acid, p-toluenesulfonic acid, monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia; trimethylamine, triethylamine, monoethanolamine, diethanolamine, etc. These amine compounds (organic bases) can be used, and one of these can be used, or two or more can be used in combination.

  The temperature of the hydrolysis / condensation reaction varies depending on the type of solvent, the type and amount of the catalyst, etc., but is preferably 0 to 80 ° C, more preferably 5 to 50 ° C, and most preferably 8 to 30 ° C.

  When the component (A) is produced by the method (c), an alkoxysilane compound other than the photochromic compound having an alkoxysilyl group and the alkoxysilane compound having a reactive group with the component (B) may be reacted. .

  Examples of such alkoxysilane compounds include dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiethylsilane, diethoxydiethylsilane, dimethoxydipropylsilane, diethoxydipropylsilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane. Dialkoxysilane compounds such as dimethoxyphenylsilane and dietoxydiphenylsilane; trialkoxyalkoxy such as trimethoxymethylsilane, triethoxymethylsilane, trimethoxyethylsilane, triethoxyethylsilane, trimethoxyphenylsilane, triethoxyphenylsilane Compounds.

<Method (d)>
Next, (d) a method for subjecting an organopolysiloxane having a thiol group to a photochromic compound having a carbon-carbon double bond having reactivity with a thiol group will be described.

  The organopolysiloxane having a thiol group is, for example, carbon-carbon bismuth having reactivity with Si-H groups in Si-H of the organopolysiloxane having Si-H groups mentioned in the method (a). A method of hydrosilylating a compound having a heavy bond and a thiol group, a method of hydrolyzing and condensing an alkoxysilane compound having a thiol group described in the method (c) and another alkoxysilane compound by a sol-gel method, etc. Can be obtained.

  As the compound having a carbon-carbon double bond having reactivity with the Si—H group and a thiol group, allyl mercaptan is preferred because of good reactivity and easy industrial availability. A 3-mercaptopropyl group is produced by a hydrosilylation reaction between the Si-H group and allyl mercaptan.

  As the group having a thiol of the alkoxysilane compound having a thiol group, a 2-mercaptoethyl group and a 3-mercaptopropyl group are preferable because of good reactivity and easy industrial availability, and 3-mercaptopropyl group is preferable. Groups are more preferred.

  Examples of the alkoxysilane compound having a 3-mercaptopropyl group include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane. Can be mentioned.

  Examples of the carbon-carbon double bond having reactivity with the thiol group include the above formulas (7-1a) to (7-18a) mentioned in the method (a). Since the reactivity with thiol is good, the formulas (7-1a), (7-2a), (7-6a), (7-7a), (7-11a), (7-17a) and (7-18a) is preferred, and formulas (7-2a) and (7-6a) are more preferred.

In addition, the linking group when the photochromic compound having the above formula (7-2a) is reacted with the organopolysiloxane having a 3-mercaptopropyl group is —CH ₂ CH ₂ CH _2.
SCH ₂ CH ₂ CH ₂ — or —CH ₂ CH (CH ₃ ) SCH ₂ CH ₂ CH ₂ —, which reacts a photochromic compound having the formula (7-8a) with an organopolysiloxane having a 3-mercaptopropyl group. In this case, the linking group is —OCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ — or —OCH ₂ CH (CH ₃ ) SCH ₂ CH ₂ CH ₂ —.

  In the case of carrying out an enethiol reaction between an organopolysiloxane having a thiol group and a photochromic compound having a carbon-carbon double bond having reactivity with a thiol group, it is described in known conditions, for example, JP-A-2003-295431 It may be performed according to the conditions.

  The reaction ratio of the reaction between the organopolysiloxane having a thiol group and the photochromic compound having a carbon-carbon double bond having reactivity with the thiol group is based on the carbon-carbon double bond having reactivity with the thiol group. The molar ratio of thiol groups is preferably 1 to 100, more preferably 1.5 to 50, and most preferably 2 to 30. The enethiol reaction of this reaction is preferably performed by ultraviolet irradiation, and active ultraviolet rays such as i-line (365 nm) and g-line (436 nm) are preferable.

  The enethiol reaction may be performed without a catalyst, but since the reaction proceeds quickly, it is preferable to use a photoreaction initiator as a catalyst.

  A known catalyst can be used as the photoinitiator, and is not particularly limited. However, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, 2,2 ' -Diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, etc. are preferable.

The amount of the catalyst used is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of organopolysiloxane having a thiol group and a photochromic compound having a carbon-carbon double bond having reactivity with the thiol group. Is preferable, and 0.1-5 mass parts is still more preferable.
Next, the component (B) will be described.

<(B) component>
The component (B) of the present invention is a siloxane compound having crosslinking reactivity with the component (A). The group having reactivity with the component (A) is determined by the reactive group in the component (A). For example, when the reactive group of the component (A) is a Si—H group, the reactive group of the component (B) is a carbon-carbon double bond having reactivity with the Si—H group, and (A When the reactive group of the component) is a thiol group, the reactive group of the component (B) is a carbon-carbon double bond having reactivity with the thiol group. Similarly, when the reactive group of component (A) is a carbon-carbon double bond having reactivity with Si-H group or a carbon-carbon double bond having reactivity with thiol group (B The reactive group of the component is a Si-H group or a thiol group.

  Preferred compounds as the component (B) include, for example, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, and Si—H at both ends of the molecule. A polydimethylsiloxane having a group, a siloxane compound having a Si-H group such as 2,4,6,8-tetramethylcyclotetrasiloxane; 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-divinyltrisiloxane, polydimethylsiloxane having vinyl groups at both ends of the molecule, 1,1,5,5-tetramethyl-3,3- Si-H group or thiol group such as diphenyl-1,5-divinyltrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane Reactive siloxane compounds; 1,3-bis (3-mercaptopropyl) -1,1,3,3-tetramethyldisiloxane, 1,5-bis (3-mercaptopropyl) -1,1,3 3,5,5-hexamethyltetrasiloxane, polydimethylsiloxane having 3-mercaptopropyl groups at both ends of the molecule, 2,4,6,8-tetrakis (3-mercaptopropyl) -2,4,6,8 -A siloxane compound having a thiol group such as tetramethylcyclotetrasiloxane.

  The mass average molecular weight of the component (B) of the present invention is preferably from 500 to 100,000, more preferably from 2,000 to 50,000, more preferably from 3,000 to 50,000 because the photobleaching sensitivity of the photochromic organopolysiloxane crosslinking reaction product is increased. Most preferably, it is 20000. In particular, since the cross-linking reaction product of the present invention obtained using the component (B) having a mass average molecular weight of 5000 or more has high flexibility, it can be preferably used as an intermediate layer of laminated glass. In applications where hardness such as a light control lens is required, the crosslinking reaction product of the present invention obtained using the component (B) having a mass average molecular weight of 4000 or less is preferable.

<Crosslinking reaction between component (A) and component (B)>
The crosslinking reaction between the component (A) and the component (B) described above can be performed by a conventionally known method. For example, when the crosslinking reaction between the component (A) and the component (B) is crosslinked by a hydrosilylation reaction between a Si—H group and a carbon-carbon double bond having reactivity with the Si—H group. The reaction can be carried out under the same conditions as described in the method (a) of the production method of the component (A). In addition, when the (A) component and the (B) component are cross-linked by an enethiol reaction between a thiol group and a carbon-carbon double bond having reactivity with the thiol group, The reaction can be performed under the same conditions as described in the method c).

The ratio of the component (A) and component (B), the ratio of the number of moles of reactive groups of the component (B) to the number of moles of reactive groups of the component (A) in the photochromic organopolysiloxane composition of the present invention, 0. It is preferably 2 to 10, more preferably 0.5 to 5, and most preferably 0.8 to 2. When the number of moles of the reactive group of the component (B) is less than 0.2, the fading sensitivity of the photochromic organopolysiloxane crosslinking reaction product deteriorates, and when the number of moles of the reactive group of the component (B) exceeds 10, The increase effect corresponding to the number of moles of the reactive group of the component B) cannot be obtained.

  In the photochromic organopolysiloxane composition of the present invention, the total content of the component (A) and the component (B) is preferably 50 to 100% by mass, and 70 to 100% by mass in the composition. More preferably, it is most preferable that it is 90-100 mass%.

  A solvent, an antioxidant, and a release agent can be added to the photochromic organopolysiloxane composition of the present invention.

  The solvent is not particularly limited, and any solvent can be used as long as it is an organic solvent that can dissolve or disperse the component (A) and the component (B), and is used for producing the component (A) and the component (B). The solvent used may be used as it is. Examples of the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, toluene, hexane, cyclopentanone, propylene glycol monomethyl ether acetate, ethylene carbonate, propylene carbonate. And dimethyl carbonate.

  Examples of the antioxidant include triphenyl phosphite, tris (4-methylphenyl) phosphite, tris (4-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, and tris (2-methyl). -4-ethylphenyl) phosphite, tris (2-methyl-4-t-butylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2,6-di--) t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, bis (monononylphenyl) pentaerythritol-di- Phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol-di-phosphite, bis ( 2,4-di-t-butyl-5-methylphenyl) pentaerythritol di-phosphite, 2,2-methylenebis (4,6-dimethylphenyl) octyl phosphite, 2,2-methylenebis (4-t- Butyl-6-methylphenyl) octyl phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (4,6-dimethylphenyl) hexyl phosphite, 2 , 2-methylenebis (4,6-di-t-butylphenyl) hexyl phosphite, 2,2-methylenebis (4,6- Phosphite compounds such as -t-butylphenyl) stearyl phosphite; pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl -2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) Propionate], 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris [2-methyl-4- (3,5-di-t) Hindered phenol compounds such as -butyl-4-hydroxyphenylpropionyloxy) -5-t-butylphenyl] butane; 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H- Examples include lactone compounds such as benzofuran-2-one.

  These antioxidants may be used alone or in combination of two or more, and it is particularly effective to use one or more of each of phosphite compounds, hindered phenol compounds and lactone compounds. When the addition amount of the antioxidant is too small, a sufficient antioxidant effect cannot be obtained, and when it is too large, the mechanical properties and the like may be lowered. It is preferably 005 to 1% by mass, more preferably 0.01 to 0.5% by mass, and most preferably 0.01 to 0.2% by mass.

  Examples of the release agent include natural, synthetic paraffins, silicone oil, perfluoroalkyl group-containing phosphate esters, perfluoroalkyl group-containing polyether compounds, polyethylene waxes, beeswax, stearic acid monoglyceride, palmitic acid monoglyceride, Examples include fatty acid esters such as pentaerythritol tetrastearate, and stearic acid monoglyceride, palmitic acid monoglyceride, and pentaerythritol tetrastearate are particularly preferable. When the composition of the present invention is used for a molded article of a plastic lens, it is preferable to use a release agent, and the addition amount is 0.005 to 2% by mass in the composition of the present invention. It is preferable.

In addition to the photochromic organopolysiloxane composition of the present invention, a lubricant, a crystal nucleating agent, a plasticizer, a fluidity improver, an antistatic agent, a flame retardant, an antistatic agent, a pigment, a dye, and the like are further added. Also good.
Next, the crosslinking reaction product of the present invention will be described.

  The photochromic organopolysiloxane crosslinking reaction product of the present invention is obtained by crosslinking reaction of the photochromic organopolysiloxane composition by a conventionally known method. The thickness of the crosslinking reaction product of the present invention is determined by the application in which the crosslinking reaction product of the present invention is used, the type and content of the group exhibiting photochromism, and the like.

  Since the crosslinking reaction product of the present invention is a crosslinking reaction product of a polysiloxane compound, the main chain has a large free volume and has less influence on the photochromic properties of the group exhibiting photochromism compared to a carbon-based polymer. In addition, since the photochromic group has little influence on the reversible structural change due to the action of light, when it has a group having T-type photochromism, it has high color development sensitivity and fading sensitivity and is excellent in repeated stability. As an intermediate layer of a transparent material such as a transparent material or a laminated glass, it can be suitably used for a light control glass or a light control lens. The light control glass and light control lens using the crosslinking reaction product of the present invention can be suitably used for building windows, vehicle windows, building openings, partitions, glasses, sunglasses, and the like. In addition, when it has a group having P-type photochromism, it is suitable for optical recording media, optical display media, optical switches, etc. because of its high response speed and excellent stability in coloring and decoloring states and repeated stability. Can be used for

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, these do not restrict | limit the scope of the present invention. In the examples, “parts” and “%” are based on mass.

<Compound (8c): Naphthopyran structure>
In a 100 ml glass container, 1.60 g (10 mol) of 2,7-dihydroxynaphthalene, 2.29 g (11 mmol) of 1,1-diphenylpropargyl alcohol, 50 g of toluene and a stirrer were added and stirred with a stirrer. The acid 0.05g was added, and it stirred at room temperature for 2 hours, and reacted. After completion of the reaction, the solvent was removed, the residue was purified by silica gel chromatography, and the following compound (8d) (3,3-diphenyl-7′-hydroxy-3H-naphtho [2,1-b] pyran, which is a hydroxy intermediate, was obtained. ) 0.92 g was obtained. (Yield 25%)

  In a 100 ml glass container, 0.368 g (1 mmol) of the above compound (8d), 0.133 g (1.1 mmol) of 3-bromo-1-propene, 0.166 g (1.2 mmol) of potassium carbonate, 20 g of acetone and a stir bar The mixture was stirred with a stirrer and subjected to an allyl etherification reaction of a hydroxyl group at 57 ° C. for 8 hours. After completion of the reaction, the solvent was removed and the residue was purified by silica gel chromatography to obtain 0.298 g of the following compound (8a) (3,3-diphenyl-7′-allyloxy-3H-naphtho [2,1-b] pyran). It was. (Yield 73%)

  In a 50 ml glass container, 0.195 g (0.5 mmol) of the above compound (8a), 0.64 g (0.6 mmol) of dimethoxymethylsilane, 20 g of toluene, 10 mg of 0.1% platinum catalyst (Karsttedt catalyst) toluene solution and stirring A child was put in, stirred with a stirrer, and reacted at 80 ° C. for 3 hours. After the reaction, the solvent was removed to obtain 0.134 g of the following compound (8c) as the target product.

<Compound (9b): Spirooxazine structure>
In a 100 ml glass container, 4.8 g (30 mmol) of 2,7-dihydroxynaphthalene, 6.0 g (3.6 mmol) of 2.4% sodium hydroxide aqueous solution and a stirrer were placed, and stirred with a stirrer. 2.28 g (33 mmol) of sodium nitrate was added. The mixture was ice-cooled, and further 13.3 g (57 mmol) of 42% sulfuric acid was added dropwise at 0 ° C. After completion of the dropwise addition, the reaction was carried out by stirring at room temperature for 18 hours. The produced precipitate was filtered off, washed with water and dried to obtain 4.5 g of a crude product of 2,7-dihydroxy-1-nitrosonaphthalene. This crude product was used for subsequent reactions without purification.

  In a 50 ml glass container, 1.59 g (10 mmol) of 2,3,3-trimethyl-3H-indolenine, 4.26 g (30 mmol) of iodomethane, 10 g of toluene and a stirrer were added, stirred with a stirrer, and 110 for 3 hours. N-methylation reaction was performed. After cooling to room temperature, the formed precipitate was filtered off and washed with a solvent to obtain 2.93 g (yield 97%) of 1,2,3,3-tetramethyl-indolenium iodozide.

  In a 100 ml glass container, put 0.301 g (1 mmol) of 1,2,3,3-tetramethyl-indolenium iodozide, 20 g of diethyl ether, 10 g of water and a stir bar, and stir with a stirrer, 12% hydroxylation A sodium aqueous solution (1.5 g, 4.5 mmol) was added, and the reaction was performed by stirring at room temperature for 1 hour. After completion of the reaction, ether extraction was performed to obtain a crude product of 1,3,3-trimethyl-2-methylene-3H-indoline. Ethanol was added to 1,3,3-trimethyl-2-methylene-3H-indoline to obtain an ethanol solution.

  In a 30 ml glass container, 0.19 g of the crude 2,7-dihydroxy-1-nitrosonaphthalene produced above, 9 g of ethanol, and a stirrer were placed, and 1,3,3-trimethyl-2-phenyl was added at 78 ° C. while stirring with a stirrer. An ethanol solution of methylene-3H-indoline was added dropwise. After completion of dropping, the reaction was carried out by stirring at 78 ° C. for 6 hours. After completion of the reaction, the solvent was removed, the residue was purified by silica gel chromatography, and the following compound (9d) (1,3,3-trimethyl-7′-hydroxy-spiro [2H-indoline-2,3 ′-[3H] naphtho [2,1-b] [1,4] oxazine]) 0.142 g was obtained.

  In a 50 ml glass container, 0.102 g (0.3 mmol) of the above compound (9d), 5 g of tetrahydrofuran and a stirrer were placed, and 0.073 g (0.6 mmol) of 3-bromo-1-propene was added at 0 ° C. while stirring with a stirrer. ) Was added. After reacting at room temperature for 18 hours, water was added, followed by ether extraction. The extract was purified by silica gel chromatography, and the following compound (9a) (1,3,3-trimethyl-7′-allyloxy-spiro [2H -Indoline-2,3 '-[3H] naphtho [2,1-b] [1,4] oxazine]) 0.074 g (yield 65%) was obtained.

  In a 50 ml glass container, 269 mg (1.95 mmol) of 1,1,3,3-tetramethyldisiloxane, 10 ml of toluene, 23.63 mg of 0.1% platinum catalyst (Karstedt catalyst) toluene solution and a stir bar were placed, and a stirrer was added. While stirring at 60 ° C., 50.3 mg (0.13 mmol) of the above compound (9a) dissolved in 10 ml of toluene was added dropwise at 60 ° C. over 1 hour. After completion of dropping, the mixture was stirred at 95 ° C. for 16 hours. After completion of the reaction, the solvent and excess 1,1,3,3-tetramethyldisiloxane were removed under reduced pressure to obtain 495 mg of a crude product containing the target compound (9b) below. As a result of analysis by H-NMR analysis, the purity of the compound (9b) in this crude product is 70%, and the yield of the compound (9b) obtained from the yield and purity of the crude product is 85%.

<Compound (10b): Spirooxazine structure>
In the production example of the above compound (9b), the same operation was carried out except that 2,6-dihydroxynaphthalene was used instead of 2,7-dihydroxynaphthalene, and a crude product containing the target compound (10b) below was obtained. 0.316 g of product was obtained. As a result of analysis by H-NMR analysis, the purity of the compound (10b) in this crude product is 70%, and the yield of the compound (10c) obtained from the yield and purity of the crude product is 85%.

<Compound (11cM): Spiropyran structure>
In a 50 ml glass container, put 1.59 g (10 mmol) of 2,3,3-trimethyl-3H-indole, 2.74 g (30 mmol) of 3-iodopropyldimethoxymethylsilane, 10 g of acetonitrile and a stir bar, and stir with a stirrer. The reaction was performed at 82 ° C. for 5 hours. Thereafter, 1.11 g (11 mmol) of triethylamine was added and stirred at room temperature for 1 hour, 2-hydroxy-5-nitrobenzaldehyde was added, and the mixture was stirred at 82 ° C. for 2 hours. After the reaction, the toluene-soluble residue of the residue from which the solvent was removed was taken out and purified by silica gel chromatography to obtain the target compound (11cM) (1- (3-dimethoxymethylsilylpropyl) -3,3-dimethyl. -6'-nitro-spiro [2H-indoline-2,3 '-[3H] naphtho [2,1-b] [1,4] oxazine]) 1.83 g was obtained. (Yield 59%) The compound (11cM) is a compound in which Z and R ⁴³ are methyl in the general formula (11c).

<Compound (12cM): Spirooxazine structure>
In the production method of the compound (11a), the same operation was carried out except that 2-hydroxy-1-nitrosonaphthalene was used instead of 2-hydroxy-5-nitrobenzaldehyde, and the target compound (12cM) (1 -(3-Dimethoxymethylsilylpropyl) -3,3-dimethyl-spiro [2H-indoline-2,3 '-[3H] naphtho [2,1-b] [1,4] oxazine]) 1.53 g Was obtained in a yield of 48%. The compound (12cM) is a compound in which Z and R ⁴³ are methyl in the general formula (12c).

<Compound (15c): Naphthopyran structure>
In a 300 ml glass container, 2.40 g (6.86 mmol) of the compound (8d) obtained in the production of the above compound (8c), 1.83 g (13.7 mmol) of 6-bromo-1-hexene, 1. 74 g (12.6 mmol), 50 ml of acetone and a stir bar were added, and the mixture was stirred with a stirrer, and refluxed at an oil bath temperature of 65 to 75 ° C. for 30 hours. The solvent was removed, water and a small amount of 3 mol / l hydrochloric acid were added to dissolve the inorganic salt, and the mixture was extracted from ethyl acetate. Purification by silica gel chromatography (ethyl acetate: n-hexane = 1: 25), recrystallization from n-hexane and the following compound (15a) (3,3-diphenyl-9- (5-hexen-1-yloxy) -3H-naphtho [2,1-b] pyran) 2.16 g. (Yield 73%)

  In the production of the above compound (8c), the same operation was carried out except that the above compound (15a) was used in place of the above compound (8a), to obtain 0.24 g of the following compound (15c) as a target product.

<Compound (8n): Naphthopyran structure>
In the production example of the above compound (8a), except that 1-bromopropane was used instead of 3-bromo-1-propene, the same operation was carried out to obtain the target compound (8n) (3,3-diphenyl). 0.13 g of -9-propoxy-3H-naphtho [2,1-b] pyran) was obtained. The compound (8n) is a compound having no carbon-carbon double bond capable of reacting with the Si—H group.

<Compound (9n): Spirooxazine structure>
In the preparation example of the previous compound (9a), the same operation was carried out except that 1-bromopropane was used instead of 3-bromo-1-propene, and the target compound (9n) (1, 3, 3) was obtained. -Trimethyl-7'-propoxy-spiro [2H-indoline-2,3 '-[3H] naphtho [2,1-b] [1,4] oxazine]) 0.31 g was obtained. The compound (9n) is a compound having no carbon-carbon double bond capable of reacting with the Si—H group.

<Compound (11n): Spiropyran structure In the production example of the above compound (11cM), the same operation was performed except that 1-bromopropane was used instead of 3-iodopropyldimethoxymethylsilane, and the target compound ( 11n) (1-propyl-3,3-dimethyl-6′-nitro-spiro [2H-indoline-2,3 ′-[3H] naphtho [2,1-b] [1,4] oxazine]) 6 g was obtained. The compound (11n) is a compound having no carbon-carbon double bond capable of reacting with the Si—H group.

<Compound (12n): Spirooxazine structure>
In the production example of the above compound (12cM), the same operation was carried out except that 1-bromopropane was used instead of 3-iodopropyldimethoxymethylsilane, and the target compound (12n) (1-propyl-3) was obtained. , 3-dimethyl-spiro [2H-indoline-2,3 ′-[3H] naphtho [2,1-b] [1,4] oxazine]) 0.9 g. The compound (12n) is a compound having no carbon-carbon double bond capable of reacting with the Si—H group.

<Compound (15n): Naphthopyran structure>
In the production example of the compound (15a), the same operation was carried out except that 1-bromohexane was used instead of 6-bromo-1-hexene, and the target compound (15n) (3,3-phenyl- 0.087 g of 9- (5-hexen-1-yloxy) -3H-naphtho [2,1-b] pyran) was obtained. The compound (15n) is a compound having no carbon-carbon double bond capable of reacting with the Si—H group.

<Main chain organopolysiloxane: Organopolysiloxane A (containing vinyl group)>
A 5 L glass container equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser was charged with 260 g of water, 1171 g (14 mol) of 48% sodium hydroxide aqueous solution, and 71 g of toluene. While stirring, a mixture of 602 g (4.64 mol) of dichlorodimethylsilane and 163 g (1.16 mol) of dichloromethylvinylsilane was added dropwise at 10 to 40 ° C. over 1 hour, followed by stirring at 110 for 2 hours. After cooling to room temperature, 350 g of toluene was added, and the toluene layer was washed with water. After the toluene layer was refluxed under reduced pressure to remove water, 10.6 g (134 mmol) of pyridine was added, and 9.1 g (83.8 mmol) of chlorotrimethylsilane was added dropwise at 10 to 30 ° C. After completion of dropping, the mixture was stirred at 65 ° C. for 30 minutes. After completion of the reaction, washing with water, solvent removal, and filtration were performed to obtain silicone A, which is a silicone polymer having a vinyl group, which is the target product. The mass average molecular weight of the polymer A by GPC analysis is 16000, and the vinyl group content calculated by the method of JIS K0070 (Testing method of acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products) Is 2.41 mmol / g, and the number of vinyl groups per molecule calculated from the mass average molecular weight and vinyl group content is 38.6.

<(A) component: Organopolysiloxane A-1 (naphthopyran structure)>
In a 50 ml glass container, 20 g of toluene, 0.039 g (0.1 mmol) of the above compound (8c), 0.415 g (2.8 mmol) of diethoxydimethylsilane, 0.055 g (0.4 mmol) of diethoxymethylsilane and stirring The mixture was added and 0.25 ml of 5% aqueous oxalic acid solution was added in 5 portions over 30 minutes at 10 ° C. while stirring with a stirrer. After stirring at 10 ° C. for 5 hours, 0.006 g (0.05 mmol) of ethoxytrimethylsilane was added, and the reaction was further stirred at 10 ° C. for 15 hours. After completion of the reaction, the solvent was removed under reduced pressure, and the residue was washed with acetonitrile to obtain organopolysiloxane A-1 having a naphthopyran structure as the target product. The mass average molecular weight of the organopolysiloxane A-1 by GPC analysis is 17000, the content of Si—H group calculated from the integrated value of NMR is 1.1 mmol / g, and calculated from the mass average molecular weight and the content of Si—H group. The number of Si—H groups per molecule is 16.5.

<(A) component: Organopolysiloxane A-2 (spiroxazine structure)>
A 30 ml glass container contains 20 g of toluene, 66.8 mg of a 1% toluene solution of a platinum catalyst (Karstedt catalyst), 2.1 g of the above organopolysiloxane A (1.36 mmol as a vinyl group), and the above compound (9b). The crude product (56.5 mg, 0.076 mmol as the compound (7b)) and a stirring bar were added, and the mixture was reacted at 95 ° C. for 19 hours while stirring with a stirrer. After completion of the reaction, the solvent was removed under reduced pressure, and the residue was washed with acetonitrile to obtain organopolysiloxane A-2 having a spirooxazine structure as the target product. The mass average molecular weight of the organopolysiloxane A-2 by GPC analysis is 17000, the vinyl group content calculated from the integrated value of NMR is 2.05 mmol / g, and per molecule calculated from the mass average molecular weight and the vinyl group content. The number of vinyl groups is 34.8.

<(A) component: Organopolysiloxane A-3 (spiroxazine structure)>
In the production example of organopolysiloxane A-2, the same operation was performed except that the crude product containing the compound (10b) was used instead of the crude product containing the compound (9b). Organopolysiloxane A-3 having a spirooxazine structure was obtained. The mass average molecular weight of the organopolysiloxane A-3 by GPC analysis is 17000, the vinyl group content calculated from the integrated value of NMR is 2.02 mmol / g, and per molecule calculated from the mass average molecular weight and the vinyl group content. The number of vinyl groups in is 34.3.

<(A) component: Organopolysiloxane A-4 (spiropyran structure)>
In the production example of organopolysiloxane A-1, the same operation was performed except that compound (11cM) was used instead of compound (8c) and diethoxymethylvinylsilane was used instead of diethoxymethylsilane. Organopolysiloxane A-4 having a spiropyran structure was obtained. Organopolysiloxane A-4 has a mass average molecular weight of 15000 by GPC analysis, the vinyl group content calculated from the integrated value of NMR is 1.16 mmol / g, and one molecule calculated from the mass average molecular weight and the vinyl group content The number of per vinyl group is 17.4.

<(A) component: Organopolysiloxane A-5 (spiroxazine structure)>
In the production example of the organopolysiloxane of Example 1, the same operation was performed except that the compound (12cM) was used instead of the compound (8c), and the organopolysiloxane A- having a spirooxazine structure as the target product was obtained. 5 was obtained. The mass average molecular weight of the organopolysiloxane A-5 by GPC analysis is 16000, the Si—H group content calculated from the integrated value of NMR is 1.16 mmol / g, and is calculated from the mass average molecular weight and the Si—H group content. The number of Si—H groups per molecule was 18.6.

<(A) component: Organopolysiloxane A-6 (naphthopyran structure)>
In a 50 ml glass container, 20 g of toluene, 48.2 mg of a 0.998% toluene solution of platinum catalyst (Karstedt catalyst), 1.52 g of the above organopolysiloxane A (1.0 mmol as vinyl group), and the above compound (15c) The crude product containing 97.7 mg (0.172 mmol) and a stirring bar were added, and the mixture was reacted at an oil bath of 65 to 75 ° C. for 40 hours while stirring with a stirrer. After completion of the reaction, the solvent was removed under reduced pressure, and the residue was washed with methanol to obtain organopolysiloxane A-6 having a naphthopyran structure as the target product. The mass average molecular weight of the organopolysiloxane A-6 by GPC analysis was 16000, the vinyl group content calculated from the integrated value of NMR was 2.10 mmol / g, and per molecule calculated from the mass average molecular weight and the vinyl group content. The number of vinyl groups in is 35.2.

As the component (B), the following siloxane compound was used.

<(B) component: Polysiloxane B-1 (Si-H group-containing)>
Polydimethylsiloxane (mass average molecular weight 13000) having Si-H groups at both ends

<(B) component: Siloxane B-2 (containing vinyl group)>
1,1,3,3-tetramethyl-1,3-vinyldisiloxane

Examples 1-8
In the combinations shown in [Table 1], the platinum catalyst (Karstedt catalyst) was mixed at 200 mass ppm and the toluene content was 20% with respect to the total amount of the components (A) and (B). The photochromic organopolysiloxane compositions of Examples 1-8 were prepared.

Comparative Examples 1-5 and 21
In the combinations shown in Table 2, the ratio of the number of moles of Si-H groups of polysiloxane B-1 to the number of moles of vinyl groups of organopolysiloxane A is 0.8, and organopolysiloxane A and polysiloxane B- 1, the platinum catalyst (Karstedt catalyst) was mixed at 200 ppm, the compounds (8n) to (15n) were 0.03 mmol / g, and the toluene content was 20%. Comparative Examples 1 to 5 and 21 photochromic organopolysiloxane compositions were prepared.

Comparative Examples 6-10 and 22
In the combinations shown in [Table 3], a 70% chloroform solution of polymethyl methacrylate (PMMA) was mixed with PMMA so that the compounds (8n) to (15n) would be 0.03 mmol / g, and a comparative example 6-10 and 22 photochromic PMMA compositions were prepared.

<Preparation of silicone film>
After apply | coating the photochromic organopolysiloxane composition of Examples 1-8 or Comparative Examples 1-5 and 21 on a glass plate, after removing a solvent, it puts into a thermostat, 80 degreeC for 1 hour, 150 degreeC 2 A 50 μm thick silicone film was prepared by heating for a period of time.

<Preparation of PMMA coating film>
After apply | coating the photochromic PMMA composition of Comparative Examples 6-10 and 22 on a glass plate, it air-dried and created the coating film with a film thickness of 50 micrometers, and used it for evaluation.

<Preparation of solution>
Compounds (8n) to (15n) were dissolved in hexamethyldisiloxane (HMDS) or ethyl acetate so as to be 0.4 mmol / L, and this solution was put in a quartz cell having an optical path length of 10 mm and used for evaluation. The HMDS solutions of the compounds (8n) to (15n) were designated as Comparative Examples 11 to 15 and 23, and the ethyl acetate solutions of the compounds (8n) to (15n) were designated as Comparative Examples 16 to 20 and 24.

<Appearance of coating film>
The prepared coating film was visually observed to evaluate the appearance. The results are shown in [Table 4].

From the results of [Table 4], since the silicone films of Comparative Examples 1 to 5 and 21 were insufficiently compatible with the photochromic compound, separation and bleeding of the photochromic compound were observed. Since the silicone film of No. 8 has a group exhibiting photochromism bonded to an organopolysiloxane skeleton, a uniform coating film was obtained without causing separation of specific components. The PMMA films of Comparative Examples 6 to 10 and 22 had good compatibility with the photochromic compound and produced uniform coatings.
Next, using the silicone films of Examples 1 to 5 and the PMMA films of Comparative Examples 6 to 10, the 1/10 fading rate was evaluated by the method described below. Moreover, about the silicone film of Examples 6-8 and the PMMA film of the comparative example 22, 1/2 fading speed and 1/4 fading speed were evaluated. The results are shown in [Table 5].

<1/10 fading speed>
A Xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics was passed through an aeromass filter (manufactured by Corning) at 20 ° C. ± 1 ° C., and the beam intensity on the polymer surface was 2.4 mW / cm 2 (365 nm), 24 μW. / Cm 2 (245 nm) was irradiated with ultraviolet light for 10 minutes to develop a color, and then the ultraviolet irradiation was stopped. The absorbance of each sample was measured before the UV irradiation and immediately after the UV irradiation was stopped until the absorbance disappeared, and the 1/10 fading rate was determined. The 1/10 fading rate is expressed as follows: ε (120) is the absorbance immediately after the UV irradiation is stopped at the maximum absorption wavelength of each sample, and ε (0) is the absorbance at that wavelength before UV irradiation. To {1/10} of {ε (120) −ε (0)}. The smaller the value of 1/10 fading speed, the higher the fading sensitivity.
<1/2 fading speed>
In the measurement of the 1/10 fading rate, the time required for the absorbance to drop from ε (120) to 1/2 of {ε (120) −ε (0)} was determined as the ½ fading rate. .
<1/4 fading speed>
In the measurement of the 1/10 fading speed, the time required for the absorbance to drop from ε (120) to ¼ of {ε (120) −ε (0)} was determined as the ¼ fading speed. .

  From the results of [Table 5], the silicone films of Examples 1 to 8 showed higher fading sensitivity than Comparative Examples 6 to 10 and 22. Although Examples 1 to 8 are films, they have a fading sensitivity equivalent to the HMDS solutions of Comparative Examples 11 to 15 and 23 and the ethyl acetate solutions of Comparative Examples 16 to 20 and 24.

Claims (8)

The following (A) component and the following (B) component are contained, and the (A) component and the (B) component are photochromic organopolysiloxane compositions having crosslinking reactivity ,
A photochromic organopolysiloxane composition, wherein the crosslinking reaction is a crosslinking reaction by hydrosilylation reaction or ene-thiol reaction .
(A) Photochromic organopolysiloxane having a group exhibiting photochromism (B) Siloxane compound The component (A) is a photochromic organopolysiloxane having at least three Si-H groups in one molecule, and the component (B) has 1 carbon-carbon double bond having reactivity to Si-H groups. The photochromic organopolysiloxane composition according to claim 1, which is a siloxane compound having at least two molecules in the molecule. The component (A) is a photochromic organopolysiloxane having at least three carbon-carbon double bonds having reactivity to Si-H groups in one molecule, and the component (B) has at least Si-H groups. The photochromic organopolysiloxane composition according to claim 1, which is a siloxane compound having two in one molecule, and the crosslinking reaction is a hydrosilylation reaction. The group exhibiting photochromism is a group selected from the group consisting of a group having a spiropyran structure, a group having a spirooxazine structure, a group having a naphthopyran structure, a spirocyclohexadiene structure and a group having a hexaarylbisimidazole structure Item 4. The photochromic organopolysiloxane composition according to any one of Items 1 to 3 . The photochromic organopolysiloxane according to any one of claims 1 to 4 , wherein a ratio of the number of moles of the reactive group of the component (B) to the number of moles of the reactive group of the component (A) is 0.2 to 10. Composition. A photochromic organopolysiloxane crosslinking reaction product obtained by crosslinking the photochromic organopolysiloxane composition according to any one of claims 1 to 5 . Laminated glass having the photochromic organopolysiloxane crosslinking reaction product according to claim 6 as an intermediate layer. A light control lens having the layer of the photochromic organopolysiloxane crosslinking reaction product according to claim 6 .