JPH04279666A - Photosetting silicone composition - Google Patents

Abstract

PURPOSE:To obtain an inexpensive composition having sufficient photosetting rate and excellent release characteristics and ink repulsion by adding a curing catalyst to a reaction product of a specific silicone compound and an organopolysiloxane. CONSTITUTION:(C) A curing catalyst is added to a reaction product of (A) a silicone compound shown by formula I (R is 1-10C alkyl, etc.; X and Y are H, halogen, amino, etc.; Z is H, halogen, 1-10C alkyl, etc.; (n) is 0 or 1) and (B) an organopolysiloxane containing a terminal shown by formula II (R2 and R3 are 1-10C alkyl, alkenyl or 6-10C aryl; (m) is >=2 integer) with silanol structure. The silicone compound of the component A is preferably a compound wherein XY is acetoxy in the formula I. The component B contains preferably 60% methyl group. The component C is preferably dimethyltin diacetate.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a photocurable silicone composition, and it relates to a photocurable silicone composition that can be used for paints, release materials, lithographic printing plate materials, etc. .

0002

BACKGROUND OF THE INVENTION Conventionally, the following photocurable silicone compositions are known.

(1) Acrylic or methacrylic group-containing silicone compositions disclosed in Japanese Patent Publication No. 49-39200.

(2) Maleimide group-containing silicone compositions disclosed in Japanese Patent Publication No. 5302/1983.

(3) Epoxy group-containing silicone compositions disclosed in US Pat. No. 4,279,717.

(4) Polyene-polythiol-containing silicone compositions disclosed in US Pat. No. 4,064,027.

However, (1) is susceptible to curing inhibition by air, (2) and (3) require materials that are difficult to obtain, and (4) requires a thiol component that remains in the cured product. There were problems in that there was an unpleasant odor associated with the curing process, and the curing speed was not sufficient. Furthermore, (1) to (4
), in order to obtain a sufficient curing speed, it is necessary to increase the concentration of photoreactive groups in the silicone, which reduces the releasability and ink repellency derived from the silicone structure. There was a problem with letting it work.

[0008]

OBJECTS OF THE INVENTION The object of the present invention is to solve the above-mentioned problems, to obtain a sufficient photocuring speed, and to avoid deterioration of releasability and ink repulsion. An object of the present invention is to provide a photocurable silicone composition that can be easily and inexpensively produced.

[0009]

[Means for Solving the Problems] The objects of the present invention are achieved by the following configuration.

(A) Silicone compound represented by general formula (I)

[0011]

[Chemical formula 3]

(In the formula, R1 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an alkenyl group having 6 to 10 carbon atoms.
at least one selected from the group of 10 aryl groups, and X and Y are each a hydrogen atom, a halogen atom, an amino group, an aminooxy group, an alkoxy group having 1 to 10 carbon atoms,
It is at least one selected from the group consisting of an amide group, an acyloxy group, an alkenyloxy group having 2 to 10 carbon atoms, and a ketoxime group having 3 to 10 carbon atoms, and each of them may be the same or different. Z is a hydrogen atom, a halogen atom,
Alkyl group having 1 to 10 carbon atoms, alkoxy group, 2 carbon atoms
-10 alkenyl group, C6-10 aryl group,
It is at least one selected from the group of acyloxy groups and alkoxycarbonyl groups. n is 0 or 1. ) and (B) an organopolysiloxane having a silanol structure at the terminal represented by general formula (II)

[0013]

[C4]

(In the formula, R2 and R3 are at least one selected from the group of substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, alkenyl groups, and substituted or unsubstituted aryl groups having 6 to 10 carbon atoms. A photocurable silicone composition prepared by adding (C) a curing catalyst to a reactant of (1 type, each of which may be the same or different; m is an integer of 2 or more).

That is, the present invention provides at least one specific phenylbenzoylmethoxy group, (2-furyl)(2-furoyl)methoxy group, and (2-thiophene)(2-thiophenecarbonyl)methoxy group.
The present invention was achieved by discovering that a photocurable silicone composition that utilizes the photodecomposition of a silicone compound having seeds and the crosslinking reaction of a silanol structure by a curing catalyst exhibits remarkable effects. . (A) used in the present invention
General formula (I) of

[0016]

[C5]

In the formula, R1 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 6 carbon atoms.
It is at least one kind selected from the group of ~10 aryl groups. In addition, X and Y are each a hydrolyzable functional group, such as a hydrogen atom, a halogen atom, an amino group, an aminooxy group, an alkoxy group having 1 to 10 carbon atoms, an amide group, an acyloxy group, and an alkenyloxy group having 2 to 10 carbon atoms. , and a ketoxime group having 3 to 10 carbon atoms, which may be the same or different. Z is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms,
At least one member selected from the group consisting of an aryl group having 6 to 10 carbon atoms, an acyloxy group, and an alkoxycarbonyl group.
species, and n is 0 or 1.

Specific examples of the silicone compound represented by the general formula (I) include diacetoxymethyl(phenylbenzoylmethoxy)silane, diacetoxymethyl[(2-
furyl)(2-furoyl)methoxy]silane, diacetoxymethyl[(2-thiophene)(2-thiophenecarbonyl)methoxy]silane, diacetoxyethyl(phenylbenzoylmethoxy)silane, diacetoxyethyl[(2-furyl)( 2-furoyl)methoxy]silane,
Diacetoxyethyl[(2-thiophene)(2-thiophenecarbonyl)methoxy]silane, diacetoxybutyl[(4-methoxyphenyl)(4-methoxybenzoyl)methoxy]silane, diacetoxybutyl[(2-furyl)(2 -furoyl)methoxy]silane, diacetoxybutyl[(2-thiophene)(2-thiophenecarbonyl)methoxy]silane, diacetoxyhexyl(phenylbenzoylmethoxy)silane, diacetoxyhexyl[(2-furyl)(2-furoyl) methoxy]silane, diacetoxyhexyl[(2-thiophene)(2-thiophenecarbonyl)methoxy]silane, diacetoxyoctyl[(4-ethylphenyl)(4-ethylbenzoyl)methoxy]silane, diacetoxyoctyl[(2-ethylphenyl)(4-ethylbenzoyl)methoxy]silane,
-furyl)(2-furoyl)methoxy]silane, diacetoxyoctyl[(2-thiophene)(2-thiophenecarbonyl)methoxy]silane, diacetoxyvinyl[
(3-Butylphenyl)(3-butylbenzoyl)methoxy]silane, diacetoxyvinyl[(2-furyl)(
2-furoyl)methoxy]silane, diacetoxyvinyl[(2-thiophene)(2-thiophenecarbonyl)methoxy]silane, diacetoxydi(phenylbenzoylmethoxy)silane, diacetoxydi[(2-furyl)(
2-furoyl)methoxy]silane, diacetoxydi[(
2-thiophene)(2-thiophenecarbonyl)methoxy]silane, methyl(phenylbenzoylmethoxy)dichlorosilane, methyl[(2-furyl)(2-furoyl)methoxy]dichlorosilane, methyl[(2-thiophene)(2- thiophenecarbonyl)methoxy]dichlorosilane, dimethoxymethyl(phenylbenzoylmethoxy)silane, dimethoxymethyl[(2-furyl)(2-
furoyl)methoxy]silane, dimethoxymethyl[(2
-thiophene)(2-thiophenecarbonyl)methoxy]silane, dimethoxyethyl(phenylbenzoylmethoxy)silane, dimethoxyethyl[(2-furyl)(2
-furoyl)methoxy]silane, dimethoxyethyl[(
2-thiophene)(2-thiophenecarbonyl)methoxy]silane, dimethoxybutyl(phenylbenzoylmethoxy)silane, dimethoxybutyl[(2-furyl)(
2-furoyl)methoxy]silane, dimethoxybutyl[
(2-thiophene)(2-thiophenecarbonyl)methoxy]silane, diethoxymethyl(phenylbenzoylmethoxy)silane, diethoxymethyl[(2-furyl)
(2-furoyl)methoxy]silane, diethoxymethyl[(2-thiophene)(2-thiophenecarbonyl)methoxy]silane, dimethoxydi(phenylbenzoylmethoxy)silane, dimethoxydi[(2-furyl)(2-
Furoyl)methoxy]silane, dimethoxydi[(2-thiophene)(2-thiophenecarbonyl)methoxy]silane, diethoxydi(phenylbenzoylmethoxy)silane, diethoxydi[(2-furyl)(2-furoyl)
methoxy]silane, diethoxydi[(2-thiophene)
(2-thiophenecarbonyl)methoxy]silane, di(
Methyl ethyl ketoxime) di(phenylbenzoylmethoxy) silane, di(methyl ethyl ketoxime) di[
(2-furyl)(2-furoyl)methoxy]silane, di(methylethylketoxime)di[(2-thiophene)
(2-thiophenecarbonyl)methoxy]silane, diisopropenylmethyl(phenylbenzoylmethoxy)silane, diisopropenylmethyl[(2-furyl)(2-
Examples include, but are not limited to, silane (furoyl)methoxy]silane, diisopropenylmethyl[(2-thiophene)(2-thiophenecarbonyl)methoxy]silane, and the like. Among these, particularly preferred are those in which X and Y are acetoxy groups.

Further, the general formula (B) used in the present invention (
II)

[0020]

[C6]

In the formula, R2 and R3 are at least one member selected from the group of substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, alkenyl groups, and substituted or unsubstituted aryl groups having 6 to 10 carbon atoms. and may be the same or different. Moreover, m is an integer of 2 or more.

The organopolysiloxane represented by the general formula (II) preferably has a molecular weight of 1,000 to 1,000,000. Specific examples include dimethylpolysiloxane, diethylpolysiloxane, dibutylpolysiloxane, dihexylpolysiloxane, dioctylpolysiloxane, methylethylpolysiloxane, methylphenylpolysiloxane, methylvinylpolysiloxane, and mixtures of these polysiloxanes. However, the methyl group is 60
% is particularly preferred.

The reaction between the silicone compound represented by the general formula (I) and the organopolysiloxane having a silanol structure at the terminal represented by the general formula (II) is as shown in the formula (III).

[0024]

[C7]

(In the formula, R1, -furoyl)methoxy group, and (2-thiophene)(2-thiophenecarbonyl)methoxy group;
The organopolysiloxane having a silanol structure at the end reacts with the organopolysiloxane to form phenylbenzoylmethoxy groups, (2-furyl)(2-furoyl)methoxy groups, and (2-furyl)methoxy groups in the molecule.
-thiophene)(2-thiophenecarbonyl)organopolysiloxane having methoxy groups is produced.

The curing catalyst added to the present invention may be any catalyst as long as it causes silanol structures to react with each other, but tin or titanium catalysts are particularly preferred. Specific examples include dimethyltin diacetate,
Examples include diethyltin diacetate, dibutyltin diacetate, dihexyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, tetramethoxytitanium, tetraethoxytitanium, and tetrabutoxytitanium.

One of the features of the present invention is that phenylbenzoylmethoxy group, (2-furyl)(2-furoyl)methoxy group, and (2-thiophene)(2-thiophenecarbonyl) group as shown in formula (IV) ) Photodecomposition of a silicone compound having at least one type selected from the group of methoxy groups and utilization of a crosslinking reaction of a silanol structure using a curing catalyst.

[0028]

[Chemical formula 8]

(In the formula, R1 is the same as above.) By adding a curing catalyst to the organopolysiloxane produced by the formula (III) and irradiating it with ultraviolet rays, etc., the formula (
Photodecomposition as shown in IV) occurs to produce a silanol structure, and the silanol structure produced here undergoes a crosslinking reaction with a curing catalyst and becomes rubber.

The proportion of each component in the photocurable silicone composition of the present invention is not particularly limited, but preferably the silicone compound represented by the general formula (I) and the silicone compound represented by the general formula (II) are combined. 0.1 to 10 parts by weight of a curing catalyst is added to 100 parts by weight of a reactant obtained by reacting an organopolysiloxane having a silanol structure at a molar ratio of 1:0.5 to 1:2. Good.

In addition to the above-mentioned components, it is also possible to add 0.1 to 10 parts by weight of a crosslinking agent such as methyltriacetoxysilane prior to irradiation with ultraviolet rays or the like to effect crosslinking in advance.

[0032] As a preferred application example of the photocurable silicone composition of the present invention, this photocurable silicone composition is applied to a thin film with a film thickness of 0.1 to 100μ, more preferably 0.5 to 50μ. Examples include plate materials for waterless planographic printing obtained by forming a transparent coating.

[0033]

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 20 g of PS340 (dimethylpolysiloxane with silanol structure at both ends) manufactured by Chisso Corporation and diacetoxymethyl (
4.4 g of phenylbenzoylmethoxy)silane was reacted in 35 g of toluene at room temperature for 3 hours. (Hereinafter, the polymer obtained by this reaction will be abbreviated as polymer (I).) Thickness: 0
．． A 5 μm thick silicone coating having the following composition was formed on a 3 mm aluminum plate.

(a) Polymer (I)

100 parts by weight (b) dibutyltin diacetate

0.2 parts by weight (c) Toluene

325 parts by weight of the above coating film
When exposed for 55 seconds using a W high pressure mercury lamp, a sufficiently cured film was obtained.

Comparative Example 1 A silicone coating film having the following composition and having a thickness of 5μ was formed on an aluminum plate having a thickness of 0.3mm.

(a) SH manufactured by Toray Dow Corning Silicone Co., Ltd.
413X (vinyl group-containing polydimethylsiloxane)

100 parts by weight (b) PS927 (polymercaptopropylmethylsiloxane) manufactured by Chisso Corporation

10 parts by weight (c) dimethyldiacetoxysilane
12 parts by weight (d) "Irgacure" 651 manufactured by Ciba Geigy
5 parts by weight (e) toluene

325 parts by weight As in Example 1, the above coating film was exposed to light using a 3 kW high pressure mercury lamp, but a sufficiently cured film could not be obtained even after exposure for 300 seconds.

Example 2 30 g of PS341 (dimethylpolysiloxane having a silanol structure at both ends) manufactured by Chisso Corporation and 4.1 g of diacetoxydi(phenylbenzoylmethoxy)silane were reacted in 49 g of toluene at room temperature for 3 hours. (Hereinafter, the polymer obtained by this reaction will be abbreviated as polymer (II).) Example 1
A coating film similar to that in Example 1 was formed using Polymer (II) instead of Polymer (I) to obtain a printing original plate.

When a positive film with an image of 150 lines/inch was vacuum-adhered to the surface of this coating film, exposed for 55 seconds using a 3kW high-pressure mercury lamp, and developed with xylene, an image faithful to the positive film was obtained. Formed. When printing was carried out using this printing plate, it was found that printed matter that faithfully reproduced the image of the positive film was obtained, and that it was possible to print more than 9,000 sheets.

Example 3 40 g of PS342.5 (dimethylpolysiloxane with silanol structure at both ends) manufactured by Chisso Corporation and 1.1 g of di[(2-furyl)(2-furoyl)methoxy]dichlorosilane
were reacted in 60 g of toluene at room temperature for 3 hours. (Hereinafter, the polymer obtained by this reaction will be abbreviated as polymer (III).) Polymer (I) was used instead of polymer (II) in Example 2.
When exposure and development were carried out in the same manner as in Example 2 using II), an image faithful to a positive film was formed in 60 seconds. When printing was carried out using this printing plate in the same manner as in Example 2, printed matter that faithfully reproduced the image of the positive film was obtained, and it was found that printing of 10,000 sheets or more was possible.

Example 4 17 g of PS340 (dimethylpolysiloxane having a silanol structure at both ends) manufactured by Chisso Corporation and diacetoxydi[(2
5.6 g of -thiophene)(2-thiophenecarbonyl)methoxy]silane were reacted in 32 g of toluene at room temperature for 3 hours. (Hereinafter, the polymer obtained by this reaction is abbreviated as Polymer (IV).) Exposure and development were carried out in the same manner as in Example 2, using Polymer (IV) instead of Polymer (II) in Example 2. When this was carried out, an image faithful to a positive film was formed in 65 seconds. When printing was carried out using this printing plate in the same manner as in Example 2, printed matter that faithfully reproduced the image of the positive film was obtained, and it was found that printing of 9000 sheets or more was possible.

[0042]

Effects of the Invention Since the present invention is constructed as described above, it is possible to obtain a photocurable silicone composition that exhibits high curability against irradiation with ultraviolet rays and the like. Further, according to the present invention, there is no deterioration in releasability or ink repellency due to the silicone structure, and there is an advantage that it can be manufactured by a simple method and at low cost.

Claims (1)

[Claims] Claim 1: (A) A silicone compound represented by the general formula (I) [Formula 1] (wherein R1 is an alkyl group having 1 to 10 carbon atoms, 2 carbon atoms
~10 alkenyl groups, and aryl groups having 6 to 10 carbon atoms
X and Y are each a hydrogen atom, a halogen atom, an amino group, an aminooxy group, an alkoxy group having 1 to 10 carbon atoms, an amide group, an acyloxy group, and a group having 2 to 10 carbon atoms. 10 alkenyloxy groups,
or at least one kind selected from the group of ketoxime groups having 3 to 10 carbon atoms, which may be the same or different. Z is hydrogen atom, halogen atom, carbon number 1-1
0 alkyl group, alkoxy group, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, acyloxy group, or alkoxycarbonyl group. n is 0 or 1. ) and (B
) An organopolysiloxane having a silanol structure at the terminal represented by the general formula (II) [Formula 2] (wherein, R2 and R3 are substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, alkenyl groups, and Carbon number 6-1
At least one type selected from the group of 0 substituted or unsubstituted aryl groups, which may be the same or different. m is an integer of 2 or more. ) to the reactant with (C
) A photocurable silicone composition containing a curing catalyst.