JPH107974A - Curable silicone resin composition excellent in stain resistance and coating film produced therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating film excellent in stain resistance, processibility, etc. SOLUTION: A curable silicone resin compsn. excellent in stain resistance is prepd. by compounding an organosilicon copolymer formed from a free- radical-polymerizable hydroxylated unsatd. monomer, a free-radical-polymerizable epoxidized unsatd. monomer, a free-radical-polymerizable unsatd. monomer having a hydroxyl and/or a hydrolyzable group bonded directly to a silicon atom, a free-radical-polymerizable unsatd. monomer having a dimethylpolysiloxane main chain, and if necessary a free-radical-polymerizable unsatd. monomer other than foregoing monomers with a metal chelate compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silicone resin curable composition having excellent stain resistance and a coated film using the same.

[0002]

2. Description of the Related Art Conventionally, a metal plate is generally coated with a coating for the purpose of imparting corrosion protection and aesthetics. However, paints used in these coatings generally contain many organic solvents and generate a large amount of organic solvents at the time of coating and baking, and thus pose a problem in terms of environment and safety.
Further, as a coated metal plate which does not use a paint, a laminated steel plate in which a plastic film of polyethylene terephthalate, polybutylene terephthalate, polychlorinated or the like is bonded to a metal plate via an adhesive is known. . However, these laminated steel plates are used, for example, in kitchen hoods.
When applied to a ventilator for filters and filters, there is a problem that the releasability from oil is inferior.

It is conceivable to coat a silicon compound such as a low-condensation product of tetraethoxysilane on the surface of the plastic film described above. However, in this case, the adhesion between the silicon compound and the plastic film is not sufficient, and the processability is poor. Is inferior. Also, polysiloxane macromonomer, oxirane group-containing vinyl monomer, and aluminum resin are used as the silicone resin.
In fact, the use of a low-temperature curable resin composition containing a compound (see JP-A-63-221123) does not sufficiently satisfy the stain resistance such as oil stains. .

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to develop a silicone resin curable composition excellent in stain resistance and processability and a coated film using the same.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the specific silicone resin curable composition has excellent stain resistance and workability. The present invention forms a cured film of a silicon-based resin, and has found that all of the conventional problems can be solved. Thus, the present invention has been completed.

That is, the present invention provides: Hydroxyl-containing radically polymerizable unsaturated monomer (a),
An epoxy group-containing radical polymerizable unsaturated monomer (b),
A radically polymerizable unsaturated monomer containing a hydroxyl group and / or a hydrolyzable group directly bonded to silicon (c), a radically polymerizable unsaturated monomer having a dimethylsiloxane bond as a main chain (d) and, if necessary, It is characterized by containing an organosilicon copolymer (i) of a radically polymerizable unsaturated monomer (e) other than the above (a) to (d) and a metal chelate compound (ii). 1. A silicone resin curable composition excellent in stainability (hereinafter, abbreviated as the composition [I] of the present invention); Hydroxyl-containing radically polymerizable unsaturated monomer (a),
An epoxy group-containing radical polymerizable unsaturated monomer (b),
A radically polymerizable unsaturated monomer containing a hydroxyl group and / or a hydrolyzable group directly bonded to silicon (c) and, if necessary, other radically polymerizable unsaturated monomers other than the above (a) to (d) (E) the organosilicon copolymer (ii)
i), a dimethylpolysiloxane-based compound (iv), and a metal chelate compound (ii), and a silicone-based resin curable composition excellent in stain resistance (hereinafter referred to as the composition of the present invention [ II]), 3. A silicone resin curable composition excellent in stain resistance, comprising the above-mentioned organosilicon copolymer (i), dimethylpolysiloxane compound (iv), and metal chelate compound (ii). (Hereinafter, the composition of the present invention [I
II]. ), 4. The above-mentioned organosilicon copolymer (i), general formula (1) S
i (OR ¹ ) _{4 wherein} R ¹ is the same or different and
Organosilicon compound (A) and / or in its low condensate 0-90 wt% and the general formula ^{(2) R 2 Si (OR} 1) 3 ( Formula represented by showing the _1-4 hydrocarbon group), R ¹ represents the same meaning as above, R ² is a hydrocarbon group of C _{1 ~ 12)}
And / or a metal chelate compound (ii) containing an organosilicon condensate (v) obtained by condensing a mixture of 10 to 100% by weight of an organosilicon compound (B) and / or a low-condensate thereof represented by 4. a curable silicone resin composition excellent in stain resistance (hereinafter, abbreviated as composition [IV] of the present invention); Stain resistance comprising the above-mentioned organosilicon copolymer (iii), dimethylpolysiloxane-based compound (iv), the above-mentioned organosilicon condensate (v), and metal chelate compound (ii) 5. A silicone resin curable composition (hereinafter, abbreviated as the composition [V] of the present invention) which is excellent in the above. Stain resistance characterized by containing the above-mentioned organosilicon copolymer (i), dimethylpolysiloxane-based compound (iv), the above-mentioned organosilicon condensate (v), and metal chelate compound (ii). 6. A silicon-based resin curable composition (hereinafter, abbreviated as the composition [VI] of the present invention) having excellent characteristics, and A silicone-based resin excellent in stain resistance, comprising a cured film [2] of the silicone-based resin-curable composition described in the above 1 to 6 formed on the surface of the base film layer [1]. Coated film (hereinafter referred to as the present film [VII]
Abbreviated. ).

The components (i) to (v) used in the compositions [I] to [VI] of the present invention are described below.

In the composition of the present invention, the hydrolyzable silicon group is a functional group that produces a hydroxyl group directly bonded to silicon by a hydrolysis reaction with water or moisture in the air, and is particularly a lower group such as methoxy, ethoxy, propoxy and the like. A group in which an alkoxyl group is directly bonded to a silicon atom is preferable because it has an excellent curability.

Organosilicon copolymer (i ): a hydroxyl-containing radically polymerizable unsaturated monomer (a), an epoxy-containing radically polymerizable unsaturated monomer (b), silicon used in the copolymer (i). Radically polymerizable unsaturated monomer containing a hydroxyl group and / or a hydrolyzable group directly bonded to
(C) a radical polymerizable unsaturated monomer having a dimethylsiloxane bond as a main chain (d) and, if necessary, other radical polymerizable unsaturated monomers other than the above (a) to (d) (e). The following can be mentioned.

(A) hydroxyl group-containing radically polymerizable unsaturated monomer, for example, 2-hydroxyethyl (meth) acrylate,
And hydroxyl-containing unsaturated monomers such as 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and adducts thereof with caprolactone.

(B) Epoxy group-containing radically polymerizable unsaturated monomers such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and allyl glycidyl ether.

(C) A radically polymerizable unsaturated monomer containing a hydroxyl group and / or a hydrolyzable group directly bonded to silicon, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, vinyltriacetooxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, γ
-(Meth) acryloyloxypropyltriethoxysilane and the like. Also, for example, one molecule described in JP-A-62-197423 has an average of one polymerizable unsaturated bond and at least two or more alkoxysilane groups and / or hydroxysilane groups in a terminal equivalent portion. A polysiloxane macromonomer having a number average molecular weight of 400 to 100,000 can be used.

(D) Radical polymerizable unsaturated monomer having a dimethylsiloxane bond as a main chain The unsaturated monomer has a radical polymerizable unsaturated group at one end of the molecule and dimethylsiloxane in the molecule. binding _{[-Si (CH 3) 2 O-} ] unsaturated monomer having two or more units - a. One (left) terminal of the residue of the dimethylsiloxane bond is bonded to a radically polymerizable unsaturated residue, and the other (right) terminal is [—Si (R ³ ) (R
⁴ ) O-] unit (R ³ or R ⁴ represents an alkyl group such as methyl, ethyl, propyl, butyl, etc., a phenyl group, an epoxy group, or an SH group, provided that both R ^{3 and} R ⁴ are methyl groups. In R ³ or R ⁴ , the epoxy group and the SH group may be bonded to Si directly or via a hydrocarbon bond or an ether bond or a combination thereof.) Or directly [-
Si (R ³ ) ₃ ] (R ³ has the same meaning as described above.
³ can be the same or different combinations. ), R ¹ (R ¹ has the same meaning as described above), or those having a hydrogen atom bonded thereto can be used. Examples of the radical polymerizable unsaturated group include, for example, CH ₂ CH
_{COOCnH 2 n-, CH 2 = CCH} 3 COOCnH 2
(n is an integer of 1 to 5, especially 1 to 4
Integers are preferred).

As the radical polymerizable unsaturated monomer, CH ₂ ＣＨCH (or CH ₃ ) COOC ₃ H _6-
[Si (CH ₃ ) ₂ O] m-Si (CH ₃ ) ₃ and C
H ₂ ＣＨCH (or CH ₃ ) COOC ₃ H _6- [Si (C
_{H 3) 2 O] m-} R 1 ( or more, m is preferably from showing) an integer of 3 to 70. Specifically, for example, CH ₂ ＣＨCH (or CH ₃ ) COOC ₃ H _6- [Si
_{(CH 3) 2 O] 11} -Si (CH 3) 3 CH 2 = CH ( or _{CH 3) COOC 3 H 6 -} [Si
_{(CH 3) 2 O] 20~30} -Si (CH 3) 3 CH 2 = CH ( or _{CH 3) COOC 3 H 6 -} [Si
_{(CH 3) 2 O] 65} -Si (CH 3) 3 CH 2 = CH ( or _{CH 3) COOC 3 H 6 -} [Si
(CH _{3) 2} O] and the like _{20 to 30} -CH _3.

(E) Other radically polymerizable unsaturated monomers other than the above (a) to (d), for example, methyl (meth) acrylate, ethyl (meth)
C of (meth) acrylic acid such as acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, etc.
_1-24 alkyl or cycloalkyl esters, styrene, vinyltoluene, (meth) acrylonitrile and the like.

The organosilicon copolymer (i) can be produced by a conventionally known radical polymerization method, for example, a solution polymerization method.

The average molecular weight of the organosilicon copolymer (i) is preferably in the range of about 3000 to 80000, particularly preferably in the range of about 8000 to 50,000. If the molecular weight is less than about 3,000, the workability of the coating film is reduced, and if it is more than about 80,000, the coating and printing workability is undesirably reduced.

Organosilicon copolymer (i ii): hydroxyl group-containing radically polymerizable unsaturated monomer (a), epoxy group-containing radically polymerizable unsaturated monomer (b) used in the copolymer (iii). Radical polymerizable unsaturated monomer containing a hydroxyl group and / or a hydrolyzable group bonded directly to silicon
(C) and other radically polymerizable unsaturated monomers (e) used as needed include those similar to the organosilicon copolymer (i).

The organosilicon copolymer (iii) can be produced by a conventionally known radical polymerization method, for example, a solution polymerization method.

The average molecular weight of the organosilicon copolymer (iii) is about 3000 to 80000, especially about 8000 to 5000.
A range of 0 is preferred. If the molecular weight is less than about 3,000, the workability of the coating film is reduced, and if it is more than about 80,000, the coating and printing workability is undesirably reduced.

Organosilicon condensate (v) : In the organosilicon compound (A), C ¹ of R ¹ represented by the general formula (1)
Examples of the hydrocarbon groups _{1 to 4} include alkyl groups such as methyl, ethyl, propyl, and butyl.
The alkyl group may be branched or unbranched. As the low condensate, those having a polymerization degree of 2 to 10 are preferable. Specific examples of the organic silicon compound (A) include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and the like.

In the organosilicon compound (B), R ¹ represented by the general formula (2) may be the same as described above. Further, as the C _1-12 hydrocarbon group for R ² , for example, methyl, ethyl, propyl, butyl,
Alkyl groups such as hexyl and octyl (the alkyl groups may be branched or unbranched), aryl groups such as phenyl, toluyl and xylyl, cycloalkyl groups such as cyclohexyl, cyclobutyl and cyclopentyl; Can be mentioned. As the low condensate, those having a polymerization degree of 2 to 10 are preferable.

Specific examples of the organosilicon compound (B) include:
For example, methyltrimethoxysilane, methyldimethoxyethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like can be given.

The organosilicon condensate (v) comprises the organosilicon compound (A) and / or its low condensate in an amount of 0 to 90% by weight, preferably 20 to 80% by weight, and the organosilicon compound (B) and / or its low condensate. 10 to 100% by weight, preferably 20 to 100% by weight of condensate
It is obtained by condensing a mixture with 80% by weight.
The above-mentioned condensation reaction is described in, for example, Japanese Patent Publication No. 4-22953.
The method can be performed by the method described in Japanese Patent Application Laid-Open Publication No. HEI 10-76, pp. The organosilicon condensate (v) is a three-dimensional condensate, having a degree of condensation of at least 20 and a molecular weight of about 3,000 to 2,000.
00.

[0025] Dimethyl polysiloxanylalkyl emissions based compound (i
v): The dimethylpolysiloxane compound (iv) has a dimethylsiloxane bond [—Si (CH ₃ ) ₂ O] in the molecule.
-] Containing 2 or more units, preferably 3 to 100 units,
Meanwhile (left) molecular end -OSi (R ⁵⁾ (R ⁶⁾
(R ⁷ ) (R ⁵ , R ⁶ or R ⁷ is methyl, ethyl,
It represents a C _1-3 lower alkyl group such as propyl, a phenyl group, a hydroxyl group and the like. ), Also the other (right) molecular end ^{-Si (R 5) (R 6} ) (R 7) (R 5, R 6,
Or, R ⁷ has the same meaning as described above. ). R
^5, R ^6, and among R ^7, it is preferable for all three of these or a methyl group, or a 2-methyl group and a hydroxyl group. [-Si (R ⁸ )
(R ⁹ ) O-] (R ⁸ or R ⁹ is methyl, ethyl,
It represents a C _1-3 lower alkyl group such as propyl, a phenyl group, a hydroxyl group and the like. However, those in which both R ⁸ and R ⁹ are methyl groups are not included. ) Units can be combined in about 1 to 50. The dimethylpolysiloxane compound (iv) has an average molecular weight of about 310 to 800.
0, especially about 380-5000 is preferred. When the average molecular weight is less than about 310, the adhesion to the base film layer is reduced or the durability of the effect is reduced. On the other hand, when the average molecular weight is more than about 8000, the effect of stain resistance is reduced, which is not preferable.

Specific examples of dimethylpolysiloxane (iv) include, for example, SH200 oil (dimethylpolysiloxane), PRX413, and BY16-80 (trade names, manufactured by Toray Dow Corning Silicone Co., Ltd.).
1, BY16-817 (above, dimethylpolysiloxane having a terminal silanol group), SH510, SH550, S
H710, SH556 (above, phenyl-modified dimethylpolysiloxane), SH203, SH230, BX16-
811F (dimethylpolysiloxane modified with an alkyl group other than a methyl group) and the like.

Metal chelate compound ( ii): metal chelate
Examples of the compound (ii) include tris (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (isopropylacetoacetate) aluminum, tris (n-butylacetoacetate) aluminum, and isopropoxybis ( Ethyl acetoacetate) aluminum, diisopropoxyethyl acetoacetate aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum, diisopropoxypropionylacetonatoaluminum, acetylacetonatobis (propionylacetonato) aluminum, Monoethyl acetoacetate bis (acetylacetonate)
Aluminum, acetylacetonato aluminum
c-butyrate, methyl acetoacetate aluminum
Aluminum chelate compounds such as di-tert-butylate, bis (acetylacetonato) aluminum mono-sec-butylate, di (methylacetoacetate) aluminum mono-tert-butylate; for example, diisopropoxy bis (ethylacetoacetate) G) titanate, diisopropoxy bis (acetylacetonato) titanate,
Titanium chelate compounds such as di-n-butoxybis (acetylacetonato) titanate; for example, tetrakis (acetylacetonato) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, etc. Zirconium chelate compounds and the like can be mentioned.

The compositions [I] to [VI] of the present invention and the film [VII] of the present invention are described below.

Composition [I] of the present invention : Composition [I] of the present invention
Is a silicon-based resin curable composition comprising an organosilicon copolymer (i) and a metal chelate compound (ii).

The mixing ratio of the metal chelate compound (ii) is about 0.01 to 20 parts by weight, especially about 0 to 20 parts by weight of the metal chelate compound (ii) per 100 parts by weight of the organosilicon copolymer (i). 0.1 to 10 parts by weight is preferred. If the amount is less than about 0.01 part by weight, the low-temperature curability is reduced. On the other hand, if the amount is more than about 20 parts by weight, the cost is increased and the processability is deteriorated.

Composition of the present invention [II] : Composition of the present invention [I]
I] is a silicon-based resin curable composition comprising an organosilicon copolymer (iii), a dimethylpolysiloxane-based compound (iv), and a metal chelate compound (ii).

Dimethyl polysiloxane compound (iv)
Is preferably about 1 to 10 parts by weight, particularly preferably about 1 to 5 parts by weight, based on 100 parts by weight of the organosilicon copolymer (iii). If the compounding ratio is less than about 1 part by weight, the stain resistance and surface hardness are inferior. On the other hand, if it is more than about 10 parts by weight, the surface smoothness, curability, transparency, adhesion to the substrate and the like are inferior. Absent.

The compounding ratio of the metal chelate compound (ii) is about 0.01 to 20 parts by weight, especially about 0 to 20 parts by weight of the metal chelate compound (ii) per 100 parts by weight of the organosilicon copolymer (iii). 0.1 to 10 parts by weight is preferred. About 0.0
If the amount is less than 1 part by weight, the low-temperature curability decreases, while about 20 parts
Exceeding the weight part is not preferred because the cost increases and the processability decreases.

Composition [III ] of the present invention : The composition [III] of the present invention is prepared by blending an organosilicon copolymer (i), a dimethylpolysiloxane compound (iv), and a metal chelate compound (ii). Silicone-based resin curable composition.

Dimethyl polysiloxane compound (iv)
Is preferably about 1 to 10 parts by weight, particularly preferably about 1 to 5 parts by weight, based on 100 parts by weight of the organosilicon copolymer (i). If the compounding ratio is less than about 1 part by weight, the stain resistance and surface hardness are inferior. On the other hand, if it is more than about 10 parts by weight, the surface smoothness, curability, transparency, adhesion to the substrate and the like are inferior. Absent.

The mixing ratio of the metal chelate compound (ii) is about 0.01 to 20 parts by weight, especially about 0 to 20 parts by weight of the metal chelate compound (ii) per 100 parts by weight of the organosilicon copolymer (i). 0.1 to 10 parts by weight is preferred. If the amount is less than about 0.01 part by weight, the low-temperature curability is reduced. On the other hand, if the amount is more than about 20 parts by weight, the cost is increased and the processability is deteriorated.

Composition of the present invention [IV] : Composition of the present invention [I]
V] is a silicon-based resin curable composition comprising an organosilicon copolymer (i), an organosilicon condensate (v), and a metal chelate compound (ii).

The mixing ratio of the organosilicon condensate (v) and the organosilicon copolymer (i) is 1 to 50% by weight, preferably 1 to 30% by weight, based on the total weight of the two. ,
50 to 99% by weight, especially 70 to 99% by weight of the organosilicon copolymer (i)
99% by weight is preferred. When the amount of the organosilicon condensate (v) is less than 1% by weight (the amount of the organosilicon copolymer (i) exceeds 99% by weight), the stain resistance decreases, while the amount of the organosilicon condensate (v) is 50% by weight. % (The content of the organosilicon copolymer (i) is less than 50% by weight) is not preferred because the processability decreases.

The mixing ratio of the metal chelate compound (ii) is based on 100 parts by weight of the total amount of the organosilicon condensate (v) and the organosilicon copolymer (i).
Is preferably about 0.01 to 20 parts by weight, particularly preferably about 0.1 to 10 parts by weight. If the amount is less than about 0.01 part by weight, the low-temperature curability is reduced. On the other hand, if the amount is more than about 20 parts by weight, the cost is increased and the processability is deteriorated.

Composition of the present invention [V]: Composition of the present invention [V]
Is an organosilicon condensate (v), an organosilicon copolymer (ii)
This is a silicone resin curable composition comprising (i) a dimethylpolysiloxane compound (iv) and a metal chelate compound (ii).

The mixing ratio of the organosilicon condensate (v) and the organosilicon copolymer (iii) is 1 to 50% by weight, preferably 1 to 30% by weight, based on the total weight of the two. And the organic silicon copolymer (iii) is preferably 50 to 99% by weight, particularly preferably 70 to 99% by weight. Organic silicon condensate (v)
Is less than 1% by weight (organic silicon copolymer (iii) exceeds 99% by weight), the stain resistance decreases, while the organic silicon condensate (v) exceeds 50% by weight (organic silicon copolymer (v)). If the content of the polymer (iii) is less than 50% by weight), the processability is undesirably reduced.

Dimethylpolysiloxane compound (iv)
Of the organic silicon condensate (v) and the organic silicon copolymer (iii) in an amount of about 1 to 1 based on a total weight of 100 parts by weight.
0 parts by weight, especially about 1 to 5 parts by weight, is preferred. If the compounding ratio is less than about 1 part by weight, stain resistance, surface hardness, etc. are inferior,
On the other hand, if it exceeds about 10 parts by weight, the surface smoothness, curability, transparency, adhesion to the substrate and the like are inferior, so that it is not preferable.

The mixing ratio of the metal chelate compound (ii) is based on 100 parts by weight of the total amount of the organosilicon condensate (v) and the organosilicon copolymer (iii).
i) is preferably about 0.01 to 20 parts by weight, especially about 0.1 to 10 parts by weight. If the amount is less than about 0.01 part by weight, the low-temperature curability is reduced. On the other hand, if the amount is more than about 20 parts by weight, the cost is increased and the processability is deteriorated.

Composition of the present invention [VI] : Composition of the present invention [V
I] is a silicon-based resin curable composition comprising an organosilicon condensate (v), an organosilicon copolymer (i), a dimethylpolysiloxane-based compound (iv), and a metal chelate compound (ii). It is.

The mixing ratio of the organosilicon condensate (v) and the organosilicon copolymer (i) is 1 to 50% by weight, preferably 1 to 30% by weight, based on the total weight of the two. ,
50 to 99% by weight, especially 70 to 99% by weight of the organosilicon copolymer (i)
99% by weight is preferred. When the amount of the organosilicon condensate (v) is less than 1% by weight (the amount of the organosilicon copolymer (i) exceeds 99% by weight), the stain resistance decreases, while the amount of the organosilicon condensate (v) is 50% by weight. % (The content of the organosilicon copolymer (i) is less than 50% by weight) is not preferred because the processability decreases.

Dimethyl polysiloxane compound (iv)
Is preferably about 1 to 10 parts by weight, particularly preferably about 1 to 5 parts by weight, based on 100 parts by weight of the organosilicon copolymer (i). If the compounding ratio is less than about 1 part by weight, the stain resistance and surface hardness are inferior. On the other hand, if it is more than about 10 parts by weight, the surface smoothness, curability, transparency, adhesion to the substrate and the like are inferior. Absent.

The compounding ratio of the metal chelate compound (ii) is 100 parts by weight of the total amount of the organosilicon condensate (v) and the organosilicon copolymer (i).
Is preferably about 0.01 to 20 parts by weight, particularly preferably about 0.1 to 10 parts by weight. If the amount is less than about 0.01 part by weight, the low-temperature curability is reduced. On the other hand, if the amount is more than about 20 parts by weight, the cost is increased and the processability is deteriorated.

The composition of the present invention is prepared by dissolving or dispersing the above components (i) to (v) in the above-mentioned mixing ratio in an organic solvent, and further adding a coloring pigment, a filler, if necessary. It can be produced by mixing additives and the like.

The composition of the present invention can be applied to a substrate which is required to be stain resistant, for example, by coating or printing on a substrate such as metal, glass, wood, paper, fiber, plastic and a combination thereof. Can do it. This is painted,
Examples of applications to be printed are vehicles, building materials (interior,
Exterior, etc.), furniture, office supplies, household items, system kitchens (hoods, ventilation fans, etc.), electrical products (refrigerators,
, Microwave oven, etc.), a unit bath, a partition and the like.

The composition of the present invention can be applied directly to the substrate of a product or part by coating or printing, or after forming a coating film as in the film [IV] of the present invention, and then contacting the base material with the base material. -The layer may be laminated or adhered (adhered) via an adhesive (adhesive) agent.

The film [VI I] of the present invention : The film [VII] of the present invention is formed on the surface of the base film layer [1], and the curable silicone resin composition according to any one of the compositions [I] to [VI] of the present invention. Is coated and printed, and then dried and cured to form a cured film [2].

Examples of the base film layer [1] include polyethylene, polypropylene, polyisobutylene, polybutadiene, polystyrene, polychloroprene, polyvinyl chloride, polyvinyl acetate, nylon, polycarbonate, cellulose, Polyethylene terephthalate
G, polyacetal, AS resin, ABS resin, melamine resin, acrylic resin, epoxy resin, fluorine resin, silicone resin, polyester resin, etc. thermoplastic or crosslinked plastic films; aluminum,
Aluminum alloy, steel, alloy steel, stainless steel, copper,
Metal films such as tin, zinc, galvanized, zinc alloy, and tin-plated steel; fibers such as natural fibers and synthetic fibers; and films in which these are combined can be used.

The surface of the base film layer [1] is coated with the composition of the present invention and subjected to a surface treatment such as corona discharge or a base coat such as a primer coat or a colored coat, if necessary, before printing. Can do it. The above-mentioned coating and printing methods can be performed by means of conventional coating (eg, spray, brush, roller, etc.) and printing (screen, gravure, etc.). The cured film [2] preferably has a cured film thickness of about 2 to 30 microns, particularly about 2 to 20 microns. Curing can be carried out at room temperature, but it can be usually carried out in a heating range of 40 to 200 ° C.

In the film [VII] of the present invention, one side of the base film layer [1] (the side opposite to the cured coating [2]) is coated with the composition of the present invention before coating and printing. Papers such as natural paper and synthetic paper, and films obtained by combining these papers.
The thickness of the base film layer [1] is usually about 30 to 20.
00 microns, particularly in the range of about 40-1000 microns. If the film thickness is less than about 30 microns, the object is liable to peel off when it comes into contact with the film, while if it exceeds about 2,000 microns, it is easy to peel off due to heat. To provide an adhesive (tacky) agent layer.

Adhesion (adhesion) for forming an adhesion (adhesion) agent layer
As the agent layer, a heat-sensitive or pressure-sensitive adhesive (tacky) agent layer can be used. Specific examples of the adhesive (tacky) agent layer include, for example, vinyl, polyurethane, polyester, rubber, polyamide, vinyl acetate, acrylic, ethylene vinyl acetate, and vinyl chloride / vinyl acetate. Curing type and curing type such as urea type, melamine type, epoxy type, phenol type, acrylic type, polyester type and urethane type can be mentioned. The adhesion (adhesion) agent layer can contain, for example, an adhesion (adhesion) imparting agent, an adhesion (adhesion) adjusting agent, an antioxidant, a stabilizer, and a coloring agent. When the adhesive is a curing system, any method such as moisture curing, moisture curing, and active energy ray curing may be used as the curing type. The thickness of the adhesive (tacky) agent layer is preferably in the range of about 10 to 1000 microns, particularly 20 to 500 microns. If the film thickness is less than about 10 microns, the substrate to be affixed is likely to be peeled off when the substrate is rough, while if it exceeds 1000 microns, it is easily undesirably peeled off by heat.

[0056]

The present invention will be described below in detail with reference to examples.

Production Example of Organosilicon Copolymer a 35 g of styrene, 20 g of glycidyl methacrylate and 20 g of 2-hydroxyethyl acrylate, CH ₂ =
CCH ₃ COOC ₃ H _6- [Si (CH ₃ ) ₂ O]
_20-30 -Si (CH ₃ ) ₃ 5 g, the following macromonomer
A monomer mixture comprising 20 g was subjected to a radical copolymerization reaction according to a usual acrylic production method to obtain an organosilicon copolymer a having a number average molecular weight of about 20,000.

Macromonomer 2720 g of methylmethoxysilane, 230 g of γ-methacryloxypropyltrimethoxysilane, deionized water 11
A mixture of 30 g, 2 g of 1% formic acid and 1 g of hydroquinone was reacted at 80 ° C. for 5 hours to obtain a polysiloxane macromonomer having a number average molecular weight of 2,000.

Production Example of Organosilicon Copolymer b 35 g of styrene, 20 g of glycidyl methacrylate and 20 g of 2-hydroxyethyl acrylate, CH ₂ =
CCH ₃ COOC ₃ H _6- [Si (CH ₃ ) ₂ O]
_A monomer mixture consisting of 8 g of _20-30 -Si (CH ₃ ) _{3 and} 17 g of γ-methacryloyloxypropyltrimethoxysilane is subjected to a radical copolymerization reaction in accordance with a usual acrylic production method to obtain an organosilicon copolymer having a number average molecular weight of about 18,000. Polymer b was obtained.

Production Example of Organosilicon Copolymer c A monomer mixture consisting of 35 g of styrene, 20 g of glycidyl methacrylate, 20 g of 2-hydroxyethyl acrylate, and 25 g of the above macromonomer was prepared according to a conventional acrylic production method. By performing a radical copolymerization reaction, an organosilicon copolymer c having a number average molecular weight of about 18,000 was obtained.

Production Example of Organosilicon Condensate 427 g of ES-40 (manufactured by Nippon Corcot Co., Ltd., low- condensation product of tetraethoxysilane), 58 g of ethyltriethoxysilane and 300 g of ethyl alcohol were added to a reaction vessel.
The contents were heated to 80 ° C. with stirring and then set to 0.
142 g of 2N hydrochloric acid was added and reacted at 80 ° C. for 30 minutes. Next, 5 g of potassium hydroxide was added to the reaction product, the pH was raised to 7 or more, and a condensation reaction was carried out at 80 ° C. for 2 hours.
The solvent was removed until the weight percentage became varnish to obtain a varnish having a viscosity of 11 centipoise.

Silicon Resin Composition 1 Silicone resin composition 1 was obtained by adding 100 g of organosilicon copolymer a (solid content) and 2 g of aluminum tris (ethyl acetoacetate) to toluene for dispersion.

Silicone resin compositions 2 to 11 Silicone resin compositions 2 to 1
1 was obtained.

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[Table 1]

In Table 1, the amounts are solid contents (g). PRX413 is a product of Toray Dow Corning Silicone Co., Ltd., trade name, OHSi (CH ₃ ) _2- (OSi
(CH ₃ ) ₂ ) ₅₀ —OSi (CH ₃ ) ₂ OH), a dimethylpolysiloxane containing a terminal silanol group.
Also, SH8416 is manufactured by Toray Dow Corning Silicone.
The product name is alkyl-modified silicon.
The metal chelate used was aluminum tris (ethyl acetoacetate).

The obtained silicone resin composition was coated on the film surface shown in Table 2 (PET was polyethylene terephthalate).
And PVC indicates polyvinyl chloride. 3) dry film thickness
Micron-coated with a bar coater, and dried and cured at 160 ° C. for 90 seconds to obtain silicone resin-coated films of Examples 1 to 8 and Comparative Examples 1 to 4 having a cured layer of the silicon-based resin. Was.

Table 2 shows the appearance and performance test results of the film.

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[Table 2]

In Table 2, appearance and performance tests were performed by the following methods.

Appearance: The surface of the coating film was visually observed for shrinkage and gloss, and evaluated according to the following criteria. ○: No abnormality was observed at all, Δ: Occurrence of shrinkage and gloss, X: Remarkable occurrence of shrinkage and gloss Transparency: The transparency of the coating film was visually observed.

Gloss: Measured according to JIS K-5400 (mirror reflectance at 60 ° reflectance).

Adhesion: JIS K-5400 (100 pieces of 1 mm square were formed on the coating with a grid cutter, and a cellophane tape was closely adhered to the surface and strongly separated.
The number of remaining squares was measured. 8.) Evaluation is 8.5.1.
(5) The evaluation was performed based on the evaluation score (10 to 0).

Oil / dust stain resistance: Used discolored (degraded) (tempered) oil (tempering oil discoloration degree is JISZ-
8721.5 2.5Y7.
0 / 12.0) was applied so as to have a thickness of about 100 μm, and then left at room temperature for 1 hour.

Applied state: (Templar) Oil applied state is visually observed (O: oil is repelled to form an independent hemisphere, Δ: continuous film but resilient, X: uniform wet and continuous Oil film).

Oil Remaining State: The applied (templar) oil was lightly wiped off with a cloth. Visual observation of the remaining amount of (templar) oil on the surface of the film after wiping (◎: lightly wiped once with no (templar) oil remaining on the film surface; ○: lightly wiped with 2-4 times film No (Tempura) oil left on the surface, △: Lightly wiped 2 to 4 times, but (Tempura) oil remains on the coating surface, ×
(A lot of (tempura) oil remained on the coating surface even after wiping lightly 2 to 4 times).

Appearance after wiping: After completely removing (templar) oil on the surface of the coating, observe the appearance (discoloration, etc.) of the coating surface (O: No abnormalities such as discoloration, Δ: Abnormalities such as discoloration) (Small ones, x: large abnormalities such as discoloration).

Oil resistance Marker: A line was drawn on the surface of the film with three colors of oily markers of red, blue and black, and then left for 24 hours at room temperature for testing. In the test, the appearance of the coating was examined after wiping it lightly with a cloth. ◎ is a marker that is wiped lightly once and no residue remains, ○ is a marker that is lightly wiped in 2 to 4 times and no residue remains, and Δ is a marker that is lightly wiped 2 to 4 times and slightly -What remains, x is lightly 2-4
Marker remains significantly after wiping. Workability: The film (so that the base film overlaps) was bent at 360 °, and cracks and peeling of the film were observed. ○: good, △: slight cracking, peeling, ×: cracking, peeling

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Since the composition of the present invention is the above-mentioned specific composition, the film formed by this composition can be easily removed from workability and stain resistance, particularly, oil stains. It has such an effect.

Claims (7)

[Claims] 1. A hydroxyl group-containing radically polymerizable unsaturated monomer.
(A) an epoxy group-containing radical polymerizable unsaturated monomer
(B) a radical polymerizable unsaturated monomer containing a hydroxyl group and / or a hydrolyzable group directly bonded to silicon (c),
Radical polymerizable unsaturated monomer having a dimethylsiloxane bond as a main chain (d) and optionally (a) to (d)
Other radical polymerizable unsaturated monomers other than (d)
A silicone resin curable composition excellent in stain resistance, comprising the organosilicon copolymer (i) of (e) and the metal chelate compound (ii). 2. A hydroxyl group-containing radically polymerizable unsaturated monomer.
(A) an epoxy group-containing radical polymerizable unsaturated monomer
(B) a radical polymerizable unsaturated monomer containing a hydroxyl group and / or a hydrolyzable group directly bonded to silicon (c) and, if necessary, other radical polymerizable monomers other than the above (a) to (d) Organosilicon copolymer of unsaturated monomer (e) (iii), dimethylpolysiloxane-based compound (i
v) and a metal-chelate compound (ii), which is a silicone-based resin curable composition excellent in stain resistance. 3. A hydroxyl group-containing radically polymerizable unsaturated monomer.
(A) an epoxy group-containing radical polymerizable unsaturated monomer
(B) a radical polymerizable unsaturated monomer containing a hydroxyl group and / or a hydrolyzable group directly bonded to silicon (c),
Radical polymerizable unsaturated monomer having a dimethylsiloxane bond as a main chain (d) and optionally (a) to (d)
Other radical polymerizable unsaturated monomers other than (d)
(E) the organosilicon copolymer (i), the dimethylpolysiloxane-based compound (iv), and the metal chelate compound (i)
A silicone resin curable composition having excellent stain resistance, characterized by containing i). 4. A hydroxyl-containing radically polymerizable unsaturated monomer.
(A) an epoxy group-containing radical polymerizable unsaturated monomer
(B) a radical polymerizable unsaturated monomer containing a hydroxyl group and / or a hydrolyzable group directly bonded to silicon (c),
Radical polymerizable unsaturated monomer having a dimethylsiloxane bond as a main chain (d) and optionally (a) to (d)
Other radical polymerizable unsaturated monomers other than (d)
(E) the organosilicon copolymer (i), the general formula (1) Si
(OR ¹ ) ₄ (wherein R ¹ is the same or different and is C
Organosilicon compound (A) and / or in its low condensate 0-90 wt% and the general formula ^{(2) R 2 Si (OR} 1) 3 ( Formula represented by showing the _1-4 hydrocarbon group), R ¹ represents the same meaning as above, R ² is a hydrocarbon group of C _{1 ~ 12)}
And / or a metal chelate compound (ii) containing an organosilicon condensate (v) obtained by condensing a mixture of 10 to 100% by weight of an organosilicon compound (B) and / or a low-condensate thereof represented by A silicone resin curable composition having excellent contamination resistance. 5. A hydroxyl group-containing radically polymerizable unsaturated monomer.
(A) an epoxy group-containing radical polymerizable unsaturated monomer
(B) a radical polymerizable unsaturated monomer containing a hydroxyl group and / or a hydrolyzable group directly bonded to silicon (c) and, if necessary, other radical polymerizable monomers other than the above (a) to (d) Organosilicon copolymer of unsaturated monomer (e) (iii), dimethylpolysiloxane-based compound (i
v), an organosilicon compound (A) represented by the general formula (1) Si (OR ¹ ) ₄ (wherein R ¹ is the same or different and represents a C _1-4 hydrocarbon group) and / or Low condensate 0
To 90% by weight and the general formula (2) R ² Si (OR ¹ )
₃ (wherein, R ¹ represents the same meaning as above, R ² is C
_An organic silicon condensate (v) obtained by condensing an organic silicon compound (B) represented by _{1 to 12} hydrocarbon groups) and / or a mixture of 10 to 100% by weight of a low condensate thereof; A silicone resin curable composition having excellent stain resistance, which comprises a chelate compound (ii). 6. A radically polymerizable unsaturated monomer containing a hydroxyl group.
(A) an epoxy group-containing radical polymerizable unsaturated monomer
(B) a radically polymerizable unsaturated monomer containing a hydroxyl group and / or a hydrolyzable group directly bonded (c), a radically polymerizable unsaturated monomer having a dimethylsiloxane bond as a main chain (d), and Accordingly, other than the above (a) to (d), an organosilicon copolymer (i) of a radically polymerizable unsaturated monomer (e), a dimethylpolysiloxane-based compound (iv), and a general formula (1) Si ( OR ¹ ) ₄ (wherein, R ¹
_Represents the same or different C _1-4 hydrocarbon groups)
0 to 90% by weight of an organosilicon compound (A) and / or a low condensate thereof represented by the formula (2): R ² Si (OR ¹ )
₃ (wherein, R ¹ represents the same meaning as above, R ² is C
_An organic silicon condensate (v) obtained by condensing an organic silicon compound (B) represented by _{1 to 12} hydrocarbon groups) and / or a mixture of 10 to 100% by weight of a low condensate thereof; A silicone resin curable composition having excellent stain resistance, which comprises a chelate compound (ii). 7. The method according to claim 1, wherein the surface of the base film layer [1] is provided.
7. A silicone-based resin-coated film excellent in stain resistance, which is obtained by forming a cured film [2] of the silicone-based resin-curable composition according to any one of Items 1 to 6.