JPH08269387A - Thermosetting coating composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition capable of imparting the surface of e.g. various plastic base materials with excellent antifogging effect and capable of giving coating film having sustainable adhesiveness and mechanical strength, thus to maintain the good appearance of the base material. CONSTITUTION: This coating composition comprises a specific block copolymer, a crosslinkable compound bearing a crosslinkable functional group such as acryloyl group, a hydrophilic solvent such as ethanol, a radical-generating curing catalyst, and a surfactant. The block copolymer is made of a hydrophilic polymer segment consisting of a monomer bearing a crosslinkable functional group such as N-methylol group and a hydriphilic monomer copolymerizable therewith and a hydrophobic polymer segment consisting of a vinyl monomer bearing a carboxyl group and a (meth)acrylic lower alkyl ester copolymerizable therewith. Further, incorporation of a surfactant and/or a carboxyl-bearing monomer in this composition can improve the sustainability of its antifogging effect.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-curable coating composition which is applied to the surface of various lenses and window glasses to form an antifogging coating.

[0002]

2. Description of the Related Art A composition for imparting antifogging property to various plastic materials is disclosed in, for example, JP-A-6-212146 or JP-A-6-172676. That is, JP-A-6-212146 discloses a hydrophobic polymer portion and a hydrophilic polymer portion containing a cross-linking functional group such as N-methylol group, N-methylol ether group or hydroxyl group. A heat-curable antifog composition comprising a block copolymer having self-crosslinking properties and a surfactant is disclosed. According to this composition, the appearance, antifogging property and adhesion are maintained in a high temperature environment, that is, at a temperature of 60 to 140 ° C.

Further, JP-A-6-172676 discloses a block copolymer composed of a hydrophilic polymer portion and a hydrophobic polymer portion having a crosslinkable functional group, a predetermined photopolymerizable compound, and a photopolymerization An ultraviolet-curable antifogging composition comprising an initiator and a surfactant is disclosed. According to this composition, an antifogging film can be formed in a short time.

[0004]

However, Japanese Patent Laid-Open No. 6-
In the heat-curable antifogging agent composition described in Japanese Patent No. 212146, the antifogging film is formed only by crosslinking due to the reaction of the crosslinkable functional groups of the hydrophilic polymer portion of the block copolymer. Therefore, there is a problem that the film becomes soft when absorbing water and the film strength is lowered.

On the other hand, in the case of the ultraviolet curable antifogging composition disclosed in JP-A-6-172676, since the coating is cured by irradiation with ultraviolet rays for a short time, unreacted substances remain in the coating, and There is a problem that the reaction product reacts with time, and the antifogging property and the adhesiveness are gradually lowered.

Further, these coatings also have a common problem that the appearance of the coatings deteriorates when they are subjected to heat bending and the like during molding of various coated plastic plates. The present invention has been made by paying attention to the problems existing in the prior art as described above. The object of the present invention is to provide a heat-curable coating composition capable of imparting excellent antifogging property to the surface of a substrate such as various plastic materials, maintaining the adhesion and strength of the coating, and maintaining good appearance quality. To do. In addition, the other purpose is to prevent the deterioration of the film strength when absorbing water, and the film appearance, anti-fog property, and adhesion after the base material such as various plastic materials is molded by various methods such as heat bending. It is to provide a heat-curable coating composition capable of preventing changes in properties and coating strength.

[0007]

In order to achieve the above object, in the invention of the heat-curable coating composition according to claim 1, any one of N-methylol group, N-methylol ether group or hydroxyl group is used. A hydrophilic polymer portion formed from at least one or more monomers having a crosslinkable functional group and at least one or more hydrophilic monomers having copolymerizability with these, a sulfonic acid group and a carboxyl group Alternatively, it has a copolymerizability with at least one vinyl type monomer having a phosphate group and this vinyl type monomer (meth).
A block copolymer (hereinafter, abbreviated as component (A)) composed of a hydrophobic polymer portion formed from at least one kind of lower alkyl acrylate [acryl and methacryl are collectively referred to as (meth) acryl] below. And a crosslinkable compound containing two or more crosslinkable functional groups of either an acryloyl group, a methacryloyl group or an allyl group (hereinafter,
At least one component (abbreviated as component (B)), a hydrophilic solvent that is a good solvent for the hydrophilic polymer portion of the block copolymer (hereinafter abbreviated as component (C)), and the crosslinkability It is composed of a curing catalyst for reacting the compound (hereinafter abbreviated as component (D)).

According to a second aspect of the present invention, in the first aspect of the present invention, the hydrophilic polymer portion of the block copolymer is either an N-methylol group, an N-methylol ether group or a hydroxyl group. Formed from at least one or more monomers having a crosslinkable functional group, at least one or more hydrophilic monomers copolymerizable with these, and at least one or more lower alkyl (meth) acrylate. (This block copolymer is
(Abbreviated as component (A ')).

According to a third aspect of the invention, in the invention according to the first or second aspect, at least one or more surfactants (hereinafter abbreviated as component (E)) are further contained. .

According to a fourth aspect of the present invention, in the first or second aspect of the present invention, a monomer having a carboxyl group, a sulfonic acid group or a phosphoric acid group, which reacts with the curing catalyst ( Hereinafter, at least one or more of (F) component) is contained.

According to a fifth aspect of the invention, the invention according to the first or second aspect further comprises at least one or more components (E) and at least one or more components (F). It is a thing.

Next, the present invention will be described in detail in order. First, the block copolymer represented by the component (A) will be described. The hydrophilic polymer portion of the component (A) is
At least one or more monomers having a cross-linking functional group of any one of an N-methylol group, an N-methylol ether group or a hydroxyl group, and at least one or more hydrophilic monomers having copolymerizability therewith Is composed of polymerized units copolymerized with. This hydrophilic polymer portion is oriented on the surface side of the coating when the hydrophilic solvent described later is evaporated, and exhibits antifogging property.

The cross-linking functional group of any one of the N-methylol group, N-methylol ether group and hydroxyl group constituting the hydrophilic polymer portion of the component (A) is blocked by the reaction between them to block the component (A). The copolymers are cross-linked with each other to exhibit the film formability, antifogging property and film strength. The amount of these monomers present in the hydrophilic polymer portion is preferably in the range of 1 to 30% by weight. More preferably, it is in the range of 5 to 25% by weight. If it is less than 1% by weight, the film strength and moldability are insufficient. On the other hand, when it exceeds 30% by weight, the antifogging property and the adhesiveness are deteriorated.

As these monomers, monomers having a cross-linking functional group of any one of N-methylol group, N-methylol ether group and hydroxyl group are used. Preferably, from the viewpoint of reactivity, N-methylol (meth) acrylamide, N-methoxymethylol (meth) acrylamide, N-butoxymethylol (meth) acrylamide, (meth) acrylic acid hydroxyethyl ester,
(Meth) acrylic acid hydroxypropyl ester, (meth) acrylic acid-3-chloro-2-hydroxypropyl ester (meth) acrylic acid hydroxy ester and the like are used. More preferably, it is N-methylol acrylamide. This is because from the viewpoint of actual performance, that is, the reactivity is high so that the crosslinking reaction is completed during the drying of the coating, and the strength, moldability, antifogging and adhesion of the coating crosslinked with this compound are good. . As these monomers, commercially available products or those synthesized according to known methods are used.

Next, the hydrophilic monomer forming the hydrophilic polymer portion of the component (A) is excellent at the initial stage of the coating formed from the heat-curable coating composition and in the environment of high humidity or high temperature. Maintains anti-fogging property for a long period of time. The amount of these monomers present in the hydrophilic polymer portion is preferably 70 to 99% by weight from the viewpoint of antifogging property.
More preferably, it is in the range of 75 to 95% by weight. If the amount of these monomers is less than 70% by weight, the antifogging property deteriorates with time. On the other hand, when it exceeds 99% by weight, the penetrating power of water into the coating becomes too strong, and the coating strength decreases.

This hydrophilic monomer is a monomer that does not participate in the cross-linking reaction between the cross-linking functional groups at all, or has significantly poor reactivity. The monomer is preferably (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N from the viewpoint of hydrophilicity.
-Diethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, diacetone (meth) acrylamide, N- (meth) acryloylpiperidine , N- (meth) acryloylmorpholine, (meth) acrylic acid, itaconic acid, maleic acid, glutaconic acid, aconitic acid,
Traconic acid, citraconic acid, mesaconic acid, fumaric acid, tiglic acid, crotonic acid, mulonic acid, isocrotonic acid, 3
Derived from (meth) acrylic acid such as alkali metal salts, ammonium salts, methacryloyloxyethyltrimethylammonium chloride, 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride of radically polymerizable unsaturated carboxylic acids such as butenoic acid Quaternary ammonium salt, methoxyethylene glycol (meth) acrylate (here, the number of ethylene oxide is preferably an integer of 1 to 10), ethoxyethylene glycol (meth) acrylate (here, The number of ethylene oxide is preferably an integer of 1 to 10), (meth)
Methoxypropylene glycol acrylate (Here, the propyl oxide number n is preferably an integer of 1 to 10)
(Meth) acrylic acid lower alkoxyalkylene glycol such as mono (2-hydroxylethyl methacrylate)
G) a phosphate of (meth) acrylic acid such as acid phosphate, (meth) acrylamido-2-methyl-1-
Vinyl monomers having a sulfonic acid group such as propanesulfonic acid and vinylsulfonic acid are used.

More preferably, N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine and N, N-dimethyl (meth) acrylamide are used from the viewpoint of actual performance, that is, good antifogging property of the coating film. And (meth) acrylic acid methoxyethylene glycol (wherein the number of ethylene oxide is preferably an integer of 1 to 10), N- (meth) acryloylmorpholine and (meth) acrylic acid methoxyethylene glycol. (Here, the number of ethylene oxide is preferably an integer of 1 to 10). As these monomers, commercially available products or those synthesized according to known methods are used.

Next, the hydrophobic polymer portion of the component (A) will be described. The hydrophobic polymer portion is at least one kind of vinyl type monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, and at least one kind of lower alkyl (meth) acrylate having copolymerizability therewith. And the above are composed of copolymerized polymer units. This hydrophobic polymer portion is oriented toward the base material side of the coating to secure the adhesiveness of the coating when the hydrophilic solvent described later is evaporated. Therefore, the hydrophilic polymer portion is fixed in the coating while being oriented on the surface of the coating, and the antifogging property is maintained.

At least one kind of vinyl type monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group in the hydrophobic polymer portion lowers the adhesiveness to the substrate on which the hydrophobic polymer portion is expressed. Rather, it retains the solubility of this hydrophobic polymer moiety in the composition.
When the solubility of the composition is poor, a transparent coating film cannot be obtained, and the performance of developing the component also deteriorates. The amount of these monomers present is preferably in the range of 1 to 30% by weight. More preferably, it is in the range of 5 to 25% by weight. If the amount of these vinyl-type monomers present is less than 1% by weight, the transparency of the coating film decreases, and if it exceeds 30% by weight, the adhesion of the coating film decreases. In addition, the polar groups of these monomers also function as a catalyst during the crosslinking reaction of the monomer having a crosslinking functional group that forms the hydrophilic polymer portion.

Examples of these monomers include (meth)
Acrylic acid-3-sulfopropyl, (meth) acrylic acid-2-sulfoethyl, 2-acrylamido-2-methylpropanesulfonic acid, (meth) acrylic acid, crotonic acid, itaconic acid, itaconic acid half ester, maleic acid half ester , Maleic acid, mono (2- (meth) acryloyloxyethyl) acid phosphate and the like are used. From the viewpoint of the solubility of the hydrophobic polymer portion in the composition without lowering the adhesion to the substrate on which the hydrophobic polymer portion is expressed, (meth) acrylic acid and (meth) acrylic acid-2 are preferable. -Sulfoethyl is used. When the solubility of the composition is poor, a transparent coating film cannot be obtained, and the performance of developing the component also deteriorates. As these monomers, commercially available products or those synthesized according to known methods are used.

Further, at least one kind of lower alkyl (meth) acrylate forming the hydrophobic polymer portion is
It is necessary to obtain adhesion. The amount of these monomers present in the hydrophobic polymer portion is preferably 70 to 99.
It is in the range of% by weight. More preferably, it is in the range of 75 to 95% by weight. If the amount of these monomers present is less than 70% by weight, the adhesiveness between the coating film and the base material will be reduced, resulting in 99% by weight.
If it exceeds the range, the transparency of the coating is lowered. As these monomers, the lower alkyl (meth) acrylate is used.

Next, in the component (A), the weight ratio of the hydrophilic polymer portion to the hydrophobic polymer portion is 50/50.
It is preferably in the range of ˜95 / 5. More preferably, it is in the range of 60/40 to 85/15. When the proportion of the hydrophilic polymer portion is less than 50% by weight, the hydrophilicity of the block copolymer is lowered and the interaction between the block copolymer and the surfactant is weakened, resulting in the initial antifogging property. Not only that, the anti-fog durability is reduced. On the other hand, when the proportion of the hydrophobic polymer portion is less than 5% by weight, the adhesiveness of the coating film is lowered.

Next, the block copolymer represented by the component (A ') will be described. The hydrophilic polymer portion of the component (A ') has at least one kind of a monomer having a cross-linking functional group such as an N-methylol group, an N-methylol ether group or a hydroxyl group, and has a reactivity with these. At least one kind of hydrophilic monomer having no copolymerization property and at least one of lower alkyl (meth) acrylate
Formed from more than one seed.

The monomer having a cross-linking functional group such as N-methylol group, N-methylol ether group or hydroxyl group forming the hydrophilic polymer portion of the component (A ') is a polymer unit based on this component. By the reaction of each other,
The block copolymers represented by the component (A ') are cross-linked with each other to exhibit the film formability, antifogging property and film strength. The amount of these monomers present in the hydrophilic polymer portion is preferably in the range of 1 to 30% by weight. More preferably, it is in the range of 5 to 25% by weight. If it is less than 1% by weight, the film strength and moldability are insufficient. On the other hand, when it exceeds 30% by weight, the antifogging property and the adhesiveness are deteriorated. These monomers are the same as the monomer having a cross-linking functional group of any one of N-methylol group, N-methylol ether group and hydroxyl group as the component (A).

Further, the hydrophilic monomer forming the hydrophilic polymer portion of the component (A ') is excellent at the initial stage of the coating formed from the heat-curable coating composition and in the environment of high humidity or high temperature. The antifogging property is maintained for a long time.
The amount of these monomers present in the hydrophilic polymer portion is preferably in the range of 50 to 94% by weight from the viewpoint of antifogging property. More preferably, it is in the range of 55 to 85% by weight. If the amount of these monomers is less than 50% by weight, the antifogging property deteriorates with time. On the other hand, when it exceeds 94% by weight, the penetrating power of water into the coating becomes too strong and the coating strength is lowered.

This hydrophilic monomer is a monomer that does not participate in the crosslinking reaction with the functional group of the monomer having a crosslinking functional group at all or has significantly poor reactivity. This monomer is the same as the hydrophilic monomer as the component (A).

Further, the hydrophilic polymer portion of the component (A ') is added to further secure the adhesiveness and the film strength,
At least one kind of lower alkyl (meth) acrylate may be contained. The abundance of these hydrophilic polymer moieties is preferably in the range of 5 to 49% by weight. More preferably, it is in the range of 10 to 40% by weight.
If the amount of these monomers is less than 5% by weight, the film strength will be insufficient. On the other hand, when it exceeds 49% by weight, since the alkyl (meth) acrylate is hydrophobic, the hydrophilicity of the coating film is lowered and the antifogging property is lowered.

The lower alkyl (meth) acrylate is the same as the lower alkyl (meth) acrylate as the component (A). Next, the hydrophobic polymer portion of the component (A ') will be described. The hydrophobic polymer portion is at least one kind of vinyl type monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, and at least one kind of lower alkyl (meth) acrylate having copolymerizability therewith. It is formed from the above.

At least one kind of vinyl-type monomer having a sulfonic acid, a carboxyl group or a phosphoric acid group in the hydrophobic polymer portion lowers the adhesiveness to the substrate on which the hydrophobic polymer portion is expressed. Nonetheless, it improves the solubility of the hydrophobic polymer moiety in the composition.
When the solubility of the composition is poor, a transparent coating film cannot be obtained, and the performance of developing the component also deteriorates. The amount of these monomers present is preferably in the range of 1 to 30% by weight. More preferably, it is in the range of 5 to 25% by weight. If the amount of these vinyl-type monomers present is less than 1% by weight, the transparency of the coating film decreases, and if it exceeds 30% by weight, the adhesion of the coating film decreases. Further, the polar groups of these monomers also function as a catalyst during a crosslinking reaction of a monomer having a crosslinking functional group forming a hydrophilic polymer portion.

These monomers are the same as the vinyl type monomers having a sulfonic acid, a carboxyl group or a phosphoric acid group as the component (A). Further, at least one kind of the copolymerizable lower alkyl (meth) acrylate forming the hydrophobic polymer portion enhances the adhesion of the coating film to the substrate. The amount of these monomers present in the hydrophobic polymer portion is preferably in the range of 70 to 99% by weight. More preferably, it is in the range of 75 to 95% by weight. If the amount of these monomers present is less than 70% by weight, the adhesion between the coating and the base material will be reduced, and if it exceeds 99% by weight, the transparency of the coating will be reduced. As these monomers, the lower alkyl (meth) acrylate is used.

Next, in the component (A '), the weight ratio of the hydrophilic polymer portion to the hydrophobic polymer portion is 50/50 to.
It is preferably in the range of 95/5. More preferably, it is in the range of 60/40 to 85/15. When the proportion of the hydrophilic polymer portion is less than 50% by weight, the hydrophilicity of the block copolymer is lowered and the interaction between the block copolymer and the surfactant is weakened, resulting in the initial antifogging effect. Not only the anti-fog property but also the anti-fog durability is decreased. On the other hand, when the proportion of the hydrophobic polymer portion is less than 5% by weight, the adhesiveness of the coating film is lowered.

The block copolymer consisting of the hydrophilic polymer portion and the hydrophobic polymer portion, which is the component (A) or (A ') of the present invention, is synthesized by a conventionally known method, but it is particularly industrial. From the viewpoint of ease of productivity and various performances, those produced by a radical polymerization method using a polymeric peroxide or a polyazo compound as a polymerization initiator are preferable. In this case, as the radical polymerization initiator to be used, a conventionally known compound having two or more peroxy bonds or azo bonds in one molecule is used. A legal method, a solution polymerization method, an emulsion polymerization method or the like is adopted.

As a typical production example of the block copolymer which is the component (A) or (A ') of the present invention, a polymerization method using a polymeric peroxide as a polymerization initiator will be described below. First, when polymerizing the monomer forming the hydrophilic polymer portion using polymeric peroxide,
A peroxy bond-containing hydrophilic polymer having a peroxy bond introduced into the chain is obtained. When a monomer that forms a hydrophobic polymer portion is added to this and polymerization is performed, the peroxy bond in the hydrophilic polymer chain is cleaved to efficiently obtain a block copolymer. Further, the block copolymer which is the component (A) or (A ') of the present invention may be polymerized from the hydrophobic polymer portion.

Next, at least one kind of the crosslinkable compound containing two or more crosslinkable functional groups of acryloyl group, methacryloyl group and allyl group, which is the component (B) of the present invention, will be explained. This component (B) forms a network structure inside the coating film by the radicals generated by the curing catalyst which is the component (D), indicating the orientation state of the block copolymer formed during the initial solvent evaporation during heating and drying, It fixes the orientation state of the block copolymer formed during the initial solvent evaporation during heating and drying, and further improves the film strength. In addition, the surfactant, which is the component (E), which will be described later, is interacted with the hydrophilic polymer portion of the block copolymer of the component (A) or (A ′) to form a network structure inside the coating film. Gradually and efficiently transferred to the coating surface. Therefore, the antifogging property can be maintained for a long time.

At least one of these crosslinkable compounds is a block copolymer of the component (A) or (A ') /
(B) Component crosslinkable compound solid content weight ratio = 100/10
It is preferably in the range of -40. More preferably, the block copolymer of component (A) or (A ') /
(B) Component crosslinkable compound solid content weight ratio = 100/15
The range is from 35 to 35. If the compounding amount of the crosslinkable compound is less than 10 parts by weight, the film strength and long-term antifogging sustainability cannot be obtained, and if it exceeds 40 parts by weight, the adhesion and antifogging property become low.

As the component (B), a cross-linking functional group such as an acryloyl group, a methacryloyl group or an allyl group is used.
Any compound containing at least one can be used. Preferably, from the viewpoint of reactivity and solubility in the composition, polyethylene glycol di (meth) acrylate (an integer of 1 to 23 ethylene oxide), polypropylene glycol di (meth) acrylate (a propylene oxide number 1 to 1).
23), 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2-bis {4-[(meth) acryloxydiethoxy] phenyl} propane, 2,2 -Bis {4-
[(Meth) acryloxypolyethoxy] phenyl} propane, pentaerythritol di (meth) acrylate,
2 such as dipentaerythritol di (meth) acrylate
Functional monomers, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone modified tris [(meth) Uses trifunctional monomers such as acryloxyethyl] isocyanurate, and multi-tubular monomers such as dipentaerythritol tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. To be done. As these crosslinkable compounds, commercially available products or compounds synthesized according to known methods are used.

Next, the hydrophilic solvent as the component (C) is
It is a good solvent for the hydrophilic polymer portion rather than for the hydrophobic polymer portion in the block copolymer which is the component (A) or (A '), and is uniformly dissolved in water at an arbitrary ratio. Say something. When the component (C) is released from the coating during heating and drying, the hydrophobic polymer portion of the block copolymer of the component (A) or (A ′) is placed on the substrate side, and the hydrophilic polymer portion is attached. It has the function of orienting in high concentration on the surface side of the coating film. In order to sufficiently exert this function, the component (C) is selected to be a better solvent for the hydrophilic polymer portion than for the hydrophobic polymer portion, depending on the composition of the block copolymer. It is necessary to.

As the component (C), methanol, ethanol, n-propanol, isopropanol, n-
Lower alcohol such as butanol, diacetone alcohol, etc.
Glycol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, etc. A ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and an amide solvent such as formamide and dimethylformamide can be used. Preferably, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and a mixed solvent thereof can be used from the viewpoint of the solubility of the composition.

Next, the curing catalyst which is the component (D) will be described. The component (D) has a function of decomposing at the time of heating and drying the coating to generate radicals and reacting the components (B) and (F).

As the component (D), an organic peroxide or an azo compound which generates radicals by heat is used. The component (D) is selected from the viewpoint that it decomposes under the drying conditions when the heat-curable coating composition is applied to various plastic materials to generate radicals. From such a viewpoint, as the organic peroxide, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1- Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,
1-bis (t-butylperoxy) cyclohexane,
1,1-bis- (t-butylperoxy) butane, n-
Butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, α, α′-bis (t-butylperoxy) diisopropylbenzene, diqua Mill peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5
-Bis (t-butylperoxy) hexyne-3, benzoyl peroxide, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t
-Hexyl peroxyisopropyl monocarbonate,
t-Butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t -Butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-
Hexyl peroxybenzoate, 2,5-dimethyl-
2,5-bis (benzoylperoxy) hexane, t-
Butyl peroxyacetate, t-butyl peroxy-
Preference is given to using m-toluoyl benzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate. Further, as the azo compound, 2,2'-azobisisobutyronitrile, 2,2 '
-Azobis (2,4-dimethylvaleronitrile) is preferably used. As these curing catalysts, commercially available products or those synthesized according to known methods are used.

Next, the surfactant as the component (E) will be described. The component (E) is subjected to an interaction with the hydrophilic polymer portion of the block copolymer of the component (A) or (A ′) to efficiently migrate gradually from the inside of the coating to the coating surface, and ( For the two reasons that a synergistic effect with the hydrophilic property of the hydrophilic polymer portion in the block copolymer of component (A) or (A ′) appears, it exerts the function of exhibiting antifogging property for a long period of time. . Therefore, even if the surfactant that has migrated to the surface of the coating flows out together with water, it is replenished from within the coating so as to supplement it, so that the antifogging property of the coating surface can be maintained.

The component (E) is generally used, and is one kind selected from nonionic surfactants, anionic surfactants, cationic surfactants and zwitterionic surfactants. The above surfactants are used.

The nonionic surfactant is preferably a polyoxyethylene higher alcohol such as polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether or polyoxyethylene oleyl ether.
Ters, polyoxyethylene octylphenol, polyoxyethylene nonylphenol and other polyoxyethylene alkyl aryl ethers, polyoxyethylene glycol monostearate and other polyoxyethylene acyl esters, polypropylene glycol -Ethylene oxide adduct, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate
Examples thereof include polyoxyethylene sorbitan fatty acid esters such as G., alkyl phosphates, phosphoric acid esters such as polyoxyethylene alkyl ether phosphates, sugar esters, and cellulose ethers.

The anionic surfactants are preferably fatty acid salts such as sodium oleate and potassium oleate, higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and alkylnaphthalene. Alkylbenzene sulfonates such as sodium sulfonate and alkylnaphthalene sulfonates, naphthalene sulfonic acid formalin condensates, dialkyl sulfosuccinates,
Examples thereof include dialkyl phosphate salts and polyoxyethylene sulfate salts such as polyoxyethylene alkylphenyl ether sulfate sodium.

The cationic surfactants are preferably ethanolamines, laurylamine acetate, triethanolamine monoformate, amine salts such as stearamidoethyldiethylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium. Examples thereof include quaternary ammonium salts such as chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride and stearyldimethylbenzylammonium chloride.

The zwitterionic surfactant is preferably a fatty acid type amphoteric surfactant such as dimethylalkyllauryl betaine and dimethylalkyl stearyl betaine,
Examples thereof include sulfonic acid type amphoteric surfactants such as dimethylalkylsulfobetaine, and alkylglycine. As these surfactants, commercially available products or those synthesized according to known methods are used.

Of these, from the viewpoint of sustainability of effects,
Nonionic surfactants or anionic surfactants are preferable, and in particular, the combination of polyoxyethylene alkyl aryl ethers and dialkyl sulfosuccinates is effective from the viewpoint of antifogging durability and prevention of change in appearance of the coating film. Is preferred.

At least one kind of the surfactant as the component (E) is a block copolymer of the component (A) or (A ′) / the solid content weight ratio of the surfactant as the component (E) = 100 /
It is preferably in the range of 0.5 to 30. More preferably, the solid content weight ratio of the block copolymer of component (A) or (A ′) / surfactant of component (E) = 100/5.
~ 20. If the amount of the surfactant present is less than 0.5 parts by weight, long-term anti-fog persistence cannot be obtained, and
When it exceeds the weight part, the film strength becomes low.

Next, a carboxyl group as the component (F),
At least one kind of vinyl type monomer having a sulfonic acid group or a phosphoric acid group is a monomer having a crosslinking functional group contained in the hydrophilic polymer portion of the block copolymer of the component (A) or (A ′). It functions as a catalyst during the crosslinking reaction of the functional groups of the monomer. At the same time, at the beginning of heating and drying (C)
When the hydrophilic solvent, which is the component, evaporates, it is oriented near the surface due to the interaction with the hydrophilic solvent, and by the curing catalyst of the component (D),
The components (F) react with each other or with the component (B) and are fixed near the surface to improve the antifogging property. Since the component (F) has a low molecular weight, it migrates to the surface of the coating film as the hydrophilic solvent evaporates, and reacts with the curing catalyst to be fixed in the coating film, like the surfactant. Therefore, the antifogging property of the coating is maintained.

The abundance of at least one of these vinyl type monomers is (A) or (A ′) in terms of solid content weight ratio.
Component block copolymer / (F) component monomer = 100
The range is / 1 to 15. More preferably, 100 /
It is in the range of 5 to 10. When the blending ratio of these vinyl type monomers is less than 1, the crosslinking reaction of the crosslinking functional group of the hydrophilic polymer in the block copolymer of the component (A) or (A ′) becomes insufficient, Moldability and antifogging property are insufficient. 15
When it exceeds the weight%, the film strength becomes insufficient.

As these vinyl type monomers, vinyl type monomers having a carboxyl group, a sulfonic acid group or a phosphoric acid group are used. Preferably, from the viewpoints of catalytic ability, reactivity with the component (B), and antifogging property, (meth) acrylic acid-3-sulfopropyl, (meth) acrylic acid-2
-Sulfoethyl, 2-acrylamido-2-methylpropanesulfonic acid, (meth) acrylic acid, crotonic acid, itaconic acid, itaconic acid half ester, maleic acid half ester, maleic acid, mono (2- (meth) acryloyloxyethyl) Acid phosphate or the like is used. As these monomers, commercially available products or those synthesized according to known methods are used.

In the heat-curable coating composition of the present invention, if necessary, metal oxide fine particles such as zinc oxide and titanium dioxide, an ultraviolet absorber of an organic compound such as benzophenone-based, benzotriazole-based, salicylic acid-based, methylstyrene-modified, Various conventional additives such as olefin-modified, polyether-modified, alcohol-modified and other silicone oil leveling agents can be added.

Next, the antifogging process using the heat-curable coating composition of the present invention will be described. That is, a heat-curable coating composition is applied to various plastic materials to be processed by, for example, a coating means for a normal coating,
An antifogging film is formed by heat curing at a temperature of ˜145 ° C. With this anti-fogging process, various plastic materials provided with anti-fogging property can maintain not only the appearance and adhesion of the film but also the anti-fog property and the film strength in an actual environment for an extremely long period of time.

The coating environment is preferably 60% relative humidity or less. This is because the heat-curable coating composition has very high hydrophilicity and has a strong tendency to absorb water. That is, when the coating is applied in an environment in which the relative humidity exceeds 60%, the appearance tends to be deteriorated due to the whitening of the coating after the heat curing. In order to suppress this whitening phenomenon, it is effective to use a part of the solvent having a low evaporation rate and a low evaporation rate of water at the time of solvent evaporation.

As a coating means, a usual coating means for coating, that is, a roll coating method, a spray method, a dipping method, a brush coating method, a spin coating method, a flow coating method, a bar coater method or the like is applied.

As described above, the coating film formed on the surface of a material such as a flat plate, a molded article or a film of various plastic materials is transparent, makes the surface hydrophilic without impairing the appearance of the material surface, and adheres to the surface. The formed water can be absorbed in the film. In addition, the coating performance can be maintained even when the coated plastic materials are molded by heat bending or the like. Therefore, for example, instrument covers and instrument viewing windows, lenses for various types of lighting, sports goggles or glasses such as underwater goggles and ski goggles,
It is preferably used for the purpose of imparting antifogging property to the surface of window glass of houses, window glass of vehicles, and the like.

[0057]

EXAMPLES The present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples. In each example, the number of copies is based on the weight. (Reference Examples 1 to 24, synthesis of block copolymer)
A block copolymer was synthesized as follows by two-step polymerization using a polymeric peroxide represented by The polymerization conditions shown below are such that the charged monomers are almost the same in each stage in both the first-stage polymerization forming the hydrophilic polymer portion and the second-stage polymerization forming the hydrophobic polymer portion. It is a condition for completely polymerizing.

First, 100 parts of propylene glycol monomethyl ether was charged into a reactor equipped with a thermometer, a stirrer and a reflux condenser, and nitrogen gas was blown into the reactor to obtain 7 parts.
It is heated to 0 ° C., and propylene glycol monomethyl ether A part Polymeric peroxide represented by the formula 1 B part Monomer having crosslinkable functional group C part Hydrophilic monomer D part Lower alkyl (meth) acrylate E A mixed solution of 1 part was charged over 2 hours, and the polymerization reaction was further performed for 2 hours (first-stage polymerization). Then, a mixture of propylene glycol monomethyl ether F part, lower alkyl (meth) acrylate G part, vinyl type monomer H part having a sulfonic acid group, a carboxyl group or a phosphoric acid group was added over 30 minutes, and the mixture was heated to 75 ° C. Polymerization was carried out for 5 hours. The numbers of parts A to H and the results of polymerization are shown in Tables 1 to 4.

[0059]

## STR1 ## - _{[CO (CH 2) 4 COO (} C 2 H 4 O) 3 CO
(CH ₂ ) ₄ COOO] ₁₀ − (Reference Examples 25 to 27, Synthesis of Random Copolymer) The reactor used in the synthesis of Reference Example 1 was charged with 100 parts of propylene glycol monomethyl ether, and while blowing nitrogen gas, 85 It is heated to ℃, and propylene glycol monomethyl ether 34 parts t-butylperoxy 2-ethylhexanoate 6 parts Crosslinkable functional group-containing monomer C part Hydrophilic monomer D part Lower alkyl (meth) acrylate Part E A mixed liquid comprising a vinyl type monomer F having a sulfonic acid group, a carboxyl group or a phosphoric acid group, F part was charged over 2 hours, and a polymerization reaction was further performed for 9 hours. The number of parts C to F and the result of polymerization are shown in Table 4.

The abbreviations in Tables 1 to 4 have the following meanings. HEMA: 2-hydroxyethyl methacrylate N-MAAm: N-methylol (meth) acrylamide ACMO: N-acryloylmorpholine DMAAm: N, N-dimethylacrylamide MMA: methyl methacrylate IBMA: isobutyl methacrylate M20G: methoxydiethylene glycol methacrylate M40G : Methoxytetraethylene glycol methacrylate AA: Acrylic acid SEM: 2-Sulfoethyl methacrylate B-QA: 2-Hydroxy-3-methacryloyloxypropyltrimethylammonium chloride AMPS: Acrylamide-2-methyl-1-propanesulfonic acid Also, polymerization The solid content in the result column indicates% by weight. The viscosity is the viscosity of the solution after polymerization at 25 ° C (poise, P).
Represents The ratio of the hydrophilic polymer portion represents the ratio (%) of the polymer synthesized in the first-stage polymerization to all the polymers. (Reference Example 28, Synthesis of Block Copolymer Having Methacryloyl Group) First, a block copolymer was synthesized by two-step polymerization using the polymeric peroxide represented by Chemical Formula 1 as a polymerization initiator to obtain a block copolymer. A methacryloyl group was introduced into the hydrophobic polymer portion. The polymerization conditions shown below are the first-stage polymerization that constitutes the hydrophilic polymer portion,
Any of the second-stage polymerization that constitutes the hydrophobic polymer portion,
The conditions are such that the charged monomers are almost completely polymerized at each stage.

First, 100 parts of propylene glycol monomethyl ether was charged into a reactor equipped with a thermometer, a stirrer and a reflux condenser, and while blowing nitrogen gas,
The mixture was heated to 0 ° C., and a mixed solution of propylene glycol monomethyl ether 36.0 parts Polymeric peroxide represented by Chemical formula 1 6.3 parts N, N-dimethylacrylamide 63.0 parts was charged over 2 hours, and further charged. The polymerization reaction was carried out for 2 hours (first stage polymerization). Then, a mixed solution of 63.0 parts of propylene glycol monomethyl ether, 21.6 parts of methyl methacrylate and 5.4 parts of acrylic acid was charged over 30 minutes, and polymerization was carried out at 75 ° C. for 5 hours. The solid content of the solution after polymerization was 31.9% by weight, and the viscosity was 2.9 poise. After diluting this solution so that the solid content becomes 20% by weight, glycidyl methacrylate and triethylbenzylammonium chloride, which are equimolar to the carboxyl groups in the block copolymer, are added to 7.
5 parts and p-methoxyphenol 0.15 part were added, respectively, and it was made to react at 90 degreeC for 6 hours. The reaction rate of glycidyl methacrylate to the block copolymer was 90%.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

[Table 5]

(Examples 1 to 37 and Comparative Examples 1 to 9) All the copolymers synthesized in Reference Examples 1 to 28 were diluted with propylene glycol monomethyl ether so that the solid content of the copolymer was 20% by weight. . Examples 1 to 37 and Comparative Examples 1 to 7 are cross-linkable compounds containing at least one cross-linkable functional group of at least one acryloyl group, methacryloyl group and allyl group in the block copolymer solution, A monomer having a carboxyl group, a sulfone group and a phosphoric acid group, a curing catalyst and a surfactant were mixed to obtain a heat-curable coating composition. Here, the curing catalyst is 1,1-bis (t
-Hexylperoxy) 3,3,5-trimethylcyclohexane was mixed in an amount of 4% by weight based on the total solid weight of the crosslinkable compound and the monomer having a carboxyl group, a sulfone group and a phosphoric acid group.

In Comparative Example 8, the block copolymer solution of Reference Example 4 was blended with 1.3 wt% of a curing catalyst p-toluenesulfonic acid and a surfactant to prepare a heat-curable protective composition. A clouding agent composition was obtained. Comparative Example 9 is Reference Example 28
A block copolymer solution of a photopolymerizable compound, a photoinitiator,
A surfactant was blended to obtain an ultraviolet curable antifogging composition. Here, as the photoinitiator, 2-hydroxy-2-methyl-1-phenylpropan-1-one was blended in an amount of 3% by weight based on the weight of the solid content of the photopolymerizable compound. Examples 1-37
And each compounding composition of Comparative Examples 1-9 is shown in Tables 6-10.

Next, Examples 1-37 and Comparative Examples 1-
Each composition of 8 is coated on various plastic substrates using a bar coater under the environment of relative humidity of 60% or less so that the dry film thickness is 5 μm, and heated under the condition that the various plastic substrates are not deteriorated by heat. It was cured. In addition, Comparative Example 9
The composition of (1) was applied to various base materials using a bar coater so that the dry film thickness was 5 μm. Then, it was heated and dried at 80 ° C. for 2 minutes, and thereafter, a cured coating film was obtained by irradiating ultraviolet rays from a distance of 25 cm using a high pressure mercury lamp of 80 W / cm (manufactured by Nippon Battery Co., Ltd.). Table 6
The abbreviations in 10 represent the following meanings. (Crosslinkable compound) (1): Polyoxyethylene glycol diacrylate (average ethylene oxide number 9), trade name NK ester A-400 manufactured by Shin-Nakamura Chemical Co., Ltd. (2): 1,6-hexanediacrylate, Kyoeisha Yushi Kagaku Kogyo Co., Ltd. product name 1,6-HX-A (3): Polyester acrylate, Osaka Organic Chemical Industry Co., Ltd. product name Viscoat 3700 (4): Pentaerythritol triacrylate, Shin-Nakamura Chemical Industry ( Brand name NK ester A-TMM-
3 (5): Caprolactone-modified tris (acryloxyethyl) isocyanurate, trade name of Toagosei Kagaku Kogyo Co., Ltd. Aronix M-325 (6): Pentaerythritol tetramethacrylate
Product name SR-36 manufactured by SARTOMER Company
7 (7): Dimentaerythritol hexaacrylate
Toagosei Chemical Industry Co., Ltd. product name Aronix M-4
00 (surfactant) (a): polyoxyethylene nonylphenyl ether,
Nippon Oil & Fat Co., Ltd. product name Nonion NS-212 (b): Polyoxyethylene stearyl ether, Nippon Oil & Fat Co., Ltd. product name Nonion S-215 (c): sodium n-dodecylbenzenesulfonate,
Nippon Oil & Fat Co., Ltd. trade name Neulex R (d): Sodium dioctyl sulfosuccinate, Nippon Oil & Fat Co., Ltd. trade name Lapizole B80 (e): Octadecyl trimethyl ammonium chloride, Nippon Oil & Fat Co., Ltd. trade name, Cation AB (F): Dimethylalkyl (coconut) betaine, trade name Anon BF (base material) manufactured by NOF CORPORATION PC: Polycarbonate sheet, PMMA: Polymethylmethacrylate sheet, PET: Polyethylene terephthalate film, PV
C: Polyvinyl chloride film

[0070]

[Table 6]

[0071]

[Table 7]

[0072]

[Table 8]

[0073]

[Table 9]

[0074]

[Table 10]

With respect to each of the coating films thus obtained, the test pieces were allowed to stand in the following environments A to B, and the physical properties were evaluated by each evaluation method. The results are shown in Table 1.
1 to 16 are shown. A: Initial environment = physical properties of the coating which was cured by heating and cooled to room temperature B: Cold environment = 60 ° C. after leaving the coating at −20 ° C. for 8 hours
(PVC, 40 ° C.), 90% relative humidity, left for 16 hours. This is set as one cycle, and 10 cycles are performed.

Evaluation method (1): (Film appearance test) The appearance of the film was visually observed and evaluated according to the following criteria. ◯: transparent, no change, Δ: slightly decreased transparency, ×: whitening Evaluation method (2): (adhesion test) JIS D 0202
The cross-cut cellophane tape peeling test according to the above was performed, and the evaluation was performed according to the following criteria.

◯: 100/100, Δ: 99 / 100-
50/100, x: 49/100 to 0/100 Evaluation method (3): (Coating strength test) JIS K 540
A pencil hardness test according to 0 was performed. The evaluation result is indicated by the hardness of the pencil.

Evaluation method (4): (Exhalation test) After the coating film was left in a thermostatic chamber at 20 ° C. for 2 hours, the surface of the coating film was exhaled, and the cloudiness was visually judged according to the following criteria to prevent fogging. The sex was evaluated.

◎: No cloudiness at all, ○: Cloudy for a moment,
Disappearing immediately, △: Some cloudiness, ×
: Fog on the entire surface Evaluation method (5): (40 ° C. steam test) Hot steam at 40 ° C. was applied to the surface of the coating in a constant temperature chamber at 20 ° C., and the time until the start of fogging was measured to test the anti-fogging persistence. . In Tables 8 to 11, “≧ 5” means 5 hours or longer, and “immediately after” means cloudy immediately.

Evaluation method (6): JIS L on the surface of the coating
Place the cotton (Kanakin No. 3) cloth used for 0830, put a load of 20 g / cm ² on it, and in this state 160 ° C
A heat history of 1 minute was applied to the sample to perform a test for evaluating the formability. After that, the appearance change of the coating film surface was visually observed and evaluated according to the following criteria.

◯: No change in appearance, Δ: Thin cotton cloth traces remained, ×: Dark cotton cloth traces remained

[0082]

[Table 11]

[0083]

[Table 12]

[0084]

[Table 13]

[0085]

[Table 14]

[0086]

[Table 15]

[0087]

[Table 16]

As shown in Tables 1 to 16 above, the heat-curable coating compositions of the respective examples had the initial film appearance, antifogging property, and
Excellent adhesion, film strength and moldability,
Even when exposed to a high humidity or high temperature environment, the film appearance, antifogging property, adhesion, film strength and moldability were maintained for a long period of time. Particularly, Examples 1 to 13 in which the blending ratio of the block copolymer composed of the preferable monomer, the crosslinkable compound, the predetermined monomer and the surfactant is preferable.
And the coating films formed from the compositions of Examples 24 to 28 are excellent in coating appearance, antifogging property, adhesion, persistence of antifogging property, coating strength and moldability even when exposed to high humidity or high temperature environment. The various performances were maintained for a long time.

The above-mentioned various performances can be maintained in Examples 33 and 36 in which only the surfactant is mixed in the copolymer solution and the crosslinkable compound. Furthermore, Examples 34 and 35
In the copolymer solution, while adding an appropriate amount of methacrylic acid to the crosslinkable compound, the composition and the number of parts of the copolymer, the appropriate crosslinkable compound and the number of parts, the antifogging sustainability is slightly reduced, It can exert its performance.
In addition, Example 3 consisting of a copolymer solution and a crosslinking compound
In Nos. 2 and 37, excellent antifogging sustainability could not be exhibited, but excellent initial performance could be exhibited.

On the other hand, when the random copolymers of Comparative Examples 1 to 3 were used, the film appearance, antifogging property and adhesion were extremely poor. The block copolymers of Comparative Examples 4 to 6,
When any of the components of the crosslinkable compound, the predetermined monomer and the surfactant was not added, any of the film appearance, antifogging property, adhesion property, film strength and moldability was inferior. In the case of the self-crosslinking block copolymer of Comparative Example 7 and the surfactant, the film strength and moldability when the film absorbed water were poor. Comparative Example 8
In the case of the UV-curable antifogging agent (1), the antifogging property and the adhesion were deteriorated with time, and the moldability was also poor.

The technical idea understood from the above embodiment will be described below. (1) The heat-curable coating composition according to claim 1 or 2, wherein the block copolymer has a hydrophilic polymer portion and a hydrophilic polymer portion in the hydrophobic polymer portion as main components.
According to this structure, the hydrophilicity of the film can be maintained and the antifogging property can be maintained. (2) The proportion of at least one lower alkyl (meth) acrylate in the block copolymer is 5 to 49% by weight.
The heat-curable coating composition according to claim 2, which is According to this configuration, it is possible to improve the film strength while maintaining the antifogging property of the film. (3) The block copolymer is produced by a two-step radical polymerization using a polymeric peroxide or a polyazo compound as a polymerization initiator.
The heat-curable coating composition as described in 1. With this configuration, the block copolymer can be easily and efficiently obtained. (4) The heat-curable coating composition according to claim 1 or 2, wherein the hydrophilic solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or propylene glycol monomethyl ether. With this configuration, the solubility of the block copolymer and the like in the coating composition can be increased. (5) The heat-curable coating composition according to claim 3, wherein the surfactant is a nonionic surfactant or an anionic surfactant. According to this structure, it is possible to improve the sustainability of effects such as antifogging property.

[0092]

As described above in detail, the heat-curable coating composition of the present invention has the following excellent effects.

According to the invention described in claim 1, excellent antifogging property can be imparted to the surface of the base material such as various plastic materials, the adhesion and strength of the coating film can be maintained, and good appearance quality can be maintained. can do. Moreover, it is possible to prevent the deterioration of the coating strength when absorbing water, and to prevent changes in the coating appearance, antifogging property, adhesion and coating strength after molding various plastic materials by various methods such as heat bending. .

According to the second aspect of the invention, the adhesion and strength of the coating film to the substrate can be improved. According to the invention described in claim 3, the antifogging property of the coating film can be exhibited for a long period of time.

According to the invention described in claim 4, the hydrophilic component can be maintained on the surface of the coating film, and the antifogging property of the coating film can be improved. According to the invention described in claim 5, the antifogging property of the coating film can be enhanced, and the antifogging property can be maintained for a long period of time.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location // C08F 290/00 MRR C08F 290/00 MRR 293/00 MRL 293/00 MRL

Claims (5)

[Claims] 1. At least one kind of a monomer having a cross-linking functional group such as an N-methylol group, an N-methylol ether group or a hydroxyl group, and a hydrophilic monomer having a copolymerizability therewith. A hydrophilic polymer portion formed from at least one or more kinds, at least one kind of vinyl type monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, and a copolymerizability with the vinyl type monomer A block copolymer consisting of a hydrophobic polymer portion formed from at least one kind of lower alkyl (meth) acrylate having a crosslinkable functional group of any of an acryloyl group, a methacryloyl group or an allyl group. At least one or more crosslinkable compounds containing two or more; a hydrophilic solvent that is a good solvent for the hydrophilic polymer portion of the block copolymer; A heat-curable coating composition comprising a curing catalyst for reacting a bridge compound. 2. The hydrophilic polymer portion of the block copolymer comprises at least one or more monomers having a cross-linking functional group of any one of an N-methylol group, an N-methylol ether group and a hydroxyl group, and these. The heat-curable coating composition according to claim 1, which is formed from at least one kind of hydrophilic monomer copolymerizable with and at least one kind of lower alkyl (meth) acrylate. 3. The heat-curable coating composition according to claim 1, which further contains at least one surfactant. 4. The heat-curable coating composition according to claim 1, further comprising at least one monomer having a carboxyl group, a sulfonic acid group or a phosphoric acid group and reacting with the curing catalyst. Stuff. 5. At least one of monomers having a carboxyl group, a sulfonic acid group or a phosphoric acid group and at least one kind of a surfactant, which reacts with the curing catalyst.
The heat-curable coating composition according to claim 1 or 2, containing one or more kinds.