JPH11335622A - Coating composition giving coating film having antistatic and highly water-resistant surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition giving a coating film excellent in, e.g. transparency, adhesion and resistance to heat, when spread over a varying base and dried at low temperature for a short period by including a polymer containing a specific component as the essential component and hardening agent. SOLUTION: This composition is composed of (A) a polymer which contains, as the essential components, (i) a polyester portion (preferably at least one of a copolymer polyester and polyurethane resin of copolymer polyester polyol), (ii) a radical polymer portion, (iii) OH group, and (iv) at least one antistatic functional group selected from the group consisting of ammonium salt, nitrogen- containing aromatic salt, sulfonate and phosphate, and (B) a hardening agent (preferably nonionic or cationic, melamine-based one). It is preferable that the component (ii) is grafted to the component (i) and that the component (iv) is contained in the component (ii), in order to provide the coating film excellent in antistatic capacity and resistance to water and solvents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a coating material which can be coated on various substrates and dried at a low temperature for a short time to obtain a coating film having excellent transparency, adhesion, especially antistatic performance and water resistance. The present invention relates to an industrial composition.

[0002]

2. Description of the Related Art Conventionally, it has been effective to provide a resin layer having a cationic functional group such as a quaternary ammonium salt on the surface of a substrate in order to impart an antistatic property to a film or fiber. Are known. Various techniques have been disclosed for these cationic polymers, such as JP-A-5-125301, JP-A-5-179155, JP-A-5-193074, and JP-A-5-194671.

[0003] However, when a resin layer is formed using these resins, the strength of the coating film is insufficient, so that the resin layer is easily damaged and the adhesion to various plastic substrates is insufficient. There's a problem. In order to solve these problems, it has been attempted to use a cationic polymer mixed with another resin or a cross-linking agent. In that case, however, the cationic polymer and the other resin (acrylic resin, polyester resin) are used. ) And a crosslinking agent, and the addition of a small amount of a cationic polymer causes the coating layer to become cloudy, making it impossible to sufficiently increase the required cationic functional group concentration in the coating.

[0004] As a technique for improving the physical properties and transparency of the coating film of such a cationic resin, JP-A-8-134152 discloses a method of graft-polymerizing acryl containing a quaternary salt onto polyester or the like, and a method using various curing agents. Formulations that cure are publicly available. However, the coating films obtained by these formulations have low general water resistance, and have a problem that swelling, whitening and peeling of the coating film due to splashing with water, and a decrease in antistatic ability occur. Further, in order to obtain sufficient water resistance, heating at a high temperature for a long time is necessary, and poor workability at a coating site has been a problem.

[0005]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems of the prior art, the present inventors have applied a variety of substrates, dried at a low temperature for a short time, and obtained transparency, adhesion, and heat resistance. In particular, the present invention has been intensively pursued for a coating composition capable of obtaining a coating film excellent in antistatic performance and water resistance and solvent resistance, and completed the present invention.

[0006]

That is, the present invention provides: (1) a coating composition comprising a polymer having the following components and a curing agent: A) a polyester portion; B) a radical polymer portion; OH group D) One or more kinds of functional groups having antistatic ability selected from the following a) group a) Group: ammonium salt, nitrogen-containing aromatic salt, sulfonate, phosphate (2) A) a coating composition, wherein the polymer according to the above) contains at least one functional group of the following group a) in the radical polymer part; a) group; ammonium salt, nitrogen-containing aromatic salt, Sulfonates and phosphates (3) The polyester portion of the polymer described in the above (1) or (2) is at least one of a copolymerized polyester and a polyurethane resin of a copolymerized polyester polyol. (4) The polymer according to any one of (1), (2) and (3) above, wherein a radical polymer portion is grafted on a polyester portion. (5) Lamination, wherein the coating composition described in any one of (1), (2), (3) and (4) above is provided on a substrate. (6) An electrostatic image receiving member, characterized in that the coating composition according to any one of (1), (2), (3) and (4) is provided on a substrate. Sheet.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer used in the present invention includes a polyester and a radical polymer, and it is necessary that the polyester and the radical polymer are chemically bonded. The polyester is preferably a copolymerized polyester containing an aromatic dicarboxylic acid and an alicyclic dicarboxylic acid as a main skeleton, and is preferably a polyester polyurethane having the copolymerized polyester as a main component. Hereinafter, when it is described as polyester, it includes such a polyester polyurethane.

[0008] As a method of chemically bonding the polyester and the radical polymer, the polyester and the radical polymer are each polymerized, and then a reactive functional group such as a hydroxyl group and a carboxylic acid group contained in the polyester and the radical polymer is used. And bonding with a compound that reacts with the reactive functional group such as an isocyanate compound and an epoxy compound. A method in which a radical polymer containing an ester bond-forming group such as a hydroxyl group or a carboxylic acid group is synthesized, and then a polycarboxylic acid and a polyol are reacted in the presence of the radical polymer to obtain a radical polymer-containing polyester. A method in which a polyester having a radical polymerizable portion (polymerizable unsaturated double bond) is polymerized, and then a radical polymerizable monomer is polymerized in the presence of the polyester to obtain a radical polymer-containing polyester. And the like. Among the radical polymer-containing polyester obtained as described above, the radical polymer graft polyester having the polyester portion as a main chain and the radical polymer portion as a side chain is used as the coating resin composition of the present invention. Is preferred.

As a method for obtaining such a radical polymer graft polyester, a radical polymer having two or more reactive functional groups such as a hydroxyl group and a carboxylic acid group at only one end is synthesized, and then an isocyanate compound is synthesized. ,
A method of bonding to a polyester with a compound such as an epoxy compound. A method of synthesizing a radical polymer having two or more ester bond forming groups such as a hydroxyl group and a carboxylic acid group at only one end, and then reacting a polycarboxylic acid and a polyol in the presence of the radical polymer. After polymerizing a polyester having a polymerizable unsaturated double bond or a polyester having a radical-capturable group such as a mercapto group, a method of polymerizing a radical polymerizable monomer in the presence of the polyester may be used. Among these, a method of polymerizing a polyester having a radically polymerizable portion and then polymerizing a radical polymerizable monomer in the presence of the polyester is the most preferred method.

The antistatic functional groups (ammonium salts, nitrogen-containing aromatic salts, sulfonates and phosphates) contained in the polymer of the present invention have good adhesion and antistatic properties of the coated film after coating. It is preferably contained in the radical polymer portion from the viewpoint of the balance of performance, and particularly when it is contained in the radical polymer portion which is a side chain of polyester, high balance performance can be exhibited.

As the functional group having an antistatic function, an ammonium salt and a nitrogen-containing aromatic salt are preferable, and more preferably, the N element of the ammonium salt and the nitrogen-containing aromatic salt is completely substituted (N-H portion is substituted). It is preferably a quaternary salt (not included).

The polymer used in the main chain is preferably a polyester containing 60 mol% or more of aromatic and alicyclic dicarboxylic acids in all carboxylic acid components, or a polyester polyurethane containing the polyester as a main component. Conventional acrylic and olefinic cationic polymers are generally brittle, and because they contain polar functional groups, the polarity of the polymer increases, resulting in poor adhesion to various substrates and compatibility. Although the transparency of the film is reduced due to the extremely limited resin to be formed, the thermoplastic resin laminated film of the present invention is the main chain of the graft in the resin layer provided on the thermoplastic resin film. Polyester or polyester urethane exhibits improved adhesion and adhesion to substrates such as various plastics and compatibility when various resins are added.

Further, since the functional group-containing polymer having an antistatic function for forming the side chain of the graft is chemically bonded, the main chain polymer and the side chain polymer component do not undergo phase separation. It was found that whitening of the membrane and bleeding out of the cationic polymer did not occur. In addition,
Since the polymer containing an OH group has a sufficiently hydrophilic group, it can be dispersed in water and can be made into a completely aqueous system containing no solvent. It is preferable that the polymer containing an OH group is an aqueous dispersion from the viewpoint of the influence of the organic solvent on the environment, which has been recently described.

Further, as the curing agent, a melamine-based curing agent,
Epoxy-based curing agents and isocyanate-based curing agents are exemplified. Among them, nonionic or cationic methylol-based melamine can be used as the melamine-based curing agent. Since the polymer containing an OH group has a cationic functional group, the system may aggregate when an anionic curing agent is added. Hereinafter, each item will be described.

(Polyester Resin) The polyester resin constituting the main chain of the graft polymer used in the present invention is one that does not inherently disperse or dissolve in water. The preferred polymerization composition is such that the dicarboxylic acid component is 60 to 99 mol% of an aromatic dicarboxylic acid, 0 to 40 mol% of an aliphatic and / or alicyclic dicarboxylic acid, a dicarboxylic acid containing a polymerizable unsaturated double bond, 0.1 to 0.1 mol%. 5-10 mol%
It is.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid and the like. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandionic acid, and dimer acid.Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. 3
-Cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and acid anhydrides thereof.

The dicarboxylic acids containing a polymerizable unsaturated double bond include α, β-unsaturated dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid,
Citraconic acid and alicyclic dicarboxylic acids containing an unsaturated double bond include 2,5-norbornanedicarboxylic anhydride, tetrahydrophthalic anhydride and the like. Most preferred among them are fumaric acid, maleic acid and 2,5-norbornene dicarboxylic acid (endo-bicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid). Further, p- (2-hydroxyethoxy) benzoic acid,
Or hydroxypivalic acid, γ-butyrolactone,
A hydroxycarboxylic acid such as ε-caprolactone can be used if necessary.

The aromatic dicarboxylic acid of the dicarboxylic acid component is more preferably 70 to 99 mol%, and the aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid is more preferably 0 to 30 mol%. 60 aromatic dicarboxylic acids
When it is less than mol%, the mechanical properties of the coating film are inferior. In addition, when the aliphatic dicarboxylic acid and / or the alicyclic dicarboxylic acid are 40
If the amount exceeds mol%, not only the hardness and stain resistance are reduced, but also the aliphatic ester bond has a lower hydrolysis resistance than the aromatic ester bond. In some cases, the degree of polymerization of the polyester may be reduced during the storage period.

The dicarboxylic acid containing a polymerizable unsaturated double bond is preferably from 0.5 to 20 mol%, more preferably from 1 to 12 mol%, and still more preferably from 1 to 9 mol%, based on all acid components. Mol%. When the amount of the dicarboxylic acid containing a polymerizable unsaturated double bond is 0.5 mol% or less, it is difficult to efficiently graft the radical polymerizable monomer to the polyester resin, and the dispersed particle size in an aqueous medium is reduced. Tends to increase, and the dispersion stability tends to decrease. Dicarboxylic acid containing a polymerizable unsaturated double bond is 2
If it exceeds 0 mol%, the viscosity will increase too much in the latter stage of the grafting reaction, and the uniform progress of the reaction will be hindered.

On the other hand, the glycol component comprises an aliphatic glycol having 2 to 10 carbon atoms and / or an alicyclic glycol having 6 to 12 carbon atoms and / or a glycol containing an ether bond. Examples of the aliphatic glycol having 2 to 10 carbon atoms include ethylene glycol and 1,2-propylene glycol.
1,3-propanediol, 1,4-butanediol
1,1,5-pentanediole, neopentyl glyco-
1,6-hexanediol, 3-methyl-1,5-
Pentandiol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, neopentyl glycol hydroxypivalionate, dimethylol heptane, etc., and an alicyclic group having 6 to 12 carbon atoms. Examples of the glycol include 1,4-cyclohexanedimethanol, tricyclodecanedimethylol and the like.

Examples of the ether bond-containing glycol include diethylene glycol, triethylene glycol, dipropylene glycol, and ethylene oxide or propylene oxide on the two phenolic hydroxyl groups of bisphenols. Glycols obtained by adding one to several moles each, for example, 2,2-bis (4-hydroxyethoxyphenyl) propane and the like can be mentioned. Polyethylene glycol, polypropylene glycol and polytetramethylene glycol may be used if necessary.

Examples of the glycol containing a polymerizable unsaturated double bond include glycerin monoallyl ether, trimethylolpropane monoallyl ether, and pentaeristol monoallyl ether. The amount of the glycol containing a polymerizable unsaturated double bond is 0.5 to 20 mol%, preferably 1 to 12 mol%, and more preferably 1 to 9 mol%. When the amount of the glycol containing a polymerizable unsaturated double bond is 0.5 mol% or less, it is difficult to efficiently graft the radical polymerizable monomer to the polyester resin, and the dispersed particle size in an aqueous medium is small. Tends to increase, and the dispersion stability tends to decrease. When the amount of the dicarboxylic acid containing a polymerizable unsaturated double bond exceeds 20 mol%, the viscosity is unduly increased at the latter stage of the grafting reaction, which hinders the uniform progress of the reaction.

In the polyester resin used in the present invention, 0 to 5 mol% of a trifunctional or higher polycarboxylic acid and / or polyol can be copolymerized. Anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenonetetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate) and the like are used. On the other hand, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like are used as trifunctional or higher functional polyols. Trifunctional or higher polycarboxylic acid and / or
Alternatively, the polyol is copolymerized in an amount of from 0 to 5 mol%, preferably from 0 to 3 mol%, based on the total acid components or all the glycol components. It becomes difficult to give.

The polyester resin used in the present invention has a weight average molecular weight in the range of 3,000 to 100,000, preferably in the range of 7,000 to 70,000, and more preferably in the range of 10,000 to 50. It must be in the range of 2,000. Weight average molecular weight of 3,000
When it is below, various physical properties decrease, and when the weight average molecular weight is 100,000 or more, during the graft reaction,
The viscosity increases, and uniform progress of the reaction is hindered. In the polyester resin of the present invention, the terminal of the polyester resin as described above may be a carboxylic acid, and the chain may be extended with an epoxy compound.

(Polyurethane Resin) The polyurethane resin in the present invention comprises a polyester polyol (a), an organic diisocyanate compound (b), and, if necessary, a chain extender (c) having an active hydrogen group, and has a molecular weight of 500.
0-100,000, urethane bond content is 500-40
00 equivalent / 10 ⁶ g, and the content of the polymerizable double bond is an average of 1.5 to 30 per molecule.

Polyester polyol used in the present invention
(a) has a hydroxyl group at both terminal groups and a molecular weight of 500 to 10
000 is desirable. The polyester polyol used in the present invention has a dicarboxylic acid component of at least 6
It is necessary that at least 0 mol%, desirably at least 70 mol% be composed of aromatic dicarboxylic acid. An aliphatic polyester polyol widely used for general polyurethane resins, for example, a polyurethane resin using adipate of ethylene glycol or neopentyl glycol has extremely low water resistance. As an example, the reduced viscosity retention of this aliphatic polyester polyurethane after immersion in hot water at 70 ° C. for 20 days is as low as 20 to 30%, while the resin having the same glycol terephthalate and isophthalate as the polyester polyol has the same conditions. The reduced viscosity retention rate is 8
It is as high as 0 to 90%. Therefore, it is necessary to use a polyester polyol mainly composed of an aromatic dicarboxylic acid for high water resistance of the coating film. In addition, polyether polyol, polyolefin polyol, etc., if necessary,
It can be used with these polyester polyols.

The organic diisocyanate compound (b) used in the present invention includes hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, p-xylylene diisocyanate, and m-xylylene diisocyanate. 1,3-diisocyanatomethylcyclohexane, 4,4′-diisocyanatodicyclohexane,
4,4′-diisocyanate cyclohexylmethane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2,4-
Naphthalene diisocyanate, 3,3'-dimethyl-
4,4'-biphenylenediisocyanate, 4,4'-
Examples include diisocyanate diphenyl ether, 1,5-naphthalenediisocyanate, and the like.

In the present invention, examples of the chain extender (c) having an active hydrogen group used as required include ethylene glycol, propylene glycol, neopentyl glycol, 2,2-diethyl-1,3-propane. Examples thereof include glycols such as diol, diethylene glycol, spiro glycol, and polyethylene glycol, and amines such as hexamethylene diamine, propylene diamine, and hexamethylene diamine.

The polyurethane resin used in the present invention comprises a polyester polyol (a), an organic diisocyanate (b),
And, if necessary, a chain extender (c) having an active hydrogen group with an active hydrogen group / isocyanate ratio of (a) + (c).
It must be a polyurethane resin obtained by reacting at a compounding ratio of 0.8 to 1.3 (equivalent ratio). When the ratio of active hydrogen groups / isocyanate groups of (a) + (c) is out of this range, the urethane resin cannot have a sufficiently high molecular weight,
The desired coating film properties cannot be obtained.

The polyurethane resin used in the present invention is produced in a known manner in a solvent at a reaction temperature of 20 to 150 ° C. in the presence or absence of a catalyst. As the solvent used at this time, for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate can be used. As a catalyst for accelerating the reaction, amines, organotin compounds and the like are used. It can also be produced by kneading a polyester polyol and an organic diisocyanate in a molten state.

The polyurethane resin used in the present invention has an average of 1.5 polymerizable double bonds per urethane chain in order to increase the efficiency of the grafting reaction with the radical polymerizable monomer.
-30, preferably 2-20, and more preferably 3-10. There are the following three methods for introducing this polymerizable double bond, and these methods can be used alone or in combination. 1) An unsaturated dicarboxylic acid such as fumaric acid, itaconic acid and norbornene dicarboxylic acid is contained in the polyester polyol. 2) An allyl ether group-containing glycol is contained in the polyester polyol. 3) Allyl ether group-containing glycol is used as a chain extender. 4) In solid phase polymerization, a mixture of a saturated copolymerized polyester polyol and an unsaturated copolymerized polyester polyol is reacted with an organic diisocyanate compound.

(Radical polymerizable monomer) The radical polymerizable monomer used in the present invention may be a functional group selected from the following group a) or a functional group selected from the following group a). It is essential to include a convertible functional group. Group a): ammonium salt, nitrogen-containing aromatic salt, sulfonate, phosphate Among these, ammonium salt and nitrogen-containing aromatic salt are preferable. Further, as the radical monomer, a radical polymerizable monomer having a quaternary ammonium group and / or a pyridinium group and / or
Radical polymerizable monomers having a functional group that can be converted to a quaternary ammonium group and / or a pyridinium group are particularly preferred, and various kinds of radical polymerizable monomers can be copolymerized with them.

As the radical polymerizable monomer having a quaternary ammonium group, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride,
(Meth) acryloyloxyethyltrimethylammonium sulfate, (meth) acryloyloxyethyltrimethylammonium phosphate, (meth) acryloyloxyethyltriethylammonium phosphate and the like can be mentioned.

Further, as a radical polymerizable monomer having a reactive functional group which can be converted into a quaternary ammonium group and / or a pyridinium group after the graft polymerization, primary,
Radical polymerizable monomers having secondary and tertiary amino groups, alkylating agents having an unsaturated bond, and the like. Examples of the former include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylamino. Ethyl (meth) acrylate,
N, N-dimethylaminoethyl (meth) acrylamide,
Nitrogen atom-containing monomers such as N, N-diethylaminoethyl (meth) acrylamide and the like.
Alkylation to a quaternary salt. Examples of the latter include chloromethylstyrene and the like, and are quaternized with a tertiary amine compound or a pyridine compound.

Examples of the radical polymerizable monomer containing a phosphate include acid phosphooxyethyl acrylate, acid phosphooxyethyl methacrylate, 3-chloro-
Alkyl metal salts such as 2-acid phosphooxypropyl methacrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate,
Amine salts.

Examples of the radical polymerizable monomer containing a sulfonate include alkyl metal salts such as sodium styrenesulfonate and 2-acrylamido-2-methylpropanesulfonic acid, and amine salts. In the present invention,
One or more of the above radical polymerizable monomers can be selected and used. The radical polymerizable monomer having a quaternary ammonium group is generally only soluble in water, and when performing grafting on a hydrophobic resin in a homogeneous system, it becomes difficult to select a reaction solvent. After that, it is preferable to convert to a quaternary ammonium group. However, even when a radical polymerizable monomer having a quaternary ammonium group is used, graft polymerization can be performed by selecting a solvent and an emulsifier.
When a radical polymerizable monomer having a primary, secondary, or tertiary amino group is used, the amino group can be converted to a quaternary ammonium group by various alkylating agents after the graft polymerization. When an alkylating agent having an unsaturated bond such as chloromethylstyrene is used, ammonia, diethylamine, dibutylamine, trimethylamine, triethylamine, triethanolamine, tributylamine,
Triethylenediamine, N-methylmorpholine, etc., primary,
The reaction of secondary and tertiary amines can introduce a quaternary ammonium group, but tertiary amines such as triethylamine, triethylenediamine and N-methylmorpholine are preferred. When a pyridine derivative such as pyridine, 2-methylpyridine or the like is reacted, the corresponding pyridinium base can be obtained.

The monomers copolymerizable with the above-mentioned radical polymerizable monomers include, for example, esters of acrylic acid and methacrylic acid such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate,
2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, Further well-known monomers such as 2-hydroxyethyl methacrylate and hydroxylpropyl methacrylate include acrylonitrile, methacrylonitrile, acrylamide, N-methylolacrylamide, diacetone acrylamide, vinyl acetate, vinyl ethers, N -
Vinylpyrrolidone, styrene, α-methylstyrene, t
-Butylstyrene, vinyltoluene and the like can be exemplified, and one or more of these can be selected and used.

In the practice of the present invention, it is usual to use a radical polymerizable monomer containing no carboxyl group in addition to these carboxyl group-containing radical polymerizable monomers. As the radical polymerizable monomer containing no carboxyl group, a wide range of radical polymerizable monomers can be exemplified. That is, esters of acrylic acid and methacrylic acid include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate , Ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, hydroxylpropyl methacrylate and the like, further vinyl acetate, vinyl ethers, Examples thereof include N-vinylpyrrolidone, styrene, α-methylstyrene, t-butylstyrene, vinyltoluene, and the like, and one or more of these can be selected and used. This makes it possible to adjust the Tg of the side chain and the compatibility with the main chain, and to introduce an arbitrary functional group. In particular, radically polymerizable monomers having an OH group, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and hydroxylpropyl methacrylate, are effectively used for controlling OHV of a resin. be able to.

The amount of the quaternary ammonium group and / or pyridinium group to be introduced is preferably 500 to 4,000 equivalents / 10 ⁶ g, more preferably 700 to 3,
000 equivalents / 10 ⁶ g. When quaternary ammonium groups and / or pyridinium groups amount is less than 500 equivalent / 10 ⁶ g, antistatic is not sufficient in the case of more than 4,000 equivalent / 10 ⁶ g, adhesion to various substrates, mechanical properties, Compatibility with other resins decreases.

Further, OHV to be introduced into the polymer, preferably from 50 and 3,000 equivalents / 10 ⁶ g, more preferably 500 to 2,000 equivalents / 10 ⁶ g. OHV is 50 equivalent / 10 ⁶
If it is less than g, water resistance, solvent resistance and heat resistance are not sufficient, and if it is more than 3000 equivalents / 10 ⁶ g, transparency is reduced.

(Graft Reaction) The graft polymer can be efficiently obtained by graft-polymerizing a radical polymerizable monomer to the polymerizable unsaturated double bond in the base resin. In the present invention, the reaction is generally carried out by reacting a radical initiator and a radical polymerizable monomer mixture in a state where the base resin is dissolved in an organic solvent. After the completion of the grafting reaction, the reaction product contains not only a graft polymer between the desired polyester-radical polymerizable monomer mixture but also a polyester that has not been grafted and a radical polymer that has not been grafted with the polyester. It is considered that, when the ratio of the graft polymer in the reaction product is low and the ratio of the non-grafted polyester and the non-graft radical polymer is high, the effect due to the modification is low, as well as the non-grafted homopolymer. In addition, adverse effects such as whitening of the coating film are observed. Therefore, it is important to select reaction conditions with a high graft polymer formation ratio.

In carrying out the grafting reaction of the radical polymerizable monomer to the polyester resin, a radical polymerizable monomer mixture and a radical initiator are added at once to the polyester resin dissolved in the solvent while heating. May be carried out, or after separately dropping over a certain period of time,
Further, the reaction may be allowed to proceed by continuing heating while stirring for a certain period of time. In addition, Qe of the polymerizable double bond of the base resin
The radical polymerizable monomer having a small difference from the e-value among the values is added at once, and then the polymerization having a large difference from the e-value among the Qe values of the polymerizable double bond of the base resin. It is one of the desirable modes of the present invention that the reactive monomer and initiator are added dropwise over a certain period of time, and then the reaction is allowed to proceed by continuing the heating with stirring for a further fixed period of time. Prior to the reaction,
A polyester resin and a solvent are charged into a reactor, and the temperature is increased with stirring to dissolve the resin. The weight ratio between the polyester resin and the solvent is preferably in the range of 70/30 to 30/70. The grafting reaction temperature is from 50 ° C to 120 ° C.
It is desirable to carry out in the range of ° C.

The weight ratio of the desired polyester resin and the radical polymerizable monomer suitable for the purpose of the present invention is 40/60 to 95 in terms of polyester / radical polymerizable monomer.
/ 5, more preferably 55 / 45-93 /
7, most preferably in the range of 60/40 to 90/10. When the weight ratio of the polyester is 40% by weight or less, the above-described excellent properties of the parent polyester, that is, high workability, excellent water resistance, and excellent adhesion to various substrates cannot be sufficiently exhibited. Conversely, the undesirable properties of the acrylic resin, that is, low workability, gloss, water resistance, etc. are added. When the weight ratio of the polyester is 95% by weight or more, the proportion of the non-grafted base resin in the graft product becomes almost undesirably low, because the effect of modification is low.

(Radical Initiator and Others) As the radical polymerization initiator used in the present invention, well-known organic peroxides and organic azo compounds can be used. That is, benzoyl peroxide, t-butyl peroxypivalate as an organic peroxide, and 2.2′- as an organic azo compound.
Azobisisobutyronitrile, 2.2′-azobis (2.4-dimethylvaleronitrile) and the like can be exemplified. The amount of the radical initiator used for performing the grafting reaction must be at least 0.2% by weight or more based on the radical polymerizable monomer, and is preferably 0.5% by weight or more.
It is necessary to use more than weight%.

Addition of a chain transfer agent, for example, thiols such as octyl mercaptan and mercaptoethanol, and α-methylstyrene dimer are also used as necessary for controlling the graft chain length. In that case, it is desirable to add in the range of 0 to 5% by weight based on the radical polymerizable monomer.

(Reaction Solvent) The grafting reaction solvent for carrying out the present invention is preferably composed of an aqueous organic solvent having a boiling point of 50 to 250 ° C. Here, the aqueous organic solvent has a solubility in water at 20 ° C. of at least 10 g /
L or more, desirably 20 g / L or more.
Those having a boiling point exceeding 250 ° C. are unsuitable because the evaporation rate is too slow to remove sufficiently even by baking the coating film at a high temperature. When the boiling point is 50 ° C. or less,
When the grafting reaction is carried out using it as a solvent, 50
The use of an initiator that decomposes into radicals at a temperature of not more than ° C. increases the danger in handling, which is not preferred.

When the purpose of dispersing the resulting graft product in water is a polymerizable monomer containing a radical polymerizable monomer, the reaction solvent that can be used for the graft reaction is one that dissolves or disperses the base resin well. Esters such as ethyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclic ethers such as tetrahydrofuran, dioxane, 1,3-dioxolan, and glycos are preferable solvents which relatively dissolve the monomer mixture and the polymer thereof relatively well. -Ethers such as ethylene glycol dimethyl ether, propylene glycol methyl ether, propylene glycol propyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, carbitols such as methyl carbitol, Ethyl carbitol, butyl carbitol, glycols or lower esters of glycol ethers such as ethylene glycol diacetate,
Ethylene glycol ethyl ether acetate, ketone alcohols such as diacetone alcohol, and N
-Substituted amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

When the grafting reaction is carried out with a single solvent, one kind can be selected from organic solvents which dissolve the base resin well. When the reaction is carried out in a mixed solvent, a plurality of types of organic solvents may be selected from the above-mentioned organic solvents and the reaction may be performed. The reaction may be carried out by adding at least one of organic solvents, and the reaction can be carried out in any solvent.

(Water dispersion) The grafting reaction product according to the present invention can be easily dispersed in water into fine particles having an average particle diameter of 500 nm or less. When performing water dispersion, the solvent contained in the grafting reaction product is removed in advance by an extruder under reduced pressure, etc.
Alternatively, a solid (pellet, powder, etc.) grafting reaction product can be poured into water and stirred under heating to form an aqueous dispersion, but most preferably immediately after the completion of the grafting reaction. A method (one-pot method) in which water is added and heating and stirring are continued to obtain an aqueous dispersion is desirable. Further, when the boiling point of the solvent is 100 ° C. or lower, a part or all of the solvent used in the grafting reaction can be easily removed by distillation. The solid content concentration of the aqueous dispersion produced according to the present invention is 20 to 60% by weight, and water can be added and diluted as needed to use.

(Curing agent) Examples of the crosslinking agent for the polymer containing an OH group described above include phenol formaldehyde resin, amino resin, polyfunctional epoxy compound, polyfunctional isocyanate compound and various blocked isocyanate compounds, polyfunctional aziridine. Various curing agents such as compounds can be used. In particular, a melamine-based curing agent can be used as a curing agent capable of obtaining a coating film excellent in antistatic performance, water / solvent resistance transparency, adhesion, and heat resistance by heating at a low temperature for a short time. In particular, a nonionic or cationic melamine-based curing agent is preferable. Since the polymer containing an OH group has a cationic functional group, the system may aggregate when an anionic curing agent is added. As nonionic melamine-based curing agents, "UMAINP" manufactured by Mitsui Chemicals, Inc.
-6300 "can be used.

The curing reaction is generally carried out according to the aqueous dispersion 1 of the present invention.
5-70 parts (solid content) of the curing resin is blended with 00 parts (solid content), and heating is performed for about 1 to 60 minutes in a temperature range of 60 to 250 ° C. depending on the type of the curing agent. If necessary, a reaction catalyst or a promoter is also used.

[(Lamination Method) With respect to the method of laminating a coating composition comprising a polymer containing an OH group and a melamine-based curing agent on a thermoplastic resin film in the present invention,
The film can be laminated on the film after the production or during the production process by the following method. 1. 1. In the present invention, a coating composition comprising a polymer containing an OH group and a melamine-based curing agent is formed into a film in advance, and is bonded to a thermoplastic resin film (lamination method). In the present invention, a coating composition comprising a polymer containing an OH group and a melamine-based curing agent is melt-extruded onto a thermoplastic resin film (extrusion coating method). 3. In the present invention, a coating composition comprising a polymer containing an OH group and a melamine-based curing agent is dissolved or dispersed in various solvents, and then applied onto a thermoplastic resin film (coating method).

Among these methods, 3. And then drying. Roll coating methods such as gravure and reverse, doctor knife method, air knife,
Nozzle coating methods can be used, and these methods can be used alone or in combination. In this case, the solid content of the applied resin solution is preferably 40% or less. In addition, the coating amount is 1 m ² of film,
0.5 to 20 g is preferred.

The thickness of the resin layer laminated by such a method differs depending on the thermoplastic resin film to be laminated and the desired antistatic property.
It is preferably from 0.05 to 50 μm. 0.05μ
If it is less than m, a sufficient effect cannot be obtained. Before the lamination, the surface of the thermoplastic resin film to be laminated may be subjected to a surface activation treatment such as a corona treatment or an anchor treatment using an anchor treatment agent, and may also have an electrostatic property after the lamination. The above treatment may be performed on the surface of the thermoplastic resin film to such an extent that the antistatic property is not impaired.

Since the thus obtained film is effectively prevented from being charged, it can be taken out one sheet at a time when stacked as a sheet. It is suitably used as a sheet. Further, since it has excellent heat resistance, a clear image can be obtained without being deteriorated by heat at the time of image fixing. Further, since the sheet is excellent in heat resistance and solvent resistance, even if characters or the like are written on the sheet with an oil-based or water-based pen, or the sheet is wiped off with water or alcohol for correction, the sheet is hardly stained.

[0056]

Hereinafter, the present invention will be described with reference to examples.
The present invention is not limited by these. In the examples, “parts” means “parts by weight”, and “%” means “% by weight”. Each measurement item followed the following method.

(1) Weight average molecular weight 0.03 g of resin was dissolved in 10 cc of tetrahydrofuran,
-LALLS apparatus Measured with a low angle light scattering photometer LS-8000 (manufactured by Tosoh Corporation, tetrahydrofuran solvent, reference: polystyrene).

(2) Particle Size of Aqueous Dispersion Aqueous dispersion is prepared by using ion-exchanged water to have a solid content of 0.1% by weight
Adjust the laser light scattering particle size distribution meter Coulter model N
4 (Coulter) at 20 ° C.

(3) Aqueous dispersion B type viscosity The viscosity of the aqueous dispersion was measured at 25 ° C. using a rotational viscometer (manufactured by Tokyo Keiki, EM type).

(4) Surface resistivity Various varnishes were coated on PET film (E510, manufactured by Toyobo Co., Ltd.).
0) Coat the dried film on top so that the film thickness becomes 3 μm, dry at 120 ° C. for 5 minutes, and apply an applied voltage of 500 V and 24 ° C. using a surface resistivity meter (manufactured by Mitsubishi Yuka). , 60% RH.

(5) Water resistance Various varnishes were made of PET film (E510, manufactured by Toyobo Co., Ltd.).
0) The coating was dried so as to have a thickness of 3 μm, dried at 120 ° C. for 5 minutes, and rubbed 50 times with a gauze impregnated with water to examine the change. ；: No change in appearance, Δ: slight peeling / scratch of coating, ×: peeling / scratch of coating

(6) Solvent resistance Various varnishes were coated with PET film (E510, manufactured by Toyobo Co., Ltd.).
0) The coating was dried so as to have a thickness of 3 μm, dried at 120 ° C. for 5 minutes, and rubbed 50 times with a gauze impregnated with acetone to examine the change. ；: No change in appearance, Δ: slight peeling / scratch of coating, ×: peeling / scratch of coating

(7) Heat resistance Various varnishes were made of PET film (E510, manufactured by Toyobo Co., Ltd.).
0) Coat the dried film on top so that the film thickness becomes 3 μm, dry at 120 ° C. for 5 minutes, leave the coated surface on a hot plate at 190 ° C. for 1 minute, and observe the change of the film surface. Examined. ；: No change in appearance, Δ: slight peeling / scratch of coating, ×: peeling / scratch of coating

(8) Transparency Various varnishes were made of PET film (E510, manufactured by Toyobo Co., Ltd.).
0) The coating was dried so as to have a thickness of 3 μm after drying, dried at 120 ° C. for 5 minutes, and visually evaluated. ○: transparent, △: slight turbidity, ×: turbid

(9) Adhesiveness Various varnishes were coated with PET film (E510, manufactured by Toyobo Co., Ltd.).
0) The coating was dried so as to have a thickness of 3 μm, dried at 120 ° C. for 5 minutes, and the adhesion was evaluated by peeling off a cellophane tape. ；: No change in appearance, △: slight peeling, ×: peeling

Production Example of Polyester Resin A-1 In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 485 parts of dimethyl terephthalate, 475 parts of dimethyl isophthalate, 401 parts of neopentyl glycol, 443 parts of ethylene glycol Parts, and 0.52 parts of tetra-n-butyl titanate.
The transesterification reaction was performed from 0 ° C to 220 ° C for 4 hours. Next, 23 parts of fumaric acid was added, and the temperature was raised from 200 ° C to 220 ° C over 1 hour to carry out an esterification reaction. Next, the temperature was raised to 255 ° C, and the pressure of the reaction system was gradually reduced.
Polyester (A-1) was reacted at a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes. The obtained polyester (A-1) was pale yellow and transparent, and had a weight average molecular weight of 12,000. The composition measured by NMR and the like was as follows.

Dicarboxylic acid component Terephthalic acid 50 mol% Isophthalic acid 49 mol% Fumaric acid 1 mol% Diol component Neopentyl glycol 50 mol% Ethylene glycol 50 mol%

Production Example of Polyester Urethane Resin A-2 In a stainless steel autoclave equipped with a stirrer, thermometer and partial reflux condenser, 594 parts of dimethyl terephthalate, 1985 parts of dimethyl isophthalate, 412 parts of neopentyl glycol, 412 parts of ethylene glycol 573 parts and 0.52 parts of tetra-n-butyl titanate were charged, and 1
The transesterification was carried out from 60 ° C to 220 ° C for 4 hours. Next, 351 parts of sebacic acid, 21 parts of fumaric acid and 0.1 part of t-butylcatechol were added, and the temperature was raised from 200 ° C to 220 ° C over 2 hours to carry out an esterification reaction. Then 255
C., and the reaction system was gradually depressurized, and then reacted for 1 hour under a reduced pressure of 0.2 mmHg to obtain a polyester. The obtained polyester was pale yellow and transparent. The composition measured by NMR and the like was as follows.

Dicarboxylic acid component Terephthalic acid 51 mol% Isophthalic acid 17 mol% Sebacic acid 29 mol% Fumaric acid 3 mol% Diol component neopentyl glycol 45 mol% ethylene glycol 55 mol%

100 parts of this polyester polyol was dissolved together with 100 parts of methyl ethyl ketone in a reactor equipped with a stirrer, a thermometer and a partial reflux condenser, and then 3 parts of neopentyl glycol and diphenylmethane diisocyanate were dissolved.
15 parts, 0.02 parts of dibutyltin laurate, 60-70 ° C
For 6 hours. Then, 1 part of dibutylamine was added, the reaction system was cooled to room temperature to stop the reaction, and methyl ethyl ketone was added to dilute to a solid concentration of 50% by weight. The molecular weight of the obtained polyurethane resin was 20,000.

Example 1 A reactor equipped with a stirrer, a thermometer, a reflux device and a metered-drip device was charged with 300 parts of a polyester resin A-1 and tetrahydrofuran.
300 parts and 75 parts of dibutyl fumarate were added and heated and stirred at 65 ° C. to dissolve the resin. After the resin is completely dissolved, 225 parts of chloromethylstyrene, 75 parts of styrene, a mixture of 75 parts of 2-hydroxyethyl methacrylate, and a solution of 27 parts of azobisisobutyronitrile dissolved in 450 parts of tetrahydrofuran at 10 ml / min. Then, the mixture was added dropwise to the polyester solution, and stirring was further continued for 2 hours to obtain a graft. A mixture of 450 parts of ethanol and 297 parts of triethylamine was added to this solution of the graft, and chloromethylstyrene in the side chain of the graft and triethylamine were reacted under reflux for 2 hours.
A quaternary ammonium salt was introduced. Furthermore, ion-exchanged water 15
After adding 00 parts, the solvent remaining in the medium was distilled off by heating to obtain an aqueous dispersion. The resulting aqueous dispersion was milky white, had an average particle size of 100 nm, and had a B-type viscosity of 5 poise at 25 ° C. The melamine-based curing agent URAMINN P-630 is added to this aqueous dispersion.
0 (manufactured by Mitsui Chemicals, Inc.) was added in an amount of 510 parts to obtain a final coating liquid C-1.

Example 2 A reactor equipped with a stirrer, a thermometer, a refluxing device and a metering dropping device was charged with 300 parts of a polyester resin A-1 and tetrahydrofuran.
300 parts and 75 parts of dibutyl fumarate were added and heated and stirred at 65 ° C. to dissolve the resin. After the resin was completely dissolved, a mixture of 170 parts of chloromethylstyrene, 105 parts of styrene, and 100 parts of 2-hydroxyethyl methacrylate, and a solution of 27 parts of azobisisobutyronitrile dissolved in 450 parts of tetrahydrofuran were added at 10 ml / min. Then, the mixture was added dropwise to the polyester solution, and stirring was further continued for 2 hours to obtain a graft. A mixture of 450 parts of ethanol and 203 parts of 2-methylpyridine was added to this graft solution, and chloromethylstyrene and 2-methylpyridine in the side chain of the graft were reacted under reflux for 5 hours to form a quaternary pyridinium salt. Introduced. The resulting varnish was brown and transparent, and had a B-type viscosity of 25 poise at 25 ° C. The melamine-based curing agent URAMINN P-630 is added to this aqueous dispersion.
0 (manufactured by Mitsui Chemicals, Inc.) was added in an amount of 510 parts to obtain a final coating liquid C-2.

Example 3 A coating liquid C-3 was prepared in the same manner as in Example 1 except that the polyurethane resin A-2 was used.

Example 4 In a reactor equipped with a stirrer, a thermometer, a reflux device and a metered addition device, 100 parts of the polyester resin A-1 and tetrahydrofuran were added.
100 parts, 100 parts of dibutyl fumarate, heated at 65 ° C,
Stir to dissolve the resin. After the resin is completely dissolved, a mixture of 700 parts of chloromethylstyrene, 100 parts of 2-hydroxyethyl methacrylate, and a solution of 54 parts of azobisisobutyronitrile dissolved in 900 parts of tetrahydrofuran are mixed in 20 ml.
The solution was dropped into the polyester solution at a rate of / min., and stirring was continued for 2 hours to obtain a graft. A mixture of 900 parts of ethanol and 924 parts of triethylamine was added to this graft solution, and chloromethylstyrene and triethylamine in the side chain of the graft were reacted under reflux for 2 hours to introduce a quaternary ammonium salt. Further, 2,000 parts of ion-exchanged water was added, and the solvent remaining in the medium was distilled off by heating to obtain an aqueous dispersion. The resulting aqueous dispersion is milky white and has an average particle size of 30n
m, the B-type viscosity at 25 ° C. was 25 poise. To this aqueous dispersion, 950 parts of a melamine-based curing agent URAMINN P-6300 (manufactured by Mitsui Chemicals) was added to obtain a final coating liquid C-4.

Example 5 In a reactor equipped with a stirrer, a thermometer, a reflux device and a metered addition device, 300 parts of the polyester resin A-1 and tetrahydrofuran were added.
300 parts and 75 parts of dibutyl fumarate were added and heated and stirred at 65 ° C. to dissolve the resin. After the resin was completely dissolved, a mixture of 225 parts of chloromethylstyrene and 150 parts of styrene, and a solution of 27 parts of azobisisobutyronitrile dissolved in 450 parts of tetrahydrofuran were dropped into the polyester solution at 10 ml / min, Stirring was further continued for 2 hours to obtain a graft. A mixture of 450 parts of ethanol and 297 parts of triethylamine was added to the graft solution, and chloromethylstyrene and triethylamine in the side chain of the graft were reacted under reflux for 2 hours to introduce a quaternary ammonium salt. Further, 1500 parts of ion-exchanged water was added, and the solvent remaining in the medium was distilled off by heating to obtain an aqueous dispersion. The resulting aqueous dispersion is milky white and has an average particle size of 100 nm and a B-type viscosity at 25 ° C of 5 p.
oise. The melamine-based curing agent UR is added to this aqueous dispersion.
510 parts of AMINN P-6300 (manufactured by Mitsui Chemicals) was added to obtain a final coating liquid C-5.

Example 6 An aqueous dispersion was produced in the same manner as in Example 1. To the obtained aqueous dispersion, 950 parts of an epoxy curing agent URAMIN P-5400 (manufactured by Mitsui Chemicals) was added to obtain a final coating liquid C-6.

Example 7 An aqueous dispersion was produced in the same manner as in Example 1. Add 400 parts of Elastron BN5 (Daiichi Kogyo Pharmaceutical Co., Ltd.) to the obtained aqueous dispersion, and apply the final coating liquid.
C-7.

Comparative Example 1 300 parts of tetrahydrofuran and 75 parts of dibutyl fumarate were placed in a reactor equipped with a stirrer, a thermometer, a reflux device, and a metering device.
The mixture was heated and stirred at 65 ° C. After complete dissolution, a mixture of 225 parts of chloromethylstyrene, 75 parts of styrene, and 75 parts of 2-hydroxyethyl methacrylate, and a solution of 27 parts of azobisisobutyronitrile dissolved in 450 parts of tetrahydrofuran were dissolved at 10 ml / min. The mixture was added dropwise, and stirring was further continued for 2 hours to obtain a polymer. A mixture of 450 parts of tetrahydrofuran and 297 parts of triethylamine was added to the polymer solution, and chloromethylstyrene and triethylamine in the polymer were reacted under reflux for 2 hours to introduce a quaternary ammonium salt. Further, 300 parts of a polyester resin A-1 was added, and 510 parts of a melamine-based curing agent URAMINN P-6300 (manufactured by Mitsui Chemicals) was added, followed by cooling to obtain a final coating liquid D-1.

Comparative Example 2 200 parts of tetrahydrofuran, 75 parts of dibutyl fumarate and 75 parts of a reactor were equipped with a stirrer, a thermometer, a reflux device, and a metered addition device.
The mixture was heated and stirred at 65 ° C. After complete dissolution, a mixture of 225 parts of chloromethylstyrene, 75 parts of styrene, and 75 parts of 2-hydroxyethyl methacrylate, and a solution of 27 parts of azobisisobutyronitrile dissolved in 450 parts of tetrahydrofuran were dissolved at 10 ml / min. The mixture was added dropwise, and stirring was further continued for 2 hours to obtain a polymer. Add ethanol 4 to this polymer solution.
A mixture of 50 parts and 297 parts of triethylamine was added, and chloromethylstyrene in the side chain of the polymer and triethylamine were reacted under reflux for 2 hours to introduce a quaternary ammonium salt. 510 parts of a melamine-based curing agent URAMINN P-6300 (manufactured by Mitsui Chemicals) was added, and the mixture was cooled to obtain a final coating liquid D-2.

[0080]

[Table 1]

As shown in Table 1, the following can be understood. 1. The coating film obtained by the coating liquid in the present invention is E9Ω
/ □ (10 ⁹ Ω / □), indicating that it has antistatic ability. This is due to the introduction of an appropriate concentration of a quaternary salt into the polymer containing OH groups. 2. The coating film obtained by the coating liquid in the present invention has high water resistance. This is due to the fact that the polymer containing OH groups is sufficiently crosslinked by the curing agent. 3. The coating film obtained by using the coating liquid in the present invention has high solvent resistance. This is due to the fact that the polymer containing OH groups is sufficiently crosslinked by the curing agent. 4. The coating film obtained by using the coating liquid in the present invention has high heat resistance. This is due to the fact that the polymer containing OH groups is sufficiently crosslinked by the curing agent. 5. The coating film obtained by the coating liquid in the present invention shows high transparency. This is due to the fact that the hydrophilic site is chemically bonded (grafted) to the high molecular weight polyester or polyester polyurethane in the structure of the polymer containing the OH group. 6. The coating film obtained by the coating liquid in the present invention shows high adhesion. This is due to the high molecular weight polyester or polyester polyurethane in the structure of the polymer containing OH groups.

[0082]

The use of the coating liquid of the present invention means that after coating on various substrates, it is dried at a low temperature for a short time, and has antistatic performance.
A coating film having excellent water resistance, solvent resistance, heat resistance, transparency and adhesion can be obtained.

Continued on the front page (72) Inventor Shinya Higashiura 2-1-1 Katata, Otsu-shi, Shiga Prefecture Inside Toyobo Co., Ltd. Research Institute (72) Inventor Toshiyuki Shimizu 2-1-1 Katata, Otsu-shi, Shiga Toyobo Co., Ltd. (72) Inventor Katsuhiro Nakayamada 2-1-1 Katata, Otsu-shi, Shiga Prefecture Toyobo Co., Ltd.

Claims (6)

[Claims] 1. A coating composition comprising a polymer having the following components and a curing agent: A) a polyester portion; B) a radical polymer portion; C) an OH group; One or more functional groups having antistatic ability a) group: ammonium salt, nitrogen-containing aromatic salt, sulfonate, phosphate 2. A coating composition, wherein the polymer according to claim 1 contains at least one functional group of the following group a) in a radical polymer portion. a) group: ammonium salt, nitrogen-containing aromatic salt, sulfonate, phosphate 3. The coating composition according to claim 1, wherein the polyester part of the polymer according to claim 1 or 2 is at least one of a copolymerized polyester and a polyurethane resin of a copolymerized polyester polyol. 4. A resin composition for coating, wherein the polymer according to claim 1, 2, or 3 is obtained by grafting a radical polymer portion to a polyester portion. 5. A laminate comprising the coating composition according to claim 1, provided on a substrate. 6. A sheet for receiving an electrostatic image, comprising the coating composition according to claim 1, provided on a substrate.