JP2003113220A - Curable resin composition and article treated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition comprising a new curing system capable of having both hydrophilicity and water resistance, and to pro vide an article treated with the curing resin composition. SOLUTION: This curable resin composition contains an N-vinylamide unit- having polymer and a compound having two or more active hydrogen-reacting functional groups as essential components. The curable resin composition contains a polyether unit-having polymer and a compound having two or more active hydrogen-reacting functional groups as essential components. The article treated with the above-described curable resin composition is also provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition and an article treated therewith. In particular, the present invention relates to a curable resin composition capable of achieving both hydrophilicity and water resistance by crosslinking a hydrophilic polymer and an article treated with the curable resin composition.

[0002]

2. Description of the Related Art There is a demand for making the surfaces of various substrates hydrophilic for the purpose of preventing the adhesion of water droplets and the resulting cloudiness, and improving the affinity with water-based inks. It was Conventionally, in response to these requirements, it has been practiced to apply a water-soluble polymer or a surfactant, but since these are eluted into water, the sustainability of the effect is very unsatisfactory. It was a thing.

It is considered that a water-soluble polymer is subjected to a crosslinking treatment with a crosslinking agent or the like in order to impart water resistance.
Hydrophilicity and water resistance are contradictory properties, and generally, when a water-soluble polymer is crosslinked, there is a tendency that the water resistance which is originally present is lost although the water resistance is exhibited. The term "crosslinking agent" as used herein refers to a compound having two or more functional groups in one molecule, and hereinafter the term "crosslinking agent" is used in that sense.

Regarding cross-linking of a polymer exhibiting hydrophilicity, JP-A-6-322292 discloses a polymer (a) having a carboxylic acid group and a polymer complex by hydrogen bonding with the polymer (a). Polymer that can be formed (b)
And a polymer for hydrophilic treatment containing a combination of at least two polymers selected from the group consisting of a polymer having a carboxylic acid group and having the ability to form a polymer complex by hydrogen bond alone. Regarding the technology relating to the composition, an example using a water-soluble melamine resin as an aqueous crosslinking agent is disclosed. In addition, JP-A-9-8
Japanese Patent No. 7576 discloses a technique relating to a hydrophilic treatment composition containing a compound having a specific polyoxyalkylene chain and fine particles of a hydrophilic crosslinked polymer crosslinked by a specific functional group.

In these techniques, it is intended to incorporate polyvinylpyrrolidone and polyoxyalkylene in an IPN-like manner into a crosslinked rope structure.
It is not intended to directly crosslink P or PEO.

Japanese Patent Application Laid-Open No. 8-291269 discloses that
(A) a copolymer of vinylpyrrolidone and acrylic acid,
(B) Polyethylene glycol diglycidyl ether is contained so that the compounding ratio of (a) to (b) is (a) / (b) = 20/80 to 70/30 in terms of solid content conversion weight ratio, (C) A hydrophilic treatment composition containing a specific weight ratio of amines is disclosed. However, in this hydrophilic treatment composition, in the copolymer of (a),
Since the pyrrolidone ring derived from vinylpyrrolidone and the carboxyl group derived from acrylic acid are hydrogen-bonded to form a polymer complex, there is a problem in solubility in water and a solvent. Ammonia and amines have to be added in order to increase the solubility in water, and the odor was not practically preferable.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a curable resin composition having a novel cross-linking system that can achieve both hydrophilicity and water resistance.

[0008]

[Means for Solving the Problems] While the inventors of the present invention are investigating to obtain a coating film having both hydrophilicity and water resistance, N-vinyl amide type polymers such as N-vinyl pyrrolidone are crosslinked to react with active hydrogen. It was found that an agent, that is, a compound having two or more functional groups that react with active hydrogen, can be crosslinked, and the cured coating film thus obtained is a coating film having both excellent hydrophilicity and water resistance. I found it.

Conventionally, N-vinylamide units such as N-vinylpyrrolidone units in polymers have no active hydrogen,
It has been believed that it is not crosslinked by crosslinkers that react with active hydrogen. However, it has been found that the N-vinylamide polymer can be crosslinked by a crosslinking agent that reacts with active hydrogen by applying sufficient heat. This is a novel reaction found out that a homopolymer of N-vinylamide polymer having no reactive functional group is cured and insolubilized by heat treatment with a crosslinking agent that reacts with active hydrogen. It is speculated that the hydrogen at the α-position of the N-vinylamide unit probably contributes to the reaction.

Furthermore, it is known that vinylamide polymers such as polyvinylpyrrolidone self-crosslink with organic peroxides and the like, but a coating film made of such a self-crosslinking product has a reduced surface hydrophilicity. While the contact angle to water becomes large and the antifogging property is not exhibited, the coating film of the vinylamide polymer crosslinked with a crosslinking agent as in the present invention retains good hydrophilicity even after crosslinking, It has been found that a coating film having both good properties and water resistance can be obtained.

The vinylamide polymer in the present invention may be a copolymer, and can be copolymerized with a monomer having a reactive functional group in order to complement the reaction between the vinylamide unit and the crosslinking agent. In that case, when a monomer having a carboxyl group as a reactive functional group is copolymerized,
The copolymer becomes insoluble in water due to the hydrogen bond between the vinylamide group and the carboxyl group, and it is necessary to use an unfavorable additive such as an amine in order to obtain water solubility. Monomers with carboxyl groups must be excluded.

Similarly, for a polymer having a polyoxyalkylene chain or a polyether unit, a coating film having both hydrophilicity and water resistance can be obtained by crosslinking with a crosslinking agent having a functional group that reacts with active hydrogen. Was found.

That is, the present invention is a curable resin composition containing as an essential component a polymer having an N-vinylamide unit and a crosslinking agent having a functional group that reacts with active hydrogen. The present invention is also a curable resin composition containing as an essential component a polymer having a polyether unit and a crosslinking agent having a functional group that reacts with active hydrogen. The present invention is also an article treated with the curable resin composition. The present invention is described in detail below.

The curable resin composition of the present invention comprises a polymer having an N-vinylamide unit and a cross-linking agent having a functional group capable of reacting with active hydrogen as essential components, and a polymer having a polyether unit. And a cross-linking agent having a functional group that reacts with active hydrogen as an essential component. However, a polymer having an N-vinylamide unit and a polymer having a polyether unit may be used in combination. ,
A polymer having an N-vinylamide unit and / or a polymer having a polyether unit and a crosslinking agent having a functional group that reacts with active hydrogen are contained as essential components.
In such a curable resin composition, a curable coating film is formed by crosslinking the curable component containing the above essential components. The cross-linking of the curable component means that the polymers in the curable component are cross-linked by the cross-linking agent, that is, the polymer and the cross-linking agent form some chemical bond or the like to form a so-called network structure. The curable component means a component composed of a polymer capable of reacting with a crosslinking agent in the curable resin composition and a crosslinking agent. In the present invention, the curable component essentially comprises a polymer having an N-vinylamide unit and / or a polymer having a polyether unit, and a crosslinking agent having a functional group that reacts with active hydrogen.

In the present invention, the N-amide unit in the polymer having the N-vinylamide unit is crosslinked by the crosslinking agent, and the polyether unit in the polymer having the polyether unit is crosslinked by the crosslinking agent. Therefore, it is not necessary to introduce a functional group capable of reacting with a cross-linking agent into a polymer having an N-vinylamide unit or a polymer having a polyether unit, but a functional group such as a hydroxyl group capable of reacting with a cross-linking agent is an N-vinylamide unit. Even if it is introduced into a polymer having a unit or a polymer having a polyether unit, the effect of the present invention is not impaired. That is, the polymer having an N-vinylamide unit or the polymer having a polyether unit used in the present invention does not need to have a functional group such as a hydroxyl group capable of reacting with a crosslinking agent, but has such a functional group. It doesn't matter.

In the curable resin composition of the present invention, the organic component other than the above essential components is 0 to 65 parts by weight based on 100 parts by weight of the polymer having the N-vinylamide unit and / or polyether unit. Preferably there is. That is, an organic component other than a polymer having an N-vinylamide unit and / or a polyether unit, which are essential components of the curable resin composition, and a cross-linking agent having a functional group that reacts with active hydrogen, is used as an N-vinylamide unit and 0 to 65 relative to 100 parts by weight of the polymer having a polyether unit.
It is preferable to use parts by weight.

In the curable resin composition, when the organic component other than the above essential components is contained in an amount of more than 65 parts by weight based on 100 parts by weight of the polymer having the N-vinylamide unit and / or the polyether unit, The physical properties of the cured film formed from the curable resin composition are deteriorated and the hydrophilicity is deteriorated, and the action by curing the curable resin composition by a new crosslinking system which has never been seen before. The effect may not be fully obtained. More preferably, it is 50 parts by weight or less, and further preferably 40 parts by weight or less, relative to 100 parts by weight of the polymer having the N-vinylamide unit and / or polyether unit.
Most preferably, it is 30 parts by weight or less.

In the above curable resin composition, the weight ratio of the polymer having N-vinylamide units and / or polyether units to the cross-linking agent having a functional group capable of reacting with active hydrogen is determined by the kind of functional group or It may be appropriately selected in consideration of the molecular weight of the crosslinking agent and the functional group equivalent. Generally, when the amount of the cross-linking agent exceeds 50% of the curable resin composition,
The hydrophilicity is impaired, which is not preferable.

The above-mentioned polymer having N-vinylamide units is a polymer formed by polymerizing a monomer component containing an N-vinylamide-based monomer, and has characteristics such as high hygroscopicity and hydrophilicity. Have. Such polymers may be used alone or in combination of two or more. Examples of the N-vinylamide-based monomer forming the polymer having the N-vinylamide unit include the following general formula (1);

[0020]

[Chemical 1]

(In the formula, R ¹ represents hydrogen or a methyl group. R ² and R ³ are the same or different and represent hydrogen, a methyl group or an ethyl group, and R ² and R ³ are bonded to each other. 3 carbons
~ 5 alkylene groups may be formed. ) And the like.

Examples of the N-vinylamide type monomer include
N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylformamide, N-methyl-N-
Vinylformamide, N-vinylpropionamide, N
-Vinylpyrrolidone and the like are preferable, and one kind or two or more kinds can be used if necessary.

In the monomer component forming the polymer having the N-vinylamide unit, the N-vinylamide monomer is preferably contained as the main component, and at this time, other monomers may be contained. However, it is preferable that the unsaturated monomer having a functional group capable of reacting with the crosslinking agent described later is included. The N-vinylamide-based monomer is preferably 50% by weight or more when the total amount of the monomer components is 100% by weight. If it is less than 50% by weight, the effects of the present invention may not be sufficiently exhibited. It is more preferably at least 70% by weight, and even more preferably at least 90% by weight. Also, N
The vinylamide-based monomer may be used alone or in combination of two or more. When a monomer component containing two or more kinds of monomers is polymerized, the polymerization form thereof may be any of block form, alternating form, random form, etc., but hydrophilicity and water resistance Graft polymers are preferred in terms of the balance of properties.

A preferred form of the polymer having an N-vinylamide unit in the present invention is to have a functional group capable of reacting with a crosslinking agent. Thereby, it becomes possible to cure at a low temperature, and the physical properties of the cured film can be further improved. The functional group is preferably a group other than a carboxyl group, and a hydroxyl group, an amino group, an oxazoline group, a glycidyl group or the like is preferable. These functional groups in the polymer may be one type or two or more types. More preferably, it has a hydroxyl group. The polymer having an N-vinylamide unit having such a functional group is obtained by copolymerizing a monomer component containing the above-mentioned N-vinylamide-based monomer and an unsaturated monomer having a functional group. Obtainable.

As the monomers other than the N-vinylamide type monomer that can be contained in the above-mentioned monomer component, N-
Examples of the polymerizable monomer copolymerizable with the vinylamide-based monomer include (1) methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth)
(Meth) acrylic acid esters such as cyclohexyl acrylate and hydroxyethyl (meth) acrylate; (2)
(Meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide,
(Meth) such as N, N-dimethyl (meth) acrylamide
Acrylamide derivatives; (3) basic unsaturated monomers such as dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, vinylpyridine, vinylimidazole and salts or quaternary compounds thereof;
(4) Imino ethers such as vinyloxazoline and isopropenyloxazoline; (5) 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-
Hydroxybutyl (meth) acrylate, methyl 2-
(Hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) ) Unsaturated monomers having a hydroxyl group such as acrylate; (6) Unsaturated anhydrides such as maleic anhydride and itaconic anhydride; (7) Vinyl esters such as vinyl acetate and vinyl propionate; (8) Vinyl Ethylene carbonate and its derivatives; (9) Styrene and its derivatives; (10) Ethyl (meth) acrylate-2-sulfonate and its derivatives; (11) Vinyl sulfonic acid and its derivatives; (12) Methyl vinyl ether, ethyl vinyl ether. , Vinyl ethers such as chill ether; (13) ethylene, propylene, octene,
Preferred are olefins such as butadiene; unsaturated monomers having a glycidyl group such as (14) glycidyl (meth) acrylate. These may be used alone or in combination of two or more. Among these, since the preferred form of the polymer is to have a hydroxyl group, an amino group, an oxazoline group, and a glycidyl group, monomers having these groups, that is, (3), (4), (5), (14)
It is preferable to use the above monomer. Moreover, it is most preferable to use 2-hydroxyethyl (meth) acrylate as the unsaturated monomer having a hydroxyl group.

In the present invention, the polymer having the N-vinylamide unit is preferably an N-vinylpyrrolidone polymer. This makes it possible to more reliably exhibit the effects of the present invention. The N-vinylpyrrolidone-based polymer is a polymer obtained by using N-vinylpyrrolidone as an N-vinylamide-based monomer in a monomer component forming a polymer having an N-vinylamide unit.

As a method for producing the above-mentioned polymer having N-vinylamide units, an aqueous solution polymerization method, a solution polymerization method in an organic solvent, a reverse phase suspension polymerization method, an emulsion polymerization method, a precipitation polymerization method and the like are preferable. The reaction conditions and the like during the polymerization are not particularly limited. As the polymerization initiator to be used, one or two or more conventionally known ones can be used, and the amount used is not particularly limited. Alternatively, a polymerization method using heat, light, or radiation may be used without using the polymerization initiator.

As for the molecular weight of the above-mentioned polymer having N-vinylamide units, the weight average molecular weight is preferably 1,000 or more, and more preferably 5,000,000 or less. When it is less than 1000, the water resistance and mechanical strength of the cured film may be insufficient,
If it exceeds 0000, the workability at the time of forming a cured coating may be insufficient. More preferably 500
It is 0 or more, and more preferably 10000 or more. Further, it is more preferably 3,000,000 or less, and further preferably 1500000 or less.

The polymer having a polyether unit in the present invention is a compound having a plurality of ether bonds in the molecule and has characteristics such as high hygroscopicity and hydrophilicity. Such polymers may be used alone or in combination of two or more. In the present invention, the polymer having a polyether unit is preferably a polymer having a polyoxyalkylene chain.

The polymer having a polyoxyalkylene chain is preferably a polymer having a polyoxyethylene chain and / or a polyoxypropylene chain represented by the following general formula (2) in the molecule.

[0031]

[Chemical 2]

In the formula, R ⁴ represents a hydrogen atom or a methyl group. k represents an integer of 3 or more. In the general formula (2), when k is less than 3, the polymer having a polyoxyalkylene chain may not have sufficient hydrophilicity. It is preferably an integer of 5 or more, and an integer of 2500. As the polymer having such a polyoxyalkylene chain, those described below are suitable. Polyoxyalkylene glycol such as polyethylene glycol, polypropylene glycol, and blocked polyoxyalkylene glycol in which a polyoxyethylene chain and a polyoxypropylene chain are linked in a block form; a hydroxyl group at the terminal or both terminals of the polyoxyalkylene glycol,
An ether compound obtained by etherification with a monoalcohol, a dihydric or higher polyalcohol or a phenol; an ester compound obtained by esterifying a hydroxyl group at the terminal or both terminals of polyoxyalkylene glycol with a monobasic acid; A polymer obtained by polymerizing a monomer component containing an unsaturated monomer having a polyoxyethylene chain and / or a polyoxypropylene chain represented by 2).

The monoalcohol, dihydric or higher polyalcohol and phenols used for the above etherification include methanol, ethanol, isopropanol and n-.
Monoalcohols such as butanol and isobutanol; dihydric or higher polyalcohols such as butanediol, neopentyl glycol, hexanediol, di (hydroxymethyl) cyclohexane, glycerin, diglycerin, trimethylolethane, trimethylolpropane and pentaerythritol; Phenols such as phenol, bisphenol A and bisphenol F are suitable, and one kind or two or more kinds can be used.

As the monobasic acid used for the above esterification, formic acid, acetic acid, propionic acid, butyric acid, hydroxybutyric acid, lactic acid, benzoic acid, pt-butylbenzoic acid and the like are preferable, and one or two kinds are preferable. The above can be used.

The above-mentioned polymer having a polyoxyalkylene chain has a polyoxyethylene chain and / or a polyoxypropylene chain portion represented by the general formula (2) based on 100% by weight of the polymer having a polyoxyalkylene chain. 50
It is preferable to have the content of not less than wt%. More preferably, 8
It is 0% by weight. Among them, polyethylene glycol is preferable as the polymer having a polyoxyethylene chain portion of 50% by weight or more.

In the present invention, polydioxolane may be used as the polymer having a polyoxyalkylene chain. The polydioxolane, the following general formula (3); - Table with _{- (CH 2 -O-CH 2} CH 2 -O-) n- (3) ( wherein, n represents an integer of 1 or more.) It is a polymer having a structural unit of Such a polymer can be obtained, for example, by polymerizing a monomer component containing 1,3-dioxolane.

In the monomer component forming the polydioxolane, it is preferable that 1,3-dioxolane is contained as a main component, and at this time, other monomer may or may not be contained. . For example, when the total amount of the monomer components is 100% by weight, 1,3-dioxolane is added to 5%.
It is preferably 0% by weight or more. If it is less than 50% by weight, the effects of the present invention may not be sufficiently exhibited. It is more preferably at least 70% by weight, and even more preferably at least 90% by weight. Also,
When a monomer component containing two or more kinds of monomers is polymerized, the polymerization form thereof may be any of block form, alternating form, random form and the like.

Other monomers copolymerizable with 1,3-dioxolane contained in the above-mentioned monomer components include unsaturated hydrocarbons such as styrene, (meth) acrylic acid, ethylene and propylene; trioxane and ethylene oxide. , Propylene oxide, cyclic ethers such as tetrahydrofuran; γ-butyrolactone, glycolide, lactide, ε-
Lactones such as caprolactone and ε-caprolactam, or lactams are preferable. These may be used alone or in combination of two or more.

The crosslinking agent having a functional group that reacts with active hydrogen in the present invention may be a compound or polymer having two or more functional groups that react with active hydrogen per molecule. That is, a compound has two or more functional groups that react with the active hydrogen per molecule, and a polymer has an average of 2 functional groups that react with the active hydrogen per molecule.
Those having three or more can be used. Such crosslinking agents may be used alone or in combination of two or more. Further, the functional group that reacts with active hydrogen present in one molecule of the cross-linking agent may be one type or two or more types.

In the above-mentioned crosslinking agent, the functional group which reacts with the active hydrogen is an isocyanate group, an epoxy group, an oxazoline group, an aziridinyl group, a carbodiimide group, an alkoxysilane group, a cyclocarbonate group, a methylol group, a methylolalkyl group, a vinyl ether. It is preferably at least one group selected from the group consisting of a group and an amino group. By including the crosslinking agent having such a functional group, the physical properties of the cured film formed from the curable resin composition can be improved and excellent properties such as hydrophilicity can be exhibited. Among these, it is preferable to use a crosslinking agent having an isocyanate group or a crosslinking agent having a methylol group or a methylolalkyl group.

Examples of the cross-linking agent having an isocyanate group include organic diisocyanate compounds such as xylylene diisocyanate, isophorone diisocyanate, alicyclic diisocyanates and other cyclic diisocyanates; tolylene diisocyanate, 4,4-diphenylmethane diisocyanate and the like. Aromatic diisocyanates;
Aliphatic diisocyanates such as hexamethylene diisocyanate are preferred. Further, as the polyisocyanate resin, an adduct of these organic diisocyanate compounds with a polyhydric alcohol, a low molecular weight polyester resin (polyester polyol) or water; a polymer of organic diisocyanate compounds containing an isocyanurate type polyisocyanate compound or Preferred are isocyanates and burettes. Further, as the blocked isocyanate resin, a resin obtained by blocking the above polyisocyanate resin with a known and commonly used blocking agent is suitable.

Commercially available products of the above-mentioned crosslinking agent having an isocyanate group include polyisocyanate resins such as "Burnock DN-980" and "Burnock DN-".
990 "(both are trade names, manufactured by Dainippon Ink and Chemicals, Inc.) and the like. Examples of the blocked isocyanate resin include" Barnock DB-980K "(trade name,
Dainippon Ink and Chemicals, Inc., "Coronate 2507"
(Product name, manufactured by Nippon Polyurethane Company), "Takenate B-
“815N” (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.), “Duranate” (trade name, manufactured by Asahi Kasei Corporation), “Elastron” (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like.

As the above-mentioned cross-linking agent having an epoxy group,
Compounds having two epoxy groups such as polyethylene glycol diglycidyl ether, bisphenol A type diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and glycerin diglycidyl ether; trifunctional or higher functional polyethylene glycol glycidyl ether, Compounds having three or more epoxy groups such as trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, and polyglycerol polyglycidyl ether are suitable.
Examples of commercially available products include Epolite (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and Denacol (trade name) manufactured by Nagase Kasei Kogyo Co., Ltd.
Etc.

Examples of the cross-linking agent having an oxazoline group include 2,2'-bis- (2-oxazoline) and 2,2 '.
-Methylene-bis- (2-oxazoline), 2,2'-
Ethylene-bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-
Tetramethylene-bis- (2-oxazoline), 2,
2'-hexamethylene-bis- (2-oxazoline),
2,2'-octamethylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-
Bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4'-dimethyl-2-oxazoline), bis -(2-oxazolinylcyclohexane) sulfide, bis- (2-oxazolinyl norbornane)
Other functional oxazoline compounds such as sulfides, and oxazoline group-containing polymers such as Epocros (trade name, manufactured by Nippon Shokubai Co., Ltd.) are suitable. As the crosslinking agent having an aziridinyl group, an aziridinyl group-containing crosslinking agent such as "Chemite DZ-22E" or "Chemite FZ-33" (trade name, manufactured by Nippon Shokubai Co., Ltd.) is preferable.

As the cross-linking agent having a methylol group or a methylol alkyl group, those having an N-methylol group and / or an N-methylol alkyl group are preferable, and so-called amino resins such as melamine resin and urea resin are preferable. is there.

As the cross-linking agent having a methylol group and / or a methylol alkyl group, melamine resin, urea resin, benzoguanamine resin and the like are suitable. Among these, melamine resin or urea resin is preferable. As the melamine resin, a complete alkyl group-type melamine resin, a methylol group-type melamine resin, an imino group-type melamine resin, a methylol-imino group-type melamine resin, and the like, methylated melamine resin, butylated melamine resin, mixed alkylation Melamine resin and the like are suitable.

If necessary, a catalyst can be added corresponding to various crosslinking agents. For example, when a crosslinking agent having an isocyanate group is used as the crosslinking agent, the reaction can be performed by using the catalyst used for the urethanization reaction. Is promoted, and an amine catalyst (triethylamine, N-ethylmorpholine,
Triethylenediamine, etc.), tin-based catalysts (dibutyltin dilaurylate, dioctyltin dilaurylate, tin octylate, etc.), and titanium-based catalysts (tetrabutyl titanate, etc.) can be used. When using a crosslinking agent having an epoxy group, an amine catalyst, an acidic catalyst, when using a crosslinking agent having an oxazoline group, when using an acidic catalyst, a crosslinking agent having a methylol group, a carboxylic acid, a phosphoric acid, a phosphoric acid ester Acidic catalysts such as sulfonic acids, sulfonic acid esters, persulfates, and onium salts are preferred.

In the curable resin composition of the present invention, if necessary, additives such as stabilizers, pigments, inorganic fillers, film forming aids, lubricants, antibacterial agents and the like can be added. As a usage form of the curable resin composition of the present invention, it is preferable to use a treating agent in which the compound is dissolved or dispersed in water or an aqueous solvent. The aqueous solvent means a mixed solvent of one kind or two or more kinds of solvents that can be mixed with water, or a mixed solvent obtained by mixing such a solvent such that water is a main component.
Further, a surfactant may be mixed with water or an aqueous solvent and used.

As the usage form of the curable resin composition of the present invention, since the surface of an article can be imparted with properties such as hydrophilicity, it is suitably applied for surface treatment of the article. Thus, the article treated with the curable resin composition of the present invention has a cured coating formed on the surface thereof, which is formed by the curable resin composition of the present invention. That is, a cured coating film having excellent physical properties and capable of exhibiting excellent properties such as hydrophilicity is formed on the surface, and can be used for various purposes. Such an article is also one aspect of the present invention. As a shape of such an article, a thin plate, a film, a fiber, a hollow fiber, a non-woven fabric or the like is suitable. The material of the article includes metals such as aluminum and aluminum alloys; glass; PET resin,
Urethane resin, epoxy resin, vinyl chloride resin, acrylic resin, ABS resin, AS resin, polystyrene resin,
Plastic such as polycarbonate resin; cellulose such as paper are preferable. Further, the surface of the article may be previously treated to improve the adhesion with the curable resin composition. Treatments that can be applied to the surface of such articles include chromate phosphate, chromate chromate,
Treatment with zircon, etc .; Organic matter treatment; Corona discharge treatment;
Low-temperature plasma treatment; short-wavelength ultraviolet irradiation treatment and the like are suitable.

The curable resin composition of the present invention is capable of forming a cured coating on the surface of an article of various materials as described above, and as the surface material of the article, among the above examples. It is preferable to use an organic base material from the viewpoint of adhesion to a cellulosic base material such as paper and a cured film. Among the organic base materials, it is preferable to apply to PET resin, urethane resin, epoxy resin and vinyl chloride resin. More preferably, it is a PET resin, and it is suitable to apply it to a PET film.

The method for forming a cured coating from the curable resin composition on the surface of the above-mentioned article includes, for example, coating, impregnation, and
Any method such as spraying may be used. In particular,
It is preferable to apply the curable resin composition in the form of a treatment agent uniformly on the surface of the article, or to impregnate the article with the treatment agent and dry-cure it. As a method of applying the treatment agent, for example, a coating machine such as a roll coater can be used.

The temperature at which the curable resin composition of the present invention is cured may be appropriately set depending on the type of crosslinking agent. For example, when the above-mentioned crosslinking agent having an isocyanate group is used, the temperature is preferably 100 ° C or higher, and preferably 200 ° C or lower. When using a cross-linking agent having an epoxy group or a cross-linking agent having an oxazoline group, 150 ° C or higher is preferable, and 200 ° C
The following are preferred. When a cross-linking agent having a methylol group is used, the temperature is preferably 170 ° C or higher and 240 ° C or lower. Further, the use of a catalyst enables crosslinking at low temperature.

As an application of the article treated with the curable resin composition of the present invention, an application in which the surface is required to be hydrophilic is conceivable. By having hydrophilicity, adhesion of condensed water can be prevented. In addition, since it can be an article provided with a function of having antistatic performance, it can be suitably used for a heat exchanger such as an air conditioner. In this case, for example, various processes such as punching and bending are performed to form fins and the like, and then the fins are attached to a copper pipe or the like.

The curable resin composition of the present invention is also suitably applied to the ink jet receiving layer and its binder. Thus, an article using the curable resin composition of the present invention as an inkjet receiving layer or a receiving layer binder is a preferred embodiment of the present invention,
It is preferable to use a PET film, a non-woven fabric or the like as the substrate. In this case, the cured film formed from the curable resin composition of the present invention has both water absorption and water resistance, and therefore excellent dryness and water resistance of printing can be obtained.

The curable resin composition of the present invention is effective for making the surface of the PET film hydrophilic as described above, but such an article is suitable for food packaging and the like. Besides,
Since antifogging and antistatic properties can be imparted to various articles, it can be suitably applied to articles requiring these properties, and can also be suitably applied to primer applications and the like. Furthermore, the cured coating formed from the curable resin composition of the present invention has biocompatibility and N-
Since a polymer having a vinylamide unit or a polymer having a polyether unit is difficult to elute, it can be suitably applied to biocompatible materials such as antithrombotic materials. Such articles include, for example, hollow fiber membranes used in the medical field such as artificial kidneys and for removing, separating and collecting specific substances. Conventionally, by melt-kneading polysulfone with PVP or spinning from a common solvent,
It was treated, but treated with the curable resin composition of the present invention,
By further curing, elution of the PVP component can be suppressed while maintaining excellent biocompatibility.

[0056]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 7 and Comparative Example 1 In the composition shown in Table 1, an N-vinylamide polymer or a polymer having a polyether unit and a crosslinking agent were used.
A varnish containing a curable resin composition and having a nonvolatile content of 10% by weight was prepared. Put this varnish on the glass plate with an applicator.
It is applied with a thickness of 0 μm, and this is applied using a hot air dryer.
It heat-processed at 0 degreeC for 10 minutes, and produced the glass plate which has a hardened film. The water resistance test and hydrophilicity test shown below were performed using the glass plate having the obtained cured coating. The results are shown in Table 1.

[0058]Water resistance test (1) Rubbing test Rubbing test is performed using a glass plate with a cured coating.
It carried out (30 times). Evaluation criteria ○: No scratch △: hurt ×: Elution XX: No gel is observed (2) Immersion A glass plate having a cured coating is immersed in ion-exchanged water at room temperature for 10
The state of the cured film after immersion for a minute was visually observed.

[0059]Hydrophilicity test By a breath test using a glass plate with a cured coating
The antifogging property was evaluated. Evaluation criteria ○: Not cloudy △: Partly cloudy ×: Cloudy

[0060]

[Table 1]

Table 1 will be described below. PVP is polyvinylpyrrolidone (trade name "K-90", manufactured by Wako Pure Chemical Industries, Ltd.), PEO is polyethylene oxide (trade name "ALCOX R-400", manufactured by Meisei Chemical Co., Ltd.), PVA is polyvinyl alcohol (trade name "PVA-220", manufactured by Kuraray Co., Ltd.), and crosslinking agent (1) is a heat-reactive water-soluble urethane resin "Elastron H-3" (trade name, Dai-ichi Kogyo). Manufactured by Pharmaceutical Industries, Ltd., and the cross-linking agent (2) is polyisocyanate “Duranate E4”.
02-90T "(trade name, manufactured by Asahi Kasei Corp.).

In Table 1, it can be seen from the results of Example 7 that the addition of PVA as an organic component other than the essential component in an amount of 65% by weight or more hinders the curing reaction between PVP and the cross-linking agent and reduces the water resistance. Conceivable. It can be seen that the organic component other than the essential components is more preferably 65% by weight or less. From the results of Comparative Example 1, it can be seen that crosslinking of the curable resin composition does not occur unless a crosslinking agent having a functional group that reacts with active hydrogen is included.

Examples 8 to 13 and Comparative Example 2 In the composition shown in Table 2, an N-vinylamide polymer or a polymer having a polyether unit and a crosslinking agent were used.
A varnish containing a curable resin composition and having a nonvolatile content of 10% by weight was prepared. Put this varnish on the glass plate with an applicator.
It is applied to a thickness of 0 μm, and this is applied with a hot air dryer for 20
It heat-processed at 0 degreeC for 20 minutes, and produced the glass plate which has a hardened film. The above water resistance test and hydrophilicity test were performed using the glass plate having the obtained cured coating. The results are shown in Table 2.

[0064]

[Table 2]

Table 2 will be described below. PVP is polyvinylpyrrolidone (trade name "K-90", manufactured by Wako Pure Chemical Industries, Ltd.), PEO is polyethylene oxide (trade name "ALCOX R-400", manufactured by Meisei Chemical Co., Ltd.), PAA is polyacrylic acid (trade name "Jurimer AC10L", manufactured by Nippon Pure Chemical Co., Ltd.), water-soluble melamine resin, trade name "Nikalac MX-035", manufactured by Sanwa Chemical Co., Ltd., and urea resin is Product name "UFR
65 ", manufactured by Mitsui Cytec.

In Table 2, it can be seen from the results of Example 13 that the addition of 65% by weight or more of PAA as an organic component other than the essential component inhibits the curing reaction between PVP and the cross-linking agent and reduces the water resistance. Conceivable. It can be seen that the organic component other than the essential components is more preferably 65% by weight or less. From the results of Comparative Example 2, it is understood that the curable resin composition does not crosslink unless a crosslinker having a methylol group and / or a methylolalkyl group is included.

Examples 14 to 15 10 parts by weight of polyvinylpyrrolidone (PX-K90L, a product developed by Nippon Shokubai Co., Ltd.) as an N-vinylamide polymer and water-soluble melamine (trade name "Nikalac MX03"
5 ", manufactured by Sanwa Chemical Co., Ltd.) and diluted with water to prepare a varnish containing a curable resin composition having a nonvolatile content of 0.1% by weight. This varnish is made of PET having a thickness of 100 μm so that the film thickness after drying is 0.03 μm.
It was applied onto a film (trade name "Lumirror", type: T, manufactured by Toray Industries, Inc.). A predetermined heat treatment shown in Table 3 was performed to obtain a test piece.

Comparative Example 3 A PET film having a thickness of 100 μm (trade name “Lumirror”, type: T, manufactured by Toray Industries, Inc.) was used as a test piece.

Using the test pieces prepared above, cellophane tape (R) peeling, moisture absorption and contact angle were evaluated. The results are shown in Table 3. (Peeling of Cellotape (R)) It was carried out according to a conventional method. Early and
After soaking in water for 24 hours and boiling water for 1 hour, 60
It was performed after drying at ℃.

(Hygroscopic rate) 2 at 30 ° C. and 90% RH
It was determined from the weight change after standing for 4 hours using the following calculation formula. Moisture absorption rate (%) = weight after moisture absorption / weight when dried

(Contact Angle) The test piece was allowed to stand for 24 hours at 20 ° C. and 90% RH, and then the contact angle with water was measured. The test pieces were immersed in water in the initial stage for 24 hours and in boiling water for 1 hour, respectively, and then dried at 60 ° C.

[0072]

[Table 3]

Table 3 will be described below. In the coating film, PVP / MX035 = 6/4 (wt) means N-
Vinylamide polymer (PX-K90L, a product developed by Nippon Shokubai Co., Ltd.) / Water-soluble melamine (trade name “Nikalac MX
035 ", manufactured by Sanwa Chemical Co., Ltd.) = 6/4 (weight ratio) means that a coating film was formed using the curable resin composition.

From Table 3, the PVP coating is PET
It showed good adhesion to the film. Also, PVP
The surface of the film was hydrophilized by the system coating, and the contact angle to water was greatly reduced. Further, it was found that the crosslinking treatment makes the water immersion, boiling water immersion, and hydrophilization effects last. That is, the PVP-based crosslinkable coating made the surface of the PET film hydrophilic at a high level, and the effect thereof continued even after the boiling water test.

Examples 16 to 18 N-vinylamide polymer (PX-K) having the composition shown in Table 4 was used.
90L, a product developed by Nippon Shokubai Co., Ltd., and water-soluble melamine (trade name “Nikalac MX035”, manufactured by Sanwa Chemical Co., Ltd.) are mixed to prepare a varnish containing a curable resin composition having a nonvolatile content of 20% by weight. did. This varnish was applied onto a PET film having a thickness of 100 μm (trade name “Lumirror”, type: T, manufactured by Toray Industries, Inc.) so that the film thickness after drying was 18 μm. The predetermined heat treatment shown in Table 4 was performed to form an inkjet receiving layer, which was used as a test piece.

Comparative Example 4 A PET film having a thickness of 100 μm (trade name “Lumirror”, type: T, manufactured by Toray Industries, Inc.) was used as a test piece.

Comparative Example 5 OHP sheet for inkjet (trade name "CF10
2 ", manufactured by Canon Inc.) was used as the test piece.

Using the test piece prepared above or a commercially available film, the moisture absorption, the drying property, the water resistance of the coating film and the water resistance of the image were evaluated. The results are shown in Table 4. (Water absorption rate) It was calculated from the weight change when immersed in ion-exchanged water for 24 hours, using the following calculation formula. Water absorption rate (%) = 100 × [(weight after immersion)-(weight when dried)] / [(weight when dried)-(weight of PET film when dried)]

(Drying property) The color transfer 30 seconds after printing was qualitatively judged by contact. Evaluation criteria ○: No color transfer △: Some color transfer ×: Color transfer

(Water resistance of coating film) Using the test piece, a rubbing test of the clear coating film (ink jet receiving layer itself) was carried out (50 times). Evaluation criteria ◎: No change ○: Scratch △: Scratch, peeling, etc. within 30 times ×: Elution (gel content is clearly recognized) XX: Elution (gel content is not recognized)

(Water resistance of image) A change was observed by dropping water drops on the image printed on the receiving layer. Evaluation criteria ◎: No change Color fading when rubbing △: No change to slightly blurring Disappear when rubbing ×: Blurring × ×: Immediately floating image and melting

[0082]

[Table 4]

Table 4 will be described below. In the film, Lumirror is a PET film manufactured by Toray Co., Ltd. having a trade name “Lumirror”, type: T, and a thickness of 100 μm, and CF102 is a trade name “CF102”, an inkjet OHP sheet manufactured by Canon Inc. . In the composition of the receiving layer, PVP / melamine (by weight) means N-
Vinylamide polymer (PX-K90L, a product developed by Nippon Shokubai Co., Ltd.) and water-soluble melamine (trade name “Nikalac M”
X035 ", manufactured by Sanwa Chemical Co., Ltd.), and 1 phr of the catalyst means that 1 part by weight of sodium persulfate was added to 100 parts by weight of the total weight of PVP and melamine.

From Table 4, the use of the PVP-based crosslinkable coating gave the appearance and the water resistance of the printing superior to those of the commercially available OHP film for inkjet. It has been found that the PVP-based crosslinkable coating film has both water absorbency and water resistance, and thus serves as an inkjet receiving layer having excellent dryness and water resistance.

Synthesis Example 1 (NVP / HEA (1): NVP
Synthesis of Random Copolymer of HEA and HEA) 80 parts by weight of ion-exchanged water and 16 parts by weight of NVP (N-vinylpyrrolidone) were charged into a reaction vessel, and a nitrogen atmosphere was added to 70
The temperature was raised to ° C. 0.2 parts by weight of a 10% IPA solution of 2,2′-azobis-2-methylbutyronitrile was added, and immediately after that, HEA (2-hydroxyethyl acrylate) 4 was added.
The weight part was dripped over 90 minutes. The internal temperature reached 95 ° C at the end of the dropping, but the reaction was maintained at 95 ° C for 2 hours.
It continued for hours. Then, it was left to cool to room temperature to obtain a colorless transparent polymer solution.

Synthesis Example 2 (NVP / HEA (2): NVP
Synthesis of Graft Copolymer of HEA and HEA) PVP (trade name “K-3
0 ", manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved, and the temperature was raised to 95 ° C under a nitrogen atmosphere. 6 parts by weight of HEA and 14 parts by weight of an aqueous solution of 1.3% ammonium persulfate were added dropwise over 90 minutes to polymerize, and after completion of the addition, the reaction was continued at 95 ° C. for another 2 hours. Then, it stood to cool to room temperature and the yellow transparent polymer solution was obtained.

Synthesis Example 3 (Synthesis of NVP / NH2: NVP and Allylamine Copolymer) 10 parts by weight of N-vinylpyrrolidone, 1 part by weight of allylamine, 39 parts by weight of isopropyl alcohol, and di-t-butyl peroxide were placed in a pressure tight container. Charge 0.5 parts by weight,
The mixture was reacted at 130 ° C for 10 hours with stirring. The obtained polymerization liquid was purified by reprecipitation with ethanol / hexane to obtain a water-soluble copolymer NVP / NH2 body.

Examples 19 to 23 The vinylpyrrolidone copolymers (VP copolymers) synthesized in Synthesis Examples 1 to 3 in the formulations shown in Table 5, a cross-linking agent and a catalyst were blended to obtain a nonvolatile content of 20% by weight. A varnish containing the curable resin composition was prepared. The film thickness after drying this varnish is 18 μm
To a thickness of 100 μm on a PET film (trade name “Lumirror”, type: T, manufactured by Toray Industries, Inc.).
The predetermined heat treatment shown in Table 5 was performed to form an inkjet receiving layer, which was used as a test piece. Using the test pieces thus produced, the water resistance test (rubbing test), the hydrophilicity test, the drying property and the water resistance of the coating film were evaluated in the same manner as above.

[0089]Water resistance test Rubbing test Using the test piece, clear coating film (inkjet receiving layer
The rubbing test of the body) was conducted in the same manner as in Examples 16 to 18.
It was applied (50 times).

[0090]Hydrophilicity test By a breath test using a glass plate with a cured coating
Antifogging property evaluation was performed in the same manner as in Examples 1 to 7.

[0091]Inkjet evaluation Dryness and water resistance of the inkjet receiving layer (water resistance of the image
Evaluation) was performed in the same manner as in Examples 16-18.

[0092]

[Table 5]

Table 5 will be described below. NVP / HEA in VP (vinylpyrrolidone) copolymer
(1) is a random copolymer of N-vinylpyrrolidone (NVP) and 2-hydroxyethyl acrylate (HEA), and NVP / HEA (2) is NVP and H
It is a graft copolymer with EA, and NVP / NH2 is a copolymer of NVP and allylamine. In the cross-linking agent, the melamine resin is Nikarac MX035
(Trade name, manufactured by Sanwa Chemical Co., Ltd.), the isocyanate cross-linking agent is Bayhijure BL5140 (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), and the epoxy-based cross-linking agent is Denacol EX810 (trade name, Nagase Kasei Co., Ltd.). Aziridine-based cross-linking agent is Chemitite FZ
-33 (trade name, manufactured by Nippon Shokubai Co., Ltd.). In the catalyst, pTS is p-toluenesulfonic acid, DB
TDL is dibutyltin dilaurylate.

From Table 5, it can be seen that the crosslinkable coating film formed from the NVP-based copolymer is compatible with both water absorption and water resistance, so that it becomes an inkjet receiving layer excellent in drying property and water resistance. It was

[0095]

Since the curable resin composition of the present invention has the above-mentioned constitution, it can be cross-linked by a new cross-linking system, and the cured film formed thereby has good physical properties. In addition, it is possible to exhibit characteristics such as excellent hydrophilicity.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 71/00 C08L 71/00 Z // C09D 5/00 C09D 5/00 Z 139/00 139/00 171 / 00 171/00 (C08L 39/00 C08L 101: 00 101: 00) (C08L 71/00 101: 00) (72) Inventor Akio Naka 5-5 Nishimitabicho, Suita City, Osaka Prefecture Nippon Shokubai Co., Ltd. (72) Miwako Yonezawa 5-8 Nishiomitabicho Suita City, Osaka Prefecture F-term within Nippon Shokubai Co., Ltd. (reference) 4F006 AA15 AA16 AA22 AA34 AA35 AA37 AB12 AB32 AB62 BA10 CA07 CA09 4J002 BJ001 CC182 CC192 CC212 CD002 CH001 CK022 CM012 ER006 EU216 FD146 GB01 GF00 GG00 GH00 4J034 AA08 AA10 BA03 DA01 DA02 DA08 DB03 DC20 DC34 DG02 HA07 HC03 HC12 HD01 4J038 CR071 DF001

Claims (5)

[Claims] 1. A curable resin composition comprising, as an essential component, a polymer having an N-vinylamide unit and a compound having two or more functional groups that react with active hydrogen. 2. A curable resin composition comprising as an essential component a polymer having a polyether unit and a compound having two or more functional groups that react with active hydrogen. 3. The curable resin composition according to claim 1, wherein the organic component other than the essential component is 0 to 65 parts by weight with respect to 100 parts by weight of the polymer. 4. The functional group which reacts with the active hydrogen is an isocyanate group, an epoxy group, an oxazoline group, an aziridinyl group, a carbodiimide group, an alkoxysilane group, a cyclocarbonate group, a methylol group, a methylolalkyl group, a vinyl ether group or an amino group. The curable resin composition according to claim 1, which is at least one group selected from the group consisting of: 5. An article obtained by treating with the curable resin composition according to claim 1, 2, 3 or 4.