JP2021059662A - Resin composition, curable composition, article with coating film, method for producing article with coating film, coating agent and method for producing base material with laminate coating films - Google Patents

Abstract

To provide a new resin composition or the like that can give lubricity to a base material surface and can prevent the base material surface from being stained.SOLUTION: A resin composition contains: at least one crosslinker selected from a group consisting of a crosslinker having an oxazoline group, a crosslinker having an epoxy group, a crosslinker having a carbodiimide group and a melamine resin crosslinker; and a copolymer that has a first constitutional unit derived from a (meth) acryl monomer having a hydroxy group and a second constitutional unit derived from a polymerizable double bond-containing monomer having a carboxy group. In the copolymer, a content of the first constitutional unit is 70 mass% or more and a content of the second constitutional unit is 1 mass% or more. A content of the crosslinker is 0.1-4 pts.mass relative to the copolymer 100 pts.mass.SELECTED DRAWING: None

Description

The present invention relates to a resin composition, a curable composition, an article with a coating film, a method for producing an article with a coating film, a coating agent, and a method for producing a substrate with a laminated coating film.

Coating agents are used in a wide variety of fields for the purpose of imparting lubricity to the surface of a substrate. For example, medical devices such as catheters are used in an environment where they come into contact with biological components such as blood and biological tissues, and medical treatment is performed so that such medical devices can be used without resistance to biological tissues such as blood vessels. A lubricious coating is applied to the surface of the tool. In addition, it is lubricious to prevent dirt (proteins, microorganisms, diatoms, seaweeds, shellfish, barnacles, etc.) from adhering to the surface of the base material, or to make it easy to remove even if dirt adheres. Various studies have also been made on the use of coatings.

For example, Patent Document 1 below proposes an antifouling agent containing an aromatic sulfonic acid-based formalin condensate for the purpose of preventing stains on a hard surface of a toilet bowl or the like. Further, Patent Document 2 below discloses a pollutant biological control agent containing a solid bleach that generates chlorine in an aqueous solution state such as a chlorinated isocyanuric acid compound.

Further, in Patent Document 3 below, a structural unit derived from a glycerol group-containing monomer and a structural unit derived from an unsaturated monomer having a structure in which an organic group having 4 or more carbon atoms is bonded to an ethylenically unsaturated group are used. It has been proposed to use a polymer having a predetermined glass transition temperature as a material for medical devices. According to the polymer of Patent Document 3, it is said to have excellent antithrombotic properties.

Japanese Unexamined Patent Publication No. 2007-99793 Japanese Unexamined Patent Publication No. 6-157222 Japanese Unexamined Patent Publication No. 2018-33846

INDUSTRIAL APPLICABILITY The present invention provides a new resin composition, a curable composition, an article with a coating film, which can impart lubricity to the surface of a base material and prevent stains from adhering to the surface of the base material. It is an object of the present invention to provide a method for producing an article with a coating film, a coating agent, and a method for producing a base material with a laminated coating film.

The present invention has at least one cross-linking agent selected from the group consisting of a cross-linking agent having an oxazoline group, a cross-linking agent having an epoxy group, a cross-linking agent having a carbodiimide group, and a melamine resin-based cross-linking agent, and a hydroxyl group (meth). A first structural unit derived from an acrylic monomer and a copolymer having a second structural unit derived from a polymerizable double bond-containing monomer having a carboxy group, and the first structural unit in the copolymer. The content of the structural unit of is 70% by mass or more, the content of the second structural unit is 1% by mass or more, and the content of the cross-linking agent is 0 with respect to 100 parts by mass of the copolymer. A resin composition having 1 to 4 parts by mass is provided.

At least 10% by mass in the first structural unit may be a structural unit derived from a (meth) acrylic monomer having 2 or more hydroxyl groups.

The structural unit derived from the (meth) acrylic monomer having two or more hydroxyl groups may contain the structural unit derived from glycerol (meth) acrylate.

The resin composition according to the present invention may be used for an antifouling paint or for coating a medical device.

The present invention also has at least one cross-linking agent selected from the group consisting of a cross-linking agent having an oxazoline group, a cross-linking agent having an epoxy group, a cross-linking agent having a carbodiimide group, and a melamine resin-based cross-linking agent, and a hydroxyl group (meth). ) The content of the (meth) acrylic monomer containing an acrylic monomer and a polymerizable double bond-containing monomer having a carboxy group and a radical generator and having a hydroxyl group is the total amount of the monomer. The content of the polymerizable double bond-containing monomer having a carboxy group is 1% by mass or more based on the total amount of the monomers, and the content of the cross-linking agent is the monomer. A curable composition having 0.1 to 4 parts by mass with respect to 100 parts by mass is provided.

The curable composition according to the present invention may be used for an antifouling paint or for coating a medical device.

The present invention also provides an article with a coating film comprising a base material and a coating film containing a crosslinked body obtained by cross-linking the resin composition or the curable composition according to the present invention provided on the base material. provide.

The present invention further comprises a coating step of applying the resin composition or the curable composition according to the present invention on at least one main surface of a base material to form a coating film. I will provide a.

The present invention also comprises a first agent containing at least one cross-linking agent selected from the group consisting of a cross-linking agent having an oxazoline group, a cross-linking agent having an epoxy group, a cross-linking agent having a carbodiimide group and a melamine resin-based cross-linking agent. , Containing a copolymer having a first structural unit derived from a (meth) acrylic monomer having a hydroxyl group and a second structural unit derived from a polymerizable double bond-containing monomer having a carboxy group, and having a copolymer weight. A coating agent comprising a second agent in which the content of the first structural unit in the coalescence is 70% by mass or more and the content of the second structural unit in the copolymer is 1% by mass or more. I will provide a.

The coating agent according to the present invention may be used for antifouling paint or for coating medical devices.

The present invention further comprises an undercoating step of applying the first agent of the coating agent according to the present invention to form a first coating film on at least one main surface of the base material, and on the first coating film. Provided is a method for producing a substrate with a laminated coating film, which comprises a coating step of applying a second agent to form a second coating film.

According to the present invention, a new resin composition, a curable composition, and a coating film can be provided, which can impart lubricity to the surface of the base material and prevent stains from adhering to the surface of the base material. It is possible to provide an article, a method for producing an article with a coating film, a coating agent, and a method for producing a substrate with a laminated coating film.

Hereinafter, one embodiment of the present invention will be described in detail, but the present invention is not limited thereto. In the present specification, the term "(meth) acrylic acid" means acrylic acid or methacrylic acid. The same applies to similar expressions such as "(meth) acrylate".

<Resin composition>
The resin composition according to the present embodiment has a predetermined cross-linking agent, a first structural unit derived from a (meth) acrylic monomer having a hydroxyl group (hereinafter, also referred to as “polymer A”), and a carboxy group. It contains a copolymer having a second structural unit derived from a polymerizable double bond-containing monomer (hereinafter, also referred to as “monomer B”). The content of the first structural unit in such a copolymer is 70% by mass or more, and the content of the second structural unit is 1% by mass or more. The content of the cross-linking agent is 0.1 to 4 parts by mass with respect to 100 parts by mass of the copolymer.

(Crosslinking agent)
The cross-linking agent is at least one selected from the group consisting of a cross-linking agent having an oxazoline group, a cross-linking agent having an epoxy group, a cross-linking agent having a carbodiimide group, and a melamine resin-based cross-linking agent.

Examples of the cross-linking agent having an oxazoline group include 2,2'-bis (2-oxazoline), 2,2'-methylene-bis (2-oxazoline), and 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) -Oxazoline norbornane) sulfide, oxazoline ring-containing polymer can be mentioned. These may be used alone or in combination of two or more. Among these, an oxazoline ring-containing polymer is preferable, and a water-soluble oxazoline ring-containing polymer is more preferable from the viewpoint of improving reactivity.

The oxazoline ring-containing polymer can be easily obtained commercially as, for example, manufactured by Nippon Shokubai Co., Ltd., trade names: Epocross WS-500, Epocross WS-700, Epocross K-2010, Epocross K-2020, Epocross K-2030, etc. can do. Among these, water-soluble oxazoline ring-containing polymers such as Nippon Shokubai Co., Ltd., trade names: Epocross WS-500 and Epocross WS-700 are preferable from the viewpoint of improving reactivity.

Examples of the cross-linking agent having an epoxy group include an epoxy group-containing compound having two or more epoxy groups.

Examples of the epoxy group-containing compound include 2 epoxy groups such as diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, bisphenol A type diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and glycerin diglycidyl ether. Compounds having 3 or more; Examples thereof include compounds having 3 or more epoxy groups such as glycidyl ether of trifunctional or higher-functional polyethylene glycol, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, and polyglycerol polyglycidyl ether.

Examples of the cross-linking agent having a carbodiimide group include a carbodiimide group-containing compound having two or more carbodiimide groups. Specific examples thereof include Carbodilite V-02 and Carbodilite E-01 (trade name; manufactured by Nisshinbo Chemical Co., Ltd.).

Examples of the melamine resin-based cross-linking agent include a compound obtained by reacting melamine with formalin or an alkyl-modified product thereof. Specific examples thereof include "Simel" (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232 manufactured by Cytec Industries. , 235, 238, 1141, 272, 254, 202, 1156, 1158, Sanwa Chemical's "Nicarac" (registered trademark) E-2151, MW-100LM, MX-750LM.

The content of the cross-linking agent in the resin composition needs to be 0.1 to 4 parts by mass with respect to 100 parts by mass of the copolymer described later, from the viewpoint of further improving lubricity and antifouling property. , 0.3 to 3 parts by mass, more preferably 0.5 to 2.5 parts by mass, and even more preferably 1 to 2 parts by mass.

(Copolymer)
The copolymer according to this embodiment has a first structural unit derived from monomer A and a second structural unit derived from monomer B.

The monomer A is, for example, a compound represented by the following formula (1). As the monomer A, one type may be used alone, or two or more types may be used in combination.

（式（１）中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は水酸基を有する有機基を示す。）

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having a hydroxyl group.)

In the formula (1), R ² is an organic group having a hydroxyl group, preferably an organic group having a hydroxyl group and having 1 to 30 carbon atoms, and more preferably an organic group having a hydroxyl group and having 1 to 20 carbon atoms. .. Examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a polyoxyalkylene group having 4 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Further, R ² may contain, for example, a halogen atom such as a fluorine atom or a chlorine atom, a nitrogen atom, a functional group other than a hydroxyl group, or the like.

The first structural unit derived from monomer A preferably contains a structural unit derived from a (meth) acrylic monomer having two or more hydroxyl groups from the viewpoint of further improving lubricity and antifouling property. In this case, the content of the structural unit derived from the (meth) acrylic monomer having 2 or more hydroxyl groups is more preferably at least 10% by mass, still more preferably 20% by mass or more in the first structural unit. , 30% by mass or more is particularly preferable. The upper limit of the content of the structural unit derived from the (meth) acrylic monomer having 2 or more hydroxyl groups is not particularly limited, and may be, for example, 100% by mass or less in the first structural unit, and 70% by mass or less. It may be.

Examples of the monomer A include an ester of a polyhydric alcohol having two or more hydroxyl groups and (meth) acrylic acid, an ester of a saccharide and (meth) acrylic acid, and a saccharide having an amino group and (meth) acrylic acid. Esther with. These esters may be prepared not only by a transesterification reaction but also by a transesterification reaction or a ring opening reaction of (meth) acrylic acid glycidyl ester.

Examples of polyhydric alcohols having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, propanediol, glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, and the like. Examples thereof include hexaglycerin, pentaerythritol, 1,2,6-hexanetriol, 2-hydroxymethyl-2-methyl-1,3-propanediol, and 2-ethyl-2-hydroxymethyl-1,3-propanediol. Examples of the saccharide include monosaccharides such as glucose, mannose, galactose, gulose, fructose, and D-ribose, glucoside, galactoside, fructoside, etc. derived from the monosaccharide, and these dimers and trimers. Can be mentioned. Examples of saccharides having an amino group include D-glucosamine.

From the viewpoint of further improving the lubricity and antifouling property, the monomer A is a monomer represented by the following formula (1A) and / or one as a (meth) acrylic monomer having two or more hydroxyl groups. As the (meth) acrylic monomer having a hydroxyl group, a monomer represented by the following formula (1B) is preferable.

（式（１Ａ）中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^３は炭素数１〜４のアルキレン基を示す。）

(In the formula (1A), R ¹ represents a hydrogen atom or a methyl group, and R ³ represents an alkylene group having 1 to 4 carbon atoms.)

（式（１Ｂ）中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^４は炭素数１〜４のアルキレン基を示す。）

(In formula (1B), R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkylene group having 1 to 4 carbon atoms.)

Examples of the monomer represented by the formula (1A) include glycerol monoacrylate (R ¹ = hydrogen atom, R ³ = methylene group) and glycerol monomethacrylate (R ¹ = methyl group, R ³ = methylene group). ..

Examples of the monomer represented by the formula (1B) include hydroxyethyl acrylate (R ¹ = hydrogen atom, R ⁴ = ethylene group) and 2-hydroxyethyl methacrylate (R ¹ = methyl group, R ⁴ = ethylene group). And so on.

The structural unit derived from the monomer represented by the formula (1A) corresponds to the structural unit represented by the following formula (1A'), and the structural unit derived from the monomer represented by the formula (1B). The unit corresponds to the structural unit represented by the following formula (1B').

（式（１Ａ’）中、Ｒ^１及びＲ^３は式（１Ａ）と同義である。）

(In formula (1A'), R ¹ and R ³ are synonymous with formula (1A).)

（式（１Ｂ’）中、Ｒ^１及びＲ^４は式（１Ｂ）と同義である。）

(In equation (1B'), R ¹ and R ⁴ are synonymous with equation (1B).)

The molecular weight of monomer A is preferably 500 or less.

The monomer 1A is preferably a monomer synthesized by a method in which a monomer having a 1,3-dioxolane structure is passed through as a raw material or an intermediate. A polymer polymerized using a monomer synthesized via a monomer having a 1,3-dioxolane structure as a raw material or an intermediate is preferable because the smoothness of the coating film is good.

The content of the first structural unit derived from the monomer A is 70% by mass or more with respect to the total amount of the copolymer. From the viewpoint of further improving the lubricity and antifouling property, the content of the first structural unit in the copolymer is preferably 80% by mass to 99% by mass, and more preferably 90% by mass to 97% by mass. preferable.

The first structural unit may be any structural unit having a hydroxyl group in the copolymer. That is, it may be a structural unit polymerized using the monomer A, and after the hydroxyl group is polymerized as a monomer protected by a protecting group, the hydroxyl group is modified by deprotecting the protecting group or the like. The structure having may be introduced.

Examples of monomer B include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, and itaconic acid monomethyl ester. Examples thereof include carboxy group-containing aliphatic monomers such as itaconic acid monobutyl ester and vinyl benzoic acid. Among these, acrylic acid, methacrylic acid or itaconic acid is preferable, and acrylic acid or methacrylic acid is more preferable. As the monomer B, one type may be used alone, or two or more types may be used in combination.

The content of the second structural unit derived from the monomer B is 1% by mass or more with respect to the total amount of the copolymer. From the viewpoint of further improving the lubricity and antifouling property, the content of the second structural unit in the copolymer is preferably 2% by mass to 25% by mass, and more preferably 3% by mass to 20% by mass. preferable.

The second structural unit may be any structural unit having a carboxy group in the copolymer. That is, it may be a structural unit polymerized using monomer B, and after polymerizing a monomer having another substituent such as an ester group, the ester group or the like is converted into a carboxy group by hydrolysis or the like. It may be a structural unit.

The copolymer according to the present embodiment may contain a structural unit derived from monomer C, which is neither of the above-mentioned monomers A and B. Examples of the monomer C include a monomer having a structure in which an organic group having 4 or more carbon atoms is bonded to an ethylenically unsaturated group. Examples of such a monomer include a (meth) acrylic acid ester represented by the following formula (2).

（式（２）中、Ｒ^５は水素原子又はメチル基を示し、Ｒ^６は炭素が連続して４個以上結合した炭素鎖を有する有機基を示す。）

(In the formula (2), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an organic group having a carbon chain in which four or more carbons are continuously bonded.)

Examples of the (meth) acrylic acid ester represented by the formula (2) include (meth) acrylic acid n-butyl, (meth) acrylic acid s-butyl, (meth) acrylic acid t-butyl, and (meth) acrylic acid n. -Amil, s-amyl (meth) acrylate, t-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic Tridecyl acid acid, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic Butyl oxy, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylate Tetrahydrofurfuryl, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, N, N-dimethylamino (meth) acrylate Acrylic can be mentioned.

Among the monomers having a structure in which an organic group having 4 or more carbon atoms is bonded to the ethylenically unsaturated group, those other than the (meth) acrylic acid ester represented by the formula (2) are butyl vinyl ether and 2 -Vinyl ethers such as ethylhexyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol vinyl ether, N-vinyls such as N-vinylmorpholin and N-vinylcarbazole (excluding those having a lactam ring), N-phenyl Examples thereof include N-substituted maleimides such as maleimide, N-benzylmaleimide, N-naphthylmaleimide, N-cyclohexylmaleimide, N-butylmaleimide, N-isopropylmaleimide and N-ethylmaleimide.

The monomer C is a (meth) acrylic acid alkyl ester of any one of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl chloride, vinylidene chloride, etc .; Olefines such as ethylene, propylene, butene, isoprene; N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, etc. Vinyl compounds; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; methyl maleimide and the like can also be used.

The content of the structural unit derived from the monomer C is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less, based on the total amount of the copolymer. preferable.

The above-mentioned copolymer can be produced by appropriately selecting the above-mentioned monomer and carrying out a polymerization reaction. The preferable amount of the monomer used in the polymerization reaction is the same as the preferable content of the structural unit derived from these monomers in the above-mentioned copolymer.

The polymerization reaction is preferably carried out in the presence of a polymerization initiator. Examples of the polymerization initiator include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis. Azo-based compounds such as (isobutyronitrile); organic peroxides such as benzoyl peroxide, peracetic acid, and di-t-butyl peroxide are suitable. These polymerization initiators may be used alone or in the form of a mixture of two or more.

The amount of the polymerization initiator used is preferably 0.01 g or more and 10 g or less, and more preferably 0.1 g or more and 5 g or less, with respect to 1 mol of the amount of the monomer used in the polymerization reaction.

The above-mentioned polymerization reaction may be carried out without using a solvent, but it is preferable to use a solvent. Examples of the solvent include water, acetonitrile, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol and the like, and water is preferable from the viewpoint of preventing environmental pollution. These solvents may be used alone or in the form of a mixture of two or more. The amount of the solvent used is preferably 40 to 250 parts by mass with respect to 100 parts by mass of the monomer used in the polymerization reaction.

The polymerization reaction is usually preferably carried out at 0 ° C. or higher, and is preferably carried out at 150 ° C. or lower. More preferably, it is 40 ° C. or higher, further preferably 60 ° C. or higher, and particularly preferably 80 ° C. or higher. Further, it is more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower. The polymerization temperature does not have to be kept substantially constant in the polymerization reaction, and may fluctuate (heat or cool) once or twice or more. The polymerization reaction may be carried out under any conditions of normal pressure, pressure and reduced pressure.

In the above polymerization reaction, the monomer, the polymerization initiator and the like may be added to the reactor all at once, or may be added sequentially or continuously.

The method for producing the copolymer may include steps other than the above-mentioned polymerization reaction step. Examples of other steps include a aging step, a neutralizing step, a deactivating step of a polymerization initiator and a chain transfer agent, a diluting step, a drying step, a concentration step, and a purification step.

Since the resin composition according to the present embodiment described above is excellent in lubricity and antifouling property, it can be suitably used for antifouling paint or medical device coating. Specifically, paints such as ship bottom paints and antifouling paints, as well as antifouling treatments and cloudproof treatments for various base materials such as metals, fibers, fabrics, glass, resins, hollow threads, ceramics, porous materials, and membranes. Suitable for surface treatments such as antistatic, hydrophilization, pollution prevention, antifouling, etc., especially for surface treatment of medical equipment and medical equipment, ships, underwater structures, fishing nets, fishing equipment, piping, irrigation canals, etc. Suitable for surface treatment of articles such as water intake facilities.

<Curable composition>
The curable composition according to the present embodiment includes a predetermined cross-linking agent, a monomer containing a (meth) acrylic monomer having a hydroxyl group and a polymerizable double bond-containing monomer having a carboxy group, and a radical generator. , Contain. The content of the (meth) acrylic monomer having a hydroxyl group is 70% by mass or more based on the total amount of the monomers, and the content of the polymerizable double bond-containing monomer having a carboxy group is based on the total amount of the monomers. As a result, it is 1% by mass or more. The content of the cross-linking agent is 0.1 to 4 parts by mass with respect to 100 parts by mass of the monomer.

(Crosslinking agent)
The cross-linking agent is at least one selected from the group consisting of a cross-linking agent having an oxazoline group, a cross-linking agent having an epoxy group, a cross-linking agent having a carbodiimide group, and a melamine resin-based cross-linking agent. The preferred type of the cross-linking agent is the same as the type of the cross-linking agent described in the above resin composition, and redundant description will be omitted here.

The content of the cross-linking agent in the curable composition needs to be 0.1 to 4 parts by mass with respect to 100 parts by mass of the monomer described later, and from the viewpoint of further improving lubricity and antifouling property, It is preferably 0.3 to 3 parts by mass, more preferably 0.5 to 2.5 parts by mass, and even more preferably 1 to 2 parts by mass.

(monomer)
The (meth) acrylic monomer having a hydroxyl group and the polymerizable double bond-containing monomer having a carboxy group contained in the monomer according to the present embodiment include the monomer A described in the above resin composition and the monomer containing the polymerizable double bond, respectively. The same as the monomer B can be used. Further, the monomer may contain a monomer C which is neither a monomer A nor a monomer B. As the monomer C, the same monomer C as described in the above resin composition can be used.

(Radical generator)
Examples of the radical generator include a photoradical generator and a thermal radical generator.

Examples of the photoradical generator include benzoins such as benzoin, benzoin methyl ether and benzoin ethyl ether and alkyl ethers thereof; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone. Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 1-hydroxycyclohexylphenyl ketone (Irgacure 184), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane- 1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides and xanthones can be mentioned.

Examples of the thermal radical generator include t-amylperoxy-2-ethylhexanoate, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t. Organic peroxides such as -butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexanoate; 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydro Chloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2' -Azobis (N, N'-dimethyleneisobutyramidine), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 1,1'-azobis (cyclohexanecarbonitrile) , 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) and other azo compounds; t-butyl hydroperoxide, hydrogen peroxide and the like. Oxides: Persulfates such as potassium persulfate and ammonium persulfate can be mentioned. These may be used alone or in combination of two or more. Further, a reducing agent such as a transition metal salt or amines may be used in combination with the polymerization initiator.

The content of the radical generator in the curable composition is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, and 0.5 to 5% by mass, for example. % Is more preferable.

Since the curable composition according to the present embodiment described above is excellent in lubricity and antifouling property, it can be suitably used for antifouling paint or medical device coating. Specifically, paints such as ship bottom paints and antifouling paints, as well as antifouling treatments and cloudproof treatments for various base materials such as metals, fibers, fabrics, glass, resins, hollow threads, ceramics, porous materials, and membranes. Suitable for surface treatments such as antistatic, hydrophilization, pollution prevention, antifouling, etc., especially for surface treatment of medical equipment and medical equipment, ships, underwater structures, fishing nets, fishing equipment, piping, irrigation canals, etc. Suitable for surface treatment of articles such as water intake facilities.

<Article with coating film>
An article with a coating film can be obtained by forming a coating film on a substrate using the resin composition or the curable composition according to the present embodiment described above. That is, the article with a coating film according to the present embodiment includes a base material and a coating film provided on the base material and containing a crosslinked body obtained by cross-linking the resin composition or the curable composition. ..

The method for forming the coating film on the base material is not particularly limited, and examples thereof include a method of immersing a solution of the resin composition or the curable composition in the base material, a method of spraying the solution on the base material, and the like. ..

A crosslinked product obtained by cross-linking the resin composition (hereinafter, also referred to as “cross-linked product A”) can be obtained by cross-linking the above-mentioned copolymer and cross-linking agent.

The copolymer and the cross-linking agent before cross-linking are preferably an aqueous solution containing the copolymer and the cross-linking agent from the viewpoint of handleability and the like. The aqueous liquid can be easily applied onto the base material, and a crosslinked body can be formed on the base material by cross-linking the obtained coating film.

The aqueous solution means a solution of water or a mixed solvent of water having a water content of 50% by mass or more and a hydrophilic organic solvent. Examples of the hydrophilic organic solvent include monohydric alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol and allyl alcohol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol and dipropylene glycol. Polyhydric alcohols such as acetone, methyl ethyl ketone, ketones such as methyl propyl ketone, aliphatic organic acid alkyl esters such as methyl formate, ethyl formate, methyl acetate, methyl acetoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl Examples thereof include alkyl ethers of polyhydric alcohols such as ethers, ethylene glycol monoethyl ethers and dipropylene glycol monomethyl ethers. These hydrophilic organic solvents may be used alone or in combination of two or more. Water is preferable as the aqueous medium.

The concentration of the copolymer and the cross-linking agent in the aqueous solution is not particularly limited, but can be, for example, 0.5 to 20% by mass.

The conditions for cross-linking the above-mentioned copolymer and the cross-linking agent can be adjusted according to the type of the cross-linking agent used. For example, the cross-linking may be carried out under the condition of heat treatment at 50 to 150 ° C. for 5 to 120 minutes. it can.

The crosslinked product obtained by cross-linking the curable composition (hereinafter, also referred to as “cross-linked product B”) can be obtained by polymerizing and cross-linking the above-mentioned cross-linking agent, monomer and radical generator.

When a photoradical generator is used as the radical generator, for example, the polymerization and cross-linking reactions can be allowed to proceed by irradiating the curable composition with ultraviolet rays.

As the ultraviolet rays, ultraviolet rays having a wavelength of 150 to 450 nm can be applied. The conditions for ultraviolet irradiation are not particularly limited, but can be, for example, conditions such as an illuminance of 0.1 to 100 mW / cm ² for ultraviolet irradiation and an irradiation time of 1 to 15 minutes.

When a thermal radical generator is used as the radical generator, for example, the polymerization and cross-linking reactions can be allowed to proceed by heat-treating the curable composition.

The heat treatment conditions are not particularly limited, but can be, for example, a heat treatment temperature of 50 to 200 ° C. and a treatment time of 0.05 to 5 hours.

The coating film thus obtained contains the above-mentioned crosslinked body A or the above-mentioned crosslinked body B. In such a coating film, for example, a solution of the above-mentioned crosslinked body or a precursor thereof is applied onto an appropriate base material. It is obtained by drying under appropriate conditions and then subjecting to cross-linking conditions as necessary.

The thickness of the coating film can be appropriately adjusted according to the intended use, and can be, for example, 0.01 μm to 200 μm, preferably 0.1 μm to 100 μm, and more preferably 0.5 μm to 10 μm.

<Coating agent, base material with laminated coating>
The coating agent according to the present embodiment includes a first agent containing the above-mentioned cross-linking agent and a second agent containing the above-mentioned copolymer. In this way, by using a coating agent containing the first agent and the second agent separately, the first coating film formed from the first agent and the second coating film formed from the second agent can be obtained. It can be formed separately, and as a result, it is provided on the base material, the first coating film provided on the base material, and the main surface on the first coating film opposite to the base material. It is possible to obtain a substrate with a laminated coating film comprising the second coating film obtained.

That is, the substrate with a laminated coating film has an undercoating step of applying the first agent of the coating agent on at least one main surface of the substrate to form the first coating film, and on the first coating film. A coating step of applying a second agent to form a second coating film is provided.

The first coating film and the second coating film thus obtained may be crosslinked by drying under appropriate conditions and then subjecting them to crosslinking conditions.

The second agent may contain a copolymer, but may also contain the above-mentioned monomer and the above-mentioned radical generator. In this case, the obtained first coating film and the second coating film are polymerized and crosslinked by drying under appropriate conditions and then subjecting them to polymerization and crosslinking conditions.

The thicknesses of the first coating film and the second coating film can be appropriately adjusted according to the intended use. The thickness of the first coating film may be, for example, 0.01 to 50 μm, and may be 0.05 to 30 μm. The thickness of the second coating film may be, for example, 0.1 to 10 μm, and may be 0.2 to 5 μm.

The total thickness of the first coating film and the second coating film can also be appropriately adjusted according to the intended use, and may be, for example, 0.1 to 200 μm, 0.5 to 100 μm. Good.

Since the coating agent according to the present embodiment is excellent in lubricity and antifouling property, it can be suitably used for antifouling paint or coating for medical devices. Specifically, paints such as ship bottom paints and antifouling paints, as well as antifouling treatments and cloudproof treatments for various base materials such as metals, fibers, fabrics, glass, resins, hollow threads, ceramics, porous materials, and membranes. Suitable for surface treatments such as antistatic, hydrophilization, pollution prevention, antifouling, etc., especially for surface treatment of medical equipment and medical equipment, ships, underwater structures, fishing nets, fishing equipment, piping, irrigation canals, etc. Suitable for surface treatment of articles such as water intake facilities.

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

<Synthesis example>
[GLMA (glycerol monoacrylate)]
A gas introduction tube, a thermometer, a cooling tube, and a distilling head connected to a distilling liquid receiver were attached to the reaction vessel containing the stirrer, and 230 g of methyl acrylate, 2,2-dimethyl-1,3 −Dioxolan-4-methanol (DOM) 70 g was charged, the reaction solution was stirred while blowing an oxygen / nitrogen mixed gas (oxygen concentration 7 vol%) through a gas introduction pipe, and heating was started in an oil bath (bath temperature 110 ° C.). .. After no water came out to the distillate, 4.5 g of titanium tetraisopropoxide was added to the reaction vessel to start the transesterification reaction. The area ratio of iPGLMA (isopropyridene glyceryl acrylate) / DOM was tracked by gas chromatography (GC) analysis while azeotropically distilling off the produced methanol with methyl acrylate. By GC analysis 7 hours after the start of the reaction, it was confirmed that the area ratio of iPGLMA / DOM exceeded 9/1, the reaction was terminated, and the mixture was cooled to room temperature. In this way, iPGLMA, which is a monomer having a 1,3-dioxolane structure, was obtained as an intermediate for GLMA synthesis. 150 g of purified water and 300 g of ethyl acetate as an extraction solvent were added to the reaction mixture, and the mixture was stirred for 10 minutes. The precipitate of titanium oxide generated by the hydrolysis of titanium tetraisopropoxide was removed by suction filtration, and the filtrate was transferred to a separatory funnel to separate the organic layer and the aqueous layer. The organic layer was washed twice with purified water and then transferred to a rotary evaporator, and residual methyl acrylate and light boiling components were distilled off to obtain 96 g of iPGLMA.

A gas introduction tube was provided in an eggplant flask containing a stirrer, and 160 ml of purified water and 80 g of iPGLMA were added and dissolved, and then 35 g of solid acid catalyst Amberlist 15Jwet (manufactured by Organo), which was previously immersed in water and air-dried, was added. The reaction solution was stirred while blowing an oxygen / nitrogen mixed gas (oxygen concentration 7 vol%) through the gas introduction pipe, and the deprotection reaction was started at room temperature. The area ratio of GLMA / iPGLMA was tracked by GC analysis, and it was confirmed that the area ratio exceeded 99/1, and the reaction was completed in 4 hours. The filtrate obtained by filtering the solid acid catalyst was washed with n-hexane to remove unreacted iPGLMA. The aqueous layer was concentrated under reduced pressure to obtain 53 g of the target GLMA.

[Copolymer]
A gas inlet tube, a thermometer, and a cooling tube are attached to a reaction vessel containing a stirrer, and 13.3 g of GLMA, 0.7 g of acrylic acid (AA) as a monomer, and 125.0 g of ion-exchanged water as a solvent are charged, and nitrogen is added. The temperature was raised to 98 ° C. while flowing gas. A solution prepared by dissolving 0.007 g of an azo radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., trade name: VA086) in 1.0 g of ion-exchanged water was added to initiate a polymerization reaction. The reaction was continued for 7 hours while maintaining the temperature at 99 ° C. or higher, during which time 0.0035 g of VA086 was dissolved in 0.5 g of ion-exchanged water 1 hour, 3 hours, and 5 hours after the start of the reaction. Was put in.

The obtained polymer 1 had a weight average molecular weight (standard polystyrene equivalent) of 369000 as measured by GPC. The solution viscosity of the reaction solution measured by the E-type viscometer was 19.1 mPa · s at 25 ° C.

<Evaluation method>
The sample films obtained in Examples 1 to 7 and Comparative Examples 1 to 4 described later were evaluated by the following methods. The results are shown in Table 1, Table 2 and Table 3.

[Coating film thickness]
Measured with a micrometer.

[Underwater sliding resistance]
Using a dynamic friction measuring machine (manufactured by Trinity Lab, trade name: TL201Tt), using a flat plate contact of stainless steel (SUS), the sample film is subjected to the conditions of a load of 400 g, a speed of 1000 mm / sec, 10 reciprocations, and a reciprocating distance of 10 mm. The sliding resistance value was measured. The sliding resistance was measured by using a commercially available cyanoacrylate adhesive, pouring a stator and ion-exchanged water into a polystyrene petri dish at the edge of the sample film, and immersing the sample film.

<Example 1>
100 parts by mass of the copolymer obtained above in terms of solid content and 2 parts by mass of Epocross WS-700 (oxazoline-based cross-linking agent: manufactured by Nippon Catalyst Co., Ltd.) as a cross-linking agent are blended in terms of solid content, and ethanol is added. Dilute with and adjust to a concentration of 5% to obtain a resin composition. The obtained resin composition was applied onto a pet film (Toray Mirror) using a bar coater, dried at room temperature, and then heat-treated at 120 ° C. for 30 minutes with a hot air dryer to prepare a sample film.

<Example 2, Comparative Example 1>
A sample film was obtained in the same manner as in Example 1 except that the type and blending amount of the cross-linking agent were changed as shown in Table 1 below. Details of the product names or abbreviations in Table 1 are shown below.

(Crosslinking agent)
WS700: Epocross WS-700 (Oxazoline group-containing cross-linking agent: manufactured by Nippon Shokubai Co., Ltd.)
V-02: Carbodilite V-02 (Carbodiimide group-containing cross-linking agent: manufactured by Nisshinbo Chemical Co., Ltd.)

<Example 3>
The first agent obtained by diluting Epocross WS-700 with isopropyl alcohol to a concentration of 0.5% and the second agent obtained by diluting the copolymer obtained above with water (concentration: 5%). ) And a coating agent was prepared. Subsequently, the first agent as an undercoat was applied onto a pet film using a bar coater, and dried at 80 ° C. for 5 minutes. Next, the second agent was overcoated and applied from above using a bar coater. After drying at room temperature, it was heat-treated at 120 ° C. for 30 minutes with a hot air dryer to prepare a sample film.

<Example 4>
A sample film was obtained in the same manner as in Example 3 except that the cross-linking agent contained in the first agent was changed to Carbodilite V-02.

<Example 5>
As a second agent, 50 parts by mass of GLMA, 45 parts by mass of hydroxyethyl acrylate (HEA), 5 parts by mass of acrylic acid (AA), and 0.5 parts by mass of Luperox 575 (organic peroxide: manufactured by Alchema Yoshitomi) as a radical generator. A sample film was obtained in the same manner as in Example 3 except that a liquid consisting of the above was prepared.

<Comparative example 2>
A sample film was obtained in the same manner as in Example 3 except that undercoating was not performed.

Table 2 shows the evaluation results of the sample films of Examples 3 to 5 and Comparative Example 2. Details of the product names or abbreviations in Table 2 are shown below.

(monomer)
GLMA: The above glycerol monoacrylate HEA: hydroxyethyl acrylate AA: acrylic acid

(Radical generator)
Luperox 575: Luperox 575 (organic peroxide: manufactured by Alchema Yoshitomi)

<Examples 6 to 7, Comparative Examples 3 to 4>
A curable composition was prepared by mixing a monomer, a cross-linking agent and a radical generator with the formulations shown in Table 3. The obtained curable composition was applied onto a pet film (Toray mirror) using a bar coater, and heat-treated at 120 ° C. for 30 minutes with a hot air dryer to obtain a sample film.

Samples of Example 8 and Comparative Example 5 described later were prepared, and a barnacle adhesion test was conducted by the following method.

<Barnacle adhesion test>
As a test organism, we used the attachment stage larvae (Cyprus) of Amphibalanus aureus, which adheres to artificial structures in the inner bay area in large quantities. Adult Amphibalanus aureus (produced along the coast of Himeji) was maintained and bred by feeding Artemia in a circulating aquarium (water temperature 23 ± 1 ° C). Nauplius larvae hatched from adults were collected, transferred to a glass beaker filled with filtered seawater, and bred by feeding them with the floating diatom Cheatocellos calcitrans to artificially obtain attachment stage larvae (Cyprus larvae). The obtained Cyprus larvae were maintained by cold and dark treatment. These larvae were returned to room temperature before the test, and active swimming solids were selected and used for the adhesion test.

The sample was allowed to stand on the bottom surface of an 80 mL polypropylene container (68 × 68 × 35 mm), and seawater and larvae in the adhesion stage were added. As the seawater, natural seawater collected from the coast of Himeji City was filtered through a mixed cellulose membrane having a pore size of 0.45 μm (Toyo filter paper). The seawater condition had a salinity of 2.88% and a pH of 8.19.

After standing at room temperature around 25 ° C., under bright light (laboratory lighting) during the day, and in the dark at night for 10 days, the adhesion rate of the larvae in the adhesion stage was calculated. The results are shown in Table 4.

<Example 8>
Using the coating agent prepared in Example 3, the first agent was applied as an undercoat on a 3 cm × 3 cm rigid vinyl chloride resin plate using a bar coater, and dried at 80 ° C. for 5 minutes. Next, the second agent was overcoated and applied from above using a bar coater. After drying at room temperature, it was heat-treated at 120 ° C. for 30 minutes with a hot air dryer to prepare a sample film.

<Comparative example 5>
A 3 cm × 3 cm rigid vinyl chloride resin plate without painting was prepared.

Claims (14)

At least one cross-linking agent selected from the group consisting of a cross-linking agent having an oxazoline group, a cross-linking agent having an epoxy group, a cross-linking agent having a carbodiimide group, and a melamine resin-based cross-linking agent.
A copolymer having a first structural unit derived from a (meth) acrylic monomer having a hydroxyl group and a second structural unit derived from a polymerizable double bond-containing monomer having a carboxy group,
Contains,
The content of the first structural unit in the copolymer is 70% by mass or more.
The content of the second structural unit in the copolymer is 1% by mass or more.
A resin composition in which the content of the cross-linking agent is 0.1 to 4 parts by mass with respect to 100 parts by mass of the copolymer. The resin composition according to claim 1, wherein at least 10% by mass in the first structural unit is a structural unit derived from a (meth) acrylic monomer having 2 or more hydroxyl groups. The resin composition according to claim 2, wherein the structural unit derived from the (meth) acrylic monomer having two or more hydroxyl groups contains a structural unit derived from glycerol (meth) acrylate. The resin composition according to any one of claims 1 to 3, which is used for an antifouling paint. The resin composition according to any one of claims 1 to 3, which is used for coating medical devices. At least one cross-linking agent selected from the group consisting of a cross-linking agent having an oxazoline group, a cross-linking agent having an epoxy group, a cross-linking agent having a carbodiimide group, and a melamine resin-based cross-linking agent.
A monomer containing a (meth) acrylic monomer having a hydroxyl group and a polymerizable double bond-containing monomer having a carboxy group,
Radical generator and
Contains,
The content of the (meth) acrylic monomer having a hydroxyl group is 70% by mass or more based on the total amount of the monomers.
The content of the polymerizable double bond-containing monomer having a carboxy group is 1% by mass or more based on the total amount of the monomers.
A curable composition in which the content of the cross-linking agent is 0.1 to 4 parts by mass with respect to 100 parts by mass of the monomer. The curable composition according to claim 6, which is used for an antifouling paint. The curable composition according to claim 6, which is used for coating medical devices. The base material is crosslinked with the resin composition according to any one of claims 1 to 5 or the curable composition according to any one of claims 6 to 8 provided on the base material. An article with a coating film, comprising a coating film containing a crosslinked product. The resin composition according to any one of claims 1 to 5 or the curable composition according to any one of claims 6 to 8 is applied and coated on at least one main surface of the base material. A method for producing a coated article, comprising a coating step of forming a film. A first agent containing at least one cross-linking agent selected from the group consisting of a cross-linking agent having an oxazoline group, a cross-linking agent having an epoxy group, a cross-linking agent having a carbodiimide group, and a melamine resin-based cross-linking agent.
It contains a copolymer having a first structural unit derived from a (meth) acrylic monomer having a hydroxyl group and a second structural unit derived from a polymerizable double bond-containing monomer having a carboxy group, and has the same weight. The content of the first structural unit in the coalescence is 70% by mass or more, and the content of the second structural unit in the copolymer is 1% by mass or more.
A coating agent. The coating agent according to claim 11, which is used for an antifouling paint. The coating agent according to claim 11, which is used for coating medical devices. An undercoating step of applying the first agent of the coating agent according to any one of claims 11 to 13 to form a first coating film on at least one main surface of a base material.
A coating step of applying the second agent onto the first coating film to form a second coating film, and
A method for producing a base material with a laminated coating film.