JP2017113689A - Hydrophilic film formation method on base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film formation method for modifying the surface of a base material and imparting hydrophilicity and which is easy, excellent in productivity and excellent in the persistence of hydrophilicity.SOLUTION: A hydrophilic film formation method on a base material includes: step (1) of forming an undercoat film layer using a composition (1) containing a binder component (A) and a compound (B) having a polysiloxane chain and a polyoxyalkylene chain; step (2) of forming a hydrophilicity imparting layer using a composition (2) containing a hydrophilicity imparting group-containing polymerizable unsaturated compound (C) on the base material formed with the undercoat film layer in the step (1); and step (3) of sequentially performing a step of irradiating activation energy rays on the base material formed with the undercoat film layer and the hydrophilicity imparting layer in the steps (1) and (2) or heating the base material.SELECTED DRAWING: None

Description

  The present invention relates to a film forming method for modifying a surface of a substrate to impart hydrophilicity.

  Generally, attempts have been made to impart hydrophilicity to various types of substrates because hydrophilicity such as stain resistance and anti-fogging properties can be imparted and added value can be increased by making the substrates hydrophilic.

  In Patent Document 1, the surface of an undercoat layer made of a polymer laminated on a substrate and having a photopolymerization start portion chemically bonded thereto is irradiated with ultraviolet rays in a state where a hydrophilic monomer is brought into contact with the undercoat layer. It is described that various functions excellent in durability, particularly hydrophilic performance, can be imparted to the base material by graft polymerization of a hydrophilic monomer to the layer. However, the surface treatment method has a problem that hydrophilic sustainability may be insufficient.

JP-A-9-77891

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for forming a hydrophilic film which is simple and excellent in productivity and excellent in hydrophilic sustainability.

  As a result of intensive studies in order to achieve the above object, the present inventors have undercoated the base material using a composition containing a binder component and a compound having a polysiloxane chain and a polyoxyalkylene chain. A film-forming method in which a film layer is formed, and then a hydrophilicity-imparting layer containing a hydrophilicity-imparting group-containing polymerizable unsaturated compound is formed, followed by irradiation with active energy rays or heating (particularly, (i) a binder An undercoat film layer is formed using a composition containing a component and a compound having a polysiloxane chain and a polyoxyalkylene chain, and then a hydrophilicity-providing group-containing polymerizable unsaturated compound, a photopolymerization initiator, and a thermal polymerization start A film-forming method in which a hydrophilicity-imparting layer containing a polymerization initiator selected from the agents is formed and then irradiated with active energy rays or heated; and (ii) An undercoat film layer is formed using a composition containing an inder component, a compound having a polysiloxane chain and a polyoxyalkylene chain, and a photopolymerization initiator, and then containing a hydrophilic unsaturated group-containing polymerizable unsaturated compound It was found that the above object can be achieved according to a film forming method in which an active energy ray is irradiated after forming a hydrophilicity imparting layer.

  That is, the present invention includes the following aspects.

Item 1, on the substrate,
Step (1): Using the composition (1) containing the binder component (A) and the compound (B) having a polysiloxane chain and a polyoxyalkylene chain, a step of forming an undercoat coating film layer,
Step (2): Using the composition (2) containing the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) on the substrate on which the undercoat coating layer has been formed in the step (1), A step of forming a hydrophilicity-imparting layer, and step (3): a step of treating the substrate on which the undercoat coating layer and the hydrophilicity-imparting layer are formed by the steps (1) and (2), At least one of the composition (1) and the composition (2) contains a polymerization initiator (D) selected from a photopolymerization initiator (D1) and a thermal polymerization initiator (D2),
When the composition (2) containing the photopolymerization initiator (D1) is used in the step (2), the substrate is irradiated with active energy rays.
When the composition (2) containing the thermal polymerization initiator (D2) is used in the step (2), the substrate is heated,
When the composition (2) not containing the polymerization initiator (D) is used in the step (2) and the composition (1) containing the photopolymerization initiator (D1) is used in the step (1) Irradiates the substrate with active energy rays,
When the composition (2) containing no polymerization initiator (D) is used in the step (2) and the composition (1) containing a thermal polymerization initiator (D2) is used in the step (1) Heating the substrate,
A method for forming a hydrophilic film on a substrate, characterized in that

Item 2, on the substrate,
Step (1): Using the composition (1) containing the binder component (A) and the compound (B) having a polysiloxane chain and a polyoxyalkylene chain, a step of forming an undercoat coating film layer,
Step (2): Hydrophilic imparting group-containing polymerizable unsaturated compound (C), photopolymerization initiator (D1), and thermal polymerization initiator on the base material on which the undercoat coating film layer has been formed in the step (1). A step of forming a hydrophilicity-imparting layer using a composition (2) containing a polymerization initiator (D) selected from (D2), and step (3): the steps (1) and (2) Is a step of treating a substrate on which an undercoat coating film layer and a hydrophilicity-imparting layer are formed, and the composition (2) containing a photopolymerization initiator (D1) is used in the step (2). Irradiating the substrate with active energy rays and heating the substrate when the composition (2) containing the thermal polymerization initiator (D2) is used in the step (2),
Item 2. The method for forming a hydrophilic film on a substrate according to Item 1, wherein the steps are sequentially performed.

Item 3, on the substrate,
Step (1): Using a composition (1) containing a binder component (A), a compound (B) having a polysiloxane chain and a polyoxyalkylene chain, and a photopolymerization initiator (D1), an undercoat coating layer Forming a process,
Step (2): Using the composition (2) containing the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) on the substrate on which the undercoat coating layer has been formed in the step (1), Step of forming a hydrophilicity imparting layer and step (3): A step of irradiating active energy rays on the substrate on which the undercoat coating layer and the hydrophilicity imparting layer are formed by the steps (1) and (2). ,
Item 2. The method for forming a hydrophilic film on a substrate according to Item 1, wherein the steps are sequentially performed.

  Item 4. The hydrophilic film forming method according to any one of Items 1 to 3, wherein the composition (1) contains a hydroxyl group-containing resin (A1) and a crosslinking agent (A2) as the binder component (A).

  Item 5. The hydrophilic film forming method according to Item 4, wherein the crosslinking agent (A2) is at least one selected from the group consisting of a polyisocyanate compound, a blocked polyisocyanate compound, and an amino resin.

  Item 6. The compound according to any one of Items 1 to 5, wherein the compound (B) having a polysiloxane chain and a polyoxyalkylene chain is a compound (B ′) having a hydroxyl group, a polysiloxane chain and a polyoxyalkylene chain. Hydrophilic film forming method.

  Item 7, The composition (1) contains 0.01 to 20% by mass of the compound (B) having a polysiloxane chain and a polyoxyalkylene chain, based on the total solid content of the composition (1). The hydrophilic film formation method of any one of -6.

  The film forming method of the present invention comprises a binder component (A) and an undercoat coating layer formed using a composition (1) containing a compound (B) having a polysiloxane chain and a polyoxyalkylene chain. A hydrophilicity-imparting layer is formed using the composition (2) containing a hydrophilicity-imparting group-containing polymerizable unsaturated compound, and the surface of the substrate is easily modified by irradiation or heating with active energy rays. And the effect that hydrophilicity can be provided can be produced.

  Hereinafter, the method for forming a hydrophilic film on a substrate of the present invention will be described in more detail.

The hydrophilic film forming method of the present invention (hereinafter sometimes abbreviated as “the present method”)
On the substrate
Step (1): Using the composition (1) containing the binder component (A) and the compound (B) having a polysiloxane chain and a polyoxyalkylene chain, a step of forming an undercoat coating film layer,
Step (2): Using the composition (2) containing the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) on the substrate on which the undercoat coating layer has been formed in the step (1), A step of forming a hydrophilicity-imparting layer, and step (3): a step of treating the substrate on which the undercoat coating layer and the hydrophilicity-imparting layer are formed by the steps (1) and (2), At least one of the composition (1) and the composition (2) contains a polymerization initiator (D) selected from a photopolymerization initiator (D1) and a thermal polymerization initiator (D2),
When the composition (2) containing the photopolymerization initiator (D1) is used in the step (2), the substrate is irradiated with active energy rays.
When the composition (2) containing the thermal polymerization initiator (D2) is used in the step (2), the substrate is heated,
When the composition (2) not containing the polymerization initiator (D) is used in the step (2) and the composition (1) containing the photopolymerization initiator (D1) is used in the step (1) Irradiates the substrate with active energy rays,
When the composition (2) containing no polymerization initiator (D) is used in the step (2) and the composition (1) containing a thermal polymerization initiator (D2) is used in the step (1) Heating the substrate,
Is a hydrophilic film forming method characterized by sequentially performing.

As the method for forming the hydrophilic film, among others,
On the substrate
Step (1): Using the composition (1) containing the binder component (A) and the compound (B) having a polysiloxane chain and a polyoxyalkylene chain, a step of forming an undercoat coating film layer,
Step (2): Hydrophilic imparting group-containing polymerizable unsaturated compound (C), photopolymerization initiator (D1), and thermal polymerization initiator on the base material on which the undercoat coating film layer has been formed in the step (1). A step of forming a hydrophilicity-imparting layer using a composition (2) containing a polymerization initiator (D) selected from (D2), and step (3): the steps (1) and (2) Is a step of treating a substrate on which an undercoat coating film layer and a hydrophilicity-imparting layer are formed, and the composition (2) containing a photopolymerization initiator (D1) is used in the step (2). Irradiating the substrate with active energy rays and heating the substrate when the composition (2) containing the thermal polymerization initiator (D2) is used in the step (2),
On the base material, and a method characterized in that
Step (1): Using a composition (1) containing a binder component (A), a compound (B) having a polysiloxane chain and a polyoxyalkylene chain, and a photopolymerization initiator (D1), an undercoat coating layer Forming a process,
Step (2): Using the composition (2) containing the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) on the substrate on which the undercoat coating layer has been formed in the step (1), Step of forming hydrophilicity imparting layer and step (3): Step of irradiating active energy rays on the substrate on which the undercoat coating layer and the hydrophilicity imparting layer are formed by the steps (1) and (2). ,
(Hereinafter, may be abbreviated as “method 2”).
Can be suitably used.

Substrate In the present invention, the substrate is a target for imparting hydrophilicity by modifying its surface. There is no restriction | limiting in particular as a base material, Any of an organic material, an inorganic material, or a hybrid material of organic and inorganic may be sufficient. The substrate in the present invention is preferably a substrate containing an organic polymer compound such as an organic material or an organic / inorganic hybrid material.

  Examples of the organic material constituting the base material include acrylic resins such as polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4, 4 ′. -Polyester resins such as dicarboxylate and polybutylene terephthalate, and epoxy resins represented by commercial products such as Epicoat (trade name: manufactured by Yuka Shell Epoxy Co., Ltd.), polycarbonate resin, polyimide resin, novolac resin, phenol Resin, acrylonitrile-butadiene-styrene (ABS) resin, vinylidene chloride resin, polyurethane resin, cellulose ester (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cell) , Acetylpropionylcellulose, nitrocellulose), polyamide, polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, poly Examples thereof include plastic materials such as ether ketone and various fiber reinforced plastic materials (hereinafter referred to as FRP material or simply FRP).

  Various types of FRP are known and mainly refer to materials whose strength is improved by including reinforcing fibers in plastic (matrix resin). As the matrix resin, an unsaturated polyester resin, an epoxy resin, a phenol resin, an acrylic resin, or the like can be used. As the reinforcing fiber, glass fiber, aramid fiber, carbon fiber, cellulose fiber or the like can be used alone or in combination of two or more. As a molding method of FRP, a known method can be used. A sheet molding compound (SMC) molding method, a resin infusion (RIMP) molding method, a prepreg / autoclave press method, and a spray-up method, which are manufactured using a mold. / RTM (Resin Transfer Molding) molding method and the like.

  Examples of the inorganic material include metal materials such as iron, aluminum, brass, copper, tinplate, stainless steel, galvanized steel, zinc alloy (Zn-Al, Zn-Ni, Zn-Fe, etc.) plated steel; glass; Cement; concrete and the like.

  The thickness of the substrate is selected according to the purpose of use and is not particularly limited, but is generally about 10 μm to 10 cm.

  The substrate is further coated on the surface (one surface of the substrate, or two or more surfaces (for example, the surface, the back surface, or two or more surfaces selected from one or more side surfaces if present)), a coating film, a gel coat A layer or the like may be formed. In the present specification, the term “substrate” includes a coating film, a gel coat layer and the like formed on the surface of the substrate.

  When the coating film is formed on the surface of the substrate, the coating film may be a single layer or a multilayer of two or more layers. The coating film may be a cured coating film or an uncured coating film. In the present invention, the cured coating film is a cured and dried state specified in JIS K 5600-1-1, that is, the center of the coating surface is strongly sandwiched between the thumb and the index finger, and the coating surface is free from dents due to fingerprints. In the coating film, the movement of the coating film is not felt, and the center of the coating surface is rubbed rapidly with the fingertip so that no trace is left on the coating surface. On the other hand, an uncured coating film is a state in which the coating film has not reached the above-mentioned cured and dried state, and includes a finger-touch dried state and a semi-cured dried state defined in JIS K 5600-1-1.

  The coating film formed on the substrate is, for example, a coating formed by a known thermosetting coating composition, an active energy ray curable coating composition, an active energy ray and a thermosetting coating composition, or the like. It can be a membrane.

  Examples of the thermosetting coating composition include coating compositions in the form of organic solvent type, aqueous type, powder type and the like containing a base resin having a crosslinkable functional group and a crosslinking agent. Examples of the crosslinkable functional group possessed by the base resin include a carboxyl group, a hydroxyl group, an epoxy group, and a silanol group. Examples of the base resin include acrylic resin, polyester resin, alkyd resin, and urethane resin. , Epoxy resin, fluorine resin, and the like. Examples of the crosslinking agent include polyisocyanate compounds, blocked polyisocyanate compounds, melamine resins, urea resins, carboxyl group-containing compounds, carboxyl group-containing resins, epoxy group-containing resins, and epoxy group-containing compounds. Among these, a coating film obtained from a paint containing a hydroxyl group-containing resin and a crosslinking agent, or a paint containing an acid group-containing resin and an epoxy group-containing resin is preferable, and a coating obtained from a paint containing a hydroxyl group-containing resin and a crosslinking agent is preferable. A film is more preferable, and a coating film obtained from a paint containing a hydroxyl group-containing resin and a polyisocyanate compound which may be blocked is more particularly preferable.

  The gel coat is used for smoothing irregularities on the surface of a substrate, improving design properties, blocking ultraviolet rays, and the like. Examples of the resin for forming the gel coat (gel coat resin) include unsaturated polyester resins, phenol resins, acrylic resins, epoxy resins, nitrified cotton (nitrocellulose) resins, or appropriate additions of pigments, dyes, and release resins. What mixed the mold etc. can be used conveniently.

  As a specific example of the base material on which the gel coat layer is formed, FRP in which the gel coat layer is formed is exemplified. The method for applying the gel coat layer is not particularly limited, and examples thereof include known methods such as a method for producing an integral molded body by a hand lay-up method, a spray-up method, and an in-mold coating method (in-mold coating method). . Specifically, a method in which a gel coat resin material that can be a surface of an outer plate is applied to the inner surface of a mold (for example, a mold) in advance, and then the FRP base material is laminated and cured, Examples thereof include a method in which a gel coat resin material is applied and then cured.

  Moreover, the base material may be one in which the coating film is formed on the gel coat layer.

  The substrate preferably has a hydroxyl group on its surface.

  The base material having a hydroxyl group is, for example, a method of coating a coating material containing a hydroxyl group-containing resin on the substrate; a hydroxyl group-containing resin and a polyisocyanate compound which may be blocked; It can be obtained by a method of applying a coating material containing an excess in an equivalent ratio (isocyanate group / hydroxyl group <1.0) with respect to an optionally blocked isocyanate group (including a blocked isocyanate group). Can do.

  Moreover, the base material which has a hydroxyl group applies the coating material containing the hydroxyl-containing resin and the polyisocyanate compound which may be blocked on a base material, and dries a coating film by the heating method with which a hydroxyl group remains. Can also be obtained. Specific examples of the heating method in which the hydroxyl group remains include a method of heating at a relatively low temperature and a method of heating for a relatively short time.

  The hydroxyl group may be originally produced by the base material or may be generated by a separate treatment. Of course, it is not hindered that both the material originally possessed by the base material and the material produced by a separate process are mixed. When a coating film, a gel coat layer, etc. are formed on the surface of the substrate, the hydroxyl group is originally possessed by the coating film, the gel coat layer, etc., or is generated by a separate process such as step (0) described later. It may be a thing. Of course, it is not hindered that both the coating film, the gel coat layer, and the like originally exist and those generated by separate processing.

Process (0)
In the coating film forming method of the present invention, before the step (1) which is an essential step, a plasma treatment, a corona discharge treatment, an active energy ray treatment is performed on a substrate to be subjected to surface modification and hydrophilicity. Then, a treatment (physical treatment) by at least one physical method selected from flame treatment, blast treatment, polishing treatment and the like can be performed. These physical treatments can be performed in combination of two or more as required.

  In the film forming method of the present invention, performing the step (0) before the step (1) is a viewpoint of improving adhesion between the base material and the undercoat film layer described later, a viewpoint of improving the wettability of the base material, and the like. To preferred. These performance improvements are considered to be caused by the following points: (i) By performing the above physical treatment (particularly, plasma treatment, corona discharge treatment, active energy ray treatment, and flame treatment) on the base material, The surface of the substrate is activated, and the adhesion and / or wettability is improved. Specifically, for example, a functional group (hydroxyl group, carboxyl group, etc.) is generated. The functional group is preferably a hydroxyl group that has reactivity with the curing agent (B) and contributes to improving the wettability of the substrate surface. (Ii) By subjecting the base material to the physical treatment (particularly polishing treatment), the material that interferes with the undercoat coating layer is removed, and the wettability of the base material is improved.

  The main chain and side chain of the polymer layer on the surface in contact with the atmosphere are separated by surface treatment such as plasma treatment, corona discharge treatment, active energy ray treatment, and flame treatment, and the separated polymer surface layer is a radical. It is considered that other radical species (for example, oxygen radicals or ozone in the air) recombine with the main chain or side chain to form a hydroxyl group, a carbonyl group, or the like.

  The physical treatment in the step (0) is preferably a plasma treatment, a corona discharge treatment, a flame treatment, a blast treatment, and a polishing treatment from the viewpoint of productivity and ease of treatment.

  Moreover, in the film formation method of this invention, before the process (1) which is an essential process, it is a strong acid process, a strong alkali process, and oxidation with respect to the base material used as the object which modifies the surface and provides hydrophilicity. You may perform the process (chemical process) by the at least 1 sort (s) of chemical method selected from the agent process. These chemical treatments can be performed in combination of two or more as required.

  In the film forming method of the present invention, the physical treatment and the chemical treatment may be used in combination.

Process (1)
In step (1), an undercoat coating layer is formed on the substrate using the composition (1) containing the binder component (A) and the compound (B) having a polysiloxane chain and a polyoxyalkylene chain. To do.

  More specifically, in the method 1, the composition (1) containing the binder component (A) and the compound (B) having a polysiloxane chain and a polyoxyalkylene chain is used to form an undercoat coating film layer. Form.

  In the method 2, the composition (1) containing a binder component (A), a compound (B) having a polysiloxane chain and a polyoxyalkylene chain, and a photopolymerization initiator (D1) is used for undercoating. A coating layer is formed.

  Prior to the step (1), when the physical treatment and / or the chemical treatment in the step (0) is performed, an undercoat coating film layer is formed on the substrate subjected to the treatment.

  The undercoat coating layer formed in the step (1) is an intermediate layer between the hydrophilicity-imparting layer and the base material formed in the later-described step (2), and an adhesive layer between the base material and the hydrophilicity-imparting layer. Is formed.

  In the film forming method of the present invention, the binder component (A) contains, as at least a part thereof, a hydroxyl group-containing resin (A1) and a crosslinking agent (A2), and has the polysiloxane chain and the polyoxyalkylene chain. When the compound (B) contains, as at least a part thereof, the compound (B ′) having a hydroxyl group, a polysiloxane chain and a polyoxyalkylene chain, the hydroxyl group-containing resin (A1), hydroxyl group, polysiloxane chain and polyoxy Since the hydroxyl group in the compound (B ′) having an alkylene chain reacts with the cross-linking agent (A2) to form a strong undercoat film layer having a cross-linked structure, an adhering reduction factor such as water enters. Is suppressed, and it is possible to easily perform modification with excellent sustainability on the substrate surface.

  Further, in the film forming method of the present invention, the cross-linking agent (A2) having reactivity with a hydroxyl group is formed using a hydroxyl group on the surface of the base material (a paint containing the hydroxyl group-containing resin and the cross-linking agent). The substrate and the undercoat coating layer are bonded to each other as a result, by reacting with those existing on the coated film, those produced by the physical treatment of the step (0)), It is presumed that a tightly bonded film in which the undercoat coating film layer and the hydrophilicity-imparting layer are integrated is formed.

  Furthermore, in the film forming method of the present invention, since the compound (B) having a polysiloxane chain and a polyoxyalkylene chain in the composition (1) has a polysiloxane chain, in the step (1), the polysiloxane chain And the compound (B) having a polyoxyalkylene chain are oriented on the surface of the undercoat coating layer, and as a result, an undercoat coating layer having a high concentration of polyoxyalkylene chains on the surface is formed. Since the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) has a high affinity with the hydrophilicity-imparting group, the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) is relatively deep on the surface of the undercoat coating layer. Since the hydrophilicity imparting group-containing polymerizable unsaturated compound (C) including the permeated hydrophilicity-providing group-containing polymerizable unsaturated compound is polymerized to form a hydrophilicity-imparting layer, Hardly hydrophilicity-imparting group falls off, it is presumed that the film excellent in maintaining hydrophilic is formed.

  Hereinafter, the composition (1) will be described.

Binder component (A)
The binder component (A) itself has a film-forming property, and may be either a non-crosslinked type or a crosslinked type, and is preferably a crosslinked type. As the binder component (A), a film-forming resin known per se that has been conventionally used as a binder component of paints can be used.

  Examples of the film-forming resin include acrylic resin, polyester resin, alkyd resin, and polyurethane resin. The film-forming resin preferably has a crosslinkable functional group such as a hydroxyl group, a carboxyl group, or an epoxy group.

  Moreover, as said binder component (A), in addition to the said film forming resin, a crosslinking agent can be used. When the crosslinking agent is used as part of the binder component (A), the film-forming resin usually has a crosslinking functional group such as a hydroxyl group, a carboxyl group, or an epoxy group, and reacts with the crosslinking agent. Thus, a resin (base resin) capable of forming a crosslinked film can be used. As the composition (1), a crosslinkable paint containing the base resin and a crosslinker can be suitably used from the viewpoints of maintaining functionality and water resistance.

  Among them, the composition (1) contains the hydroxyl group-containing resin (A1) as at least a part of the base resin, and the reactivity with the hydroxyl group-containing resin (A1) as at least a part of the crosslinking agent. It is preferable to contain the crosslinking agent (A2) which has.

Hydroxyl-containing resin (A1)
The hydroxyl group-containing resin (A1) is a resin having at least one hydroxyl group in one molecule. Examples of the hydroxyl group-containing resin (A1) include hydroxyl group-containing resins such as acrylic resins, polyester resins, acrylic modified polyester resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, and alkyd resins. These can be used alone or in combination of two or more. The hydroxyl group-containing resin (A1) may have a polymerizable unsaturated group. Especially, it is preferable that hydroxyl-containing resin (A1) is a hydroxyl-containing acrylic resin from viewpoints, such as hydrophilic maintenance property and hydrolysis resistance.

  The hydroxyl group-containing acrylic resin is prepared by a method known per se, for example, a mixture containing a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, It can be produced by copolymerization by a method such as a solution polymerization method in an organic solvent or an emulsion polymerization method in water.

  The hydroxyl group-containing polymerizable unsaturated monomer is a compound having at least one hydroxyl group and one polymerizable unsaturated bond in one molecule. Examples of the hydroxyl group-containing polymerizable unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Monoesterified product of (meth) acrylic acid and C2-C8 dihydric alcohol; ε-caprolactone modified product of monoesterified product of (meth) acrylic acid and C2-C8 dihydric alcohol; N -Hydroxymethyl (meth) acrylamide; allyl alcohol, and (meth) acrylate having a polyoxyalkylene chain whose molecular end is a hydroxyl group. However, in the present invention, the monomer having a hydroxyl group corresponding to the polymerizable unsaturated monomer having an ultraviolet absorbing functional group described later (xvii) is another polymerizable compound copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer. It should be defined as an unsaturated monomer and is excluded from hydroxyl-containing polymerizable unsaturated monomers. These can be used alone or in combination of two or more.

As the other polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, the following monomers (i) to (xx) can be used. These polymerizable unsaturated monomers can be used alone or in combination of two or more.
(I) Alkyl or cycloalkyl (meth) acrylate: for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl ( (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) a Acrylate, cyclododecyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and the like.
(Ii) Polymerizable unsaturated monomer having an isobornyl group: isobornyl (meth) acrylate and the like.
(Iii) Polymerizable unsaturated monomer having an adamantyl group: adamantyl (meth) acrylate and the like.
(Iv) Polymerizable unsaturated monomer having a tricyclodecenyl group: tricyclodecenyl (meth) acrylate and the like.
(V) Aromatic ring-containing polymerizable unsaturated monomers: benzyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene and the like.
(Vi) Polymerizable unsaturated monomer having an alkoxysilyl group: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) Acryloyloxypropyltriethoxysilane and the like.
(Vii) Polymerizable unsaturated monomer having a fluorinated alkyl group: perfluoroalkyl (meth) acrylate such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; fluoroolefin and the like.
(Viii) A polymerizable unsaturated monomer having a photopolymerizable functional group such as a maleimide group.
(Ix) Vinyl compound: N-vinyl pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate and the like.
(X) Carboxy group-containing polymerizable unsaturated monomer: (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl (meth) acrylate and the like.
(Xi) Nitrogen-containing polymerizable unsaturated monomer: (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylamino Propyl (meth) acrylamide, methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, an adduct of glycidyl (meth) acrylate and an amine compound.
(Xii) Polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule: allyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and the like.
(Xiii) Epoxy group-containing polymerizable unsaturated monomer: glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl ether and the like.
(Xiv) (meth) acrylate having a polyoxyalkylene chain whose molecular end is an alkoxy group.
(Xv) polymerizable unsaturated monomer having a sulfonic acid group: 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, allylsulfonic acid, 4-styrenesulfonic acid, etc .; sodium salt of these sulfonic acids And ammonium salts.
(Xvi) Polymerizable unsaturated monomer having a phosphate group: acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxypoly (oxyethylene) glycol (meth) acrylate, acid phosphooxypoly (Oxypropylene) glycol (meth) acrylate and the like.
(Xvii) polymerizable unsaturated monomer having an ultraviolet-absorbing functional group: 2-hydroxy-4 (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) ) Benzophenone, 2,2′-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2- ( 2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole and the like.
(Xviii) Light-stable polymerizable unsaturated monomer: 4- (meth) acryloyloxy 1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetra Methylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6- Tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetra Methylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6 -Tetramethylpiperidine and the like.
(Xix) Polymerizable unsaturated monomer having a carbonyl group: acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone) , Vinyl ethyl ketone, vinyl butyl ketone) and the like.
(Xx) Polymerizable unsaturated monomer having an acid anhydride group: maleic anhydride, itaconic anhydride, citraconic anhydride and the like.

  In the present specification, the polymerizable unsaturated group means an unsaturated group capable of radical polymerization. Examples of the polymerizable unsaturated group include a vinyl group, a (meth) acryloyl group, an allyl group, a propenyl group, an isopropenyl group, a maleimide group, and a vinyl ether group.

  In the present specification, “(meth) acrylate” means acrylate or methacrylate. “(Meth) acrylic acid” means acrylic acid or methacrylic acid. “(Meth) acryloyl” means acryloyl or methacryloyl. “(Meth) acrylamide” means acrylamide or methacrylamide.

  The above-mentioned mixture for producing a hydroxyl group-containing acrylic resin is composed of an aromatic polymerizable unsaturated monomer and / or an alicyclic polymerizable unsaturated monomer as a copolymerization monomer component from the viewpoint of hydrophilicity maintenance, water resistance, and the like. It is preferable to contain.

  Examples of the aromatic polymerizable unsaturated monomer include benzyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene and the like, and preferable examples include styrene.

  Examples of the alicyclic polymerizable unsaturated monomer include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tricyclodecanyl ( Examples include meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and preferable examples include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate.

  The aromatic polymerizable unsaturated monomer and the alicyclic polymerizable unsaturated monomer can be used alone or in combination of two or more.

  When the mixture for producing a hydroxyl group-containing acrylic resin contains the aromatic polymerizable unsaturated monomer and / or alicyclic polymerizable unsaturated monomer as a copolymerizable monomer component, the aromatic polymerizable unsaturated monomer In addition, the total content of the alicyclic polymerizable unsaturated monomer is 10 to 90% by mass, preferably 20 to 85% by mass, based on the total amount of the copolymerizable monomer components, from the viewpoints of hydrophilicity maintenance, water resistance, and the like. %, More preferably in the range of 30 to 80% by mass.

  The hydroxyl group-containing acrylic resin may be a hydroxyl group-containing acrylic resin having a polymerizable unsaturated group.

  In addition, as said hydroxyl-containing acrylic resin, it is preferable to use the hydroxyl-containing acrylic resin which does not have a polymerizable unsaturated group mainly from viewpoints of the coating film performance etc. of the undercoat coating layer obtained.

  The hydroxyl value of the hydroxyl group-containing resin (A1) is in the range of 15 to 240 mgKOH / g, preferably 20 to 220 mgKOH / g, more preferably 25 to 200 mgKOH / g, from the viewpoints of hydrophilicity maintenance, water resistance and the like. Preferably it is.

  In addition, the weight average molecular weight of the hydroxyl group-containing resin (A1) is 3,000 or more, preferably 3,000 to 100,000, more preferably 4,000 to 4,000, from the viewpoint of hydrophilicity maintenance, coating film appearance, and the like. It is suitable that it is in the range of 80,000, more preferably 5,000 to 50,000.

  In this specification, the number average molecular weight and the weight average molecular weight are the retention time (retention capacity) measured using a gel permeation chromatograph (GPC) and the retention time of a standard polystyrene with a known molecular weight measured under the same conditions. (Retention capacity) is a value obtained by converting to the molecular weight of polystyrene. Specifically, “HLC-8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph apparatus, and “TSKgel G4000HXL”, “TSKgel G3000HXL”, “TSKgel G2500HXL” and “TSKgel” are used as columns. G2000HXL "(trade name, all manufactured by Tosoh Corporation), using a differential refractometer as the detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C, flow rate: 1 mL / min Can be measured below.

  The glass transition temperature (Tg) of the hydroxyl group-containing resin (A1) is −35 to 100 ° C., preferably −25 to 95 ° C., more preferably −5 to 90 ° C. from the viewpoints of hydrophilicity maintenance, water resistance, and the like. It is preferable to be within the range.

In this specification, when the hydroxyl group-containing resin (A1) is a hydroxyl group-containing acrylic resin, the glass transition temperature (Tg) of the hydroxyl group-containing acrylic resin is a value calculated by the following formula. 1 / Tg (K) = W ₁ / T ₁ + W ₂ / T ₂ +... W _n / T _n
Tg (° C.) = Tg (K) -273
In the formula, W ₁ , W ₂ ,... W _n are mass fractions of each monomer, and T ₁ , T _2, ... T _n are glass transition temperatures Tg (K) of homopolymers of each monomer. .

  In addition, the glass transition temperature of the homopolymer of each monomer is POLYMER HANDBOOK Fourth Edition, J. MoI. Brandrup, E .; h. Immergut, E .; A. The glass transition temperature of a monomer not described in the document, which is a value according to Grulk (1999), is a static value when a homopolymer of the monomer is synthesized with a weight average molecular weight of about 50,000. The glass transition temperature is assumed.

  The static glass transition temperature is obtained by, for example, using a differential scanning calorimeter “DSC-50Q type” (manufactured by Shimadzu Corporation, trade name), taking a sample in a measuring cup, and removing the solvent completely by vacuum suction. It can be measured by measuring the change in calorie in the range of −100 ° C. to 150 ° C. at a temperature increase rate of ° C./min, and setting the first baseline change point on the low temperature side as the static glass transition temperature.

  When the hydroxyl group-containing resin (A1) is other than a hydroxyl group-containing acrylic resin, the glass transition temperature (Tg) of the hydroxyl group-containing resin (A1) is a static glass transition temperature and can be measured in the same manner as described above. .

  In the composition (1) according to the present invention, the content of the hydroxyl group-containing resin (A1) is 20 to 20 based on the total solid content of the composition (1) from the viewpoint of hydrophilicity maintenance, water resistance, and the like. It is suitable to be in the range of 90% by mass, preferably 30 to 85% by mass, more preferably 40 to 80% by mass.

  In the present specification, the “solid content” means non-volatile components such as a resin, a curing agent and a pigment contained in the composition remaining after drying at 110 ° C. for 1 hour. For this reason, for example, the total solid content of the composition (1) is 110 ° C. after weighing the composition (1) into a heat-resistant container such as an aluminum foil cup and spreading the composition (1) on the bottom of the container. The weight of the components in the composition (1) in the composition (1) remaining after drying is weighed, and the components remaining after drying with respect to the total weight of the composition (1) before drying are measured. It can calculate by calculating | requiring the ratio of mass.

Cross-linking agent (A2)
A crosslinking agent (A2) is a compound which has a functional group which can react with the hydroxyl group in the said hydroxyl-containing resin (A1).

  Specifically, as the crosslinking agent (A2), for example, a polyisocyanate compound, a blocked polyisocyanate compound, an amino resin, or the like can be preferably used. Of these, polyisocyanate compounds and blocked polyisocyanate compounds are preferred, and polyisocyanate compounds are more preferred from the viewpoint of maintaining hydrophilicity. The crosslinking agents (A2) can be used alone or in combination of two or more.

  The polyisocyanate compound is a compound having at least two isocyanate groups in one molecule, and includes, for example, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, and the polyisocyanate. And the like.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3. -Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, methyl 2,6-diisocyanatohexanoate (common name: lysine diisocyanate); 2 , 6-Diisocyanatohexanoic acid 2-isocyanatoethyl, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,6 1-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl Examples thereof include aliphatic triisocyanates such as octane.

  Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name) : Isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis (isocyanato) Methyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, methylenebis (4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), alicyclic diisocyanate such as norbornane diisocyanate 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2 .1) Heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5- Di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) ) Heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanate) Toethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3 An alicyclic triisocyanate such as -isocyanatopropyl) -bicyclo (2.2.1) heptane can be used.

  Examples of the araliphatic polyisocyanate include methylene bis (4,1-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω′-diisocyanato- Aromatic aliphatic diisocyanates such as 1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof; 1,3 And araliphatic triisocyanates such as 5-triisocyanatomethylbenzene.

  Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate (common name: 2,4- TDI), 2,6-tolylene diisocyanate (common name: 2,6-TDI) or mixtures thereof, aromatic diisocyanates such as 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; triphenylmethane-4 , 4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene and the like; 4,4′-diphenylmethane-2,2 ′ , 5,5'-tetraisocyanate and other aromatics Mention may be made of the tiger isocyanate.

  Examples of the polyisocyanate derivatives include dimer, trimer, biuret, allophanate, uretdione, uretoimine, isocyanurate, oxadiazine trione, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI). And Crude TDI.

  The above polyisocyanates and derivatives thereof may be used alone or in combination of two or more. Of these polyisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and derivatives thereof are preferred.

  Further, as the polyisocyanate compound, a prepolymer obtained by reacting the polyisocyanate and a derivative thereof with a compound capable of reacting with the polyisocyanate under conditions of excess isocyanate groups may be used. Examples of the compound capable of reacting with the polyisocyanate include compounds having an active hydrogen group such as a hydroxyl group and an amino group. Specifically, for example, polyhydric alcohol, low molecular weight polyester resin, amine, water, etc. Can be used.

  The polyisocyanate compound may be a polymer of an isocyanate group-containing polymerizable unsaturated monomer, or a polymerizable unsaturated monomer other than the isocyanate group-containing polymerizable unsaturated monomer and the isocyanate group-containing polymerizable unsaturated monomer. A copolymer may be used.

  Moreover, as said polyisocyanate compound, you may use the polyisocyanate which has a polymerizable unsaturated group.

  The polyisocyanate having a polymerizable unsaturated group can be obtained, for example, by reacting a part of the isocyanate group of the polyisocyanate compound with a hydroxyl group-containing polymerizable unsaturated compound.

  Examples of the polyisocyanate having a polymerizable unsaturated group include a compound obtained by reacting a part of an isocyanate group of a polyisocyanate compound having three or more isocyanate groups with a hydroxyl group-containing polymerizable unsaturated compound; carbodiimide Compound obtained by reacting a part or all of the carbodiimide group of the group-containing isocyanate compound with a carboxyl group-containing unsaturated compound; “Desmolux D100”, “Desmolux D200”, “Desmolux VP LS 2396”, “ Desmolux XP2510 ”,“ Desmolux XP2765 ”;“ Laromer LR9000 ”manufactured by BASF, etc. can be used.

  Specific examples of the compound obtained by reacting a part of the isocyanate group of the polyisocyanate compound having three or more isocyanate groups with a hydroxyl group-containing polymerizable unsaturated compound include, for example, hydroxyalkyl (meth) acrylate. And a reaction product of a hydroxyl group-containing (meth) acrylate such as a polyisocyanate compound having three or more isocyanate groups or an isocyanate group-terminated urethane prepolymer.

  More specifically, for example, a reaction product of 1 mol of hydroxyalkyl (meth) acrylate and 1 mol of triisocyanate compound, a reaction product of 1 mol of di (meth) acrylate of triol and 1 mol of triisocyanate compound, etc. Can be mentioned.

  As a compound obtained by reacting a part of the isocyanate group of the polyisocyanate compound with a hydroxyl group-containing polymerizable unsaturated compound, from the viewpoint of raw material costs and the like, isocyanurate cycloadduct of hexamethylene diisocyanate and hydroxyl group-containing polymerizability A compound obtained by reacting with an unsaturated compound can be preferably used.

  The hydroxyl group-containing polymerizable unsaturated compound is a compound having at least one hydroxyl group and one polymerizable unsaturated group in one molecule, specifically, for example, 2-hydroxyethyl (meth) acrylate, 2 A monoesterified product of (meth) acrylic acid such as hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and a dihydric alcohol having 2 to 8 carbon atoms; Ε-caprolactone modified product of monoesterified product of (meth) acrylic acid and dihydric alcohol having 2 to 8 carbon atoms; N-hydroxymethyl (meth) acrylamide; allyl alcohol, and polyoxyethylene chain whose molecular terminal is a hydroxyl group (Meth) acrylate having glycerin di (meth) acrylate, trimethylo And tri (meth) such as pentaerythritol tri (meth) acrylate acrylate compounds; propanedioic (meth) acrylate, di (meth) acrylate compounds such as pentaerythritol di (meth) acrylate.

  The reaction of the polyisocyanate compound and the hydroxyl group-containing polymerizable unsaturated compound can be carried out by a known method for reacting the polyisocyanate compound and the hydroxyl group-containing compound.

  The above reaction can usually be carried out in an organic solution. Examples of organic solvents include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate. Can be mentioned. These can be used alone or in combination of two or more.

  The reaction temperature is usually from room temperature to about 100 ° C., and the reaction time is about 1 to 10 hours.

  In the above reaction, if necessary, tin octylate, dibutyltin diacetate, dibutyltin di (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, dioctyltin di (2-ethylhexanoate) , Dibutyltin oxide, dibutyltin sulfite, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, fatty acid zincs, bismuth octanoate, bismuth 2-ethylhexanoate, olein Organometallic compounds such as bismuth oxide, bismuth neodecanoate, bismuth versatate, bismuth naphthenate, cobalt naphthenate, calcium octylate, copper naphthenate, tetra (2-ethylhexyl) titanate; containing a catalyst such as a tertiary amine Can do. The amount of the catalyst is preferably 0.01 to 1% by mass, particularly 0.1 to 0.5% by mass, based on the total amount of the reaction raw materials.

  Further, a polymerization inhibitor such as hydroquinone monomethyl ether can be further contained as required. The amount of the polymerization inhibitor is preferably 0.01 to 1% by mass with respect to the total amount of the reaction raw materials.

  Since the polyisocyanate having a polymerizable unsaturated group has an isocyanate group, the mixing ratio in the reaction between the hydroxyl group-containing polymerizable unsaturated compound and the polyisocyanate compound is usually such that the isocyanate group of the polyisocyanate compound is hydroxyl group-containing polymerizable. It becomes a mixing ratio that is excessive in an equivalent ratio with respect to the hydroxyl group of the unsaturated compound. By adjusting the mixing ratio, the concentration (isocyanate equivalent) of the isocyanate group of the polyisocyanate having a polymerizable unsaturated group can be adjusted.

  The isocyanate equivalent of the polyisocyanate having a polymerizable unsaturated group is from 100 to 1,500, preferably from 120 to 900, more preferably from the viewpoints of adhesion to a substrate, hydrophilicity maintenance, water resistance and the like. It is suitable to be in the range of ~ 450.

  Here, in this specification, an isocyanate equivalent is the molar mass per isocyanate group. When the molecular weight of the polyisocyanate having a polymerizable unsaturated group is M and the number of isocyanate groups contained in one molecule of the compound is ν, the isocyanate equivalent is a value represented by M / ν.

  Moreover, in this specification, an isocyanate equivalent is an isocyanate equivalent calculated | required by back titration using a dibutylamine. The reverse titration can be performed by adding an excess of dibutylamine to the sample and reacting, and titrating the remaining dibutylamine with an aqueous hydrochloric acid solution using bromophenol blue as a titration indicator.

  The polyisocyanate having a polymerizable unsaturated group has an unsaturated group equivalent of 90 to 2,500, preferably 100 to 2,000, more preferably 150 to 1, from the viewpoint of improving adhesion to the hydrophilicity-imparting layer. 500, more particularly preferably 200 to 1,000.

  The molecular weight of the polyisocyanate having a polymerizable unsaturated group is from 200 to 4,000, preferably from 400 to 2,500, more preferably from 500 to 2,000, from the viewpoint of improving the strength of the undercoat coating layer. 500, more particularly preferably 500 to 1,500.

  The blocked polyisocyanate compound that can be used as the crosslinking agent (A2) is a compound obtained by blocking the isocyanate group of the polyisocyanate compound with a blocking agent.

  Examples of the blocking agent include phenols such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and hydroxybenzoic acid methyl; ε-caprolactam, δ-valerolactam, lactams such as γ-butyrolactam, β-propiolactam; aliphatic alcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, lauryl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Ethers such as glycol monomethyl ether and methoxymethanol; benzyl alcohol, glycolic acid, methyl glycolate, ethyl glycolate, butyl glycolate, lactic acid, methyl lactate, ethyl lactate, butyl lactate, methylol urea, methylol melamine, diacetone alcohol Alcohols such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate; oximes such as formamide oxime, acetamide oxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexane oxime; dimethyl malonate, diethyl malonate , Active methylenes such as ethyl acetoacetate, methyl acetoacetate, acetylacetone; butyl mercaptan, t-butyl mercapta , Hexyl mercaptans, t-dodecyl mercaptans, 2-mercaptobenzothiazoles, thiophenols, methylthiophenols, ethylthiophenols and other mercaptans; Acid amides; succinimides, phthalic imides, maleic imides and other imides; diphenylamines, phenylnaphthylamines, xylidines, N-phenylxylidines, carbazoles, anilines, naphthylamines, butylamines, dibutylamines, butylphenylamines, etc. System: Imidazoles such as imidazole and 2-ethylimidazole; urea, thiourea, ethylene urea, ethylene thiourea, diphenyl urea N- phenylcarbamate ester of carbamic acid such as phenyl; ethyleneimine, imine and propylene imine; urea in sodium bisulfite, sulfite, such as bisulfite potassium; compounds such azole systems. Examples of the azole compounds include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3, Pyrazole or pyrazole derivatives such as 5-dimethylpyrazole and 3-methyl-5-phenylpyrazole; Imidazole or imidazole derivatives such as imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole and 2-phenylimidazole; 2-methylimidazoline And imidazoline derivatives such as 2-phenylimidazoline.

  Among them, preferred blocking agents include oxime blocking agents, active methylene blocking agents, pyrazoles or pyrazole derivatives.

  When blocking (reacting the blocking agent), a solvent can be added as necessary. As the solvent used for the blocking reaction, those not reactive to isocyanate groups are preferable. For example, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and N-methyl-2-pyrrolidone (NMP) Such solvents can be mentioned.

  When the composition (1) contains the polyisocyanate compound and / or the blocked polyisocyanate compound as the cross-linking agent (A2), the blending ratio is such as hydrophilicity maintainability and performance of the obtained coating film. From the viewpoint, the equivalent ratio (NCO / OH) of the total isocyanate group (including the blocked isocyanate group) of the polyisocyanate compound and the blocked polyisocyanate compound to the hydroxyl group of the hydroxyl group-containing resin (A1) is usually 0.5. It is preferable to use it in a ratio that is in the range of -2.0, particularly 0.8-1.5.

  In addition, since the polyisocyanate compound and the blocked polyisocyanate compound, particularly the polyisocyanate compound, can react with a hydroxyl group at a relatively low temperature to form a crosslinked coating film, the substrate is a substrate that is easily deformed by heat, such as plastic. In some cases, it can be used particularly preferably.

  As an amino resin that can be used as the crosslinking agent (A2), a partially methylolated amino resin or a completely methylolated amino resin obtained by a reaction between an amino component and an aldehyde component can be used. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

  Moreover, what methylated the methylol group of the said methylolated amino resin partially or completely with suitable alcohol can also be used. Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, and 2-ethylhexanol.

  As the amino resin, a melamine resin is preferable. As the melamine resin, for example, an alkyl etherified melamine resin obtained by partially or completely etherifying a methylol group of a partially or completely methylolated melamine resin with the above alcohol can be used.

  Examples of the alkyl etherified melamine resin include a methyl ether melamine resin obtained by partially or fully etherifying a methylol group of a partially or completely methylolated melamine resin with methyl alcohol; a methylol group of a partially or completely methylolated melamine resin; Butyl etherified melamine resin partially or fully etherified with butyl alcohol; methyl-butyl mixed etherification in which methylol groups of partially or fully methylolated melamine resin are partially or fully etherified with methyl alcohol and butyl alcohol A melamine resin etc. can be used conveniently.

The melamine resin preferably has a weight average molecular weight in the range of 400 to 6,000, preferably 500 to 5,000, more preferably 800 to 4,000. A commercially available product is used as the melamine resin. it can. Examples of commercially available product names include “Cymel 202”, “Cymel 203”, “Cymel 238”, “Cymel 251”, “Cymel 303”, “Cymel 323”, “Cymel 324”, “Cymel 325”, “Cymel 327”, “Cymel 350”, “Cymel 385”, “Cymel 1156”, “Cymel 1158”, “Cymel 1116”, “Cymel 1130” (above, made by Nippon Cytec Industries, Inc.), “Uban 120”, “ “Uban 20HS”, “Uban 20SE60”, “Uban 2021”, “Uban 2028”, “Uban 28-60” (manufactured by Mitsui Chemicals, Inc.), and the like.

  The melamine resins described above can be used alone or in combination of two or more.

  When the composition (1) contains the amino resin as a crosslinking agent (A2), the blending ratio is 5 based on 100 parts by mass of the total solid content of the hydroxyl group-containing resin (A1) and the crosslinking agent (A2). It is suitable to be in the range of ˜70 parts by mass, preferably 10 to 60 parts by mass, more preferably 15 to 40 parts by mass.

  The crosslinking agents (A2) can be used alone or in combination of two or more.

Compound (B) having polysiloxane chain and polyoxyalkylene chain
The compound (B) having a polysiloxane chain and a polyoxyalkylene chain is a compound having one or more polysiloxane chains and one or more polyoxyalkylene chains in the molecule.

  As the compound having a polysiloxane chain and a polyoxyalkylene chain, a copolymer having a polysiloxane chain and a polyoxyalkylene chain can be preferably used.

  Various methods can be applied to prepare the copolymer having the polysiloxane chain and the polyoxyalkylene chain. For example, the polysiloxane chain-containing polymerizable unsaturated monomer and the polyoxyalkylene chain-containing polymerizable unsaturated monomer can be used. And the method of copolymerizing the other polymerizable unsaturated monomer in an organic solvent as necessary is most convenient and preferred.

  The polysiloxane chain-containing polymerizable unsaturated monomer is a compound having one or more polysiloxane chains and one or more polymerizable unsaturated groups in the molecule.

  Examples of the polysiloxane chain-containing polymerizable unsaturated monomer include the following general formula (1):

[Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrocarbon group having 2 to 10 carbon atoms, preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms. R ³ is the same as or different from each other and represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, and n is an integer, preferably 3 Represents an integer of ~ 300, more preferably an integer of 4 to 100]
The polymerizable unsaturated monomer shown by these can be mentioned.

  As a commercial item of the said polysiloxane chain containing polymerizable unsaturated monomer, for example, Silaplane FM-0721, Silaplane FM-0711, Silaplane FM-0725 (above, manufactured by JNC, trade name); X-22- 174ASX, X-22-174BX, KF-2012, X-22-2426, X-22-2404, X-22-2475 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) and the like.

  The number average molecular weight of the polysiloxane chain-containing polymerizable unsaturated monomer is 400 to 8,000, preferably 600 to 600 from the viewpoints of hydrophilicity maintenance, coating film appearance, ease of production of the copolymer, and the like. It is suitable that it is in the range of 4,000, more preferably 800 to 3,000.

  The polysiloxane chain-containing polymerizable unsaturated monomers can be used alone or in combination of two or more.

  The use ratio of the polysiloxane chain-containing polymerizable unsaturated monomer in the copolymer having the functional group and the polysiloxane chain is based on the total amount of the copolymerization monomer components from the viewpoint of hydrophilicity maintenance, coating film appearance, and the like. Is preferably in the range of 0.5 to 80% by mass, preferably 2 to 50% by mass, and more preferably 3 to 30% by mass.

  The polyoxyalkylene chain-containing polymerizable unsaturated monomer is a monomer containing a polyoxyalkylene chain and a polymerizable unsaturated group in one molecule.

  Examples of the polyoxyalkylene chain include a polyoxyethylene chain, a polyoxypropylene chain, a chain composed of a polyoxyethylene block and a polyoxypropylene block, and a chain formed by randomly bonding polyoxyethylene and polyoxypropylene. These polyoxyalkylene chains generally have a molecular weight in the range of 100 to 5,000, preferably 200 to 4,000, more preferably 300 to 3,000.

  Representative examples of the polyoxyalkylene chain-containing polymerizable unsaturated monomer include, for example, the following general formula (2)

[Wherein R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, and R ⁶ has 2 to 4 carbon atoms, preferably a carbon number. 2 or 3, more preferably represents an alkylene group having 2 carbon atoms, m represents an integer of 2 to 120, preferably 4 to 90, more preferably 5 to 70, and m oxyalkylene units (R ⁶ —O ) May be the same as or different from each other]
The polymerizable unsaturated monomer shown by these can be mentioned.

  Specific examples of the polymerizable unsaturated monomer represented by the general formula (2) include, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene (propylene) glycol (meth) acrylate, methoxypolyethylene glycol ( (Meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, methoxypolyethylene (propylene) glycol (meth) acrylate, ethoxypolyethylene (propylene) glycol (meth) acrylate, etc. These may be used alone or in combination of two or more. In the present specification, “polyethylene (propylene) glycol” means a copolymer of ethylene glycol and propylene glycol, and includes both a block copolymer and a random copolymer.

  Of these, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene (propylene) glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and methoxypolyethylene (propylene) glycol (meth) acrylate are preferred. (Meth) acrylate and polypropylene glycol (meth) acrylate are more preferable, and polyethylene glycol (meth) acrylate is more preferable.

  The polyoxyalkylene chain-containing polymerizable unsaturated monomer generally has a molecular weight in the range of 100 to 5,000, preferably 200 to 4,000, and more preferably 300 to 3,000.

  Further, the polyoxyalkylene chain-containing polymerizable unsaturated monomer is used in an amount of 5 to 80% by mass, preferably 15 based on the total amount of raw material monomers of the copolymer having a polysiloxane chain and a polyoxyalkylene chain. It is suitable that it is in the range of ˜70% by mass, more preferably 30 to 60% by mass.

  Examples of the other polymerizable unsaturated monomer include, for example, the hydroxyl group-containing polymerizable unsaturated monomer described in the explanation column of the hydroxyl group-containing resin (A1) and other copolymerizable monomers with the hydroxyl group-containing polymerizable unsaturated monomer. Polymerizable unsaturated monomers other than the polysiloxane chain-containing polymerizable unsaturated monomer and the polyoxyalkylene chain-containing polymerizable unsaturated monomer among the polymerizable unsaturated monomers (i) to (xiii) and (xv) to (xx) Monomers and the like can be used.

  Various kinds of polymerization initiators and organic solvents can be used for the preparation of the copolymer having a polysiloxane chain and a polyoxyalkylene chain.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis-methylbutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1'-azobis-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis- (2-amidinopropene) dihydrochloride Salt, 2-tert-butylazo-2-cyanopropane, 2,2′-azobis (2-methyl-propionamide) dihydrate, 2,2′-azobis [2- (2-imidazolin-2-yl) Propene], azo compounds such as 2,2′-azobis (2,2,4-trimethylpentane); benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxy Id, potassium persulfate, tert-butylperoxyneodecanoate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, 1,1- Bis-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butylperoxy-laurate, tert-butylperoxyisophthalate, tert-butylperoxyacetate, tert-butylperoxybenzoate, dicumylper Ketone peroxide compounds such as oxide and di-tert-butyl peroxide; peroxyketal compounds; hydroperoxide compounds; dialkyl peroxide compounds; diacyl peroxide compounds; Ester compounds; peroxydicarbonate compounds; hydrogen peroxide, and the like.

  Examples of the organic solvent include alkyl alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, and isopentanol; methyl cellosolve , Ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and other glycol ether solvents; benzene, toluene, xylene , Aromatic hydrocarbon solvents such as ethylbenzene; Exon Aromatic Naphtha No. Mixed hydrocarbon solvent containing aromatic hydrocarbon such as 2 (manufactured by Exxon USA); aliphatic hydrocarbon solvent such as n-pentane, n-hexane and n-octane; Isopar C, Isopar E, Exol DSP100 / 140, Exol D30 (all manufactured by Exxon USA), mixed solvent containing aliphatic hydrocarbon such as IP Solvent 1016 (Idemitsu Petrochemical Co., Ltd.); cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. Alicyclic hydrocarbon solvents such as: tetrahydrofuran, dioxane, diisopropyl ether, di-n-butyl ether and other ether solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketone solvents; methyl acetate, ethyl acetate, n-propyl acetate , Isopropyl acetate, n acetate Butyl, isobutyl acetate, n- amyl, isoamyl acetate, hexyl acetate, ethyl propionate, and ester solvents such as butyl propionate. A small amount of water can be used in combination with these organic solvents.

  Furthermore, when preparing the copolymer having the polysiloxane chain and the polyoxyalkylene chain, a chain transfer agent may be used as necessary. Examples of the chain transfer agent include dodecyl mercaptan, lauryl mercaptan, thioglycolic acid ester, mercaptoethanol, α-methylstyrene dimer, and the like.

  In addition, the compound (B) having a polysiloxane chain and a polyoxyalkylene chain is a compound (B ′) having a hydroxyl group, a polysiloxane chain and a polyoxyalkylene chain from the viewpoint of hydrophilicity maintenance. preferable.

  In particular, when the binder component (A) contains, as at least a part thereof, a hydroxyl group-containing resin (A1) and a crosslinking agent (A2), at least the compound (B) having a polysiloxane chain and a polyoxyalkylene chain. By using the compound (B ′) having a hydroxyl group, a polysiloxane chain and a polyoxyalkylene chain as a part, a hydroxyl group-containing resin (A1) and a compound having a hydroxyl group, a polysiloxane chain and a polyoxyalkylene chain (B ′ ) And the cross-linking agent (A2) react to form a strong undercoat film layer having a cross-linked structure, so that the ingress of adhesion reducing factors such as water is suppressed, Thus, it is possible to easily perform the modification with excellent sustainability.

  As the compound (B ′) having a hydroxyl group, a polysiloxane chain and a polyoxyalkylene chain, a copolymer having a hydroxyl group, a polysiloxane chain and a polyoxyalkylene chain can be preferably used.

  The copolymer having a hydroxyl group, a polysiloxane chain and a polyoxyalkylene chain is, for example, at least one of other polymerizable unsaturated monomers in the method for producing a copolymer having a polysiloxane chain and a polyoxyalkylene chain. Can be obtained by using the above-mentioned hydroxyl group-containing polymerizable unsaturated monomer.

  The hydroxyl value of the compound (B ′) having a hydroxyl group, a polysiloxane chain and a polyoxyalkylene chain is from 5 to 160 mgKOH / g, preferably from 10 to 120 mgKOH / g, more preferably from the viewpoint of maintaining hydrophilicity. It is preferable to be within the range of 15 to 100 mgKOH / g.

  The weight average molecular weight of the compound (B) having a polysiloxane chain and a polyoxyalkylene chain is 1,000 to 200,000, preferably 2,000 to 150,000, more preferably from the viewpoint of hydrophilicity maintenance and the like. Is preferably in the range of 3,000 to 100,000.

  In addition, the content of the polysiloxane chain in the compound (B) having a polysiloxane chain and a polyoxyalkylene chain has the polysiloxane chain and the polyoxyalkylene chain from the viewpoint of hydrophilicity maintenance, coating film appearance, and the like. It is suitable that it is in the range of 0.3 to 75% by mass, preferably 1 to 45% by mass, more preferably 2 to 30% by mass based on the mass of the compound (B).

  The adjustment of the content of the polysiloxane chain in the compound (B) having the polysiloxane chain and the polyoxyalkylene chain is, for example, the adjustment of the length of the polysiloxane chain in the polysiloxane chain-containing polymerizable unsaturated monomer, It can be performed by adjusting the amount of the polysiloxane chain-containing polymerizable unsaturated monomer.

  In the composition (1) according to the present invention, the content of the compound (B) having a polysiloxane chain and a polyoxyalkylene chain is that of the composition (1) from the viewpoint of hydrophilicity maintenance, coating film appearance, and the like. Based on the total solid content, 0.01 to 20% by mass, preferably 0.03 to 10% by mass, more preferably 0.05 to 5% by mass, and still more preferably 0.05 to 2% by mass. It is preferable that

Photopolymerization initiator (D1)
In Method 2, composition (1) contains a photopolymerization initiator (D1).

  The photopolymerization initiator (D1) is a compound that absorbs active energy rays and generates free radicals (even in the form of an intermediate) or a mixture of these compounds.

Photoinitiators (D1) include photochemically activatable compounds (for example, benzoin), combinations of chromophores and coinitiators (for example, benzophenone and tertiary amines), mixtures thereof, sensitizers, Redox systems such as combinations of coinitiators (eg thioxanthone and tertiary amine) or chromophores (eg thioxanthone and aminoketone), combinations of H ₂ O ₂ and iron (II) salts, dyes and boron Examples thereof include electron transport pairs such as acid salts and / or amines.

  Specific examples of the photopolymerization initiator (D1) include, for example, α-diketone compounds such as benzyl and diacetyl; acyloin compounds such as benzoin; acyloin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; Thioxanthone compounds such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; benzophenone, o-methylbenzoylbenzoate, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4′-bis (dimethyl) Benzophenone compounds such as amino) benzophenone and 4,4′-bis (diethylamino) benzophenone; Michler's ketone compound; acetophenone, 2- (4-toluenesulfonyloxy) 2-phenylacetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl]- 2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, α-isohydroxyisobutylphenone, α, α′-dichloro-4-phenoxy Acetophenone compounds such as acetophenone and 1-hydroxy-cyclohexyl-phenyl-ketone; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (acyl) phosphine oxide; anthraquinone; , 4-quinone of naphthoquinone; can be exemplified peroxides such as di -t- butyl peroxide or the like; phenacyl chloride, trihalomethyl phenyl sulfone, tris (trihalomethyl) -s-halogen compounds such as triazines.

  Examples of commercially available photopolymerization initiators (D1) include IRGACURE-127, IRGACURE-184, IRGACURE-261, IRGACURE-369, IRGACURE-500, IRGACURE-651, IRGACURE-754, IRGACURE-819, Irgacure-907, Irgacure-CGI-1700, Irgacure-2959, Irgacure-TPO, Darocur-1173 (trade name, manufactured by BASF); Kayacure-MBP, Kayacure-DETX-S, Kayacure- DMBI, Kayacure-EPA, Kayacure-OA (above, Nippon Kayaku Co., Ltd., trade name); Vicure-10, Vicure-55 (above, STAUFER o., LTD., trade name); Trigonal P1 (manufactured by AKZO Co., LTD., trade name); Sandoray 1000 (SANDOZ Co., LTD.) Product name); Deep (DEAP) (manufactured by APJOHN Co., LTD., Product name); Cantacur-PDO, CantaCure-ITX, CantaCure-EPD (above, Ward Brekinsop ( WARD BLEKINSSOP Co., LTD., Trade name), ESACURE KIP 150, ESACURE ONE (LABMERTI, trade name), and the like.

  Moreover, in the said composition (1), when a binder component (A) contains a hydroxyl-containing resin (A1) and a crosslinking agent (A2) as at least one part, as said photoinitiator (D1), A photopolymerization initiator having reactivity with a film-forming component in the composition (1), a photopolymerization initiator having a hydroxyl group (D1-1), and a photopolymerization having a functional group reactive with the hydroxyl group. At least one photoinitiator selected from initiators (D1-2) can be preferably used.

Photopolymerization initiator having a hydroxyl group (D1-1)
The photopolymerization initiator (D1-1) having a hydroxyl group is a photopolymerization initiator having at least one hydroxyl group in one molecule. The photopolymerization initiator (D1-1) having a hydroxyl group has reactivity with the crosslinking agent (A2) in the composition (1).

  Examples of the photopolymerization initiator (D1-1) having a hydroxyl group include 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (product) Name: IRGACURE 2959, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (trade name) : IRGACURE127, manufactured by BASF) and the like.

Photopolymerization initiator having a functional group capable of reacting with a hydroxyl group (D1-2)
The photopolymerization initiator (D1-2) having a functional group capable of reacting with a hydroxyl group is a photopolymerization initiator having a functional group capable of reacting with at least one hydroxyl group in one molecule. The photopolymerization initiator (D1-2) having a functional group capable of reacting with the hydroxyl group has reactivity with the hydroxyl group-containing resin (A1) in the composition (1).

  Examples of the functional group capable of reacting with the hydroxyl group include an isocyanate group (including those in which an isocyanate group is blocked), an amino group, an epoxy group, an alkoxysilyl group, a carboxyl group, and the like. preferable. Therefore, the photopolymerization initiator (D1-2) having a functional group capable of reacting with the hydroxyl group is preferably a photopolymerization initiator having an isocyanate group.

  The photopolymerization initiator having an isocyanate group can be obtained, for example, by a method in which the photopolymerization initiator having a hydroxyl group (D1-1) is added to a part of the isocyanate group of a polyisocyanate compound.

  As said polyisocyanate compound, the polyisocyanate compound described in the description column of the said crosslinking agent (A2) can be used, for example. These may be used alone or in combination of two or more.

  As a compound obtained by addition reaction of a photopolymerization initiator (D1-1) having a hydroxyl group on a part of the isocyanate group of the polyisocyanate compound, isocyanurate ring addition of hexamethylene diisocyanate from the viewpoint of raw material costs and the like. A compound obtained by reacting a product with a photopolymerization initiator (D1-1) having a hydroxyl group can be preferably used.

  The reaction of the polyisocyanate compound and the photopolymerization initiator (D1-1) having a hydroxyl group can be carried out by a known method for reacting the polyisocyanate compound and the hydroxyl group-containing compound.

  Since the photopolymerization initiator having an isocyanate group has an isocyanate group, the mixing ratio in the reaction between the photopolymerization initiator having a hydroxyl group (D1-1) and the polyisocyanate compound is usually that of the isocyanate group of the polyisocyanate compound. The mixing ratio becomes an excess (isocyanate group / hydroxyl group> 1.0) in an equivalent ratio with respect to the hydroxyl group of the photopolymerization initiator (D1-1) having a hydroxyl group. By adjusting the mixing ratio, the isocyanate group concentration (isocyanate equivalent) of the photopolymerization initiator having an isocyanate group can be adjusted.

  The isocyanate equivalent of the photopolymerization initiator having an isocyanate group is from 90 to 1,500, preferably from 100 to 900, more preferably from 150 to 1500, from the viewpoints of adhesion to a substrate, hydrophilicity maintenance, water resistance and the like. It is preferable to be within the range of 450.

  Moreover, in the said composition (1), when a binder component (A) contains a polymerizable unsaturated compound as at least one part, as said photoinitiator (D1), this polymerizable unsaturated compound and The photopolymerization initiator (D1-3) having two or more photopolymerization initiators, which is a photopolymerization initiator having the above reactivity, can be suitably used.

  As the polymerizable unsaturated compound used as at least a part of the binder component (A), for example, a hydroxyl group-containing acrylic resin having a polymerizable unsaturated group described in the explanation column of the hydroxyl group-containing resin (A1), The polyisocyanate which has the polymerizable unsaturated group described in the description column of the said crosslinking agent (A2), etc. are mentioned.

Photopolymerization initiator having two or more photopolymerization initiators (D1-3)
The photopolymerization initiator (D1-3) having two or more photopolymerization initiators is a photopolymerization initiator having two or more photopolymerization initiators in one molecule. The photopolymerization initiator (D1-3) having two or more photopolymerization initiators has reactivity with the polymerizable unsaturated compound.

  As the photopolymerization initiator (D1-3) having two or more photopolymerization initiators, for example, an oligomer type photopolymerization initiator having a structure represented by the following formula (3) is preferably used. it can.

(In the formula, X is a linear alkylene group or a branched alkylene group, R ^1a and R ^2a are each a linear alkyl group or a branched alkyl group, R ^3a is a substituent, and m is an integer of 0-4. And n is an integer from 2 to 50.)
The number of carbon atoms of the linear alkylene group or branched alkylene group of X is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3. Specific examples of X include> CH—CH ₂ —,> C (CH ₃ ) —CH ₂ —,> C (C ₂ H ₅ ) —CH ₂ —,> C (n—C ₃ H ₇ ) —CH. _{2 -,> C (i-} C 3 H 7) -CH 2 -,> C (i-C 4 H 9) -CH 2 -,> C (i-C 8 H 17) -CH 2 -,> C _{(tert-C 8 H 17)} -CH 2 - and the like. Here, “>” means having two connectors.

The carbon number of the linear alkyl group or branched alkyl group represented by R ^1a and R ^2a is not particularly limited, but is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1. Specific examples of R ^1a and R ^2a are —CH ₃ , —C ₂ H ₅ , —CH (CH ₃ ) ₂ , — (nC ₃ H ₇ ), and — (iC ₃ H ₇ ), respectively. _{, - (i-C 4 H} 9), - (i-C 8 H 17), - and the like _{(tert-C 8 H 17)} .

^Examples of the substituent represented by R ^3a include —CH ₃ , —C ₂ H ₅ , —CH (CH ₃ ) ₂ , — (n—C ₃ H ₇ ), and — (i—C ₃ H ₇ ). It is done.

  m is preferably 0. n is preferably from 2 to 20, and more preferably from 3 to 10.

  Moreover, the hydrogen atom or the substituent is normally couple | bonded with the terminal of the compound containing the structure represented by Formula (3). Here, examples of the substituent include a hydrocarbon group, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group. Examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the cycloalkyl group include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and substituted alkyl groups thereof. Examples of the aryl group include a phenyl group and an alkyl group-substituted product thereof.

  Specific examples of the oligomer photopolymerization initiator having two or more photopolymerization initiators include, for example, poly [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone]. Poly [2-hydroxy-2-methyl-1- [4-vinyl-phenyl] propanone], poly [2-hydroxy-2-ethyl-1- [4- (1-methylvinyl) phenyl] propanone], poly [2-hydroxy-2-ethyl-1- [4-vinyl-phenyl] propanone], poly [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] butanone], poly [2 -Hydroxy-2-methyl-1- [4-vinyl-phenyl] butanone], poly [2-hydroxy-2-ethyl-1- [4- (1-methylvinyl) phenyl] butanone], poly [2 Hydroxy-2-ethyl-1- [4-vinyl - phenyl] butanone] and the like.

  Examples of commercially available oligomer-type photopolymerization initiators having two or more photopolymerization initiators include ESACURE-KIP150 and ESACURE-ONE (trade name, manufactured by LAMBERTI). Among these, ESACURE-KIP150 is oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] including a structure represented by the following formula (4).

(In the formula, n is an integer of 2 to 5.)
The photopolymerization initiator (D1-3) having two or more photopolymerization initiators has a weight average molecular weight of 200 to 4,000, preferably 300 to 3,000, from the viewpoint of the hydrophilicity of the formed film. 000, more preferably in the range of 400 to 1,500.

  The photopolymerization initiators (D1) can be used alone or in combination of two or more.

  The content of the photopolymerization initiator (D1) in the composition (1) is based on 100 parts by mass of the total solid content of the binder component (A) and the compound (B) having a polysiloxane chain and a polyoxyalkylene chain. It is suitable that it is in the range of 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, and more preferably 0.5 to 12 parts by mass.

  In the method 1, the composition (1) comprises the binder component (A) and the compound (B) having a polysiloxane chain and a polyoxyalkylene chain as essential components, and in the method 2, the binder component (A) and the polysiloxane are used. The compound (B) having a chain and a polyoxyalkylene chain and the photopolymerization initiator (D1) are essential components.

  The composition (1) can further contain a polymerizable unsaturated compound. Examples of the polymerizable unsaturated compound include a monofunctional polymerizable unsaturated group-containing compound and a polyfunctional polymerizable unsaturated group-containing compound.

  Examples of the monofunctional polymerizable unsaturated group-containing compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, Styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate Monoesterified product of (meth) acrylic acid such as 4-hydroxybutyl (meth) acrylate and a dihydric alcohol having 2 to 8 carbon atoms; the (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms; Ε-caprolactone modified product of a monoester product of: having one isocyanate group such as isocyanate methyl (meth) acrylate, isocyanate ethyl (meth) acrylate, isocyanate propyl (meth) acrylate and one polymerizable unsaturated group Compound: N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylate having a polyoxyethylene chain whose molecular terminal is a hydroxyl group.

  Examples of the polyfunctional polymerizable unsaturated group-containing compound include an esterified product of a polyhydric alcohol and (meth) acrylic acid, a compound having one isocyanate group and two or more polymerizable unsaturated groups. It is done. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A ethylene Di (meth) acrylate compounds such as oxide-modified di (meth) acrylate and isocyanuric acid ethylene oxide-modified diacrylate; glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri Tri (meth) acrylate compounds such as tyrolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate; penta Examples include tetra (meth) acrylate compounds such as erythritol tetra (meth) acrylate; and dipentaerythritol hexa (meth) acrylate.

  The said polymerizable unsaturated compound can be used individually or in combination of 2 or more types.

  The molecular weight of the polymerizable unsaturated compound is less than 3,000, preferably from 100 to 2,500, more preferably from 150 to 2,000, and even more preferably from 200 to 1, from the viewpoint of maintaining hydrophilicity. It is preferable to be within the range of 000.

  Moreover, as said polymerizable unsaturated compound, it is preferable to use the polymerizable unsaturated compound which has a hydroxyl group from a viewpoint of hydrophilic maintenance property. Examples of the polymerizable unsaturated compound having a hydroxyl group include those described above, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meta ) Monoesterified product of (meth) acrylic acid such as acrylate and dihydric alcohol having 2 to 8 carbon atoms; ε-caprolactone of monoesterified product of (meth) acrylic acid and dihydric alcohol having 2 to 8 carbon atoms Modified body; N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end; pentaerythritol triacrylate; isocyanuric acid ethylene oxide-modified diacrylate.

  Among these, from the viewpoint of maintaining hydrophilicity, the polymerizable unsaturated compound having a hydroxyl group is more preferably a polyfunctional polymerizable unsaturated compound having a hydroxyl group. Examples of the polyfunctional polymerizable unsaturated compound having a hydroxyl group include pentaerythritol triacrylate, isocyanuric acid ethylene oxide-modified diacrylate, and the like.

  Moreover, a commercial item can be used as a polymerizable unsaturated compound which has the said hydroxyl group. Commercially available product names include, for example, “Aronix M-215”, “Aronix M-303”, “Aronix M-305”, “Aronix M-306”, “Aronix M-5700” (above, Toagosei Co., Ltd.) Manufactured) and the like.

  When the composition (1) contains the polymerizable unsaturated compound, the content thereof is 1 to 40% by mass, preferably 3 to 30% by mass, further based on the total solid content of the composition (1). Preferably it is in the range of 5 to 25% by mass.

  The composition (1) has a catalyst, a solvent, a pigment, an ultraviolet absorber, a light stabilizer, an antioxidant, a surface conditioner, an antifoaming agent, an emulsifier, and a surfactant, as long as the effects of the present invention are not impaired. Other additive components ordinarily used in the field of coating such as an agent, an antifouling agent, a wetting agent, a thickener, a dye, and a gloss adjusting agent can be appropriately contained.

  The composition (1) may be in the form of a melt, a solution, a suspension, or an emulsion, but the productivity and work of the composition (1) should be in the form of a solution in which the above essential components are dissolved in a solvent. From the viewpoint of sex. In this case, the composition (1) contains the binder component (A) in the case of the method 1, the compound (B) having a polysiloxane chain and a polyoxyalkylene chain and a solvent, and the binder component (A in the case of the method 2). ), A compound (B) having a polysiloxane chain and a polyoxyalkylene chain, a photopolymerization initiator (D1), and a solvent.

  Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, esters such as ethyl acetate and butyl acetate, and aromatic hydrocarbons such as toluene and xylene. And alcohols such as methanol, ethanol, propanol and butanol, tetrahydrofuran, dimethylformamide, petroleum hydrocarbons and the like.

  Among the above solvents, esters can be preferably used from the viewpoint of solubility of the compound (B) having a polysiloxane chain and a polyoxyalkylene chain. In the case where the substrate is plastic or the like, petroleum hydrocarbons can be preferably used.

  Moreover, when the composition (1) contains the polyisocyanate compound and / or the blocked polyisocyanate compound as the crosslinking agent (A2), or photopolymerization having an isocyanate group as the photopolymerization initiator (D1). When an initiator is contained, the composition (1) can contain a urethanization reaction catalyst.

  Specific examples of the urethanization reaction catalyst include, for example, tin octylate, dibutyltin diacetate, dibutyltin di (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, dioctyltin di (2 -Ethylhexanoate), dibutyltin oxide, dibutyltin sulfide, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, fatty acid zincs, bismuth octanoate, 2-ethyl Organometallic compounds such as bismuth hexanoate, bismuth oleate, bismuth neodecanoate, bismuth versatate, bismuth naphthenate, cobalt naphthenate, calcium octylate, copper naphthenate, tetra (2-ethylhexyl) titanate; tertiary amines, etc. These are mentioned Either alone or 2 or more kinds in combination may be used.

  Moreover, when using the said urethanization reaction catalyst, as a catalyst amount, it is 0.0001-0.5 mass% with respect to the solid content total amount of a composition (1), Especially 0.0005-0.1 mass%. It is preferable to be within the range.

  When the composition (1) contains the urethanization reaction catalyst, the composition (1) is acetic acid, propionic acid, butyric acid, isopentanoic acid, hexanoic acid, 2-ethyl from the viewpoints of storage stability and curability. Butyric acid, naphthenic acid, octylic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, isobutyric anhydride Organic acids such as itaconic anhydride, acetic anhydride, citraconic anhydride, propionic anhydride, maleic anhydride, butyric anhydride, citric anhydride, trimellitic anhydride, pyromellitic anhydride, phthalic anhydride; hydrochloric acid, phosphoric acid, etc. Inorganic acids; metal coordinating compounds such as acetylacetone and imidazole compounds may be contained.

  When a melamine resin is used as the crosslinking agent (A2), the composition (1) is a sulfonic acid such as para-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid as a curing catalyst; monobutyl phosphoric acid, dibutyl phosphoric acid Alkyl phosphates such as mono-2-ethylhexyl phosphate and di-2-ethylhexyl phosphate; salts of these acids with amine compounds, and the like.

  Moreover, when using the said melamine resin curing catalyst, as a catalyst amount, it is 0.1-5 mass% with respect to the solid content total amount of a composition (1), Preferably it is 0.2-3 mass%, Furthermore, Preferably it is in the range of 0.5-2 mass%.

  Examples of the pigment include a luster pigment, a color pigment, and an extender pigment. The pigments can be used alone or in combination of two or more.

  Examples of the bright pigment include aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, glass flakes, aluminum oxide, mica, titanium oxide and / or iron oxide coated with iron oxide, titanium oxide, and the like. Examples thereof include mica coated with iron oxide.

  Examples of the color pigment include titanium oxide, zinc oxide, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, and perylene. Pigments, dioxazine pigments, diketopyrrolopyrrole pigments and the like.

  Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white.

  When the composition (1) contains the pigment, the amount of the pigment is 0.01 to 70% by mass, preferably 0.02 to 50% by mass, based on the total solid content of the composition (1). %, More preferably in the range of 0.03 to 30% by mass.

  Formation of the undercoat coating film layer by the composition (1) can be performed by dipping, spraying, brush coating, knife coating, roller coating, roll coating, curtain coating, printing, spin coating, pouring and the like.

  The thickness of the undercoat coating layer formed by the composition (1) after curing is 5 to 100 μm, preferably 21 to 60 μm, from the viewpoint of the smoothness, hydrophilicity, water resistance, and the like of the formed coating. Preferably it is in the range of 23-40 μm.

  The formed undercoat coating layer is preferably subjected to heat treatment and dried quickly from the viewpoint of productivity and workability.

  By the heat treatment, a cured coating film is usually formed from the binder component (A) and the compound (B) having a polysiloxane chain and a polyoxyalkylene chain. In particular, the binder component (A) contains, as at least a part thereof, a hydroxyl group-containing resin (A1) and a crosslinking agent (A2), and a compound (B) having a polysiloxane chain and a polyoxyalkylene chain is at least one of them. As a part, when the compound (B ′) having a hydroxyl group, a polysiloxane chain and a polyoxyalkylene chain is contained, it usually has a hydroxyl group-containing resin (A1), a polysiloxane chain and a polyoxyalkylene chain by the heat treatment. The hydroxyl group in the compound (B) reacts with the crosslinking agent (A2) to form a strong crosslinked coating film.

  In addition, the compound (B) having a polysiloxane chain and a polyoxyalkylene chain in the composition (1) is undercoated during standing after coating of the composition (1) and / or during the heat treatment. It is presumed that the film moves to the surface of the film layer. As a result, it is presumed that an undercoat coating layer having a strong cross-linked structure and a high concentration of polyoxyalkylene chains on the surface is formed.

  When a hydroxyl group is present on the substrate surface, the above heat treatment causes the hydroxyl group on the substrate surface to react with the functional group having reactivity with the hydroxyl group in the cross-linking agent (A2), thereby causing the substrate and the undercoat to react. The coating layer can be bonded.

  A known method in this field can be appropriately used for drying the undercoat coating layer by heat treatment.

  Specifically, for example, hot air, hot gas, an infrared heater, an IR radiator, an oven, a heat roller, and a microwave can be used.

  In the present invention, it is preferable to perform drying and baking with hot air, an infrared heater or the like from the viewpoints of ease of work and low temperature.

  The temperature of the heat treatment applied to the undercoat coating layer is in the range of 40 to 160 ° C., preferably 50 to 150 ° C., more preferably 70 to 140 ° C., from the viewpoints of productivity, workability, and thermal stability of the substrate. It is preferable to be within. The time for the heat treatment applied to the undercoat coating layer is preferably 5 minutes to 24 hours, preferably 10 to 180 minutes, more preferably 20 to 120 minutes.

  Thus, an undercoat coating layer is formed on the substrate. The formed undercoat coating film layer is preferably a cured coating film.

Process (2)
In the step (2), the composition (2) containing the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) is used on the undercoat coating layer formed on the substrate in the step (1). Thus, a hydrophilicity imparting layer is formed.

  More specifically, in the method 1, a polymerization initiator (D) selected from a hydrophilicity-providing group-containing polymerizable unsaturated compound (C), a photopolymerization initiator (D1), and a thermal polymerization initiator (D2). ) Is used to form the hydrophilicity-imparting layer.

  Moreover, in the said method 2, a hydrophilic provision layer is formed using the composition (2) containing a hydrophilic provision group containing polymerizable unsaturated compound (C).

  The polymerizable unsaturated group in the hydrophilicity imparting group-containing polymerizable unsaturated compound (C) contributes to polymerization in the hydrophilicity imparting layer.

Hydrophilic group-containing polymerizable unsaturated compound (C)
The hydrophilicity imparting group-containing polymerizable unsaturated compound (C) is a compound having one or more polymerizable unsaturated groups and one or more hydrophilicity imparting groups in the molecule.

  Examples of the polymerizable unsaturated group include acryloyl group, methacryloyl group, vinyl group, allyl group, propenyl group, isopropenyl group, maleimide group, vinyl ether group and the like. Among these, from the viewpoint of excellent reactivity, an acryloyl group, a methacryloyl group, and a vinyl group are preferable, an acryloyl group and a methacryloyl group are more preferable, and an acryloyl group is more particularly preferable.

Examples of the hydrophilicity-imparting group include acid groups such as carboxyl group, sulfonic acid group, and phosphoric acid group; betaine structure-containing groups such as carboxybetaine, sulfobetaine, and phosphobetaine;
Polyoxyalkylene groups such as polyoxyethylene groups, polyoxypropylene groups, polyoxyalkylene groups containing both oxyethylene groups and oxypropylene groups;
Hydroxyl group, amide;
A tertiary amino group, a quaternary ammonium salt, etc. can be mentioned.

  Specific examples of the hydrophilicity-providing group-containing polymerizable unsaturated compound (C) include, for example, (meth) acrylic acid or alkali metal salts thereof, amine salts and ammonium salts, itaconic acid or alkali metal salts thereof, amine salts and ammonium. Salt, vinyl sulfonic acid, allyl sulfonic acid, 2-sulfoethyl (meth) acrylate, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylate, 4-styrene sulfonic acid alkali metal salts of these sulfonic acids Amine salts and ammonium salts, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate, Alkali metal salts, amine salts and ammonium salts of phosphoric acid; methacryloyloxyethyl-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine, methacryloyloxyethyl-N, N-dimethylammonium-α-methylcarboxybetaine Polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate; 2-hydroxyethyl (meth) acrylate, N-vinyl-2-pyrrolidone, acrylamide, N, N-dimethylacrylamide; hydroxy N-hydroxyalkyl (meth) acrylamides such as ethylacrylamide; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate Rate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, 2 -(Methacryloyloxy) ethyltrimethylammonium chloride, 2- (methacryloyloxy) ethyltrimethylammonium bromide, 2- (meth) acryloyloxyethyl-2 '-(trimethylammonium) ethyl phosphate, 2- (methacryloyloxy) ethyltrimethylammonium dimethyl A phosphate etc. can be mentioned.

  Examples of the alkali metal salt in the hydrophilicity-providing group-containing polymerizable unsaturated compound include lithium salts, sodium salts, potassium salts and the like.

  The unsaturated group-containing polymerizable unsaturated compound (C) has an unsaturated group equivalent of 90 to 1,500, preferably 100 from the viewpoints of adhesion to the undercoat coating layer and curability of the hydrophilicity-imparting layer. It is suitable to be in the range of ˜1,000, more preferably 100˜500.

  The molecular weight of the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) is preferably 100 to 3,000, particularly preferably 100 to 1,000, from the viewpoint of the reactivity of the unsaturated group.

  As the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C), those having one hydrophilicity-imparting group in the compound can be suitably used from the viewpoint of polymerization reactivity.

  The hydrophilicity imparting group-containing polymerizable unsaturated compound (C) can be used alone or in combination of two or more.

Polymerization initiator (D)
In Method 1, the composition (2) contains a polymerization initiator (D) selected from a photopolymerization initiator (D1) and a thermal polymerization initiator (D2).

Photopolymerization initiator (D1)
As the photopolymerization initiator (D1) that can be contained in the composition (2) in the method 1, for example, the photopolymerization initiator described in the explanation column of the step (1) can be used.

  The said photoinitiator (D1) can be used individually or in mixture of 2 or more types.

  In Method 1, the amount of the photopolymerization initiator (D1) in the composition (2) is from the viewpoint of curability and the like based on 100 parts by mass of the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C). It is suitable that it is in the range of 1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, and more preferably 0.5 to 12 parts by mass.

Thermal polymerization initiator (D2)
The thermal polymerization initiator (D2) that the composition (2) can contain in the method 1 is a compound that generates free radicals (even in the form of an intermediate) or a mixture of these compounds when heated.

  Examples of the thermal polymerization initiator (D2) include benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, cumene hydroperoxide, tert-butyl peroxide, tert-butyl peroxylaurate, and tert- Organic peroxides such as butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, diisopropylbenzene hydroperoxide; azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), azobis (2-methylpropiononitrile) ), Azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyanobutanoic acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- (2- Azo compounds such as droxyethyl) -propionamide] and azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}; persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate Can be mentioned.

  Commercially available products of the thermal polymerization initiator (D2) include, for example, VA-044, VA-046B, V-50, VA-057, VA-061, VA-067, VA-086, V-60, V-70. , V-65, V-601, V-59, V-40, VF-096, VAm-110 (above, manufactured by Wako Pure Chemical Industries, Ltd., trade name), perbutyl H (manufactured by NOF Corporation, trade name), etc. Can be mentioned.

  The thermal polymerization initiator (D2) may be used as a redox initiator in combination with a reducing agent such as sugar, sodium formaldehyde sulfoxylate, or iron complex, if necessary.

  The said thermal-polymerization initiator (D2) can be used individually or in mixture of 2 or more types.

  In Method 1, the amount of the thermal polymerization initiator (D2) in the composition (2) is from the viewpoint of curability and the like based on 100 parts by mass of the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C). It is suitable that it is in the range of 1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, and more preferably 0.5 to 12 parts by mass.

  In the method 1, the composition (2) is a polymerization selected from the hydrophilicity-providing group-containing polymerizable unsaturated compound (C), and the photopolymerization initiator (D1) and the thermal polymerization initiator (D2). The initiator (D) is an essential component, and in the method 2, the hydrophilicity imparting group-containing polymerizable unsaturated compound (C) is an essential component. In Method 2, the composition (2) may contain the photopolymerization initiator (D1).

  In addition, the composition (2) is hydrophilic in the range that does not impair the adhesion and hydrophilic expression effect with the undercoat coating layer from the viewpoint of improving the curability of the hydrophilicity-imparting layer and maintaining the hydrophilicity. Polymerizable unsaturated compounds other than the imparting group-containing polymerizable unsaturated compound (C) can also be used.

  Examples of the polymerizable unsaturated compound other than the hydrophilicity-providing group-containing polymerizable unsaturated compound (C) include monofunctional polymerizable unsaturated group-containing compounds and polyfunctional polymerizable unsaturated group-containing compounds.

  Examples of the monofunctional polymerizable unsaturated group-containing compound include esterified products of polyhydric alcohol and (meth) acrylic acid. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl Monohydric alcohols such as (meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and (meth ) Esterified products with acrylic acid; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and α-chlorostyrene.

  Examples of the polyfunctional polymerizable unsaturated group-containing compound include esterified products of a polyhydric alcohol and (meth) acrylic acid. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Di (meth) acrylate compounds such as 1,6-hexanediol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, and isosorbide di (meth) acrylate; glycerin tri (Meth) acrylate, glycerin ethylene oxide modified tri (meth) acrylate, glycerin propylene oxide modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene Oxide-modified tri (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, pentaerythritol Tri (meth) acrylate compounds such as li (meth) acrylate and ε-caprolactone modified tris (acryloxyethyl) isocyanurate; pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide modified tetra (meth) acrylate, pentaerythritol propylene oxide Modified tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane ethylene oxide modified tetra (meth) acrylate, ditrimethylolpropane propylene oxide modified tetra (meth) acrylate, diglycerin tetra (meth) acrylate, diglycerin Ethylene oxide modified tetra (meth) acrylate, diglycerin propylene oxide modified tetra (me ) Tetra (meth) acrylate compounds such as acrylate and the like; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.

  Further, examples of the polyfunctional polymerizable unsaturated group-containing compound include ethylene oxide-modified phosphoric acid di (meth) acrylate, ethylene oxide-modified phosphoric acid tri (meth) acrylate, polyfunctional (meth) acrylamide compound, urethane (meta ) Acrylate resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin and the like.

  Examples of the polyfunctional (meth) acrylamide compound include N, N′-methylenebisacrylamide, N- [tris (3-acrylamidepropoxymethyl) methyl] acrylamide, and the like.

  The urethane (meth) acrylate resin reacts in an amount such that the hydroxyl group is equimolar or excessive with respect to the isocyanate group, using, for example, a polyisocyanate compound, a hydroxylalkyl (meth) acrylate and a polyol compound as raw materials. Can be obtained.

  The polymerizable unsaturated compounds other than the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) can be used alone or in combination of two or more.

  Among the polymerizable unsaturated compounds other than the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C), from the viewpoints of improving the curability of the hydrophilicity-imparting layer, maintaining the hydrophilicity, etc., a polyfunctional polymerizable unsaturated group A containing compound can be used conveniently.

  The polymerizable unsaturated compound other than the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) has an unsaturated group equivalent of 30 to 700 from the viewpoint of improving the curability of the hydrophilicity-imparting layer and maintaining the hydrophilicity. In particular, it is preferably in the range of 70 to 700, more preferably 100 to 700.

  When the composition (2) uses a polymerizable unsaturated compound other than the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C), the amount used is improved in curability of the hydrophilicity-imparting layer and maintained in hydrophilicity. From the viewpoint of improving the solubility, etc., based on 100 parts by mass of the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C), 0.3 to 80 parts by mass, preferably 0.5 to 50 parts by mass, and more preferably 0. It is suitable to be within the range of 8 to 30 parts by mass.

  In particular, when the polyfunctional polymerizable unsaturated group-containing compound is used as a polymerizable unsaturated compound other than the hydrophilicity-providing group-containing polymerizable unsaturated compound (C), the polyfunctional polymerizable unsaturated group-containing compound is used. Is used in an amount of 0.3 to 70 on the basis of 100 parts by mass of the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) from the viewpoint of improving the curability of the hydrophilicity-imparting layer and improving the maintenance property of hydrophilicity. It is suitable that it is in the range of 0.5 to 40 parts by mass, more preferably 0.8 to 20 parts by mass.

  The composition (2) may be in the form of a melt, a solution, a suspension, or an emulsion, but the productivity and work must be in the form of a solution in which the above essential components are dissolved in a solvent. From the viewpoint of sex.

  The composition (2) has a polymerizable unsaturation other than the above-described essential components and the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) used as necessary, as long as the effects of the present invention are not impaired. Other compounds commonly used in the field of coating such as solvents, surface conditioners, antifoaming agents, emulsifiers, surfactants, antifouling agents, wetting agents, thickeners, pigments, dyes, gloss adjusting agents, etc. Additive components can be appropriately contained.

  Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, esters such as ethyl acetate and butyl acetate, and aromatic hydrocarbons such as toluene and xylene. , Methanol, ethanol, 1-propanol, 2-propanol (common name: isopropyl alcohol), 1-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol and other alcohols, tetrahydrofuran, dimethylformamide, water Etc.

  The content of the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) in the composition (2) is 0.01 to 30% by mass relative to the total amount of the composition (2), in particular 0.1 to It is preferable to be in the range of 20% by mass, more particularly 1 to 15% by mass.

  Formation of the hydrophilicity imparting layer by the composition (2) can be performed by dipping, spraying, brush coating, knife coating, roller coating, roll coating, curtain coating, printing, spin coating, pouring and the like.

  The thickness after curing of the hydrophilicity-imparting layer formed by the composition (2) is 10 μm or less, preferably 5 μm or less, more preferably 1 μm or less, from the viewpoint of imparting hydrophilicity, adhesion and final finished appearance. More particularly preferably, it is in the range of 0.05 to 0.7 μm.

Step (3)
Step (3) is a step of treating the substrate on which the undercoat coating film layer and the hydrophilicity-imparting layer are formed by the steps (1) and (2),
When the composition (2) containing the photopolymerization initiator (D1) is used in the step (2), the substrate is irradiated with active energy rays.
When the composition (2) containing the thermal polymerization initiator (D2) is used in the step (2), the substrate is heated,
When the composition (2) not containing the polymerization initiator (D) is used in the step (2) and the composition (1) containing the photopolymerization initiator (D1) is used in the step (1) Irradiates the substrate with active energy rays,
When the composition (2) containing no polymerization initiator (D) is used in the step (2) and the composition (1) containing a thermal polymerization initiator (D2) is used in the step (1) Is a step of heating the substrate.

  Specifically, for example, in the method 1, when the composition (2) containing the photopolymerization initiator (D1) is used in the step (2), active energy ray irradiation is performed, and a thermal polymerization initiator is used. When the composition (2) containing (D2) is used, heating is performed. In the method 2, active energy ray irradiation is performed.

  By this step (3), it is possible to obtain a coated article having a modified surface and newly imparted hydrophilicity, in which the base material, the undercoat coating layer and the hydrophilicity-imparting layer are integrally and firmly bonded.

A well- known thing can be used as an active energy ray irradiated with active energy ray irradiation . Specific examples include ultraviolet light, visible light, laser light (near infrared laser, visible light laser, ultraviolet laser, etc.), microwave, electron beam, electromagnetic wave, and the like.

  Of these active energy rays, ultraviolet rays can be suitably used from the viewpoint of economy.

  Irradiation with active energy rays can be performed using any light source that emits electromagnetic waves having a wavelength that can be absorbed by the photopolymerization initiator (D1). Such a light source usually emits an electromagnetic wave having a wavelength in the range of 200 nm to 2,000 nm.

  A well-known thing can be used as an irradiation source of an active energy ray. Specifically, for example, ultra high pressure, high pressure, medium pressure, low pressure mercury lamp, electrodeless lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, LED (Light Emitting Diode), light emitting diode ), Sunlight, etc. can be used. In addition, a pulsed emission type active energy ray irradiation apparatus can also be used.

  In addition, the irradiation with active energy rays may be performed on the entire region and / or part of the region through, for example, a mask or a laser beam. It is also possible to cure the coating only in a specific area by the means.

The irradiation amount of the active energy ray may be within a range that can complete the curing of the hydrophilicity-imparting layer. Usually, for example, in the case of a high-pressure mercury lamp, 50 to 3,000 mJ / cm ² , in the case of a metal halide lamp , 100~5,000mJ / cm ^2, especially for a high-pressure mercury lamp, 100~1,000mJ / cm ^2, in the case of a metal halide lamp, is preferably in the range of 500~2,000mJ / cm ^2.

  Irradiation of active energy rays can be performed in air or under an inert gas. As the inert gas, nitrogen gas, carbon dioxide, argon, helium, or a mixture thereof can be used.

Moreover, you may heat together with hardening by an active energy ray. As the heating means, for example, hot air, hot gas, infrared heater, IR radiator, oven, heat roller and microwave can be used. When heating is performed, the heating conditions are productivity, workability, and base material. Although determined from the viewpoint of thermal stability, etc., the heating temperature is preferably in the range of 30 to 120 ° C., particularly 50 to 90 ° C., and the heating time is in the range of 1 to 60 minutes, particularly 1 to 20 minutes It is preferable to be within.

  When heating, the order of active energy ray irradiation and heating is not particularly limited, heating may be performed after active energy ray irradiation, active energy ray irradiation may be performed after heating, and active energy ray irradiation. Heating may be performed simultaneously.

  When performing active energy ray irradiation and heating at the same time, heat from an active energy ray irradiation source (for example, heat generated by a lamp) may be used as a heat source. Further, when the active energy ray irradiation is performed after the heating, the active energy ray irradiation may be performed in a state in which the film-forming substrate is heated (a state having residual heat).

For heating and heating, a method known in this field can be appropriately used.

  Specifically, for example, hot air, hot gas, an infrared heater, an IR radiator, an oven, a heat roller, and a microwave can be used.

  In the present invention, it is preferable to perform heating with hot air, an infrared heater or the like from the viewpoints of ease of work and ability to perform at a low temperature.

  The heating temperature is preferably in the range of 30 to 150 ° C., preferably 40 to 140 ° C., and more preferably 50 to 130 ° C. from the viewpoints of productivity, workability, and thermal stability of the substrate. It is.

  The heating time is preferably 1 to 60 minutes, preferably 1 to 40 minutes.

  After irradiation with active energy rays or after heating, the hydrophilically imparting group-containing polymerizable unsaturated compound (C) and the like remaining without reacting can be removed as necessary.

  The residue can be removed, for example, by immersion in a solvent, washing with water, acetone, or the like. From the viewpoint of residue removability, it is possible to employ means such as ultrasonic waves during the cleaning.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples. However, the present invention is not limited to these. In each example, “parts” and “%” are based on mass unless otherwise specified. Moreover, the film thickness of a coating film is based on a cured coating film.

Production and production example 1 of hydroxyl group-containing resin (A1)
Into a reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, nitrogen inlet tube and dropping device, 45 parts of butyl acetate was charged and stirred at 115 ° C. while blowing nitrogen gas. A monomer mixture consisting of 28 parts of methacrylate, 20 parts of styrene, 32 parts of cyclohexyl methacrylate, 15 parts of methyl methacrylate, 5 parts of n-butyl acrylate, 10 parts of butyl acetate and 2 parts of 2,2′-azobisisobutyronitrile for 4 hours The solution was added dropwise at a uniform speed and aged at the same temperature for 1 hour. Thereafter, a mixture of 15 parts of butyl acetate and 1.0 part of 2,2′-azobisisobutyronitrile was added dropwise to the reaction vessel over 3 hours. After completion of the addition, the mixture was aged for 1 hour and then diluted with butyl acetate. Then, a hydroxyl group-containing acrylic resin (A1-1) solution having a solid content of 50% was obtained.

  The obtained hydroxyl group-containing acrylic resin (A1-1) has a hydroxyl value of 120 mgKOH / g, a weight average molecular weight of 20,000, a glass transition temperature of 65 ° C., an aromatic polymerizable unsaturated monomer and an alicyclic polymerizable unsaturated. The total monomer content was 52% by mass relative to the total amount of monomer components.

Production Example 2
Into a reaction vessel equipped with a thermometer, thermostat, stirring device, reflux condenser, nitrogen inlet tube and dropping device, 45 parts of butyl acetate was charged and stirred at 115 ° C. while blowing nitrogen gas. Monomer mixture comprising 24 parts of methacrylate, 3 parts of 2-hydroxyethyl acrylate, 20 parts of styrene, 30 parts of cyclohexyl methacrylate, 23 parts of n-butyl acrylate, 10 parts of butyl acetate and 2 parts of 2,2′-azobisisobutyronitrile. Was dropped at a uniform rate over 4 hours, and further aged at the same temperature for 1 hour. Thereafter, a mixture of 15 parts of butyl acetate and 1.0 part of 2,2′-azobisisobutyronitrile was added dropwise to the reaction vessel over 3 hours. After completion of the addition, the mixture was aged for 1 hour and then diluted with butyl acetate. Then, a hydroxyl group-containing acrylic resin (A1-2) solution having a solid content of 50% was obtained.

  The obtained hydroxyl group-containing acrylic resin (A1-2) has a hydroxyl value of 118 mgKOH / g, a weight average molecular weight of 20,000, a glass transition temperature of 26 ° C., an aromatic polymerizable unsaturated monomer and an alicyclic polymerizable unsaturated. The total content of monomers was 50% by mass with respect to the total amount of monomer components.

Production Example 3
Into a reaction vessel equipped with a stirrer, thermostat, thermometer, reflux condenser, nitrogen introduction tube and dropping device, 45 parts of butyl acetate was charged and stirred at 115 ° C. while blowing nitrogen gas, into which 20 parts of ethyl acrylate, A monomer mixture consisting of 20 parts of methyl methacrylate, 60 parts of glycidyl methacrylate and 2 parts of 2,2′-azobisisobutyronitrile was added dropwise at a uniform rate over 4 hours, and further aged at the same temperature for 1 hour. Thereafter, a mixture of 10 parts of butyl acetate and 0.5 part of 2,2′-azobisisobutyronitrile was added dropwise to the reaction vessel over 1 hour, aged for 1 hour after completion of the addition, and a glycidyl group-containing acrylic resin solution. Got. Further, while blowing air into the reaction vessel, 30 parts of acrylic acid, 0.15 part of hydroquinone monomethyl ether and 0.5 part of t-butylammonium bromide were added to the glycidyl group-containing acrylic resin solution, and the mixture was heated at the same temperature. After reacting for a period of time, it was diluted with butyl acetate to obtain a hydroxyl group-containing acrylic resin (A1-3) solution having a polymerizable unsaturated group having a solid content of 50%. The obtained hydroxyl group-containing acrylic resin (A1-3) having a polymerizable unsaturated group had a hydroxyl value of 180 mgKOH / g, a weight average molecular weight of 20,000, and an unsaturated group equivalent of 312.

Production Example 4 of Compound (B) Having Polysiloxane Chain and Polyoxyalkylene Chain 4
In a four-necked flask equipped with a stirrer, thermostat, thermometer, condenser, nitrogen gas inlet and dropping device, 80 parts of butyl acetate was charged and heated to 120 ° C. under a nitrogen atmosphere while stirring. After reaching 120 ° C., 30 parts of “X-22-2404” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., one-end type methacryl-modified polydimethylsiloxane, unsaturated functional group equivalent 420 g / mol), “Blemmer AE-400” (Trade name, manufactured by NOF Corporation, polyethylene glycol monoacrylate, number of repeating oxyethylene units≈10) 54 parts, methyl methacrylate 16 parts, tert-butylperoxy-2-ethylhexanoate 3.5 parts and butyl acetate A monomer mixture consisting of 100 parts was added dropwise over 3 hours. Next, after aging at 120 ° C. for 0.5 hour, a mixture of 0.5 part of tert-butylperoxy-2-ethylhexanoate and 10 parts of butyl acetate was added dropwise over 1 hour, and further aged for 1 hour. Then, the compound (B-1) solution which has a polysiloxane chain | strand of 30% of solid content, and a polyoxyalkylene chain | strand was obtained by diluting with butyl acetate and cooling to room temperature. The obtained compound (B-1) having a polysiloxane chain and a polyoxyalkylene chain had a hydroxyl value of 59 mgKOH / g and a weight average molecular weight of 51,000.

Production Examples 5 to 15
In Production Example 4, a compound having a polysiloxane chain and a polyoxyalkylene chain having a solid content of 30% (B-2) in the same manner as in Production Example 4 except that the composition of the monomer mixture is shown in Table 1. A (B-12) solution was obtained. Table 1 shows the hydroxyl value and the weight average molecular weight of the compound having each polysiloxane chain and polyoxyalkylene chain.

  (Note) in Table 1 means the following.

  (Note 1) “X-22-174ASX”: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., one-end type methacryl-modified polydimethylsiloxane, unsaturated functional group equivalent 900 g / mol.

  (Note 2) “Silaplane FM0711”: trade name, manufactured by JNC, one-end type methacryl-modified polydimethylsiloxane, molecular weight 1,000.

  (Note 3) “X-22-174BX”: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., one-end type methacryl-modified polydimethylsiloxane, unsaturated functional group equivalent 2,300 g / mol.

  (Note 4) “KF-2012”: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., one-end type methacryl-modified polydimethylsiloxane, unsaturated functional group equivalent 4,600 g / mol.

  (Note 5) “Blemmer AME-400”: trade name, manufactured by NOF Corporation, methoxypolyethylene glycol acrylate, number of oxyethylene repeating units≈9.

  (Note 6) “Blemmer PME-400”: trade name, manufactured by NOF Corporation, methoxypolyethylene glycol methacrylate, number of oxyethylene repeating units≈9.

  (Note 7) “Blemmer PME-1000”: trade name, manufactured by NOF Corporation, methoxypolyethylene glycol methacrylate, number of oxyethylene repeating units≈23.

Production and production example 16 of photopolymerization initiator (D1-2) having a functional group capable of reacting with a hydroxyl group
In a reaction vessel equipped with a stirrer, thermostat, thermometer, reflux condenser, nitrogen introduction tube and dropping device, "Sumidule N-3300" (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., isocyanurate ring addition of hexamethylene diisocyanate) Product, solid content 100%) 81 parts, “IRGACURE2959” (trade name, manufactured by BASF, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 1-one, photopolymerization initiator having a hydroxyl group, solid content 100%) 19 parts and 25 parts of butyl acetate were added and stirred at 90 ° C. for 8 hours while blowing nitrogen gas to obtain an isocyanate group having a solid content of 80%. The photoinitiator (D1-2-1) which has was obtained. The NCO equivalent determined by titration was 193 g / eq before the reaction, but 296 g / eq after the reaction. Addition of the hydroxyl group in “IRGACURE2959” to the isocyanate group in “Sumidule N-3300” It was confirmed that the reaction proceeded normally.

Production Production Example 17 of Composition (1)
200 parts of hydroxyl group-containing acrylic resin (A1-1) solution obtained in Production Example 1 (100 parts of solid content), “Sumijour N-3300” (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., isocyanurate of hexamethylene diisocyanate) Cycloadduct, solid content 100%) 41 parts, 3.3 parts of the compound (B-4) solution having a polysiloxane chain and a polyoxyalkylene chain obtained in Production Example 7 (solid part 1 part), “ IRGACURE2959 "(trade name, manufactured by BASF, photopolymerization initiator having a hydroxyl group, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, solid 5 parts content), 0.001 part dibutyltin diacetate and “TINUVIN123” (trade name, manufactured by BASF, light stabilizer, solids content 100%) 0.1 parts were uniformly mixed, and further diluted stirred with butyl acetate so that the solid content became 30% to obtain a composition (1-1).

Production Examples 18 to 45
In Production Example 17, compositions (1-2) to (1-29) having a solid content of 30% were obtained in the same manner as in Production Example 17 except that the composition was as shown in Table 2. In addition, the compounding composition shown in Table 2 is based on the solid content mass of each component.

  (Note) in Table 2 means the following.

  (Note 8) Polyisocyanate compound (A2-1) having a polymerizable unsaturated compound: An equimolar adduct of “Sumidule N-3300” and 4-hydroxybutyl acrylate. NCO equivalent weight 323. Weight average molecular weight 650. On average, it has 2 isocyanate groups and 1 unsaturated group per molecule.

  (Note 9) “Cymel 251”: trade name, manufactured by Nippon Cytec Industries, Inc., melamine resin, solid content 80%.

  (Note 10) “IRGACURE127” (trade name, manufactured by BASF, photopolymerization initiator having a hydroxyl group, 2-hydroxy-1- {4- [2- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl } -2-methyl-propan-1-one, solid content 100%).

  (Note 11) “ESACURE-ONE”: trade name, manufactured by LAMBERTI, oligomer type photopolymerization initiator having two or more photopolymerization initiators, solid content 100%.

  (Note 12) “ESACURE-KIP150”: trade name, manufactured by LAMBERTI, oligomer type photopolymerization initiator having two or more photopolymerization initiators, oligo [2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone], solid content 100%.

  (Note 13) “Aronix M-305”: trade name, manufactured by Toagosei Co., Ltd., pentaerythritol tri- and tetraacrylate, solid content 100%.

  (Note 14) “GX-180A”: trade name, manufactured by Asahi Kasei Metals Corporation, aluminum pigment paste, solid content 74%.

  (Note 15) “Xiallic Sunbeam Gold T60-20”: trade name, manufactured by MERCK, titanium oxide-coated alumina flake pigment.

  (Note 16) “Monarch 1300”: trade name, manufactured by Cabot Corporation, carbon black pigment.

  The composition (1-28) of Production Example 44 and the composition (1-29) of Production Example 45 are for comparative examples.

Production and production example 46 of composition (2)
10 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.5 part of “IRGACURE 184”, 65 parts of ethanol, 17 parts of deionized water and 9.7 parts of 20% aqueous sodium hydroxide solution were mixed to prepare a composition (2- 1) was obtained.

Production Example 47
A composition (2-2) was obtained by mixing 10 parts of 2-acrylamido-2-methylpropanesulfonic acid, 65 parts of ethanol, 17 parts of deionized water and 9.7 parts of a 20% aqueous sodium hydroxide solution.

Production Example 48
10 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.5 part of “IRGACURE 184”, 65 parts of ethanol, 3 parts of deionized water and 23.1 parts of 5% aqueous lithium hydroxide solution were mixed to prepare a composition (2- 3) was obtained.

Production Example 49
A composition (2-4) was obtained by mixing 10 parts of 2-acrylamido-2-methylpropanesulfonic acid, 65 parts of ethanol, 3 parts of deionized water and 23.1 parts of a 5% aqueous lithium hydroxide solution.

Production Example 50
2-acrylamido-2-methylpropanesulfonic acid 10 parts, "Aronix M-313" (trade name, manufactured by Toagosei Co., Ltd., isocyanuric acid ethylene oxide modified di- and triacrylate, solid content 100%), 1 part, "IRGACURE 184" 0 .5 parts, ethanol 65 parts, deionized water 17 parts and 20% aqueous sodium hydroxide solution 9.7 parts were mixed to obtain a composition (2-5).

Production Example 51
10 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1 part of “Aronix M-306” (trade name, manufactured by Toagosei Co., Ltd., pentaerythritol tri- and tetraacrylate, solid content 100%), 0.5 part of “IRGACURE 184” Then, 65 parts of ethanol, 17 parts of deionized water and 9.7 parts of 20% aqueous sodium hydroxide solution were mixed to obtain a composition (2-6).

Production Example 52
2-acrylamido-2-methylpropanesulfonic acid 10 parts, N, N′-methylenebisacrylamide 1 part, “IRGACURE184” 0.5 part, ethanol 65 parts, deionized water 3 parts and 5% aqueous lithium hydroxide solution 23. 1 part was mixed and the composition (2-7) was obtained.

Production Example 53
2-acrylamido-2-methylpropanesulfonic acid 10 parts, “A-GLY-9E” (trade name, Shin-Nakamura Chemical Co., Ltd., glycerin ethylene oxide-modified triacrylate (ethylene oxide 9 mol), solid content 100%) 1 part, 0.5 parts of “IRGACURE184”, 65 parts of ethanol, 3 parts of deionized water, and 23.1 parts of 5% aqueous lithium hydroxide solution were mixed to obtain a composition (2-8).

Production Example 54
2-acrylamido-2-methylpropanesulfonic acid 10 parts, “V-50” (trade name, manufactured by Wako Pure Chemical Industries, Ltd., thermal polymerization initiator) 0.5 part, ethanol 65 parts, deionized water 17 parts and 20 A composition (2-9) was obtained by mixing 9.7 parts of an aqueous sodium hydroxide solution.

Production Example 55
2-acrylamido-2-methylpropanesulfonic acid 10 parts, “Aronix M-306” (trade name, manufactured by Toagosei Co., Ltd., pentaerythritol tri- and tetraacrylate, solid content 100%), 1 part “V-50” 0. 5 parts, 65 parts of ethanol, 17 parts of deionized water and 9.7 parts of a 20% aqueous sodium hydroxide solution were mixed to obtain a composition (2-10).

Production Example 56
A composition (2-11) was prepared by mixing 10 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.5 parts of ammonium persulfate, 65 parts of ethanol, 17 parts of deionized water and 9.7 parts of 20% aqueous sodium hydroxide. )

Preparation of test plate
Base material <ABS base material>
The surface of a 100 mm × 150 mm × 3.0 mm acrylonitrile-butadiene-styrene (ABS) plate was degreased with isopropyl alcohol to obtain a substrate.

<Coating substrate (ABS plate)>
The surface of a 100 mm × 150 mm × 3.0 mm acrylonitrile-butadiene-styrene (ABS) plate was degreased with isopropyl alcohol. Next, “Letane PG Hybrid Eco Sun Metallic Paint” (trade name, manufactured by Kansai Paint Co., Ltd.) was applied on this ABS plate so as to have a film thickness of 15 μm, and dried at 80 ° C. for 5 minutes as a base material.

<Coating substrate (steel plate)>
On a cold rolled steel sheet treated with zinc phosphate of 100 mm x 150 mm x 0.8 mm, "ELECRON GT-10" (trade name, manufactured by Kansai Paint Co., Ltd., cationic electrodeposition coating composition) It was applied and cured by heating at 170 ° C. for 30 minutes. Next, “TP-65-2” (trade name, manufactured by Kansai Paint Co., Ltd., intermediate coating composition) was applied on the electrodeposition coating film so as to have a film thickness of 35 μm, and heated at 140 ° C. for 30 minutes. Cured. Next, “Letane PG Hybrid Eco Sun Metallic Paint” (trade name, manufactured by Kansai Paint Co., Ltd.) was applied to the intermediate coating film so as to have a film thickness of 15 μm and dried at 80 ° C. for 5 minutes to form a substrate. did.

Example 1
On the ABS substrate, the composition (1-1) obtained in Production Example 17 was applied using an air spray so that the film thickness was 25 μm, set at room temperature for 10 minutes, and then at 80 ° C. Heated for 30 minutes to obtain a cured coating film. Next, on the cured coating film, the composition (2-1) obtained in Production Example 46 was spread using a micro wipe so that the film thickness was 0.1 μm, and then allowed to stand for 15 minutes. . Next, using a UV irradiation apparatus “CV-1200-G” (manufactured by Fusion UV Systems Japan Co., Ltd.), the distance between the base material and the high-pressure mercury lamp is set to 15 cm, the irradiance is 120 mW / cm ² , and the radiation is UV irradiation was performed with two passes at a speed of 3 m / min under the condition of an energy amount of 500 mJ / cm ² . Finally, the surface on which the film was formed was washed with water and naturally dried at room temperature to obtain a coated article on which the film was formed.

Examples 2-33 and 37-70, Comparative Examples 1-3
As a base material, a composition (1), and a composition (2), except using the thing of Table 3, and changing the film thickness and heating temperature of a composition (1) as shown in Table 3, In the same manner as in Example 1, a coated article on which each film was formed was obtained.

Example 34
On the ABS base material, the composition (1-21) obtained in Production Example 37 was applied using an air spray so that the film thickness was 25 μm, set at room temperature for 10 minutes, and then at 80 ° C. Heated for 30 minutes to obtain a cured coating film. Next, on the cured coating film, the composition (2-9) obtained in Production Example 54 was spread using a micro wipe so that the film thickness became 0.1 μm, and then allowed to stand for 15 minutes. . Next, heating was performed at 90 ° C. for 30 minutes. Finally, the surface on which the film was formed was washed with water and naturally dried at room temperature to obtain a coated article on which the film was formed.

Examples 35-36 and 71-73
Example 34 except that the materials shown in Table 3 were used as the substrate, the composition (1) and the composition (2), and the film thickness of the composition (1) was changed as shown in Table 3. In the same manner as above, a coated article on which each film was formed was obtained.

Evaluation of Painted Articles Formed with Films Various tests were performed on the obtained coated articles formed with the respective films. The evaluation results are shown in Table 3.

Test Method Smoothness: The smoothness of the coated article on which each coating film was formed was evaluated according to the following criteria. A: Very smooth and very good B: Smooth and good B: Slightly rough and slightly bad X: Rough and bad

  Function maintenance property: About the coating article in which each film was formed, the water contact angle after the initial stage and the following warm water immersion test was measured.

  <Warm water immersion test> The film-forming substrate was immersed in warm water of 50 ° C for 10 days and dried, and then the water contact angle was measured.

  The water contact angle was measured using a CA-X contact angle meter manufactured by Kyowa Interface Science Co., Ltd., by dropping 5 mg of deionized water on a film-forming substrate in an atmosphere of 23 ° C. and 65% RH. The measurement was performed by measuring the contact angle 15 seconds after the dropping.

  In the initial coating film that has been washed with water, the higher the degree of hydrophilicity, and the smaller the difference in water contact angle between the initial stage and the hot water immersion test, the better the function maintainability. If the water contact angle is 30 ° or less, the hydrophilicity is good.

  Water resistance: The appearance and adhesion of each film-forming substrate washed with water after being immersed in hot water at 50 ° C. for 10 days or 30 days were evaluated according to the following criteria. The evaluation results after immersion for 10 days are shown in the water resistance (1) column, and the evaluation results after immersion for 30 days are shown in the water resistance (2) column.

<Appearance [after water resistance test]>
◎: No change in appearance with respect to the coating before the test ○: Slightly blurred, blistering or discoloration is seen with respect to the coating before the test, but there is no problem when it is used as a product △ : Slightly glossy, blistering or discoloration is observed with respect to the film before the test, and the product is inferior. X: Significant glossiness, blistering or discoloration is observed with respect to the film before the test.

<Adhesion [after water resistance test]>
In accordance with JIS K 5600-5-6 (1990), 100 2 mm × 2 mm gobang eyes were made on the coated surface of the coated article on which each film was formed, and an adhesive tape was stuck on the surface and peeled off rapidly. Later, the number of goby eye coatings remaining on the coating surface was evaluated.
A: Remaining number / total number = 100/100, no missing edges ○: Remaining number / total number = 100/100, no edges missing Δ: Remaining number / total number = 99 to 90/100 X: Remaining number / total number = 89 or less / 100.

  In Comparative Examples 1 to 3, it is considered that the layer of the composition 2-1 was almost removed by washing with water after UV irradiation.

Claims (7)

On the substrate
Step (1): Using the composition (1) containing the binder component (A) and the compound (B) having a polysiloxane chain and a polyoxyalkylene chain, a step of forming an undercoat coating film layer,
Step (2): Using the composition (2) containing the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) on the substrate on which the undercoat coating layer has been formed in the step (1), A step of forming a hydrophilicity-imparting layer, and step (3): a step of treating the substrate on which the undercoat coating layer and the hydrophilicity-imparting layer are formed by the steps (1) and (2), At least one of the composition (1) and the composition (2) contains a polymerization initiator (D) selected from a photopolymerization initiator (D1) and a thermal polymerization initiator (D2),
When the composition (2) containing the photopolymerization initiator (D1) is used in the step (2), the substrate is irradiated with active energy rays.
When the composition (2) containing the thermal polymerization initiator (D2) is used in the step (2), the substrate is heated,
When the composition (2) not containing the polymerization initiator (D) is used in the step (2) and the composition (1) containing the photopolymerization initiator (D1) is used in the step (1) Irradiates the substrate with active energy rays,
When the composition (2) containing no polymerization initiator (D) is used in the step (2) and the composition (1) containing a thermal polymerization initiator (D2) is used in the step (1) Heating the substrate,
A method for forming a hydrophilic film on a substrate, characterized in that On the substrate
Step (1): Using the composition (1) containing the binder component (A) and the compound (B) having a polysiloxane chain and a polyoxyalkylene chain, a step of forming an undercoat coating film layer,
Step (2): Hydrophilic imparting group-containing polymerizable unsaturated compound (C), photopolymerization initiator (D1), and thermal polymerization initiator on the base material on which the undercoat coating film layer has been formed in the step (1). A step of forming a hydrophilicity-imparting layer using a composition (2) containing a polymerization initiator (D) selected from (D2), and step (3): the steps (1) and (2) Is a step of treating a substrate on which an undercoat coating film layer and a hydrophilicity-imparting layer are formed, and the composition (2) containing a photopolymerization initiator (D1) is used in the step (2). Irradiating the substrate with active energy rays and heating the substrate when the composition (2) containing the thermal polymerization initiator (D2) is used in the step (2),
The method for forming a hydrophilic film on a substrate according to claim 1, wherein the steps are sequentially performed. On the substrate
Step (1): Using a composition (1) containing a binder component (A), a compound (B) having a polysiloxane chain and a polyoxyalkylene chain, and a photopolymerization initiator (D1), an undercoat coating layer Forming a process,
Step (2): Using the composition (2) containing the hydrophilicity-imparting group-containing polymerizable unsaturated compound (C) on the substrate on which the undercoat coating layer has been formed in the step (1), Step of forming a hydrophilicity imparting layer and step (3): A step of irradiating active energy rays on the substrate on which the undercoat coating layer and the hydrophilicity imparting layer are formed by the steps (1) and (2). ,
The method for forming a hydrophilic film on a substrate according to claim 1, wherein the steps are sequentially performed.   The hydrophilic film formation method of any one of Claims 1-3 in which a composition (1) contains a hydroxyl-containing resin (A1) and a crosslinking agent (A2) as a binder component (A).   The hydrophilic film forming method according to claim 4, wherein the crosslinking agent (A2) is at least one selected from the group consisting of a polyisocyanate compound, a blocked polyisocyanate compound, and an amino resin.   The hydrophilic property according to any one of claims 1 to 5, wherein the compound (B) having a polysiloxane chain and a polyoxyalkylene chain is a compound (B ') having a hydroxyl group, a polysiloxane chain and a polyoxyalkylene chain. Film formation method.   The composition (1) contains 0.01 to 20% by mass of the compound (B) having a polysiloxane chain and a polyoxyalkylene chain, based on the total solid content of the composition (1). The hydrophilic film formation method of any one of these.