WO2018079539A1

WO2018079539A1 - Hydrophilic polymer and aqueous resin composition for paint using said polymer

Info

Publication number: WO2018079539A1
Application number: PCT/JP2017/038329
Authority: WO
Inventors: 和也渡邉
Original assignee: 株式会社日本触媒
Priority date: 2016-10-24
Filing date: 2017-10-24
Publication date: 2018-05-03
Also published as: JP6647419B2; JPWO2018079539A1

Abstract

Provided is a composition useful for paints and the like. The composition includes an emulsion (A) and a polymer (B) containing at least a vinyl lactam-based monomer and a hindered amine-based monomer as polymerization components.

Description

Hydrophilic polymer and aqueous resin composition for paints using this polymer

The present invention relates to a polymer useful as a hydrophilizing material and a composition containing the polymer.

For coatings for buildings and exteriors, low contamination (stain resistance) of the coating film is required, but as such a technology, for example, the surface of the coating film is made hydrophilic with a hydrophilic polymer, and rainwater is contaminated with the coating film. A technique is known that facilitates cleaning of dirt by making it easier to reach the interface with a substance.

JP 2001-72928 A (Patent Document 1) discloses (a) an emulsion of an organic synthetic resin, (b) a coupling agent, and (c) the organic synthetic resin, other than (a) and the coupling agent. A resin composition for a low-contamination water-based paint comprising a hydrophilic compound having a group capable of reacting with (b) is disclosed.

In addition, the pamphlet of International Publication No. 2008/102816 (Patent Document 2) includes (meth) acrylic emulsion (A) obtained by emulsion polymerization and water-soluble resin (B) as essential components. An aqueous resin composition for paints in which the emulsion (A) and the water-soluble resin (B) can form a crosslinked structure is disclosed.

In such circumstances, there is a demand for a technology for further reducing paint contamination using a hydrophilic polymer.

JP-A-2001-72928 (Claims, Examples) WO 2008/102816 pamphlet (claims, examples)

An object of the present invention is to provide a novel polymer useful as a hydrophilic material (for example, a hydrophilic polymer for paint) and a composition containing the polymer.

Another object of the present invention is to provide a polymer useful for maintaining low contamination (hydrophilicity) of a coating film over a long period of time and a composition containing this polymer.

Still another object of the present invention is to provide a polymer useful for forming a coating film excellent in water resistance, weather resistance, stretchability, adhesion and the like and a composition containing the polymer.

Another object of the present invention is to provide a composition capable of forming a highly glossy coating film.

Still another object of the present invention is to provide a composition having good handleability.

The inventors of the present invention have studied a technique for reducing contamination using a hydrophilic polymer, and found that the hydrophilicity of the coating film gradually decreases.
And based on such knowledge, like the technique of patent document 2, the technique which forms a crosslinked structure with an emulsion and a hydrophilic polymer was examined, but the drop-off inhibitory effect of a water-soluble polymer may not be enough. I found that there was room for further improvement.

Under these circumstances, as a result of further earnest studies to solve the above-mentioned problems, the present inventors have focused on N-vinyl lactam polymers among hydrophilic polymers, and N-vinyl lactam monomers (N It has been found that by copolymerizing a hindered amine monomer with vinylpyrrolidone or the like, a composition capable of maintaining the effect of reducing the contamination of the coating film (hydrophilization effect) over a long period of time in combination with the emulsion.

The hindered amine compound is known as a light stabilizer, but in the present invention, it is unexpectedly assumed from the light resistance stabilization effect by polymerizing a hindered amine monomer in combination with an N-vinyl lactam polymer. It was found that a polymer capable of improving the long-term effect of reducing contamination was obtained.

In addition to the above, the present inventors have obtained various new findings and have made further studies to complete the present invention.

That is, the polymer (copolymer) of the present invention is a polymer (polymer (B)) having a vinyl lactam monomer and a hindered amine monomer as at least a polymerization component (monomer component (b)).

In the polymer of the present invention, the proportion of the vinyl lactam monomer may be 50% by mass or more based on the entire polymerization component. In the polymer of the present invention, the proportion of the vinyl lactam monomer may be 80 mol% or more based on the entire polymerization component.
In the polymer of the present invention, the ratio of the hindered amine monomer may be 0.01 to 15 mol with respect to 100 mol of the vinyl lactam monomer. Typically, in the polymer of the present invention, the proportion of the vinyl lactam monomer is 80 mol% or more of the entire polymerization component, and the proportion of the hindered amine monomer is 0.05 to 10 mol with respect to 100 mol of the vinyl lactam monomer. It may be.

In the polymer of the present invention, the polymerization component may further contain a monomer having a functional group (functional group β), for example, a carbonyl group, an acid group, a carbonate group, an isocyanate group, an oxazoline group, an oxazolidine group. , A monomer having at least one functional group selected from hydrazino group, epoxy group, amino group, hydroxyl group, and mercapto group [for example, carbonyl group-containing monomer (for example, diacetone (meth) acrylamide) A monomer having a functional group containing (functional group β)].

Representative polymers of the present invention include:
The vinyl lactam monomer contains N-vinylpyrrolidone,
The polymerization component further includes a monomer having at least one functional group selected from a carbonyl group-containing monomer, an acid group-containing monomer, and a hydroxy group-containing monomer,
The proportion of the vinyl lactam monomer is 70% by mass or more based on the entire polymerization component,
The polymer etc. whose ratio of the hindered amine-type monomer and the monomer which has a functional group are 10 mass parts (or 10 mol) or less with respect to 100 mass parts (or 100 mol) of vinyl lactam monomers, respectively are contained.

In particular, when the polymerization component contains a monomer having a functional group, the monomer having a functional group may contain at least a carbonyl group-containing monomer (for example, diacetone (meth) acrylamide).

The polymer of the present invention can be suitably used as a hydrophilizing material (hydrophilizing agent) and the like, for example, a polymer for use in combination with an emulsion (particularly a polymer for constituting an aqueous composition for paint). Also good. Therefore, the present invention also includes a hydrophilizing agent composed of the polymer (polymer (B)) [for example, a hydrophilizing agent for paint (particularly for water-based paint)].

The present invention includes a composition comprising an emulsion (A) and the polymer (B).
In such a composition, the emulsion (A) may in particular be an acrylic emulsion.

In the composition of the present invention, the emulsion (A) may be anionic (for example, may have an anionic group). Typically, the emulsion (A) may be an emulsion satisfying the following (1) and / (2).
(1) Consists of a resin comprising a monomer component (a) containing an anionic group-containing monomer as a polymerization component (2) The emulsifier constituting the emulsion (A) contains an anionic emulsifier

In the composition of the present invention, the emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group α as a polymerization component, and the polymerization component of the polymer (B) is functional. A monomer having a functional group β capable of forming a cross-linking structure with the group α may be included.

The composition of the present invention may further contain a crosslinking agent (C) capable of forming a bond by reacting between the functional group α and the functional group β.

Typically, in the composition of the present invention, a monomer having a functional group α includes a carbonyl group-containing monomer, a monomer having a functional group β includes a carbonyl group-containing monomer, and a hydrazine-based crosslinking agent. The emulsion (A) and the polymer (B) can form a crosslinked structure via (C1), and / or the monomer having the functional group α includes a carboxyl group-containing monomer, and the functional group β The composition may contain a carboxyl group-containing monomer and the emulsion (A) and the polymer (B) can form a crosslinked structure via the oxazoline-based crosslinking agent (C1).

In the composition of the present invention, the ratio of the emulsion (A) to the polymer (B) may be, for example, the former / the latter (mass ratio) = 99/1 to 60/40.

The composition of the present invention may be an aqueous composition for paints containing an emulsion (A) and a polymer (B), and particularly for a top coat (especially for a top coat of an exterior material).

The present invention includes a coating film formed from the composition. The present invention also includes a base material (coated base material) composed of a base material (base base material) and the coating film (coating film) formed on the base material.

In the present invention, by combining the polymer (B) with the emulsion (A), low contamination (hydrophilicity) of the coating film can be maintained, and adhesion of dirt to the coating film (coating film) can be suppressed or prevented.

Therefore, the present invention provides a stain-proofing agent (an agent for suppressing or preventing the adhesion of dirt) to a coating film formed from a composition containing the emulsion (A), which comprises a polymer (B) (vinyl lactam). Also included are antifouling agents (contamination prevention agents) composed of (or containing the polymer (B)) at least as a polymerization component (a polymer having the monomer component (b)) with a monomer and a hindered amine monomer.

The novel polymers and compositions (especially aqueous resin compositions) of the present invention are useful as hydrophilizing materials (for example, hydrophilic or water-soluble polymers for paints).
Such polymers and compositions can maintain the low contamination (hydrophilicity) of the coating film over a long period of time despite being hydrophilic or water-soluble.

Also, the polymer and composition of the present invention can form a coating film excellent in coating film physical properties (for example, water resistance, weather resistance, extensibility, adhesion, etc.).

Furthermore, according to the polymer and composition of the present invention, a highly glossy coating film (or a coating film with strong gloss) can be formed.

Furthermore, the polymer and composition of the present invention have good handleability (for example, excellent storage stability).

In particular, the polymer and composition of the present invention can be produced by combining these excellent effects in a well-balanced manner, and are extremely useful as a paint.

<Polymer>
The polymer of the present invention (corresponding to the polymer (B) described later) is a polymer comprising a vinyl lactam monomer and a hindered amine monomer as at least a polymerization component (or a monomer component, corresponding to the monomer component (b) described later). It is.

(Vinyl lactam monomer)
Examples of vinyl lactam monomers include vinyl pyrrolidone (N-vinyl pyrrolidone), vinyl caprolactam (N-vinyl caprolactam), and the like.

Among them, vinyl pyrrolidone is preferable, and therefore the vinyl lactam monomer may be composed of at least vinyl pyrrolidone.

In the case where the vinyl lactam monomer is composed of vinyl pyrrolidone and another vinyl lactam monomer, the ratio of vinyl pyrrolidone to the whole vinyl lactam monomer is, for example, 50 mol% or more, preferably 70 mol% or more, Preferably, 90 mol% or more may be sufficient.

In the polymerization component (monomer component (b)), the proportion of the vinyl lactam monomer depends on the type of other monomers, but from the viewpoint of imparting hydrophilicity (water solubility) to the polymer, for example, the polymerization component It may be 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, particularly 80% by mass or more, and particularly preferably 85% by mass or more (for example, 90% by mass or more).
In the polymerization component (monomer component (b)), the proportion of the vinyl lactam monomer depends on the type of other monomers, but from the viewpoint of imparting hydrophilicity (water solubility) to the polymer, for example, the polymerization component It may be 30 mol% or more of the whole, preferably 50 mol% or more, more preferably 70 mol% or more, particularly 80 mol% or more, particularly preferably 85 mol% or more (for example, 90 mol% or more). That is, the ratio of the vinyl lactam monomer to the entire polymerization component may be in the same range in terms of mass (mass%) and mol (mol%). Hereinafter, the same may be applied to the ratio (for example, hindered amine monomer, monomer having a functional group, etc.) in the polymerization component (for example, mass% may be mol%).

(Hindered amine monomers)
Examples of the hindered amine monomer include a polymerizable compound having a piperazine skeleton (particularly a 2,2,6,6-tetramethylpiperidine skeleton) (a compound having a piperazine skeleton and a polymerizable group).

In the hindered amine monomer, the polymerizable group is not particularly limited, and examples thereof include an alkenyl group (such as a vinyl group and an allyl group) and an alkenylcarbonyl group [such as a (meth) acryloyl group and a crotonoyl group].

The number of polymerizable groups in the hindered amine monomer may be 1 or more, and may be 1 to 4, preferably 1 to 3, and more preferably 1. A preferred hindered amine monomer is a monofunctional monomer (a compound having one polymerizable group). Therefore, the hindered amine monomer may be composed of at least a monofunctional monomer.

Typical hindered amine monomers include compounds represented by the following formula (I).

(Wherein R ¹ and R ² are hydrogen atoms or alkyl groups, R ³ , R ⁴ , R ⁵ and R ⁶ are alkyl groups, X is an oxygen atom (—O—) or imino group (—NH—), Y And Z represents a hydrogen atom or a substituent.)

In R ¹ to R ⁶ , examples of the alkyl group include C _1-20 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a s-butyl group, and a t-butyl group. Preferably, a C _1-10 alkyl group, more preferably a C _1-4 alkyl group, particularly a methyl group.

Typical R ¹ and R ² are a hydrogen atom or a methyl group, and it is particularly preferable that R ¹ is a hydrogen atom and R ² is a hydrogen atom or a methyl group. Representative R ³ to R ⁶ are methyl groups.

Examples of the substituent for Y and Z include hydrocarbon groups such as alkyl groups (for example, the above-exemplified alkyl groups such as a methyl group (C _1-20 alkyl group, preferably C _1-4 alkyl group), etc.) ], An alkoxy group (for example, a C _1-20 alkoxy group such as a methoxy group or an ethoxy group, preferably a C _1-10 alkoxy group, more preferably a C _1-4 alkoxy group, particularly a methoxy group), an acyl group (for example, C _1-10 acyl group such as acetyl group), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.), cyano group, hydroxyl group, polymerizable group (eg (meth) acryloyl group, crotonoyl group) ) And the like.

Typical examples of Y include a hydrogen atom, an alkyl group (for example, a C _1-4 alkyl group such as a methyl group), an alkoxy group (for example, a C _1-4 alkoxy group such as a methoxy group), an acyl group (for example, an acetyl group). A C _1-4 acyl group such as a group), a (meth) acryloyl group, a crotonoyl group, and the like. Particularly, a hydrogen atom or a methyl group is preferable.

Further, representative Z includes a hydrogen atom or a cyano group, and a hydrogen atom is particularly preferable.

As a specific hindered amine monomer, for example,
4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine having a substituent {for example, 4- ( (Meth) acryloyloxy-2,2,6,6-tetramethyl-1-alkylpiperidine [eg 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine etc. ) Acryloyloxy-1-C _1-4 alkyl-2,2,6,6-tetramethylpiperidine], 4- (meth) acryloyloxy-2,2,6,6-tetramethyl-1-alkoxypiperidine [for example 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, such as 4- (meth) acryloyloxy _{-1-C 1-4} a N-substituted (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, such as 4-hydroxy-4- (meth) acryloyloxy- 4- (meth) acryloyloxy-2 such as 4-substituted-4- (meth) acryloyloxy-2, such as 2,2,6,6-tetramethylpiperidine, 2,6,6-tetramethylpiperidine, etc.} 2,6,6-tetramethylpiperidines;
4-crotonoyloxy-2,2,6,6-tetramethylpiperidines such as 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine;
4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine having a substituent {for example, 4- (meta ) Acryloylamino-2,2,6,6-tetramethyl-1-alkylpiperidine [eg 4- (meth) such as 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine N-substituted (meth) acryloylamino-2,2,6,6-tetramethylpiperidine such as acryloylamino-2,2,6,6-tetramethyl-1-C _1-4 alkylpiperidine]; 4-cyano- 4-Substituted-4- (meth) acryloylamino-2,2,6,6-teto such as 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidines such as lamethylpiperidine etc .;
4-crotonoylamino-2,2,6,6-tetramethylpiperidines such as 4-crotonoylamino-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, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidines such as 6,6-tetramethylpiperidine;
1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidines such as 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine;
Etc.

Among these, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidines [for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethyl-1-alkylpiperidine etc.] are preferred.

The hindered amine monomers may be used alone or in combination of two or more.

The ratio of the hindered amine monomer is, for example, 30% by mass or less (for example, 0.001 to 25% by mass), preferably 20% by mass or less (for example, based on the entire polymerization component (monomer component (b)). 0.01 to 15% by mass), more preferably 10% by mass or less (for example, 0.05 to 8% by mass), and usually 0.05 to 10% by mass (for example, 0.1 to 5% by mass). %).
The ratio of the hindered amine monomer is, for example, 30 mol% or less (for example, 0.001 to 25 mol%), preferably 20 mol% or less (for example, for the entire polymerization component (monomer component (b)). 0.01 to 15 mol%), more preferably 10 mol% or less (for example, 0.05 to 8 mol%), and usually 0.05 to 10 mol% (for example, 0.1 to 5 mol%). %).

The ratio of the hindered amine monomer is, for example, 30 parts by mass or less (for example, 0.001 to 25 parts by mass), preferably 20 parts by mass or less (for example, 0.01 to 15 parts) with respect to 100 parts by mass of the vinyl lactam monomer. Part by mass), more preferably 10 parts by mass or less (eg, 0.05 to 8 parts by mass), and usually 0.05 to 10 parts by mass (eg, 0.1 to 5 parts by mass). Also good.
The ratio of the hindered amine monomer is, for example, 30 mol or less (for example, 0.001 to 25 mol), preferably 20 mol or less (for example, 0.01 to 15 mol), relative to 100 mol of the vinyl lactam monomer, Preferably, it may be 10 mol or less (for example, 0.05 to 8 mol), and may generally be 0.05 to 10 mol (for example, 0.1 to 5 mol).

(Monomer having a functional group)
The polymerization component (monomer component (b)) may contain a monomer (monomer) having a functional group (corresponding to a functional group β described later). By including a monomer having such a functional group in the polymerization component, it may be more advantageous in terms of long-term hydrophilicity.

Examples of the functional group (functional group β) include a carbonyl group (or a carbonyl group-containing group such as a ketone group, an aldehyde group, and an acyl group), an acid group (or an anionic group such as a carboxyl group, and an acid anhydride). Group, acid halide group, sulfonic acid group, etc.), carbonate group, isocyanate group, oxazoline group, oxazolidine group, hydrazino group, epoxy group, amino group, hydroxyl group, mercapto group and the like.

The monomer having a functional group may have these functional groups alone or in combination of two or more.

Among these functional groups, a carbonyl group, an acid group (anionic group), an oxazoline group, a hydrazino group, a hydroxyl group, and the like are preferable, and a carbonyl group, a carboxyl group, and a hydroxyl group are particularly preferable.

The functional group (functional group β) is a functional group that can form a crosslinked structure (or bond) in combination with a functional group (functional group α) (a monomer having a functional group α) in an emulsion described later. There may be. Such a crosslinked structure (or bond) may be formed by a direct reaction between the functional group α and the functional group β. As described later, the functional group α and the functional group β are formed via a crosslinking agent. A crosslinked structure may be formed.

Specific monomers having a functional group include, for example, carbonyl group-containing monomers, acid group-containing monomers (anionic group-containing monomers), hydroxyl group-containing monomers, and the like.

Examples of the carbonyl group-containing monomer include unsaturated aldehydes [eg, alkenals (eg, C _3-10 alkenals such as acrolein, methacrolein), (meth) acryloxyalkyl alkenals (eg, acryloxyalkylpropenal). , Methacryloxyalkylpropenal), formylstyrene, etc.], unsaturated ketones (eg, alkenones (eg, methyl vinyl ketone, ethyl vinyl ketone, vinyl butyl ketone), (meth) acryloyloxyalkanones (eg, acetonyl acrylate) , Acetonyl methacrylate, etc.), N- (meth) acryloylaminoalkanone (eg, diacetone acrylamide, diacetone methacrylamide, etc.), alkanediol (meth) acrylate acetyl Acetoacetoxy (eg, C _2-6 alkanediol (meth) acrylate acetyl acetate such as 2-hydroxypropyl acrylate acetyl acetate, 2-hydroxypropyl methacrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate), acetoacetoxyalkyl (Meth) acrylates (for example, 2- (acetoacetoxy) ethyl acrylate, 2- (acetoacetoxy) ethyl methacrylate, etc.) and the like.

Examples of the acid group-containing monomer (anionic group-containing monomer) include carboxylic acid group-containing monomers [for example, unsaturated monocarboxylic acids (for example, aliphatic acids such as acrylic acid, methacrylic acid, crotonic acid). Unsaturated monocarboxylic acid), unsaturated dicarboxylic acid (for example, aliphatic unsaturated monocarboxylic acid such as maleic acid and fumaric acid)], sulfonic acid group-containing monomer [for example, styrenic monomer (for example, Styrene sulfonic acid, etc.)] and the like.

The acid group-containing monomer may be anionized (or may form a salt or may be neutralized). The method for anionization is not particularly limited, and examples thereof include a method of reacting with a basic compound (neutralizing or forming a salt). Examples of the basic compound include inorganic bases {eg, hydroxide (eg, alkali metal or alkaline earth metal hydroxide such as sodium hydroxide), ammonia [eg, ammonia water (25% ammonia water, etc.)] Use] and the like, and organic bases [for example, amine (eg, monomethylamine, monoethanolamine, diethanolamine, dimethylethanolamine, isopropanolamine, etc.)] and the like. Two or more basic compounds may be used in combination.

Examples of the oxazoline group-containing monomer include alkenyl oxazolines (for example, C _2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline and 2-isopropenyl-2-oxazoline, preferably vinyl or isopropenyl oxazoline), Alkenyl-alkyloxazolines (eg 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl- C _2-6 alkenyl-C _1-10 alkyl oxazoline such as 5-ethyl-2-oxazoline, preferably vinyl or isopropenyl-C _1-4 alkyl oxazoline) and the like.

Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylate [for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy Hydroxy C _2-10 alkyl (meth) acrylate such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, preferably hydroxy C _2-6 alkyl (meth) acrylate, more preferably hydroxy C _2-4 alkyl ( (Meth) acrylates, etc.] (meth) acrylates of polyols having 3 or more hydroxyl groups [eg (meth) acrylates of tri to hexahydroxy C _3-10 polyols such as glycerol mono (meth) acrylate ] And other hydroxyl group-containing acrylic monomers (particularly hydroxyl group-containing (meth) acrylate).

Monomers having a functional group may be used alone or in combination of two or more.

Of these, unsaturated ketones, unsaturated monocarboxylic acids (such as acrylic acid), and hydroxyl group-containing (meth) acrylates are preferred. Among them, diacetone (from the point of being advantageous in coating film properties (water whitening resistance, etc.) Meth) acrylamide is preferred. Therefore, the monomer having a functional group may contain at least such a monomer (particularly diacetone (meth) acrylamide).

When diacetone (meth) acrylamide is used at least as the monomer having a functional group, the ratio of diacetone (meth) acrylamide to the whole monomer having a functional group is, for example, 10% by mass or more, preferably May be 20% by mass or more, more preferably 30% by mass or more.

Monomers having a functional group (functional group β) may be used alone or in combination of two or more.

When using the monomer which has a functional group, the ratio of the monomer which has a functional group is 30 mass% or less (for example, 0.00%) with respect to the whole polymerization component (monomer component (b)). 001 to 25% by mass), preferably 20% by mass or less (eg 0.01 to 15% by mass), more preferably 10% by mass or less (eg 0.05 to 8% by mass). It may be 0.05 to 10% by mass (for example, 0.1 to 5% by mass).
When using the monomer which has a functional group, the ratio of the monomer which has a functional group is 30 mol% or less (for example, 0.00%) with respect to the whole polymerization component (monomer component (b)). 001-25 mol%), preferably 20 mol% or less (eg, 0.01-15 mol%), more preferably 10 mol% or less (eg, 0.05-8 mol%). It may be 0.05 to 10 mol% (for example, 0.1 to 5 mol%).

When using a monomer having a functional group, the proportion of the monomer having a functional group is, for example, 30 parts by mass or less (for example, 0.001 to 25 parts by mass) with respect to 100 parts by mass of the vinyl lactam monomer. ), Preferably 20 parts by mass or less (eg 0.01 to 15 parts by mass), more preferably 10 parts by mass or less (eg 0.05 to 8 parts by mass), and usually 0.05 to 10 parts by mass. It may be part by mass (for example, 0.1 to 5 parts by mass).
When using a monomer having a functional group, the ratio of the monomer having a functional group is, for example, 30 mol or less (for example, 0.001 to 25 mol) with respect to 100 mol of the vinyl lactam monomer, It may be preferably 20 mol or less (for example, 0.01 to 15 mol), more preferably 10 mol or less (for example, 0.05 to 8 mol), and usually 0.05 to 10 mol (for example, 0.1 mol). 1-5 moles).

When a monomer having a functional group is used, the ratio of the hindered amine monomer to the monomer having a functional group is the former / the latter (mass ratio) = 100/1 to 0.01 / 1, preferably 50 / 1 to 0.02 / 1 (for example, 30/1 to 0.03 / 1), more preferably about 20/1 to 0.05 / 1 (for example, 10/1 to 0.1 / 1). Also good.
When using a monomer having a functional group, the ratio of the hindered amine monomer to the monomer having a functional group is the former / the latter (molar ratio) = 100/1 to 0.01 / 1, preferably 50 / 1 to 0.02 / 1 (for example, 30/1 to 0.03 / 1), more preferably about 20/1 to 0.05 / 1 (for example, 10/1 to 0.1 / 1). Also good.

The polymerization component may contain other monomers as long as the effects of the present invention are not impaired. Examples of other monomers include the monomers exemplified in the monomer component (a) described later (for example, alkyl (meth) acrylates, aromatic monomers, silicon atom-containing monomers, fluorine atoms). Containing monomer, epoxy group-containing monomer, UV-absorbing monomer, etc.), but not particularly limited.

Other monomers may be used alone or in combination of two or more.

When the polymerization component (monomer component (b)) contains another monomer, the proportion of the other monomer in the polymerization component (monomer component (b)) is, for example, 20% by mass or less (for example, 0.01 To 18% by mass), preferably 15% by mass or less (for example, 0.1 to 12% by mass), and more preferably 10% by mass or less (for example, 0.3 to 5% by mass).
When the polymerization component (monomer component (b)) contains another monomer, the proportion of the other monomer in the polymerization component (monomer component (b)) is, for example, 20 mol% or less (for example, 0.01 To 18 mol%), preferably 15 mol% or less (for example, 0.1 to 12 mol%), and more preferably 10 mol% or less (for example, 0.3 to 5 mol%).

The copolymerization mode of the polymer of the present invention may be any of random copolymer, block copolymer, graft copolymer and the like.

The weight average molecular weight of the polymer of the present invention can be appropriately selected depending on the kind of the monomer and is not particularly limited. However, from the viewpoint of the physical properties of the coating film, for example, 1,000 to 3,000,000, more preferably 3,000 to 1,000,000, Preferably, it may be 5,000 to 500,000, particularly 7,000 to 300,000, particularly preferably 10,000 to 250,000. In particular, the polymer of the present invention has a relatively high molecular weight [eg, weight average molecular weight of 50,000 or more (eg, 550,000 to 500,000), preferably 60,000 or more (eg, 650,000 to 300,000), More preferably, it may be 70,000 or more (for example, 75,000 to 200,000), particularly 80,000 or more (for example, 850,000 to 180,000), and usually 50,000 to 250,000].
The molecular weight distribution (the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn) of the polymer of the present invention is, for example, 25 or less (for example, 1.5 to 25), preferably 20 or less (for example, 2.0 to 2.0). 20), more preferably (for example, 2.0 to 10), and 8 or less (for example, 7 or less, preferably 5 or less, more preferably 4 or less, particularly preferably 3.5 or less). May be. In the present invention, a polymer having a relatively narrow molecular weight distribution may be suitably used.

The weight average molecular weight is, for example, gel permeation chromatography (for example, manufactured by Nippon Waters Co., Ltd., product number: E-2695, column: TSKgel α-M and TSKgel α-M used in series). It may be a weight average molecular weight (in terms of polyethylene oxide) that can be used and measured.

The polymer of the present invention may usually be water-soluble.

The polymer of the present invention may be basic.

(Method for producing polymer)
The polymer of the present invention can be obtained by polymerizing a polymerization component (monomer component (b)). As the polymerization method, for example, a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a precipitation polymerization method can be used. Among these polymerization methods, the solution polymerization method is preferable, and the solution polymerization method using water as a solvent is more preferable.

When preparing by solution polymerization method, a solvent is used. Examples of the solvent include water, alcohol, ether, ketone, ester, amide, sulfoxide, hydrocarbon compound, and the like, but the present invention is not limited to such examples. Suitable solvents include, for example, water, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, tert-butyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran, 1,4-dioxane, 1 , 3-dioxolane, toluene, ethyl acetate and the like, but the present invention is not limited to such examples.
These solvents may be used alone or in combination of two or more.

Note that the solvent may contain an appropriate amount of an organic amine compound, ammonia, an alkali metal hydroxide, or the like, if necessary.

The polymerization temperature for preparing the polymer is not particularly limited, but may be, for example, about 0 to 100 ° C., preferably 30 to 95 ° C., and more preferably about 50 to 90 ° C. Further, the pressure during the polymerization reaction may be normal pressure, reduced pressure, or increased pressure. The atmosphere during the polymerization reaction is preferably an inert gas such as nitrogen gas, argon gas or carbon dioxide gas.

In the polymerization, a polymerization initiator can be used. Examples of the polymerization initiator include persulfates (eg, ammonium persulfate, sodium persulfate, potassium persulfate, etc.), hydrogen peroxide, organic peroxides, azo compounds [eg, 2,2′-azobis (2- Methyl propionamidine) dihydrochloride, etc.]. The polymerization initiators may be used alone or in combination of two or more.

The amount of the polymerization initiator per 100 parts by mass of the polymerization component (monomer component (b)) used for the polymerization is not particularly limited, but may be, for example, about 0.01 to 10 parts by mass. The polymerization initiator may be charged all at once at the start of the polymerization reaction, or may be sequentially added during the polymerization reaction.

The polymerization initiator can be used in combination with an appropriate amount of a reducing agent. Examples of the reducing agent include iron (II) salt, sodium dithionite, sodium hydrogen sulfite, sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, etc., but the present invention is only such examples. It is not limited to.

<Composition>
The polymer of the present invention has hydrophilicity (particularly water solubility) and can be suitably used as a hydrophilic material (hydrophilizing agent). In particular, a composition useful for forming a hydrophilic coating film can be formed by combining with an emulsion.

Hereinafter, the composition containing the emulsion (referred to as emulsion (A)) and the polymer of the present invention (referred to as polymer (B)) will be described in detail.

[Emulsion (A)]
The resin (polymer, polymer) constituting the emulsion (A) (resin emulsion (A)) is not particularly limited, and examples thereof include addition polymerization resins [for example, acrylic resins, vinyl alcohol resins (for example, polyvinyl resins). Alcohol, etc.), fluorine resin, etc.], condensation resin [eg, polyamide resin, polyester resin, polyurethane resin, etc.], heat or photocurable resin (eg, alkyd resin, epoxy resin, etc.), etc. .

These resins (polymer, polymer) may be used alone or in combination of two or more to constitute the emulsion (A). Moreover, an emulsion (A) may be used independently or may combine 2 or more types of emulsion.
In addition, emulsion (A) (or resin which comprises an emulsion) is a particulate form normally. Therefore, the emulsion can also be called emulsion particles.

Hereinafter, typical resins will be described.
The resin (polymer, polymer) usually has the monomer component (a) as a polymerization component. The monomer component (a) may be usually an addition polymerizable monomer (or a radical polymerizable monomer, a monomer having an ethylenically unsaturated bond, etc.).

Examples of the monomer component (a) include aliphatic (meth) acrylates, alicyclic monomers (monomers having an alicyclic structure), hydroxyl group-containing (meth) acrylates, aromatic monomers, Acid group-containing monomer (or anionic group-containing monomer), silicon atom-containing monomer, fluorine atom-containing monomer, nitrogen atom-containing monomer, epoxy group-containing monomer, UV-absorbing monomer And hindered amine monomers (ultraviolet stable monomers).

Monomer component (a) may be used alone or in combination of two or more.

In particular, the emulsion (A) is an acrylic (acrylic resin) emulsion, for example, as a monomer component (a) from the viewpoint of physical properties of the coating film, for example, at least aliphatic (meth) acrylate (particularly alkyl (meth) acrylate). ) Containing a resin emulsion.

Typical acrylic emulsions include emulsions of resins containing at least an alkyl (meth) acrylate and a monomer having an alicyclic structure, preferably at least an alkyl (meth) acrylate and a single amount having an alicyclic structure And an emulsion of a resin containing a hydroxyl group-containing (meth) acrylate, more preferably at least an alkyl (meth) acrylate, a monomer having an alicyclic structure, a hydroxyl group-containing (meth) acrylate and an aromatic monomer An emulsion of a resin containing

(Aliphatic (meth) acrylate)
Examples of the aliphatic (meth) acrylate include alkyl (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, sec-butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) ) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, etc. _1-20 alkyl (meth) acrylate], alkoxyalkyl (meth) acrylate [eg, alkoxyalkyl (meth) acrylate (eg, C _1-12 alkoxy C _1-12 alkyl methacrylate of 2-methoxyethyl (meth) acrylate, etc.) Etc.].

Aliphatic (meth) acrylates may be used alone or in combination of two or more.

Among these aliphatic (meth) acrylates, C _1-12 alkyl (meth) such as methyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. Acrylates (eg, C _1-8 alkyl (meth) acrylate) are preferred.

When the monomer component (a) contains an aliphatic (meth) acrylate, the content (content) of the aliphatic (meth) acrylate in the monomer component (a) is, for example, 10 to 90% by mass, The amount may be preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and particularly preferably about 30 to 80% by mass.

(Monomer having an alicyclic structure)
Examples of the monomer having an alicyclic structure include monomers having an alicyclic structure (for example, a cycloalkyl group having 4 to 20 carbon atoms, preferably a cycloalkyl group having 4 to 10 carbon atoms). Specific examples of the monomer having an alicyclic structure include, for example, alicyclic (meth) acrylate [for example, C _4-20 cycloalkyl (meth) acrylate such as cycloalkyl (meth) acrylate (for example, cyclohexyl (meth) acrylate). ) Acrylate, preferably C _4-10 cycloalkyl (meth) acrylate), cycloalkylalkyl (meth) acrylate (eg, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate, 4- C _4-10 cycloalkyl C _1-4 alkyl (meth) acrylates such as methylcyclohexylmethyl (meth) acrylate), bridged cyclic (meth) acrylates (eg isobornyl (meth) acrylate, adamantyl (meth)) Acrylate etc.)] and the like.

The monomer having an alicyclic structure is a substituent (for example, alkyl group such as methyl group, tert-butyl group, nitro group, nitrile group, alkoxyl group, acyl group, sulfone group, hydroxyl group, halogen atom, etc. ).

Monomers having an alicyclic structure may be used alone or in combination of two or more.

Among the monomers having an alicyclic structure, C _4-20 cycloalkyl (meth) acrylate is preferable, C _4-10 cycloalkyl (meth) acrylate is more preferable, and isobornyl (meth) acrylate and cyclohexyl (meth) acrylate are preferable. Further preferred.

When the monomer component (a) contains a monomer having an alicyclic structure, the content (content) of the monomer having an alicyclic structure in the monomer component (a) is, for example, 5 to It may be about 80% by mass, preferably 10 to 70% by mass, more preferably 15 to 65% by mass, particularly preferably about 20 to 60% by mass.

In addition, when the monomer component (a) contains an aliphatic (meth) acrylate and a monomer having an alicyclic structure, these ratios are the monomer having an aliphatic (meth) acrylate / alicyclic structure. (Mass ratio) = 95/5 to 5/95 (for example, 90/10 to 10/90), preferably 80/20 to 20/80, more preferably about 80/20 to 40/60. .

Further, when the monomer component (a) contains an aliphatic (meth) acrylate and a monomer having an alicyclic structure, the aliphatic (meth) acrylate and alicyclic structure in the monomer component (a) The ratio of the total amount of the monomers having is, for example, 10% by mass or more (for example, 15 to 99.5% by mass), preferably 20% by mass or more (for example, 25 to 99% by mass), and more preferably 30% by mass. It may be about (for example, 40 to 98% by mass), particularly preferably about 50% by mass or more (for example, 60 to 97% by mass), and usually 70% by mass or more (for example, 75 to 95% by mass). May be.

(Hydroxyl group-containing (meth) acrylate)
Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylate [for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy Hydroxy C _2-10 alkyl (meth) acrylate such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, preferably C _2-6 alkyl (meth) acrylate, more preferably C _2-4 alkyl (meth) Acrylates, etc.] (meth) acrylates of polyols having 3 or more hydroxyl groups [for example, (meth) acrylates of tri to hexahydroxy C _3-10 polyols such as glycerol mono (meth) acrylate] and the like. It is.

The hydroxyl group-containing (meth) acrylate may be used alone or in combination of two or more.

Among the hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth) acrylate and glycerol mono (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.

When the monomer component (a) contains a hydroxyl group-containing (meth) acrylate, the content ratio (content ratio) of the hydroxyl group-containing (meth) acrylate in the monomer component (a) is, for example, 0.1 to 20 mass. %, Preferably 0.3 to 10% by mass, more preferably 0.5 to 8% by mass, and particularly preferably about 1 to 5% by mass.

When the monomer component (a) contains an aliphatic (meth) acrylate and / or a monomer having an alicyclic structure, and a hydroxyl group-containing (meth) acrylate, the content ratio of the hydroxyl group-containing (meth) acrylate ( Content) is, for example, 0.1 to 20 parts by weight, preferably 0.3 to 15 parts by weight, based on 100 parts by weight of the monomer having an aliphatic (meth) acrylate and / or alicyclic structure, Preferably it may be about 0.5 to 10 parts by mass, particularly preferably about 1 to 8 parts by mass.

(Aromatic monomer)
Examples of aromatic monomers include styrene monomers [eg, styrene, α-alkyl styrene (eg, α-C _1-4 alkyl styrene such as α-methyl styrene), alkyl styrene (eg, vinyl toluene, etc. C _1-4 alkyl styrene), halostyrene (eg, chlorostyrene, etc.)], aromatic (meth) acrylate [eg, aryl (meth) acrylate (eg, C _6-10 aryl (eg, phenyl (meth) acrylate) ( (Meth) acrylates), aralkyl (meth) acrylates (eg C _6-10 aryl C _1-4 alkyl (meth) acrylates such as benzyl (meth) acrylate, phenethyl (meth) acrylate), aryloxyalkyl methacrylates (eg phenoxy) Ethyl methacrylate Over _{C 6-10} aryloxy _{C 1-4} alkyl methacrylates) such as such as preparative] and the like.

The aromatic monomers may be used alone or in combination of two or more.

When the monomer component (a) contains an aromatic monomer, the content (content) of the aromatic monomer in the monomer component (a) is, for example, 0.1 to 30 mass. %, Preferably 0.5 to 20% by mass, more preferably about 1 to 15% by mass.

(Acid group-containing monomer)
Examples of the acid group-containing monomer (anionic group-containing monomer) include the above-exemplified monomers, for example, carboxylic acid group-containing monomers [for example, unsaturated monocarboxylic acids (for example, acrylic acid, methacrylic acid). , Aliphatic unsaturated monocarboxylic acids such as crotonic acid), unsaturated dicarboxylic acids (eg, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid)], sulfonic acid group-containing monomers [eg, styrene Based monomers (for example, styrenesulfonic acid, etc.)] and the like.
In addition, the acid group-containing monomer may be anionized (or may form a salt).

The acid group-containing monomers may be used alone or in combination of two or more.

Typical acid group-containing monomers include acrylic acid and methacrylic acid.

When the monomer component (a) contains an acid group-containing monomer (anionic group-containing monomer), the content ratio (content ratio) of the acid group-containing monomer in the monomer component (a) is For example, it may be about 0.01 to 10% by mass, preferably about 0.02 to 5% by mass, and more preferably about 0.05 to 3% by mass.

(Silicon atom-containing monomer)
Examples of the silicon atom-containing monomer include vinyl group-containing silane [eg, vinyl group-containing halosilane (eg, vinyl mono to trihalosilane such as vinyltrichlorosilane), vinyl group-containing alkoxysilane [vinyl alkoxysilane (eg, Vinyl mono to trialkoxy silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, preferably vinyl mono to tri C _1-4 alkoxy silanes), vinyl alkoxy alkoxy silanes (eg vinyl mono to tris (β-methoxyethoxy) silane etc. (C _1-4 alkoxy C _1-4 alkoxy) silane, etc.)], (meth) acryloyl group-containing silane [eg, alkoxysilane having a (meth) acryloyl group (eg, γ- (meth) acryloyl) (Meth) acryloyloxyalkyl mono to trialkoxysilane such as oxypropyltrimethoxysilane, preferably (meth) acryloyloxy C _2-4 alkyl mono to tri C _1-4 alkoxysilane), trialkylsiloxyalkyl (meth) acrylate (For example, tri-C _1-4 alkylsiloxy C _2-4 alkyl (meth) acrylate such as trimethylsiloxyethyl (meth) acrylate)) and the like.

The silicon atom-containing monomers may be used alone or in combination of two or more.

Typical silicon atom-containing monomers include alkoxysilanes having a (meth) acryloyl group such as γ- (meth) acryloyloxypropyltrimethoxysilane.

When the monomer component (a) contains a silicon atom-containing monomer, the content ratio (content ratio) of the silicon atom-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.

(Fluorine atom-containing monomer)
Examples of the fluorine atom-containing monomer include fluorine atom-containing acrylic monomers [for example, fluoroalkyl (meth) acrylate (for example, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl). (meth) fluoroalkyl _{C 1-10} alkyl (meth) acrylates such as acrylates, preferably such as fluoro _{C 2-6} alkyl (meth) acrylate)], and others.

Fluorine atom-containing monomers may be used alone or in combination of two or more.

When the monomer component (a) contains a fluorine atom-containing monomer, the content ratio (content ratio) of the fluorine atom-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.

(Nitrogen atom-containing monomer)
Examples of the nitrogen atom-containing monomer include (meth) acrylamide compounds {for example, (meth) acrylamide, N-substituted (meth) acrylamide [for example, N-alkyl (meth) acrylamide (for example, N, N-dimethyl). N, N-diC _1-4 alkyl (meth) acrylamide, such as (meth) acrylamide; N, N-dimethylaminopropyl (meth) acrylamide, etc.), etc.], nitrogen atom-containing (meth) acrylate compounds {for example, N-substituted aminoalkyl (meth) acrylate [for example, N, N-diC _1-4 alkylamino C _2-4 alkyl (meth) acrylate such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate], etc. }.

The nitrogen atom-containing monomers may be used alone or in combination of two or more.

When the monomer component (a) contains a nitrogen atom-containing monomer, the content ratio (content ratio) of the nitrogen atom-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.

(Epoxy group-containing monomer)
Examples of the epoxy group-containing monomer include epoxy group-containing (meth) acrylate [for example, glycidyloxy such as glycidyl (meth) acrylate, glycidyloxyalkyl (meth) acrylate (for example, 2-glycidyloxyethyl (meth) acrylate), etc. C _2-4 alkyl (meth) acrylate)], and allyl glycidyl ether.

The epoxy group-containing monomers may be used alone or in combination of two or more.

When the monomer component (a) contains an epoxy group-containing monomer, the content ratio (content ratio) of the epoxy group-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.

(UV absorbing monomer)
Examples of the ultraviolet absorbing monomer (monomer having an ultraviolet absorbing group) include a benzotriazole ultraviolet absorbing monomer and a benzophenone ultraviolet absorbing monomer.

Examples of the benzotriazole-based UV-absorbing monomer include benzotriazole-based UV absorbers having a polymerizable group (for example, (meth) acryloyl group), such as 2- [2′-hydroxy-5 ′-(meth) acryloyl Oxymethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyl Oxymethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloylaminomethyl-5'-tert-octylphenyl] -2H-benzotriazole, 2 -[2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl] 2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyhexylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-(meta ) Acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5′-tert-butyl-3 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl]- 5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) act Liloyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [ And 2′-hydroxy-5 ′-(β- (meth) acryloyloxyethoxy) -3′-tert-butylphenyl] -4-tert-butyl-2H-benzotriazole.

Examples of the benzophenone-based UV-absorbing monomer include benzophenone-based UV absorbers having a polymerizable group (for example, (meth) acryloyl group), such as 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy- 4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy -2-hydroxypropoxy] benzophenone, 2-hydroxy-3-tert-butyl-4- [2- (meth) acryloyloxy] butoxybenzophenone, and the like.

The ultraviolet absorbing monomers may be used alone or in combination of two or more.

When the monomer component (a) contains an ultraviolet absorbing monomer, the content (content) of the ultraviolet absorbing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.

(Hindered amine monomers)
Examples of hindered amine monomers (ultraviolet-stable monomers, light stabilizers having a polymerizable group, and monomers having light stability) include the hindered amine monomers exemplified above, such as 4- (meth) acryloyloxy-2. , 2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-penta Methylpiperidine, 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2 6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6- Tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetra Examples include methylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine.

The hindered amine monomers may be used alone or in combination of two or more.

When the monomer component (a) contains a hindered amine monomer, the content (content) of the hindered amine monomer in the monomer component (a) is, for example, 0.01 to 20% by mass, preferably 0.8. It may be about 05 to 10% by mass, more preferably about 0.1 to 5% by mass.

(Monomer having functional group α)
The monomer component (a) may contain a monomer having a functional group (referred to as a functional group α).
Since the resin in the emulsion (A) has a structural unit derived from a monomer having such a functional group α, an emulsion (by the functional group β described later) can be selected by selecting a functional group (functional group β described later). A bond between A) and polymer (B) can be formed efficiently. Such bond formation is a preferable form because it can suppress the outflow of the polymer (B) from the surface of the coating film and also improves the water resistance and the elastic modulus of the coating film.

Moreover, since the affinity with the polymer (B) can be improved by the functional group α, the polymer (B) is more efficiently adsorbed to the coating film, and it is easy to improve long-term contamination resistance.

As the functional group α, the same functional group as the functional group β (functional group exemplified in the polymer (B)), for example, a carbonyl group (or a carbonyl group-containing group such as a ketone group, an aldehyde group, an acyl group, etc.), Acid group or anionic group (for example, carboxyl group, acid anhydride group, acid halide group, sulfonic acid group, etc.), carbonate group, isocyanate group, oxazoline group, oxazolidine group, hydrazino group, epoxy group, amino group, hydroxyl group And a mercapto group. When bond formation with the functional group β is desired or intended, the functional group α may be selected in combination with the functional group β.

The monomer having the functional group α may have these functional groups alone or in combination of two or more.

Among these functional groups, a carbonyl group, an acid group (anionic group), an oxazoline group, a hydrazino group, a hydroxyl group, and the like are preferable from the viewpoint of physical properties of the coating film, and a carbonyl group and a carboxyl group are particularly preferable.
Moreover, among these, you may use suitably the monomer which has an acid group (anionic group). Since the acid group (or anionic group) exhibits high affinity for the hindered amine skeleton of the polymer (B), the polymer (B) is efficiently adsorbed on the coating film, and it is easy to improve long-term stain resistance.

Examples of the acid group-containing monomer (anionic group-containing monomer) include the above-exemplified monomers, for example, carboxylic acid group-containing monomers [for example, unsaturated monocarboxylic acids (for example, acrylic acid, methacrylic acid). , Aliphatic unsaturated monocarboxylic acids such as crotonic acid), unsaturated dicarboxylic acids (eg, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid)], sulfonic acid group-containing monomers [eg, styrene Based monomers (for example, styrenesulfonic acid, etc.)] and the like.
The acid group-containing monomer may be anionized (or may form a salt or be neutralized). The method for anionization is not particularly limited. For example, the basic compound includes, for example, an inorganic base {for example, hydroxide (for example, alkali metal or alkaline earth metal hydroxide such as sodium hydroxide), Ammonia [for example, aqueous ammonia (used as 25% aqueous ammonia, etc.), etc.], organic base [eg, amine (eg, monomethylamine, monoethanolamine, diethanolamine, dimethylethanolamine, isopropanolamine, etc.), etc.] be able to. Two or more basic compounds may be used in combination.

Examples of the hydroxyl group-containing monomer include the monomers exemplified above (for example, hydroxyl group-containing (meth) acrylate).

Monomers having a functional group α may be used alone or in combination of two or more.

Of these, carbonyl group-containing monomers (such as unsaturated ketones), unsaturated monocarboxylic acids (such as acrylic acid), and hydroxyl group-containing (meth) acrylates are preferred, with diacetone (meth) acrylamide being preferred. Therefore, the monomer having the functional group α may contain at least such a monomer (particularly diacetone (meth) acrylamide).

Also, as mentioned above, from the viewpoint of affinity with the polymer (B), acid group-containing monomers (anionic group-containing monomers) such as (meth) acrylic acid are also preferable.

When at least diacetone (meth) acrylamide is used as the monomer having the functional group α, the ratio of diacetone (meth) acrylamide to the whole monomer having the functional group α is, for example, 10% by mass or more. , Preferably 20% by mass or more, more preferably 30% by mass or more.

Further, when at least an acid group-containing monomer is used as the monomer having a functional group α, the ratio of the acid group-containing monomer to the whole monomer having the functional group α is, for example, 10% by mass or more. , Preferably 20% by mass or more, more preferably 30% by mass or more.

When the monomer component (a) contains a monomer having a functional group α, the content (content) of the monomer having a functional group α in the monomer component (a) is 30% by mass or less. (For example, 20% by mass or less) can be selected from a range, for example, 0.01 to 10% by mass, preferably 0.02 to 5% by mass, more preferably about 0.05 to 3% by mass. About 0.1 to 10% by mass (for example, 0.1 to 5% by mass).

In particular, when an acid group-containing monomer is used as the monomer having a functional group α, the content ratio (content ratio) of the acid group-containing monomer in the monomer component (a) is 0.01 mass. % Or more (for example, 0.01 to 3% by mass), preferably 0.1% by mass or more (for example, 0.1 to 2% by mass), more preferably 0.3% by mass or more (for example, 0.3 to 3% by mass). 1.5% by mass).

In addition, when the monomer component (a) contains an aliphatic (meth) acrylate and / or a monomer having an alicyclic structure and a monomer having a functional group α, the monomer having the functional group α The content ratio (content ratio) of the body is, for example, 10 parts by mass or less (for example, 0.01 to 10 parts by mass) with respect to 100 parts by mass of the monomer having an aliphatic (meth) acrylate and / or an alicyclic structure. ), Preferably 5 parts by mass or less (eg, 0.2 to 5 parts by mass), more preferably about 3 parts by mass or less (eg, 0.3 to 3 parts by mass), particularly 2 parts by mass or less. (For example, 0.05 to 1.5 parts by mass).

(Emulsion (A) and production method thereof)
The emulsion (A) is a resin (particle) in an emulsion state, for example, a resin (resin particle) having the monomer component (a) as a polymerization component (or the resin (or resin particle) dispersed in a solvent). ). Therefore, the emulsion (A) may be composed of a resin (particles) and an emulsifier (emulsifier that coats the resin particles).

Such an emulsion (A) may be usually obtained by emulsion polymerization of the monomer component (a) in a solvent.

Examples of the solvent usually include aqueous solvents such as water and water-containing solvents [such as a mixed solvent of water and alcohol (such as C _1-4 alcohol such as methanol and ethanol)].

As a method for emulsion polymerization of the monomer component (a), for example, the monomer component (a) (and the polymerization initiator) is mixed in a solvent (solution) containing an emulsifier (dispersant, surfactant) ( And a method of polymerizing by mixing (e.g., dropping) the monomer component (a) emulsified in advance with a solvent, but the present invention is limited only to such a method. Is not to be done.

In addition, what is necessary is just to set the quantity of a solvent (medium) suitably considering the non volatile matter amount etc. which are contained in the resin emulsion obtained.

Examples of emulsifiers (dispersing agents, surfactants) include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers (for example, alkylammonium salts such as decylammonium chloride), amphoteric emulsifiers (for example, betaine ester type emulsifiers), and the like. Can be mentioned.

Examples of the anionic emulsifier include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; Examples include polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinates; aryl sulfonic acid-formalin condensates; fatty acid salts such as ammonium laurate and sodium stearate.

Nonionic emulsifiers include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and aliphatic Examples thereof include condensates with amines.

Further, the emulsifier includes a polymer emulsifier. Examples of the polymer emulsifier include anionic emulsifiers (poly (meth) acrylates such as sodium polyacrylate) and nonionic emulsifiers (polyhydroxyalkyl (meth) acrylates such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyhydroxyethyl acrylate). ), Polymers having one or more monomers among these monomers as a copolymerization component.

Also, as the emulsifier, from the viewpoint of physical properties of the coating film, an emulsifier having a reactive group, that is, a so-called reactive emulsifier may be suitably used. Among such reactive emulsifiers, non-nonylphenyl emulsifiers may be suitably used, particularly from the viewpoint of environmental protection.

Examples of the reactive emulsifier include an anionic emulsifier [for example, propenyl-alkylsulfosuccinate ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt [for example, Sanyo Kasei Co., Ltd.] Manufactured by Kogyo Co., Ltd., trade name: Eleminol RS-30, etc.], polyoxyethylene alkyl propenyl phenyl ether sulfonate salt (for example, trade name: Aqualon HS-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), allyloxymethyl Sulfonate salt of alkyloxypolyoxyethylene [for example, product name: Aqualon KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], sulfonate salt of allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [for example, ADEKA Corporation Product name : Adekaria soap SE-10, etc.], allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate salts (for example, ADEKA Corporation, trade names: Adeka soaps SR-10, SR-30, etc.), bis (poly Oxyethylene polycyclic phenyl ether) methacrylated sulfonate salts [for example, manufactured by Nippon Emulsifier Co., Ltd., trade name: Antox MS-60, etc.], nonionic emulsifiers [for example, allyloxymethylalkoxyethylhydroxypolyoxyethylene [ For example, ADEKA Co., Ltd., trade name: ADEKA rear soap ER-20, etc.], polyoxyethylene alkylpropenyl phenyl ether [eg, Daiichi Kogyo Seiyaku Co., Ltd., trade name: AQUALON RN-20, etc.], allyl Oxymethylnonylphenoxyethyl Hydroxypolyoxyethylene [for example, product name: ADEKA rear soap NE-10 manufactured by ADEKA Corporation] and the like.

Emulsifiers may be used alone or in combination of two or more.

Among these emulsifiers, anionic emulsifiers, particularly anionic reactive emulsifiers, may be preferably used. Such an anionic emulsifier functions in the same manner as the acid group-containing monomer, and easily improves the affinity with the polymer (B). Therefore, the polymer (B) is more efficiently adsorbed to the coating film. Easy to improve long-term pollution resistance.

The amount of the emulsifier per 100 parts by mass of the monomer component (a) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more from the viewpoint of polymerization stability, etc. Therefore, it may be 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less.

The polymerization may be usually performed in the presence of a polymerization initiator.
Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyananovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate; Examples thereof include hydrogen, peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.

These polymerization initiators may be used alone or in combination of two or more.
The amount of the polymerization initiator per 100 parts by mass of the monomer component (a) is preferably 0.05 parts by mass or more from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component. More preferably, it is 0.1 part by mass or more, and from the viewpoint of physical properties of the coating film, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less.

The method for adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, divided charging, and continuous dripping. Further, from the viewpoint of accelerating the completion time of the polymerization reaction, a part of the polymerization initiator may be added to the reaction vessel before or after the monomer component (a) is added to the reaction system. Good.

In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium bisulfite and a polymerization initiator decomposition agent such as transition metal salt such as ferrous sulfate are added in an appropriate amount to the reaction system. Also good.

Further, in the reaction system, additives such as a chain transfer agent such as a compound having a thiol group (such as tert-dodecyl mercaptan), a pH buffering agent, a chelating agent, and a film forming aid may be present as necessary. Also good.

The amount of the additive per 100 parts by mass of the monomer component (a) varies depending on the type of the monomer component (a) and cannot be determined unconditionally. For example, it is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts. A mass part may be sufficient.

The atmosphere for emulsion polymerization of the monomer component (a) is not particularly limited, but may be an inert gas such as nitrogen gas from the viewpoint of polymerization efficiency.

The polymerization temperature for emulsion polymerization of the monomer component (a) is not particularly limited, but may be, for example, 50 to 100 ° C., preferably 60 to 95 ° C. The polymerization temperature may be constant or may be changed during the polymerization reaction.

The polymerization time for emulsion polymerization of the monomer component (a) is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is usually 1 hour or longer (eg, 1 to 24 hours), preferably May be about 2 to 12 hours (eg, 2 to 9 hours).

The emulsion (A) may have a single-layer structure (consisting of only one layer) or a multilayer structure (or core-shell structure) (even if the inner layer is configured, the outer layer (outermost layer) ) And an inner layer). A multilayer structure (core-shell structure) may be advantageous in terms of physical properties of the coating film.

When the emulsion (A) has a multilayer structure, the number of layers may be 2 or more, for example, 2 to 6, preferably 2 to 5, more preferably 2 to 4 (eg 2 to 3). In particular, it may be 3.

When the emulsion (A) has a multi-layer structure, the outer layer (shell) and the inner layer (core) are different resins as long as they are composed of the resin having the monomer component (a) exemplified above as a polymerization component. Also good.

For example, as long as the monomer component (a) is a polymerization component, the multilayer structure may be composed (relatively composed) of a hard layer (hard layer) and a soft layer (soft layer). In such a case, either the outer layer or the inner layer may be a hard layer, that is, the outer layer may be a hard layer and the inner layer may be a soft layer, and the outer layer may be a soft layer and the inner layer may be a hard layer. There may be. When the inner layer is composed of a plurality of layers, a hard layer and a soft layer may be configured between the plurality of inner layers.

In addition, when the emulsion (A) having a multilayer structure is composed of the polymer of the monomer component (a) containing a monomer having a functional group α, usually a single amount containing a monomer having a functional group α The polymer of the body component (a) usually constitutes at least the outer layer, and may constitute the outer layer and the inner layer.

As described above, in the emulsion (A) having a multilayer structure, each layer may be independently composed of a resin having the monomer component (a) as a polymerization component, and the composition of the resin in each layer is the same as described above. You can choose from a range of

When the emulsion (A) has an inner layer, from the viewpoint of physical properties of the coating film, for example, in the monomer component (a) that is a raw material of the resin constituting the inner layer, the content of the alkyl (meth) acrylate is preferably 5 to 25% by mass, more preferably 10 to 20% by mass, and the content of the alicyclic structure-containing monomer is preferably 55 to 80% by mass, more preferably 60 to 75% by mass, and hydroxyl group-containing The content of (meth) acrylate is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass, and the content of aromatic monomer is preferably 0 to 20% by mass, more The content of the silicon atom-containing monomer is preferably 5 to 15% by mass, preferably 0 to 5% by mass, more preferably 1 to 3% by mass, and the content of the carboxyl group-containing monomer is , Preferably 0-5% by mass The content of the UV-stable monomer is preferably 0 to 5% by mass, and the content of the carbonyl group-containing monomer is preferably 0 to 5% by mass, more preferably 0 to 3% by mass. It may be.

The solubility parameter (SP value) of the resin constituting the outer layer is preferably higher than the SP value of the resin constituting the inner layer from the viewpoint of improving the flexibility and film-forming property of the coating film. Moreover, it is preferable that the difference (absolute value) between the SP value of the resin constituting the inner layer and the SP value of the resin constituting the outer layer is large from the viewpoint of forming a layer separation structure in the emulsion.

The SP value is a value defined by the regular solution theory introduced by Hildebrand, and is also a measure of the solubility of the binary solution. In general, substances having similar SP values tend to be mixed with each other. Therefore, the SP value is also a measure for judging the ease of mixing of the solute and the solvent.

The mass ratio of the polymer (resin, polymer) constituting the inner layer to the polymer (resin, polymer) constituting the outer layer (polymer constituting the inner layer / polymer constituting the outer layer) is determined by the coating strength and the coating thickness. For example, 95/5 to 5/95 (for example, 90/10 to 10/90), preferably 88/12 to 12/88 (for example, 85/15 to 15). / 85) or 95/5 to 20/80 (for example, 90/10 to 30/70, preferably 88/12 to 40/60).

In particular, when the emulsion (A) has a three-layer structure, the ratio of the first layer is 10 to 25% by mass with respect to the whole emulsion particles (A), and the ratio of the second layer is 40 to 40%. The ratio of the 55% by mass and the third layer may be about 20 to 45% by mass.

Note that the emulsion polymerization method and polymerization conditions for forming the inner layer may be the same as the method and polymerization conditions for producing the resin emulsion cake.

The resin (polymer) constituting the emulsion (A) may have a crosslinked structure.

The weight average molecular weight of the resin constituting the emulsion (A) is, for example, 100,000 or more, preferably 300,000 or more, more preferably 550,000 or more, particularly preferably from the viewpoint of improving the water resistance of the coating film. It may be 600,000 or more.

Further, the upper limit value of the weight average molecular weight of the resin constituting the emulsion (A) is not particularly limited because it is difficult to measure the weight average molecular weight of the resin having a crosslinked structure. For example, the resin does not have a crosslinked structure. In the case of a resin, it is preferably 5 million or less from the viewpoint of improving the film forming property.

The weight average molecular weight can be measured using, for example, gel permeation chromatography (for example, manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L in series). It may be a weight average molecular weight (polystyrene conversion).

The glass transition temperature of the emulsion (A) (in the case of a multi-layer emulsion particle) is preferably −20 ° C. or higher, more preferably −10 ° C. or higher, and still more preferably from the viewpoint of physical properties of the coating film. May be 0 ° C. or higher, and may be preferably 50 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower, and even more preferably 20 ° C. or lower from the viewpoint of physical properties of the coating film. .

When the emulsion (A) has a multilayer structure, the inner layer and the outer layer may have different glass transition temperatures. For example, the emulsion (A) has a multilayer structure composed of a layer having a high glass transition temperature and a layer having a low glass transition temperature. Also good.

For example, the glass transition temperature of the resin constituting the layer having a high glass transition temperature (for example, the inner layer or the outer layer) is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, further preferably, from the viewpoint of physical properties of the coating film. Is 65 ° C. or higher, and may be 120 ° C. or lower, more preferably 110 ° C. or lower, and even more preferably 100 ° C. or lower from the viewpoint of physical properties of the coating film.

The glass transition temperature of the resin constituting the layer having a low glass transition temperature (for example, the outer layer or the inner layer) is preferably −70 ° C. or higher, more preferably −60 ° C. or higher, from the viewpoint of increasing the coating strength. In view of improving the water crack resistance, it may be preferably 0 ° C. or lower, more preferably −10 ° C. or lower, and further preferably −20 ° C. or lower.

When the inner layer is composed of a plurality of layers, all the layers may be low glass transition temperature layers or high glass transition temperature layers, and the inner layers may be a high glass transition temperature layer and a low glass transition temperature layer. You may comprise.

In addition, in this specification, the glass transition temperature of resin uses the glass transition temperature of the homopolymer of the monomer currently used for the monomer component which comprises the said resin (polymer),
Formula (I): 1 / Tg = Σ (Wm / Tgm) / 100 (I)
[Wherein Wm represents the content (% by mass) of the monomer m in the monomer component constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
It may mean a temperature determined based on a Fox equation represented by:

In the present specification, the glass transition temperature of the polymer constituting the emulsion (A) may mean the glass transition temperature obtained based on the formula (I) unless otherwise specified.
For example, the glass transition temperature of the whole polymer constituting the emulsion (A) having a multilayer structure corresponds to the mass fraction of each monomer in all monomer components used in the multistage emulsion polymerization. It means the glass transition temperature determined from the glass transition temperature of the homopolymer of the monomer. For monomers with unknown glass transition temperature, such as special monomers and polyfunctional monomers, the total amount of monomers with unknown glass transition temperature in the monomer component is the mass fraction. If it is 10% by mass or less, the glass transition temperature can be determined using only the monomer whose glass transition temperature is known.

When the total amount of monomers with unknown glass transition temperature in the monomer component exceeds 10% by mass, the glass transition temperature of the polymer is determined by differential scanning calorimetry (DSC) or differential calorimetry. (DTA), thermomechanical analysis (TMA), etc.

The glass transition temperature of the polymer can be easily adjusted by adjusting the composition of the monomer component. Considering the glass transition temperature of the polymer constituting the emulsion (A), the composition of the monomer component used as the raw material for the polymer constituting the emulsion (A) can be determined.

The glass transition temperature of the polymer is, for example, -70 ° C. for 2-ethylhexyl acrylate homopolymer, 83 ° C. for cyclohexyl methacrylate homopolymer, 100 ° C. for styrene homopolymer, γ-methacryloxypropyltrimethoxysilane 70 ° C. for homopolymers of 2-hydroxyethyl methacrylate, 55 ° C. for homopolymers of 2-hydroxyethyl methacrylate, 105 ° C. for homopolymers of methyl methacrylate, 130 ° C. for homopolymers of methacrylic acid, and for homopolymers of tert-butyl methacrylate 107 ° C., about 130 ° C. for 1,2,2,6,6-pentamethylpiperidyl methacrylate homopolymer, 77 ° C. for diacetone acrylamide homopolymer, 55 ° C. for glycerol monomethacrylate homopolymer, n- Butyl methacrylate homopolymer Is 20 ° C., a homopolymer of n- butyl acrylate is -56 ° C..

The average particle diameter of the emulsion (A) is preferably 50 nm or more, more preferably 100 nm or more, from the viewpoint of mechanical stability of the emulsion (A) itself, preferably from the viewpoint of physical properties of the coating film, etc. May be 300 nm or less, more preferably 200 nm or less. The average particle size of the emulsion (A) may typically be about 50 to 300 nm (for example, 60 to 250 nm), preferably 80 to 200 nm, and more preferably about 100 to 180 nm.
In the present specification, the average particle size of the emulsion (A) is measured using a particle size distribution measuring instrument (Particulate Sizing Systems, trade name: NICOMP Model 380) by a dynamic light scattering method. Means the volume average particle diameter measured by

The content of the resin in the emulsion (A) (in the case of a multilayer structure, the total content of resins constituting the inner layer and the outer layer) is, for example, 20% by mass or more (for example, 25 to 100% by mass), preferably 30% by mass or more (eg 35 to 90% by mass), more preferably 40% by mass or more (eg 45 to 85% by mass).

The solid content (non-volatile content) of the particles (or solid content) in the emulsion (A) is preferably 30% by mass or more, more preferably 40% by mass or more from the viewpoint of productivity and the like, and improves the handleability. In view of the above, it may be preferably 70% by mass or less, more preferably 60% by mass or less.

The non-volatile content in the emulsion is, for example, weighing 1 g of the resin emulsion and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour.
Formula: [Nonvolatile content in resin emulsion (mass%)] = ([residue mass] ÷ [resin emulsion 1 g]) × 100
Can be determined based on

In the emulsion (A), the proportion of the emulsifier is, for example, 0.1 to 30 parts by mass, preferably 0.5 to 20 parts per 100 parts by mass of the resin (or monomer component (a)) constituting the emulsion. It may be about 1 to 10 parts by mass (for example, 0.7 to 15 parts by mass).

The minimum film-forming temperature of the emulsion is preferably 60 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 40 ° C. or lower from the viewpoint of improving the film-forming property. The minimum film-forming temperature of the emulsion can be adjusted, for example, by adjusting the glass transition temperature of the whole emulsion particle or the glass transition temperature of the outermost layer.

In this specification, the minimum film-forming temperature of the emulsion is, for example, by applying the resin emulsion on a glass plate placed on a thermal gradient tester with an applicator so that the thickness is 0.2 mm, and cracking. It can be determined as the temperature at which this occurs.

The emulsion (A) may particularly have an anionic group (or may be anionic). By having an anionic property (anionic group), the affinity with the polymer (B) can be improved, and the dropping of the polymer (B) from the coating film can be further suppressed.

The anionic emulsion (A) is not particularly limited, but can be obtained, for example, by introducing an anionic group into the emulsion. An anionic group can be introduce | transduced using the monomer and emulsifier which comprise an emulsion as mentioned above, for example.
The emulsion (A) having a specific anionic property (anionic group) includes an emulsion satisfying the following (1) and / or (2).
(1) Consists of a resin comprising a monomer component (a) containing an anionic group-containing monomer as a polymerization component (2) The emulsifier constituting the emulsion (A) contains an anionic emulsifier

In addition, the composition of this invention should just contain emulsion (A), and contains emulsion (A) as an emulsion (emulsion which emulsion (A) disperse | distributed to the solvent) containing a solvent (or medium). Also good.

(Composition and its use)
In the composition of the present invention, the ratio of the emulsion (A) to the polymer (B) (solid content when a solvent is included) is, for example, the former / the latter (mass ratio) = 99.9 / 0.1 to 20 / 80 (for example, 99.8 / 0.2 to 30/70), preferably 99.5 / 0.5 to 40/60 (for example, 99.2 / 0.8 to 50/50), coating film properties In view of advantages (such as weather resistance and water whitening resistance), it is more preferably 99/1 to 60/40 (for example, 98.5 / 1.5 to 70/30), particularly 98/2 to 80 /. It may be about 20 (for example, 97/3 to 85/15), or 99.5 / 0.5 to 90/10.

In such a composition, the presence form of the emulsion (A) and the polymer (B) is not particularly limited, but may be separated from each other or may be bonded (crosslinked) to each other. In addition, when couple | bonding, an emulsion (A) and a polymer (B) should just couple | bond together in at least one part.
In addition, in the composition, even if it is not bonded (or a crosslinked structure), a bonded or crosslinked structure may be formed afterwards or with time (for example, in a coating film or the like). Therefore, in the composition of the present invention, the emulsion (A) and the polymer (B) may be capable of forming a bond (or a crosslinked structure).

In the case of bonding (or bond formation is possible), the bonding form of the emulsion (A) and the polymer (B) is not particularly limited, and (i) the emulsion (A) and the polymer (B) are directly (Ii) a combination of emulsion (A) and polymer (B) via a crosslinking agent (C) (formation of a crosslinked structure), (iii) a combination of these The form etc. are mentioned.

As the form (i), for example, the emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group α as a polymerization component, and the polymer (B) is a functional group. It is composed of a polymer having a monomer component (a) containing a monomer having β (functional group β that can react and bond with functional group α) as a polymerization component, and between functional group α and functional group β. In which a bond (or a crosslinked structure) is formed by reaction (or a bond or a crosslinked structure can be taken) is included.

Further, as the form (ii), the emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group α as a polymerization component, and the polymer (B) has a functional group β It is composed of a polymer having a monomer component (b) containing a monomer having a functional group α and a functional group β capable of forming a crosslinked structure via a crosslinking agent (C) as a polymerization component, and the functional group α And a mode in which the functional group β reacts with the crosslinking agent (C) to form a bond (or a crosslinked structure) (or can take a bond or a crosslinked structure).

In such a form (i) and form (ii), the combination of the functional group α and the functional group β, the combination of the functional group α and the functional group β and the functional group (functional group γ) of the crosslinking agent, Not particularly limited, for example, epoxy group and hydroxyl group, epoxy group and carboxyl group, epoxy group and carboxyl group, epoxy group and amino group, epoxy group and amino group, carbonate group and carboxyl group, hydroxyl group and alkoxycarbonyl group, hydroxyl group and Isocyanate group, hydroxyl group and carboxylic anhydride group, acetoacetoxy group and isocyanate group, oxazoline group and carboxyl group, hydroxyl group and carboxylic anhydride group, oxazolidine group and isocyanate group or carboxylic anhydride group, hydrazino group and carbonyl group Can be mentioned. You may use these in combination of 1 or 2 or more.

In the form (i), the combination of the representative functional group α and the functional group β is not particularly limited as long as it is a combination capable of forming a crosslinked structure or a bond by reaction with each other. For example, a carboxyl group and an oxazoline group A combination of a carbonyl group and a hydrazino group, a combination of an isocyanate group and a hydroxy group, a carboxyl group, an amino group, and the like.

In the form (ii), the combination of the representative functional group α and the functional group β can be appropriately selected according to the type of the crosslinking agent (C), and may be the same functional group. Examples of such combinations include combinations in which the functional group α and the functional group β are both carboxyl groups or carbonyl groups. In such a combination, a hydrazine-based crosslinking agent or an oxazoline-based crosslinking agent described later can be suitably used as the crosslinking agent (C).

As the cross-linking agent (C), a bond (or a cross-linked structure) can be formed by reacting between the functional group α and the functional group β (a bond or a cross-linked structure can be formed with both the functional group α and the functional group β). The cross-linking agent (C) is not particularly limited and can be appropriately selected according to the type of the functional group α and the functional group β. Usually, the polyfunctional compound (multifunctional having a plurality of functional groups (γ)) Compound). Examples of the functional group γ include the functional groups exemplified as the functional group α and the functional group β, and examples thereof include a carboxyl group, a hydrazino group, an oxazoline group, a carbodiimide group, an epoxy group, an isocyanate group, and an amino group.

The polyfunctional compound may have the same or different functional groups. In the polyfunctional compound, the number of functional groups (functional group γ) may be two or more. For example, in the case of a low molecular type (non-polymer type or non-resin type) polyfunctional compound, It is 2 to 10, preferably 2 to 6, more preferably 2 to 4, particularly 2.

Typical crosslinking agents (C) include hydrazine crosslinking agents (compounds having a plurality of hydrazino groups), oxazoline crosslinking agents, carbodiimide crosslinking agents, isocyanate crosslinking agents, amine crosslinking agents, epoxy crosslinking agents, and the like. Can be mentioned. In particular, the crosslinking agent (C) may be water-soluble (water-soluble crosslinking agent).

Examples of the hydrazine-based crosslinking agent include dicarboxylic acid dihydrazide [for example, alkane dicarboxylic acid dihydrazide (for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid hydride, etc.) _{C 2-20} alkane dicarboxylic acid dihydrazide, preferably _{C 2-10} alkane dicarboxylic acid dihydrazide), alkene dicarboxylic acid dihydrazide (e.g., maleic acid dihydrazide, fumaric acid dihydrazide, _{C 2-10} alkene dicarboxylic acid dihydrazide and itaconic acid dihydrazide ) Aliphatic dicarboxylic acid dihydrazide; isophthalic acid dihydrazide and other aromatic dicarboxylic acid hydrazide], dihydrazines [for example Ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, aliphatic dihydrazine, such as butylene-1,4-dihydrazine, preferably like _{C 2-4} aliphatic dihydrazine.

Examples of the oxazoline-based crosslinking agent include polymers having an oxazoline group-containing monomer as a polymerization component. Examples of such a polymer include a homopolymer or a copolymer of an oxazoline group-containing monomer, a copolymer of an oxazoline group-containing monomer and another copolymerizable monomer, and the like.

As the oxazoline group-containing monomer, the above-exemplified monomers, for example, alkenyl oxazolines (for example, C _2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, preferably Vinyl or isopropenyl oxazoline), alkenyl-alkyl oxazolines (eg 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline) C _2-6 alkenyl-C _1-10 alkyl oxazoline such as 2-isopropenyl-5-ethyl-2-oxazoline, preferably vinyl or isopropenyl-C _1-4 alkyl oxazoline) and the like.

The other copolymerizable monomer is not particularly limited as long as it is a copolymerizable monomer that does not react with the oxazoline group. For example, (meth) acrylic acid ester [for example, methyl (meth) acrylate , Alkyl (meth) acrylates as exemplified above such as ethyl (meth) acrylate; hydroxy group-containing (meth) acrylates as exemplified above such as hydroxyethyl (meth) acrylate], (meth) acrylic acid amide, vinyl acetate, aromatic Group monomers (for example, the above-described styrene monomers such as styrene and α-methylstyrene).

In the oxazoline-based crosslinking agent, the oxazoline group equivalent may be, for example, about 200 to 5000 g / equivalent, preferably about 250 to 4000 g / equivalent, and more preferably about 300 to 3000 g / equivalent.

Such an oxazoline-based crosslinking agent can also be obtained as an Epocross series (for example, Epocross K-2010E, K-2020E, K-2030E, WS-500, etc.) manufactured by Nippon Shokubai Co., Ltd.

The carbodiimide-based crosslinking agent (carbodiimide compound) may be a compound having at least one carbodiimide group [—N═C═N—] in the molecule, may be a monocarbodiimide compound, or may be a polycarbodiimide compound. May be.
In particular, the carbodiimide compound may be water-soluble (hydrophilic or aqueous). Such a water-soluble carbodiimide compound may usually have a hydrophilic group (hydrophilic skeleton, hydrophilic segment). The hydrophilic group (hydrophilic skeleton) is not particularly limited, and examples thereof include a hydroxy group, a carbamate group, a (poly) oxyalkylene group, and a substituted amino group (tertiary amino group). The hydrophilic group may form a salt (for example, an amine salt).

Such a hydrophilic group may be located at the end of carbodiimide, for example. In such a water-soluble carbodiimide compound (aqueous carbodiimide compound), for example, the terminal of the carbodiimide compound serving as a base may be blocked with a hydrophilic group (or a hydrophilic skeleton).

Specific examples of the carbodiimide compound include a carbodiimide having an N, N-disubstituted amino group [eg, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide], a carbodiimide having an isocyanate group at its terminal and a hydrophilic group. A compound having a reactive group (such as a hydroxyl group) capable of forming a bond by reacting with a reactive segment and an isocyanate group [eg, polyalkylene glycol monoalkyl ether, oxycarboxylic acid ester (such as glycolic acid ester), N, N And a reaction product with a substituted amino alcohol (such as a dialkylamino alcohol).

Isocyanate-based crosslinking agents include polyisocyanates [for example, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Aliphatic polyisocyanates such as lysine isocyanate; 1,3-diisocyanatecyclohexane, 1,4-diisocyanatecyclohexane, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, dicyclohexylmethane-4 , 4′-diisocyanate, isophorone diisocyanate, norbornane diisocyanate, and the like; xylylene diisocyanate, tetramethyl Le xylylene diisocyanate, 4,4-bis such araliphatic polyisocyanates such as (isocyanatomethyl) diphenylmethane], reaction products of polyisocyanate and polyol.

Examples of amine crosslinking agents include urea resins (eg, urea resins, thiourea resins, etc.), triazine resins (eg, melamine resins, isomelamine resins, benzoguanamine resins, acetoguanamine resins, guanylmelamine resins, etc.). Can be mentioned.

Examples of the epoxy-based crosslinking agent include polyglycidyl ether, epoxy resin (for example, novolac type epoxy resin, brominated epoxy resin, alicyclic epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, etc.). It is done.

The crosslinking agent (C) may be used alone or in combination of two or more.

Among these crosslinking agents (C), a water-soluble crosslinking agent is preferable. Also preferred are hydrazine-based crosslinking agents, oxazoline-based crosslinking agents, carbodiimide-based crosslinking agents, and the like.

Representative forms (ii) include the following forms (ii-1) and (ii-2).

(Ii-1) The emulsion (A) is composed of a polymer of a monomer component (a) containing a carbonyl group-containing monomer as a monomer having a functional group α, and the polymer (B) has a functional group β It is composed of a polymer of a monomer component (b) containing a carbonyl group-containing monomer as a monomer having a structure, and the emulsion (A) and the polymer (B) are bonded via a hydrazine-based crosslinking agent (C1). Form (or connectable)

(Ii-2) The emulsion (A) is composed of a polymer of a monomer component (a) containing a carboxyl-containing monomer as a monomer having a functional group α, and the polymer (B) has a functional group β. It is composed of a polymer of a monomer component (b) containing a carboxyl group-containing monomer as a monomer, and the emulsion particles (A) and the polymer (B) are bonded via an oxazoline-based crosslinking agent (C2). Form (or connectable)

In the forms (i) and (ii), the ratio of the monomer having the functional group α and the monomer having the functional group β is, for example, the former / the latter (mass ratio) = 0.1 / 1 to 1000 / It may be about 1, preferably 0.5 / 1 to 500/1, more preferably about 1/1 to 300/1 (for example, 1/1 to 240/1).

The ratio of the total amount of the monomer having the functional group α and the monomer having the functional group β to the total amount of the monomer component (a) and the monomer component (b) is, for example, 0. It may be about 01 to 40% by mass, preferably about 0.05 to 30% by mass, and more preferably about 0.1 to 20% by mass.

In the form (ii), the ratio of the crosslinking agent (C) is, for example, 0.01 to 500 with respect to 100 parts by mass of the total amount of the monomer having the functional group α and the monomer having the functional group β. It may be about 1 part by mass, preferably about 0.1 to 300 parts by mass, and more preferably about 1 to 100 parts by mass.

The composition of the present invention may be a composition containing a solvent. In particular, the composition of the present invention may be a composition in which the emulsion (A) and the polymer (B) are dispersed (or dissolved) in a solvent.

As the solvent, the same solvents as those exemplified above can be used. A preferable solvent is an aqueous solvent such as water, a solvent containing water [for example, a mixed solvent containing water and an alcohol (a lower alcohol such as methanol or ethanol)]. In particular, the composition of the present invention may be a composition (aqueous composition) in which the emulsion (A) and the polymer (B) are dispersed (or dissolved) in an aqueous solvent.

In the composition containing the solvent, the ratio of the total amount of the emulsion (A) and the polymer (B) can be appropriately selected depending on the application and the like, for example, 0.1 to 95% by mass, preferably 1 to 90% by mass, More preferably, it may be about 3 to 80% by mass.

In addition, the composition of this invention may contain the other component according to a use etc.

The method for producing the composition of the present invention is not particularly limited, and can be produced, for example, by mixing the emulsion (A) and the polymer (B) (and, if necessary, a solvent and other components).

When a crosslinked structure is formed between the emulsion (A) and the polymer (B), they may be mixed under appropriate crosslinking conditions. For example, the emulsion (A), the polymer (B), and the crosslinking agent (C) may be mixed and crosslinked in a solvent (for example, in the aqueous solvent).

The composition of the present invention (for example, an aqueous composition) is particularly suitable for paint (for coating). Such a coating composition (particularly, an aqueous coating composition) is used, for example, for surface finishing of a substrate formed of various materials (for example, metal, glass, porcelain, concrete, siding board, resin, etc.). May be used.

The composition of the present invention can be suitably used for a topcoat (or topcoat material, for example, a topcoat for exterior materials (building materials)), among others.

Such a composition or paint of the present invention (a paint composition, for example, an aqueous building / exterior paint) contains other components in addition to the above-described components (eg, emulsion (A) and polymer (B)). May be included.
Examples of other components include pigments (pigments described later), pigment dispersants, precipitation inhibitors, ultraviolet absorbers, light stabilizers, film forming aids, thickeners, surface conditioners, antiseptic / antifungal agents, and the like. , Leveling agents, antifreezing agents, wetting agents, pH adjusting agents, antifoaming agents and the like.
These components may be used alone or in combination of two or more.

As exterior materials, for example, various building materials (for example, flexible boards, calcium silicate boards, gypsum slag perlite boards, wood cement boards, precast concrete boards, ALC boards, gypsum boards, etc .; for example, tiles, outer wall materials, etc. Ceramic building materials). Ceramic-based building materials, for example, add inorganic fillers, fibrous materials, etc. to hydraulic glue, which is a raw material for inorganic hardened bodies, mold the resulting mixture, and cure and cure the resulting molded body Can be obtained.

The surface of such an exterior material (building material) is usually coated with a top coating material (water-based paint) in order to give a desired design. More specifically, the top coat or top coat material (water-based paint) is a paint that forms a coating film that protects the building from the external environment such as sunlight or wind and rain, or has the aesthetics and design of the building. Used as (architectural and exterior paint). The composition of the present invention can be suitably used for this top coat or as a top coating material (water-based paint).

Especially, among paints, it is preferable to apply directly to the outer wall (exterior material) of the building and use it for the exterior paint that is dried and cured (normal temperature drying) in a natural environment. A coating film formed with a paint that is dry-cured at room temperature is often soft, and because of its softness, the surface of the coating film becomes sticky and causes contaminants to adhere to it. The paint (or paint composition) of the present invention can be used as a stain-proofing agent for such a soft coating film, and by adding it to the coating, the stain resistance is improved by the hydrophilic effect of the coating film surface. sell.

The state of the surface coating film formed using the above-mentioned exterior coating material can be in various forms from transparent to colored translucent to colored concealment. For the purpose of concealing the coating layer, the colored concealed state is particularly numerous.
Therefore, the paint (coating composition) of the present invention may be a paint containing a pigment (aqueous paint, aqueous exterior paint, etc.).

As the pigment, known pigments can be used in a wide range. The pigment may be a colorant or an extender pigment (a bulking agent). Typical pigments include, for example, inorganic pigments (for example, inorganic color pigments such as titanium oxide, iron oxide, aluminum, pearl pigments), organic pigments (for example, quinacridone, anthraquinone, perylene, diketopyrrolopyrrole, And organic pigments such as benzimidazolone, isoindolinone, anthrapyrimidine, phthalocyanine, selenium, dioxazine, and carbon black) and extender pigments (eg, calcium carbonate, barium sulfate, kaolin, mica, talc, etc.) .
You may use a pigment individually or in combination of 2 or more types.

In particular, it is preferable to use at least titanium oxide from the standpoint of color hiding and high gloss on the coating surface. The amount of the pigment blended is, for example, 5 to 70 parts by weight, preferably 7 to 7 parts by weight with respect to 100 parts by weight of the solid content of the resin component (or emulsion (A) and polymer (B)) in the coating film after drying. It may be about 65 parts by mass, more preferably about 10 to 60 parts by mass.

When the composition of the present invention is used for paint (coating), it may be applied alone in one layer, or may be applied by recoating two or more layers. When the coating is performed by overcoating two or more layers, only a part of the layers may be formed by the composition of the present invention, or all the layers may be formed by the composition of the present invention. For overcoating, for example, a first layer (eg, undercoat layer) coating is applied to an object that has been subjected to primer treatment or sealer treatment, and then dried, and then applied to the second layer (eg, topcoat layer). Although the method of overcoating and drying a paint etc. is mentioned, this invention is not limited by this method. When applying the paint, for example, spray, roller, brush, or iron can be used.

Next, the present invention will be described in more detail based on examples. However, the present invention is not limited to such examples. In the following examples, “part” means “part by mass”.

(Production Example A1)
750 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.

In a dropping funnel, 163 parts of deionized water, 80 parts of 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: Adekaria soap SR-10, a reactive anionic emulsifier), 300 parts of 2-ethylhexyl acrylate, 250 parts of cyclohexyl methacrylate, 50 parts of 2,2,6,6-tetramethylpiperidyl methacrylate (4-methacryloyloxy-2,2,6,6-tetramethylpiperidine), 50 parts of butyl acrylate, 10 parts of diacetone acrylamide, styrene A pre-emulsion for dripping consisting of 250 parts, hydroxyethyl methacrylate 10 parts, tert-butyl methacrylate 30 parts and methyl methacrylate 50 parts was prepared, 74 parts of which were added into the flask, and 80 ° C. while gently blowing nitrogen gas. Ma The temperature was raised, by 5% aqueous solution of 10 parts of potassium persulfate is added to the flask to initiate polymerization.

Next, the remaining part of the pre-emulsion for dripping, 10 parts of a 5% aqueous solution of potassium persulfate and 20 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly dropped into the flask over 120 minutes. After completion of the dropping, the contents of the flask were maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added into the flask, the pH was adjusted to 9, and the polymerization reaction was terminated.

The obtained reaction liquid was cooled to room temperature, and then filtered through a 300 mesh (JIS mesh, hereinafter the same) wire mesh to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass. The emulsion particles contained in the obtained aqueous resin dispersion had a single-layer structure with an average particle diameter of 150 nm, and the glass transition temperature of the entire emulsion particles was 14.7 ° C.

(Production Example A2)
750 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.

In a dropping funnel, 163 parts of deionized water, 80 parts of 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: Adekaria soap SR-10, a reactive anionic emulsifier), 300 parts of 2-ethylhexyl acrylate, A first-stage dripping pre-treatment comprising 400 parts of cyclohexyl methacrylate, 150 parts of styrene, 80 parts of methyl methacrylate, 20 parts of tert-butyl methacrylate, 10 parts of diacetone acrylamide, 20 parts of hydroxyethyl methacrylate, 10 parts of methacrylic acid and 10 parts of acrylic acid. An emulsion was prepared, 74 parts thereof were added into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 20 parts of a 5% aqueous solution of potassium persulfate was added to initiate polymerization.

Next, the remainder of the pre-emulsion for dripping, 10 parts of a 5% aqueous solution of potassium persulfate and 10 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were uniformly dropped into the flask over 120 minutes. After completion of the dropping, the contents of the flask were maintained at 80 ° C. for 60 minutes. The polymerization reaction was completed by adding 25% aqueous ammonia into the flask and adjusting the pH to 9.

The obtained reaction liquid was cooled to room temperature and then filtered through a 300 mesh wire netting to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass. The emulsion particles contained in the obtained aqueous resin dispersion had a single-layer structure with an average particle diameter of 160 nm, and the glass transition temperature of the entire emulsion particles was 20.2 ° C.

(Production Example A3)
507 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.

In a dropping funnel, 163 parts of deionized water, 80 parts of a 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: Adekari Soap SR-10, a reactive anionic emulsifier), 15 parts of 2-ethylhexyl acrylate, A pre-emulsion for first-stage dropping comprising 210 parts of cyclohexyl methacrylate, 250 parts of methyl methacrylate, 5 parts of γ-methacryloyloxypropyltrimethoxysilane, 10 parts of styrene, 5 parts of acrylic acid and 5 parts of hydroxyethyl methacrylate was prepared. Polymerization was started by adding 74 parts into the flask, raising the temperature to 80 ° C. while gently blowing nitrogen gas, and adding 20 parts of a 5% aqueous solution of potassium persulfate into the flask.

Next, the remainder of the pre-emulsion for dripping, 10 parts of a 5% aqueous solution of potassium persulfate and 10 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were uniformly dropped into the flask over 120 minutes. After completion of the dropping, the contents of the flask were maintained at 80 ° C. for 60 minutes, and 5 parts of 25% aqueous ammonia was added.

Subsequently, 163 parts of deionized water, 80 parts of a 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: ADEKA rear soap SR-10, a reactive anionic emulsifier), 225 parts of 2-ethylhexyl acrylate, Pre-emulsion for second-stage dropping and potassium persulfate comprising 150 parts of butyl acrylate, 105 parts of cyclohexyl methacrylate, 10 parts of hydroxyethyl methacrylate, 10 parts of 2,2,6,6-tetramethylpiperidyl methacrylate, and 10 parts of diacetone acrylamide 10 parts of a 5% aqueous solution and 10 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise uniformly over 120 minutes. After completion of the dropping, the content of the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added, and the pH was adjusted to 9, thereby terminating the polymerization reaction.

The obtained reaction liquid was cooled to room temperature and then filtered through a 300 mesh wire netting to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass. The emulsion particles contained in the obtained aqueous resin dispersion have a two-layer structure with an average particle diameter of 150 nm, the glass transition temperature of the inner layer is 85.3 ° C., and the glass transition temperature of the outer layer is −38.6 ° C. Yes, the glass transition temperature of the entire emulsion particles was 9.1 ° C.

(Production Example A4)
507 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.

In a dropping funnel, 163 parts of deionized water, 80 parts of 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: ADEKA rear soap SR-10, a reactive anionic emulsifier), 2-ethylhexyl acrylate 330 For first-stage dripping comprising 50 parts of cyclohexyl methacrylate, 40 parts of styrene, 20 parts of methyl methacrylate, 15 parts of tert-butyl methacrylate, 30 parts of butyl acrylate, 5 parts of acrylic acid, 5 parts of methacrylic acid and 5 parts of hydroxyethyl methacrylate. A pre-emulsion was prepared, 74 parts thereof were added into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 20 parts of a 5% aqueous solution of potassium persulfate was added into the flask to polymerize. The reaction was started.

Subsequently, 163 parts of deionized water, 80 parts of a 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: ADEKA rear soap SR-10, a reactive anionic emulsifier), 50 parts of 2-ethylhexyl acrylate, 15 parts butyl acrylate, 120 parts methyl methacrylate, 120 parts tert-butyl methacrylate, 120 parts cyclohexyl methacrylate, 40 parts styrene, 5 parts γ-methacryloyloxypropyltrimethoxysilane, 10 parts hydroxyethyl methacrylate, 2, 2, 6, 6 -A second stage pre-emulsion consisting of 10 parts of tetramethylpiperidyl methacrylate and 10 parts of diacetone acrylamide, 10 parts of a 5% aqueous solution of potassium persulfate and 10 parts of a 2.5% aqueous sodium hydrogen sulfite solution over 120 minutes. It was uniformly added dropwise into the flask. After completion of the dropping, the content of the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added, and the pH was adjusted to 9, thereby terminating the polymerization reaction.

The obtained reaction liquid was cooled to room temperature and then filtered through a 300 mesh wire netting to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass. The emulsion particles contained in the obtained aqueous resin dispersion have a two-layer structure with an average particle diameter of 150 nm, the inner layer has a glass transition temperature of −39.9 ° C., and the outer layer has a glass transition temperature of 62.0 ° C. Yes, the glass transition temperature of the entire emulsion particles was 1.9 ° C.

(Production Example A5)
750 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser. In a dropping funnel, 163 parts of deionized water, 80 parts of a 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: ADEKA rear soap SR-10, a reactive anionic emulsifier), 250 parts of 2-ethylhexyl acrylate, 2,2,6,6-tetramethylpiperidyl methacrylate (4-methacryloyloxy-2,2,6,6-tetramethylpiperidine) 60 parts, butyl acrylate 30 parts, styrene 50 parts, hydroxyethyl methacrylate 10 parts, butyl methacrylate Prepare a pre-emulsion for dropping consisting of 350 parts, 10 parts of acrylic acid and 240 parts of methyl methacrylate, add 74 parts of the emulsion into the flask, raise the temperature to 80 ° C. while gently blowing nitrogen gas, and potassium persulfate Add 10 parts of 5% aqueous solution to the flask. By and, to initiate the polymerization.

The obtained reaction liquid was cooled to room temperature, and then filtered through a 300 mesh (JIS mesh, hereinafter the same) wire mesh to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass. The emulsion particles contained in the obtained aqueous resin dispersion had a one-layer structure with an average particle diameter of 150 nm, and the glass transition temperature of the whole emulsion particles was 9.5 ° C.

(Example B1)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.

In the dropping funnel A, 255 parts of N-vinylpyrrolidone, 2.6 parts of diacetone acrylamide, and 2.6 parts of 2,2,6,6-tetramethylpiperidyl methacrylate were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.

The contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.

Next, the dropping funnel A and the dropping funnel B were each washed with 51 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the polymer obtained had a weight average molecular weight of 20000.

(Example B2)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.

In the dropping funnel A, 234 parts of N-vinylpyrrolidone, 13 parts of diacetone acrylamide and 13 parts of 2,2,6,6-tetramethylpiperidyl methacrylate were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.

(Example B3)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.

In the dropping funnel A, 255 parts of N-vinylpyrrolidone, 2.6 parts of diacetone acrylamide, and 2.6 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.

(Example B4)
300 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.

In the dropping funnel A, 252 parts of N-vinylpyrrolidone, 2.6 parts of diacetone acrylamide, 2.0 parts of 25% aqueous ammonia, 2.1 parts of acrylic acid and 2,2,6,6-tetramethylpiperidyl methacrylate 6 parts were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.

Next, the dropping funnel A and the dropping funnel B were each washed with 345 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the obtained polymer had a weight average molecular weight of 40000.

(Example B5)
198 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.

In dropping funnel A, 252 parts of N-vinylpyrrolidone, 2.6 parts of diacetone acrylamide, 2.6 parts of hydroxyethyl methacrylate, 1.3 parts of 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2 , 6,6-Pentamethylpiperidylmethacrylate 1.3 parts was added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.

Next, the dropping funnel A and the dropping funnel B were each washed with 447 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the obtained polymer had a weight average molecular weight of 200,000.

(Production Example B6)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.

In the dropping funnel A, 255 parts of N-vinylpyrrolidone and 2.6 parts of diacetone acrylamide were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.

Next, the dropping funnel A and the dropping funnel B were each washed with 48 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the polymer obtained had a weight average molecular weight of 20000.

(Production Example B7)
198 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.

In the dropping funnel A, 252 parts of N-vinylpyrrolidone and 2.6 parts of diacetone acrylamide were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.

Next, the dropping funnel A and the dropping funnel B were each washed with 430 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the obtained polymer had a weight average molecular weight of 200,000.

(Example B8)
300 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere. In dropping funnel A, 226 parts of N-vinylpyrrolidone, 26 parts of hydroxyethyl methacrylate, 4.0 parts of 25% aqueous ammonia, 4.2 parts of acrylic acid and 2.6 parts of 2,2,6,6-tetramethylpiperidyl methacrylate Was added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2′-azobis (2-methylpropionamidine) dihydrochloride were added.

Example 1
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids was 97/3 As a result, an aqueous resin composition was obtained.

(Example 2)
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids was 93/7. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.

(Example 3)
The water-soluble polymer B3 obtained in Example B3 was added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B3) of both solids was 97/3 As a result, an aqueous resin composition was obtained.

Example 4
The water-soluble polymer B2 obtained in Example B2 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B2) of both solids was 90/10. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.

(Example 5)
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A2 obtained in Production Example A2 so that the mass ratio (A2 / B1) of both solids was 97/3. A composition was obtained.

(Example 6)
The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A2 obtained in Production Example A2 so that the mass ratio (A2 / B4) of both solids was 95/5. An aqueous resin composition was obtained by adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent to 100 parts of the mixture.

(Example 7)
The water-soluble polymer B5 obtained in Example B5 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B5) of both solids was 90/10. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.

(Example 8)
The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A3 obtained in Production Example A3 so that the mass ratio (A3 / B4) of both solids was 95/5. By adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent and 10 parts of a 5% aqueous solution of a hydrazine-based crosslinking agent (adipic acid dihydrazide) An aqueous resin composition was obtained.

Example 9
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A4 obtained in Production Example A4 so that the mass ratio (A4 / B1) of both solids was 95/5. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.

(Example 10)
The water-soluble polymer B8 obtained in Example B8 was added to the aqueous resin dispersion A5 obtained in Production Example A5 so that the mass ratio (A5 / B8) of both solids was 97/3. By adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent to 100 parts of the mixture, an aqueous resin composition was obtained.

(Example 11)
The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A3 obtained in Production Example A3 so that the mass ratio of both solids (A3 / B4) was 80/20. By adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent and 10 parts of a 5% aqueous solution of a hydrazine-based crosslinking agent (adipic acid dihydrazide) to 100 parts of the resulting mixture, An aqueous resin composition was obtained.

(Comparative Example 1)
The water-soluble polymer B6 obtained in Production Example B6 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B6) of both solids was 97/3. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.

(Comparative Example 2)
The water-soluble polymer B6 obtained in Production Example B7 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B7) of both solids was 90/10. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.

Next, the physical properties of the aqueous resin composition were examined based on the following method.

〔Weatherability〕
(1) Preparation of evaluation sample 2,2,4-trimethyl-1,3-pentanediol isobutyrate (product number: CS-12, manufactured by JNC Corporation) as a film-forming auxiliary agent in 100 parts of an aqueous resin composition 10 parts of a mixed solution obtained by mixing butyl cellosolve in equal amounts and stirring with a homodisper at a rotation speed of 1500 times / minute for 10 minutes, followed by 30 parts of white paste and an antifoaming agent [Sannopco Corp. Product name: NOPCO 8034L] 0.5 part is added so that the viscosity is 80 KU when measured at 25 ° C. using a Craves unit viscometer (Brookfield, product number: KU-1). A sample was prepared by adding a thickener [manufactured by Nippon Shokubai Co., Ltd., trade name: ACRRESET WR-503A] and stirring in that state for 30 minutes.

The white paste consists of 210 parts of deionized water, 60 parts of a dispersant (trade name: Demol EP, manufactured by Kao Corporation), and a dispersant (trade name: DISCOAT N-14, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). ] 50 parts, 10 parts of wetting agent [trade name: Emulgen LS-106], propylene glycol 60 parts, titanium oxide [product of Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts and glass beads It was prepared by dispersing 200 parts (diameter: 1 mm) with a homodisper at a rotational speed of 3000 times / minute for 60 minutes.

(2) Preparation and Test of Evaluation Coating Film A slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm) and sealer [manufactured by SK Kaken Co., Ltd., trade name: EX sealer ] Was uniformly applied by air spray at an application amount of 150 g / m ² and dried at 23 ° C. for 1 week.

Next, the sample was applied on the slate film with a 10 mil applicator and dried at 23 ° C. for 1 week, and then the side and back of the slate plate on which the sample was applied were sealed with aluminum tape, and the sample was applied. The 60 ° specular gloss of the surface was measured with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: VG-7000), and the weather resistance test was repeated continuously for 1000 hours under the following conditions as one cycle. Measure the gloss of the painted surface of the slate plate with a gloss meter, formula:
[Gloss retention (%)] =
[[Gloss after weather resistance test] ÷ [Gloss before weather resistance test]] × 100
The gloss retention was determined based on the above, and the weather resistance was evaluated based on the following evaluation criteria.

(Test conditions for weather resistance test)
・ Testing machine: Metal weather [Daipura Wintes Co., Ltd., product number: KU-R4]
・ Irradiation: Irradiation for 4 hours in an atmosphere with a temperature of 65 ° C. and a relative humidity of 50% (irradiation intensity: 80 mW / cm ² )
-Wet: exposed for 4 hours in an atmosphere with a relative humidity of 98% at a temperature of 35 ° C-Shower: Shower for 30 seconds before and after wetting

(Evaluation criteria)
○: Gloss retention is 80% or more Δ: Gloss retention is 60% or more and less than 80% ×: Gloss retention is less than 60% or cannot be measured [water whitening resistance]
(1) Preparation of evaluation sample 2,2,4-trimethyl-1,3-pentanediol isobutyrate (product number: CS-12, manufactured by JNC Corporation) as a film-forming auxiliary agent in 100 parts of an aqueous resin composition 10 parts of a mixed solution obtained by mixing butyl cellosolve with equal mass and stirring with a homodisper at a rotation speed of 1500 times / minute for 10 minutes, followed by defoaming agent (trade name, manufactured by San Nopco Co., Ltd.) : Nopco 8034L] 0.5 part was added, and a thickener [((No .: KU-1 manufactured by Brookfield Co., Ltd.) was used to increase the viscosity to 60 KU when measured at 25 ° C. A product was manufactured by Nippon Shokubai Co., Ltd., trade name: Acryset WR-503A], and stirred in that state for 30 minutes to prepare a sample.

(2) Preparation and Test of Evaluation Coating Film A slate plate [manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm] on a sealer [manufactured by SK Kaken Co., Ltd., trade name: EX sealer ] By air spray at a coating amount of 150 g / m ² and dried at 23 ° C. for 1 week.

Next, the sample obtained above was applied onto a slate plate coating with a 6 mil applicator and dried at 23 ° C. for 1 week.

The L value (L ₀ ) of the test plate was measured with a color difference meter [manufactured by Nippon Denshoku Industries Co., Ltd., product number: ZE-6000], and this test plate was immersed in water at 23 ° C. for 24 hours, The water content was wiped off with Kim Towel (manufactured by Nippon Paper Crecia Co., Ltd.), and the L value (L ₁ ) was measured with the color difference meter within 1 minute.

Next, the change value of the L value is expressed by the formula:
ΔL = (L ₁ ) − (L ₀ )
And evaluated based on the following evaluation criteria.

[Evaluation criteria]
○: ΔL is less than 5 Δ: ΔL is 5 or more and less than 10 x: ΔL is 10 or more

[Contamination resistance (1), (2)]
(1) Preparation of evaluation sample 2,2,4-trimethyl-1,3-pentanediol isobutyrate (product number: CS-12, manufactured by JNC Corporation) as a film-forming auxiliary agent in 100 parts of an aqueous resin composition 10 parts of a mixed solution obtained by mixing butyl cellosolve with equal mass and stirring with a homodisper at a rotation speed of 1500 times / minute for 10 minutes, followed by 30 parts of white paste and an antifoaming agent [Sannopco Corp. Product name: NOPCO 8034L] 0.5 part is added so that the viscosity is 80 KU when measured at 25 ° C. using a Craves unit viscometer (Brookfield, product number: KU-1). A sample was prepared by adding a thickener [manufactured by Nippon Shokubai Co., Ltd., trade name: ACRRESET WR-503A] and stirring in that state for 30 minutes.

(2) Preparation and test of coating for evaluation The above white paint was applied to an aluminum plate [manufactured by Nippon Test Panel Co., Ltd., length: 400 mm, width: 100 mm, thickness: 1 mm] with a 6 mil applicator at 23 ° C. Dry for 1 week.

The test plate was bent so as to have an inclination of 30 degrees on the south surface at half (200 mm) in the vertical direction. The initial L value (L ₀ ) of the sloped part of the test plate was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: ZE-6000), and in accordance with JIS Z2381 (general rules for atmospheric exposure test methods) An outdoor exposure test was conducted under the following conditions. After 3 months and 6 months, the test plate was pulled up, and the L value (L ₁ ) was measured with respect to the slope portion of the test plate with the color difference meter.
-Test conditions-
(South surface 30 degrees, direct exposure (exposure location: Suita City, Osaka / Nippon Catalyst Co., Ltd.)).

Next, the change value of the L value is expressed by the formula:
ΔL = (L ₁ ) − (L ₀ )
The contamination resistance of the slope was evaluated based on the following evaluation criteria.

[Contamination Resistance (1) (Slope Contamination Resistance) Evaluation Criteria]
○: ΔL is less than 5 Δ: ΔL is 5 or more and less than 10 x: ΔL is 10 or more

Next, rain stripe contamination was visually evaluated on the vertical part of the test plate according to the following evaluation criteria.

[Contamination Resistance (2) (Vertical Surface Pollution Resistance (Rainline Contamination) Evaluation Criteria)]
○: No rain stripes are seen △: Light rain stripes are seen ×: Dark rain stripes are seen

〔Comprehensive evaluation〕
In the evaluation of each physical property, an evaluation of “◯” was 5 points, an evaluation of “Δ” was 3 points, an evaluation of “x” was 0 points, and the total score was obtained by summing up each score.

Results are shown in Tables 1 and 2. In the table, “OX” represents Epocros WS-500 (oxazoline-based crosslinking agent), and “ADH” represents adipic acid dihydrazide (hydrazine-based crosslinking agent).

As is clear from the results in the above table, according to the polymers and compositions of the examples, excellent coating performance including long-term hydrophilicity could be realized.

(Example 12)
The water-soluble polymer B1 obtained in Example B1 is added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids is 50/50. As a result, an aqueous resin composition was obtained.
When the “stain resistance (1)” and “stain resistance (2)” of the obtained aqueous resin composition were examined by the same method as described above, both evaluations were “Δ”.

The present invention can provide a polymer useful for coatings and the like and a composition containing this polymer.

Claims

Polymers containing at least a vinyl lactam monomer and a hindered amine monomer as polymerization components.
2. The polymer according to claim 1, wherein the ratio of the hindered amine monomer is 0.01 to 15 mol with respect to 100 mol of the vinyl lactam monomer.
The polymer according to claim 1 or 2, wherein the ratio of the vinyl lactam monomer is 80 mol% or more of the entire polymerization component, and the ratio of the hindered amine monomer is 0.05 to 10 mol with respect to 100 mol of the vinyl lactam monomer.
The polymerization component further comprises at least one functional group selected from a carbonyl group, an acid group, a carbonate group, an isocyanate group, an oxazoline group, an oxazolidine group, a hydrazino group, an epoxy group, an amino group, a hydroxyl group, and a mercapto group. The polymer according to any one of claims 1 to 3, comprising a monomer having
The polymer according to any one of claims 1 to 3, wherein the polymerization component further comprises a monomer having a functional group containing a carbonyl group-containing monomer.
The polymer according to any one of claims 1 to 3, wherein the polymerization component further contains a monomer containing a functional group containing diacetone (meth) acrylamide.
A composition comprising an emulsion (A) and the polymer (B) according to any one of claims 1 to 6.
The composition according to claim 7, wherein the emulsion (A) is an acrylic emulsion.
The composition according to claim 7 or 8, wherein the emulsion (A) is anionic.
The emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group α as a polymerization component, and the polymerization component of the polymer (B) forms a crosslinked structure with the functional group α. The composition according to any one of claims 7 to 9, comprising a monomer having a functional group β that can be treated.
11. The composition according to claim 7, wherein the ratio of the emulsion (A) to the polymer (B) is the former / the latter (mass ratio) = 99/1 to 60/40.
The composition according to any one of claims 7 to 11, which is an aqueous composition for coatings comprising an emulsion (A) and a polymer (B).
A coating film formed from the composition according to any one of claims 7 to 12.
A coated substrate composed of a substrate and the coating film according to claim 13 formed on the substrate.
An antifouling agent for a coating film formed from a composition containing the emulsion (A), the antifouling agent containing the polymer (B) according to any one of claims 1 to 6.