JP2021188033A - Aqueous dispersion, coating agent for metal, and coating - Google Patents

Abstract

To provide: an aqueous dispersion capable of forming a coating excellent in adhesion to metal, weather resistance and wear resistance; a coating agent for metal containing the aqueous dispersion; and a coating formed from the aqueous dispersion or the coating agent for metal.SOLUTION: The aqueous dispersion contains a polymer comprising polyoxyalkylene styrenated propenylphenyl ether phosphate and/or a salt thereof (A) as a constituent monomer; and is obtained by synthesizing the polymer using a reactive emulsifier (C) (excluding the polyoxyalkylene styrenated propenylphenyl ether phosphate and/or salt thereof (A)).SELECTED DRAWING: None

Description

The present invention relates to aqueous dispersions, metal coatings and coatings.

Known are sulfate esters (salts) and phosphoric acid esters (salts) obtained by reacting polyoxyalkylene styrene-ized propenylphenyl ether with a sulfate agent or a phosphorylating agent. For example, Patent Documents 1 and 2 describe that the phosphoric acid ester (salt) is used as a reactive emulsifier for emulsion polymerization. For example, when emulsion polymerization is carried out using a phosphate ester metal salt as a reactive emulsifier, the phosphate ester metal salt is contained as a constituent unit in the obtained polymer.

By using the phosphate ester metal salt as a reactive emulsifier, the stability during emulsion polymerization is improved, and the aqueous dispersion (polymer dispersion) of the polymer obtained by such emulsion polymerization is foamed. It is unlikely to occur, and the polymer film obtained from this aqueous dispersion has various properties such as water resistance improved.

International Publication No. 2013/108588 Japanese Unexamined Patent Publication No. 2015-013921

However, a coating film formed by applying an aqueous dispersion of a polymer containing the phosphoric acid ester metal salt as a constituent monomer to a metal surface is excellent in water resistance, and is therefore suitable for coating metal, for example. .. However, in recent years, in applications such as coating on metals, it has been required to improve the adhesion of a coating film formed from an aqueous dispersion to a metal and the wear resistance performance of the coating film. That is, in applications for coating a metal or the like, it is required that the formed coating film adheres strongly to the metal and that the coating film has excellent wear resistance, and water dispersion capable of forming such a coating film is required. The development of the body was an urgent task.

The present invention has been made in view of the above, and is an aqueous dispersion capable of forming a coating film having excellent adhesion to metal and abrasion resistance, a coating agent for metals containing the aqueous dispersion, and the aqueous dispersion. Alternatively, it is an object of the present invention to provide a coating film formed from the metal coating agent.

As a result of diligent research to achieve the above object, the present inventors have found that the above object can be achieved by using a polymer having a specific structure in which a structural unit based on a reactive emulsifier is introduced. Has been completed.

That is, the present invention includes, for example, the subjects described in the following sections.
Item 1
A polymer containing a polyoxyalkylene styrenated propenylphenyl ether phosphate ester and / or a salt thereof (A) as a constituent monomer is contained.
An aqueous dispersion obtained by synthesizing the polymer using the reactive emulsifier (C) (excluding the polyoxyalkylene styrenated propenylphenyl ether phosphate ester and / or its salt (A)).
Item 2
Item 2. The aqueous dispersion according to Item 1, wherein the reactive emulsifier (C) contains an anionic reactive emulsifier.
Item 3
Item 2. The aqueous dispersion according to Item 1, wherein the reactive emulsifier (C) contains a nonionic reactive emulsifier.
Item 4
The anionic reactive emulsifier is a compound having a polymerizable unsaturated group, a polyoxyalkylene group and an anionic group (provided that the polyoxyalkylene styrated propenylphenyl ether sulfate ester salt and the polyoxyalkylene alkyl propenylphenyl ether sulfate are used. Item 2. The aqueous dispersion according to Item 2, which comprises (excluding ester salts).
Item 5
Item 1 to any of Items 1 to 4, wherein the polymer further contains at least one monomer (B) selected from the group consisting of (meth) acrylic acid ester, aromatic vinyl compound and vinyl carboxylate as a constituent monomer. The aqueous dispersion according to item 1.
Item 6
The salt (A) of the polyoxyalkylene sylated propenylphenyl ether phosphate ester is at least one selected from the group consisting of an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an alkylammonium salt and an alkanolamine salt. Item 5. The aqueous dispersion according to Item 1-5.
Item 7
A coating agent for metals, which comprises the aqueous dispersion according to any one of Items 1 to 6.
Item 8
A coating film obtained by using the aqueous dispersion according to any one of Items 1 to 6 or the metal coating agent according to claim 7.

According to the aqueous dispersion according to the present invention, it is possible to form a coating film having excellent adhesion to metal and abrasion resistance.

Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification, the expression "contains" and "contains" includes the concepts of "contains", "contains", "substantially consists" and "consists only".

1. 1. Aqueous dispersion The aqueous dispersion of the present invention contains a polymer containing a polyoxyalkylene styrenated propenylphenyl ether phosphate ester and / or a salt (A) thereof as a constituent monomer. In particular, the aqueous dispersion of the present invention synthesizes the polymer using the reactive emulsifier (C) (excluding the polyoxyalkylene styrenated propenylphenyl ether phosphate ester and / or its salt (A)). It is obtained by doing so. That is, the aqueous dispersion of the present invention is produced by a method including a step of polymerizing a polyoxyalkylene styrenated propenylphenyl ether phosphate ester and / or a salt (A) thereof in the presence of the reactive emulsifier (C). be able to.

According to the aqueous dispersion of the present invention, it is possible to form a coating film having excellent adhesion to metal, weather resistance and abrasion resistance. Further, since the aqueous dispersion of the present invention has excellent wettability to a metal, for example, it also has excellent coating properties.

In the present specification, the polyoxyalkylene styrenated propenylphenyl ether phosphate ester and / or a salt thereof (A) is abbreviated as "monomer (A)".

In the aqueous dispersion of the present invention, the polymer contains the monomer (A) as a constituent monomer. As a reminder, as used herein, a polymer constituent monomer means a repeating building block for forming a polymer. Strictly speaking, the polymer contains a structural unit derived from the monomer (A). As used herein, the term "monomer-derived structural unit" refers to a structural unit formed by polymerizing a monomer or a derivative thereof. The derivative here means a structural unit or the like formed by further neutralizing or hydrolyzing a structural unit formed by polymerizing a monomer. For example, when the monomer is the monomer (A) and the structural unit formed after the polymerization is a salt type, the structural unit obtained by converting this salt type into an acid type corresponds to the derivative. Alternatively, when the monomer is the monomer (A) and the structural unit formed after the polymerization is an acid type, the structural unit obtained by neutralizing this acid type and converting it into a salt type also corresponds to the derivative. ..

The monomer (A) may be a polyoxyalkylene styrated propenylphenyl ether phosphoric acid ester (hereinafter, may be referred to as an acid type phosphoric acid ester), or may be in the form of a salt thereof. Alternatively, the monomer (A) may be a mixture thereof. That is, the polymer comprises both a polyoxyalkylene styrated propenylphenyl ether phosphoric acid ester (acid-type phosphoric acid ester) and a salt of the polyoxyalkylene styrated propenylphenyl ether phosphoric acid ester as a constituent monomer. Can also have as.

When the monomer (A) is in the form of a salt, the type of salt is not particularly limited, and is selected from the group consisting of, for example, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an alkylammonium salt and an alkanolamine salt. It can be at least one species. Examples of the alkali metal include Na, K and the like, and examples of the alkaline earth metal include Mg, Ca and the like. Examples of the alkylammonium include monomethylammonium and dipropylammonium, and examples of the alkanolamine include monoethanolamine, diethanolamine and triethanolamine.

The monomer (A) is more preferably at least one selected from the group consisting of acid-type phosphoric acid esters, alkali metal salts, ammonium salts and alkanolamine salts, in which case the aqueous dispersion is relative to the metal. It is possible to form a coating film having excellent adhesion, abrasion resistance, and water whitening resistance.

For example, when the monomer (A) is an ammonium salt, most of the ammonia is eliminated when the aqueous dispersion is heated and dried. As a result, the monomer (A) can be the acid-type phosphoric acid ester described above, so that the polymer can contain the acid-type phosphoric acid ester as a constituent monomer in the state of the coating film described later.

The monomer (A) may be a phosphoric acid monoester or a phosphoric acid diester. The monomer (A) can also be a mixture of both.

As a further specific example of the monomer (A), for example, the following general formula (1)
(X) _k P (= O) (OL) _3-k (1)
Examples thereof include compounds represented by.

In formula (1), k is 1 or 2, and L is at least selected from the group consisting of a hydrogen atom or an alkali metal, an alkaline earth metal, an ammonium residue, an alkylammonium residue and an alkanolamine residue. Shows one type. In the formula (1), X is a monovalent group represented by the following (2).

In formula (2), R ¹ represents a 1-propenyl group or an allyl group (that is, a 2-propenyl group), A represents an alkylene group having 2 to 4 carbon atoms, and n represents an average addition molar of an oxyalkylene group. It represents a number, and m represents the number of substituents in the range 1-3.

In the formula (1), when a plurality of L's are contained in one molecule, the plurality of L's may be the same, or some or all of them may be different.

In the formula (1), when L is an alkali metal, Na, K and the like are exemplified as the alkali metal, and when L is an alkaline earth metal, Mg, Ca and the like are exemplified as the alkaline earth metal. Will be done. When L is an alkylammonium residue in the formula (1), a monomethylammonium residue, a dipropylammonium residue and the like are exemplified as the alkylammonium residue, and in the formula (1), L is an alkanolamine residue. In the above case, examples of the alkanolamine residue include a monoethanolamine residue, a diethanolamine residue, a triethanolamine residue and the like.

In the formula (1), L is more preferably at least one selected from the group consisting of a hydrogen atom or an alkali metal, an ammonium residue and an alkanolamine residue, and in this case, the aqueous dispersion is a metal. It is possible to form a coating film having excellent adhesion to water, excellent wear resistance, and excellent water whitening resistance.

In the compound represented by the formula (1), R ¹ is preferably a 1-propenyl group. The substitution position of R ¹ is preferably the ortho-position and / or the para-position, and more preferably the ortho-position.

In the formula (2), the oxyalkylene group represented by AO may be linear or branched, and examples thereof include an oxyethylene group, an oxypropylene group, and an oxybutylene group.

In the formula (2), when the AO is an alkylene oxide having 2 to 4 carbon atoms, the (AO) _n- chain moiety is 1 such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran (1,4-butylene oxide). It can be a seed or an addition polymer using two or more kinds. The addition form of the oxyalkylene group is not particularly limited, and it may be a single adduct using one kind of alkylene oxide, a random adduct using two or more kinds of alkylene oxides, a block adduct, or a random adduct and a block adduct thereof. It may be a combination of.

The oxyalkylene group is preferably an oxyethylene group, and when two or more kinds of oxyalkylene groups are contained, one of them is preferably an oxyethylene group. The (AO) _n- chain moiety preferably contains 50 to 100 mol%, more preferably 70 to 100 mol%, of an oxyethylene group with respect to the total number of moles of (AO).

In the formula (2), n represents the average number of moles of oxyalkylene group added, preferably in the range of 1 to 9, and more preferably 2 to 8. In one embodiment, n may be 2 to 6 or 2 to 4.

In the formula (2), m represents the number of substituents of the α-methylbenzyl group, and the average value is in the range of 1 to 3, preferably in the range of 1 to 2. The substitution position of the α-methylbenzyl group is preferably the ortho-position and / or the para-position.

In the monovalent group represented by the formula (2) (that is, X in the formula (1)), the group represented by the following formula (2-1) is preferable.

In formula (2-1), n and m are synonymous with n and m in formula (2).

The monomer (A) may be a mixture of an acid-type compound in which L is a hydrogen atom and a compound in which L is in the form of various salts in the compound represented by the formula (1).

Further, the monomer (A) may be a mixture of a compound having k = 1 (phosphoric acid monoester) and a compound having k = 2 (phosphoric acid diester) in the compound represented by the formula (1). can. When the monomer (A) is a phosphoric acid monoester, a phosphoric acid diester, or a mixture thereof, the phosphoric acid monoester can exemplify a compound represented by the following formula (1-1), and is phosphoric acid. As the diester, a compound represented by the following formula (1-2) can be exemplified.

In formulas (1-1) and ^{(1-2), R 1, A} , L, n, m ^{is, R 1, A, L,} n, m synonymous in the formula (1) and (2) Is. When the monomer (A) is a mixture of both, both ^{R 1, A, L, n} , m may be be the same or different from each other. Further, when the monomer (A) contains a compound represented by the formula (1-2), R ^{1 in} one molecule may be the same or different.

In the compounds represented by the formulas (1-1) and (1-2), R ¹ is preferably a 1-propenyl group. The substitution position of R ¹ is preferably the ortho-position and / or the para-position, and more preferably the ortho-position.

The method for producing the monomer (A) is not particularly limited, and for example, the monomer (A) can be synthesized by adopting a known method. For example, the monomer (A) can be produced from styrenated phenol and allyl halide as raw materials. Specifically, styrene phenol and allyl halide are reacted with a basic substance such as sodium hydroxide and potassium hydroxide to obtain styrylated allylphenyl ether, which is heated to form an allyl group. The rearrangement is carried out to obtain styllylated allylphenol. Then, an alkylene oxide is added to the styllized allylphenol under an alkaline catalyst at a high temperature and under high pressure to obtain a polyoxyalkylene styrated propenylphenyl ether, which is reacted with a known phosphorylating agent. Can be used to obtain a phosphoric acid ester. Then, if necessary, it can be neutralized with an alkaline neutralizing agent to obtain a neutralized salt. The neutralizing agent is not particularly limited.

In the aqueous dispersion of the present invention, the polymer contains the monomer (A) as a constituent monomer, and at least one selected from the group consisting of (meth) acrylic acid ester, aromatic vinyl compound and vinyl carboxylate. The seed monomer (B) can also be contained as a constituent monomer. That is, the polymer can contain a structural unit derived from the monomer (B).

When the polymer contains the monomer (B) as a constituent monomer, the coating film obtained from the aqueous dispersion tends to have improved adhesion to the metal. Therefore, the monomer (B) is preferably the main component of the constituent monomer forming the polymer.

In the monomer (B), the (meth) acrylic acid ester means one or both of the acrylic acid ester and the methacrylic acid ester. Examples of the (meth) acrylic acid ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-butyl (meth) acrylic acid, isobutyl (meth) acrylic acid, and sec-butyl (meth) acrylic acid. (Meta) tert-butyl acrylate, (meth) n-octyl acrylate, (meth) 2-ethylhexyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, (meth) ) Hexadecyl acrylate, (meth) octadecyl acrylate, (meth) octadecenyl acrylate, (meth) icosyl acrylate, (meth) docosyl acrylate, (meth) cyclopentyl acrylate, (meth) cyclohexyl acrylate, (meth) Examples thereof include benzyl acrylate. These can be used alone or in combination of two or more.

In the monomer (B), examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-, m-, p-methylstyrene, o-, m-, p-ethylstyrene, o-, m-, Examples thereof include p-isopropylstyrene, o-, m-, p-tert-butylstyrene and the like. Any one of these may be used, or two or more thereof may be used in combination.

In the monomer (B), examples of the vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate, and the like, and any one of these may be used, or two or more thereof may be used in combination.
The preferred vinyl carboxylate is vinyl acetate.

The method for producing the monomer (B) is not particularly limited, and for example, a known production method can be widely adopted. The monomer (B) can also be obtained from a commercially available product or the like.

As described above, since the polymer is obtained by the polymerization reaction in the presence of the reactive emulsifier (C), the polymer may contain the reactive emulsifier (C) as a so-called constituent monomer. That is, the reactive emulsifier (C) can be copolymerized with a monomer component for forming a polymer such as the monomer (A), and the polymer is a monomer (A) and a reactive emulsifier (C). It can also be called a copolymer. However, not all of the reactive emulsifier (C) used in the polymerization reaction is incorporated into the polymer (that is, not all of the reactive emulsifier (C) is contained as a constituent monomer of the polymer). The reactive emulsifier (C) that was not incorporated into the polymer can be contained in the aqueous dispersion as an emulsifier or dispersant. The reactive emulsifier (C) is a compound other than the monomer (A), and specifically, a compound other than the polyoxyalkylene styrenated propenylphenyl ether phosphoric acid ester and a salt thereof (A).

The type of the reactive emulsifier (C) is not particularly limited, and known reactive emulsifiers can be widely applied. Examples of the reactive emulsifier (C) include an anionic reactive emulsifier and a nonionic reactive emulsifier.

Examples of the anionic reactive emulsifier include compounds having a polymerizable unsaturated group, a polyoxyalkylene group (for example, the alkylene has 2 to 4 carbon atoms and 1 to 20 oxyalkylene units) and an anionic group. Can be mentioned. Hereinafter, such a compound is abbreviated as "Compound C1". However, the compound C1 excludes the polyoxyalkylene styrene-ized propenylphenyl ether sulfate ester salt and the polyoxyalkylene alkyl propenylphenyl ether sulfate ester salt, and the compound C1 can be a compound other than these. As a result, the finally obtained aqueous dispersion tends to have improved wettability with respect to the metal, facilitates the formation of a coating film, and has particularly excellent weather resistance of the formed coating film.

As a reminder, the anionic emulsifier is a combination of compound C1 with a polyoxyalkylene styrene-modified propenylphenyl ether sulfate ester salt and / or a polyoxyalkylene alkyl propenylphenyl ether sulfate ester salt. It does not exclude even. That is, when the reactive emulsifier (C) contains an anionic reactive emulsifier, the anionic reactive emulsifier contains at least compound C1, so that the finally obtained aqueous dispersion has improved wettability with respect to metal. It becomes easy to form a coating film, and the weather resistance of the formed coating film is particularly excellent.

Examples of the polymerizable unsaturated group include a 1-propenyl group, a 2-methyl-1-propenyl group, a (meth) allyl group, a (meth) acrylic group and the like, and the group has one or more of these groups. You can also do it. Examples of the polyoxyalkylene group include an oxyethylene group, an oxypropylene group, an oxybutylene group and the like, and one or more of these may be used. The polyoxyalkylene group preferably contains 50 to 100 mol% of an oxyethylene group, more preferably 70 to 100 mol%, and preferably a polyoxyethylene group.

Further specific examples of the anionic reactive emulsifier include, for example, in the case of the above-mentioned compound C1, a polyoxyalkylene-1- (allyloxymethyl) alkyl ether sulfate ester and a salt thereof, and a polyoxyalkylene-1- (allyloxy). Methyl) alkyl ether phosphate ester and its salts, polyoxyalkylene-1-alkoxymethyl-2- (2-propenyloxy) ethyl ether sulfate ester and its salts, and polyoxyalkylene-1-alkoxymethyl-2- (2) 2-Propenyloxy) One or more selected from the group consisting of ethyl ether phosphate ester and salts thereof and the like can be mentioned. In addition, examples of the anionic emulsifier other than compound C1 include one or more selected from the group consisting of alkylalkenyl sulfosuccinates.

On the other hand, the nonionic reactive emulsifier has a polymerizable unsaturated group and is not particularly limited in type as long as it is nonionic. For example, a known nonionic reactive emulsifier is widely used. Can be done. For example, a compound having a polymerizable unsaturated group and a polyoxyalkylene moiety (for example, the alkylene has 2 to 4 carbon atoms and the number of oxyalkylene units is 10 to 200) can be mentioned. The nonionic reactive emulsifier may have a styrenated phenyl moiety.

Specific examples of the nonionic reactive emulsifier include polyoxyalkylene styrated propenylphenyl ether, polyoxyalkylene alkyl propenylphenyl ether, polyoxyalkylene-1- (allyloxymethyl) alkyl ether, and polyoxyalkylene-1. One or more selected from the group consisting of −alkoxymethyl-2- (2-propenyloxy) ethyl ether can be mentioned.

When the reactive emulsifier (C) contains an anionic reactive emulsifier, or when it contains a nonionic reactive emulsifier, the coating film formed from the aqueous dispersion will have adhesion, weather resistance and abrasion resistance to the metal. It is easy to increase the sex. The reactive emulsifier (C) may be only an anionic reactive emulsifier or may be only a nonionic reactive emulsifier. Further, the reactive emulsifier (C) may be a mixture of an anionic reactive emulsifier and a nonionic reactive emulsifier, and in this case, the mixing ratio of both is not particularly limited and may be any ratio. can.

In the aqueous dispersion of the present invention, the polymer may contain, if necessary, other monomers as constituent monomers in addition to the monomers (A) and (B) and the reactive emulsifier (C). Examples of other monomers include conjugated diolefin monomers such as (meth) acrylic acid, acrylonitrile, vinyl chloride, vinylidene chloride, butadiene, isoprene, and chloroprene, ethylene, maleic anhydride, and methyl maleate.

As described above, in the aqueous dispersion of the present invention, as described above, the polymer contains the monomer (A) as an essential constituent monomer, and the reactive emulsifier (C) is also present in the polymer. The reactive emulsifier (C) can be copolymerized with a monomer component for forming a polymer. The polymer (A) can contain a monomer (B) in addition to the monomer (A) and the reactive emulsifier (C), and can further contain other monomers as constituent monomers.

The content of the monomer (A) in all the constituent monomers of the polymer is not particularly limited. For example, the content ratio of the monomer (A) can be 0.1 to 20% by mass, preferably 0.2 to 15% by mass, and 0.5 to 10% by mass with respect to the total mass of the polymer. % Is more preferable.

The content of the monomer (B) in all the constituent monomers of the polymer is not particularly limited. For example, the content ratio of the monomer (B) can be 70 to 99.8% by mass, preferably 80 to 99.4% by mass, and 85 to 99% by mass with respect to the total mass of the polymer. It is more preferable to have.

The content ratio of the component derived from the reactive emulsifier (C) contained in the polymer can be, for example, 0.1 to 20% by mass and 0.2 to 15% by mass with respect to the total mass of the polymer. It is preferably 0.5 to 10% by mass, and more preferably 0.5 to 10% by mass.

When the polymer contains other monomers as constituent monomers, the content thereof may be, for example, 20% by mass or less and 10% by mass with respect to the total mass of the polymer. It is more preferably 5% by mass or less, and even more preferably 5% by mass or less.

The weight average molecular weight (Mw) of the polymer is not particularly limited, and can be, for example, 100,000 to 10 million, preferably 1 million to 5 million. Here, the weight average molecular weight of the polymer can be measured by a known method in terms of polyethylene glycol by gel permeation chromatography (GPC).

The shape and size of the polymer are also not particularly limited and may be, for example, the shape and size applied in the metal coating agent, and in particular, the shape and size formed by known emulsion polymerization are widely adopted. be able to.

The aqueous dispersion of the present invention may contain an emulsifier in addition to the polymer. The emulsifier may include the reactive emulsifier (C) used in producing the polymer. That is, the reactive emulsifier (C) that was not incorporated into the polymer may be dissolved in water in the aqueous dispersion. Further, the aqueous dispersion may contain a reactive emulsifier other than the reactive emulsifier (C). Further, the emulsifier can also include a non-reactive emulsifier. The non-reactive emulsifier is an emulsifier that does not have a radically polymerizable functional group and does not exhibit polymerization reactivity in emulsion polymerization.

The type of non-reactive emulsifier is not particularly limited. For example, as the non-reactive emulsifier, at least one emulsifier selected from the group consisting of an anionic emulsifier and a nonionic emulsifier can be mentioned.

In the non-reactive emulsifier, as the anionic emulsifier, for example, known anionic emulsifiers can be widely mentioned. For example, as an anionic emulsifier, a compound having a polyoxyalkylene alkyl ether moiety, a compound having a polyoxyalkylene alkenyl ether moiety, a compound having a polyoxyalkylene alkenyl phenyl ether moiety, a compound having a polyoxyalkylene alkyl phenyl ether moiety, and a poly Examples thereof include compounds having an oxyalkylene styrene phenyl ether moiety.

Specific non-reactive anionic emulsifiers include polyoxyalkylene alkyl ether sulfate ester and its salt, polyoxyalkylene alkenyl ether sulfate ester and its salt, polyoxyalkylene alkenyl phenyl ether sulfate ester and its salt, and polyoxyalkylene alkyl. Ether phosphate ester and its salt, polyoxyalkylene alkenyl ether phosphate ester and its salt, polyoxyalkylene alkylphenyl ether phosphoric acid ester and its salt, polyoxyalkylene alkenyl phenyl ether phosphoric acid ester and its salt, polyoxyalkylene styrene Phenyl ether phosphate ester and its salts, polyoxyalkylene alkyl sulfosuccinic acid and its salts, polyoxyalkylene alkenyl sulfosuccinic acid and its salts, alkyl sulfosuccinic acid and its salts, dialkyl sulfosuccinic acid and its salts, alkenyl sulfosuccinic acid and its salts. , Polyoxyalkylene alkyl ether acetate and its salts, polyoxyalkylene alkenyl ether acetate and its salts, polyoxyalkylene alkyl phenyl ether acetate and its salts, polyoxyalkylene alkenyl phenyl ether acetate and its salts, polyoxyalkylene Examples thereof include styrene phenyl ether acetate and its salts, alkylbenzene sulfonic acid and its salts, alkyl sulfuric acid and its salts, and alkyl phosphate and its salts. These can be used alone or in combination of two or more. Further, the anionic emulsifier may be a mixture of a salt form and a non-salt form.

In the non-reactive emulsifier, the anionic emulsifier preferably contains one selected from the group consisting of a polyoxyalkylene alkyl ether sulfate ester and a salt thereof, and a polyoxyalkylene alkenyl ether sulfate ester and a salt thereof.

In another aspect of the present invention, the anionic emulsifier as a non-reactive emulsifier may also contain a polyoxyalkylene styrene phenyl ether sulfate ester salt and a polyoxyalkylene alkyl phenyl ether sulfate ester salt. In this case, the polyoxyalkylene styrene phenyl ether sulfate ester salt is preferably a polyoxyethylene styrene phenyl ether sulfate ester salt, and the polyoxyalkylene alkyl phenyl ether sulfate is preferable because the polymerization stability is easily improved. The ester salt is preferably a polyoxyethylene alkyl phenyl ether sulfate ester salt.

In the non-reactive emulsifier, as the non-ionic emulsifier, for example, known non-ionic emulsifiers can be widely mentioned. For example, examples of the nonionic emulsifier include compounds having a polyoxyalkylene moiety.

Specific non-reactive non-ionic emulsifiers include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkenyl phenyl ether, polyoxyalkylene styrene phenyl ether, and polyoxyalkylene. Examples thereof include naphthyl ether and polyoxyalkylene triblock polymer (eg, polyoxyethylene polyoxypropylene glycol, etc.). These can be used alone or in combination of two or more.

The non-reactive emulsifier preferably contains at least an anionic emulsifier from the viewpoint that the adhesion of the coating film to the metal is easily improved and the abrasion resistance is also easily improved. In this case, the non-reactive emulsifier can be a combination of an anionic emulsifier and a nonionic emulsifier, or may be only an anionic emulsifier. In the case of the combined use of the anionic emulsifier and the nonionic emulsifier, for example, the content ratio of the anionic emulsifier to the total mass of the anionic emulsifier and the nonionic emulsifier is 50% by mass, preferably 60% by mass or more, more preferably. Is 70% by mass or more, more preferably 80% by mass or more.

The emulsifier contained in the aqueous dispersion may be a reactive emulsifier and a non-reactive emulsifier, respectively. In this case, the type of emulsifier may be only one type, or two or more types may be used. Further, the emulsifier contained in the aqueous dispersion may be a mixture of a reactive emulsifier and a non-reactive emulsifier. In the case of a mixture, the mixing ratio of the reactive emulsifier and the non-reactive emulsifier contained in the aqueous dispersion is not particularly limited. For example, the content of the non-reactive emulsifier is preferably 1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, and 10 to 100 parts by mass with respect to 100 parts by mass of the reactive emulsifier. Is even more preferable. The "100 parts by mass of the reactive emulsifier" includes both a reactive emulsifier that reacts with the monomer component and is incorporated into the polymer and a reactive emulsifier that is not incorporated and exists in water.

Examples of the medium of the aqueous dispersion include an aqueous solvent. Examples of the aqueous solvent include water, a lower alcohol (for example, an alcohol having 1 to 3 carbon atoms), or a mixed solvent thereof. The aqueous medium is preferably water in that the dispersibility of the polymer is easy to stabilize.

In the aqueous dispersion, the concentration of the polymer is not particularly limited. The concentration of the polymer in the aqueous dispersion can be 20 to 70% by mass, preferably 35 to 55% by mass, from the viewpoint that a coating film is easily formed from the aqueous dispersion.

The aqueous dispersion may also contain various additives in addition to the polymer and emulsifier as long as the effects of the present invention are not impaired. Examples of the additive include a colorant, a pH adjuster, a thickener, a pigment, an antiseptic and the like. One or more of these additives may be contained in the aqueous dispersion. The additive is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 1 part by mass or less per 100 parts by mass of the polymer.

Since the polymer contained in the aqueous dispersion of the present invention contains the monomer (A) as a constituent monomer and is obtained by using the reactive emulsifier (C), the coating film obtained from the aqueous dispersion can be obtained. , It is possible to form a coating film having excellent adhesion to metal, weather resistance and abrasion resistance. In addition, since it is excellent in wettability to metal, it is also suitable for use as a metal coating agent or the like.

2. 2. Method for Producing an Aqueous Dispersion The method for producing an aqueous dispersion according to the present embodiment is not particularly limited, and for example, a known emulsification polymerization method can be widely applied. As an example of the emulsion polymerization method, a polymer is synthesized by using water as a polymerization solvent, emulsifying a polymerization monomer into water using an emulsifier, and adding a polymerization initiator to the emulsion to react, if necessary. By neutralizing with alkali, an aqueous dispersion can be obtained. As the alkali, known compounds can be widely used, among which ammonia; hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydroxylation of alkaline earth metals such as calcium hydroxide and magnesium hydroxide. Substances; Alkaline amines such as monomethylamine and dipropylamine; Alkanol amines such as monoethanolamine and diethanolamine;

The polymerization monomer contains at least the monomer (A). As the monomer (A), it is preferable to use the above-mentioned acid-type phosphoric acid ester in one embodiment. The polymerization monomer may contain a monomer (B) in addition to the monomer (A). The content ratio of the monomer (A) can be 0.1 to 20% by mass, preferably 0.2 to 15% by mass, and 0.5 to 10% by mass with respect to the total amount of the polymerization monomer. Is more preferable. Further, the content ratio of the monomer (B) can be 70 to 99.8% by mass, preferably 80 to 99.4% by mass, and 85 to 99% by mass with respect to the total amount of the polymerization monomer. Is more preferable.

In the method for producing an aqueous dispersion, an emulsifier is used, and in particular, an emulsifier containing at least the reactive emulsifier (C) is used. The emulsifier may be only the reactive emulsifier (C), or, for example, the non-reactive emulsifier may be used in combination as long as the desired aqueous dispersion can be produced. The reactive emulsifier (C) may be partially or partially copolymerized with the monomer (A) and incorporated into the polymer, or a part thereof may be incorporated into the polymer and a part thereof may not be incorporated. It may remain as it is and be contained in the aqueous dispersion as an emulsifier or a dispersant.

The amount of the reactive emulsifier (C) used can be, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, preferably 0.1 part by mass with respect to 100 parts by mass of the monomer for polymerization. It is more preferably parts by mass or more, more preferably 0.2 parts by mass or more, and particularly preferably 0.3 parts by mass or more. Further, the amount of the reactive emulsifier (C) used can be 20 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the monomer for polymerization. It is more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less.

When a non-reactive emulsifier is used in combination, the amount used is not particularly limited. For example, the content of the non-reactive emulsifier is preferably 1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, and 10 to 100 parts by mass with respect to 100 parts by mass of the reactive emulsifier used. It is more preferable to have.

In emulsion polymerization, as the polymerization initiator used in the polymerization reaction, for example, a known polymerization initiator used in emulsion polymerization can be widely used. For example, hydrogen peroxide, a persulfate compound, an azo compound and the like can be mentioned. Examples of the persulfate compound include ammonium persulfate, sodium persulfate, potassium persulfate and the like, and examples of the azo compound include 2,2'-azobis-2-methylpropionamidine hydrochloride, 2,2'-. Examples thereof include azobis-2- (2-imidazolin-2-yl) propane hydrochloride, 2-carbamoyl azoisobutyronitrile and the like. Further, a known reaction accelerator may be used in combination.

In emulsion polymerization, the polymerization conditions such as the polymerization temperature and the polymerization time are not particularly limited, and can be appropriately set according to the type of the monomer used and the like.

2. 2. Coating Agents and Coating Films for Metals The aqueous dispersion of the present invention can be applied to various uses, and in particular, the aqueous dispersion according to the present invention has excellent adhesion to metals and a coating film having excellent wear resistance. It is suitable for use as a coating agent for metals because it can form.

(Metal coating agent)
The coating agent for metals of the present invention is not particularly limited as long as it contains the aqueous dispersion. The coating agent for metal may be composed of only the aqueous dispersion, or may contain other additives and the like. The other additives of the metal coating agent are not particularly limited, and additives contained in known metal coating agents can be widely mentioned.

According to the coating agent for metals of the present invention, it is possible to form a coating film having excellent adhesion to metal, weather resistance and abrasion resistance. Further, since it has excellent wettability to metal, it is easy to coat and a uniform coating film is easily formed.

The type of metal to be coated with the metal coating agent is not particularly limited, and various metal substrates such as a substrate of a single metal, a metal alloy containing two or more kinds of metals, and a metal alloy can be targeted. Above all, the coating agent for metals can form a coating film having excellent adhesion to stainless steel.

(Coating film)
The coating film can be obtained by using an aqueous dispersion or a coating agent for metals. The method for forming the coating film is not particularly limited, and for example, a known method for forming a coating film can be widely adopted. As an example of the method for forming a coating film, a coating film can be formed on the surface of the base material by applying an aqueous dispersion or a coating agent for metal to the base material, heating and drying the base material. Therefore, the coating film contains a dried product of an aqueous dispersion or a coating agent for metals. As the base material, the metal substrate can be used.

Since the coating film is formed from an aqueous dispersion or a coating agent for metals, it is excellent in adhesion to metals, weather resistance and abrasion resistance, and in addition, it is also excellent in water whitening resistance and rust prevention.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the embodiments of these Examples.

(Monomer A)
[Synthesis Example 1: Synthesis of Monomer (A-1)]
230 g (1.0) of styrenated phenol (mixture of monostyrenated phenol: distyrenated phenol: tristyrenated phenol = 80: 19: 1 (molar ratio)) in a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube. Mol), 40 g (1.0 mol) of NaOH and 210 g of acetone were charged, and the internal temperature was raised to 40 ° C. with stirring. Next, 91 g (1.2 mol) of allyl chloride was added dropwise over 1 hour. After completion of the dropping, the reaction was carried out by keeping the temperature at 40 ° C. for 2 hours. The reaction product was filtered to remove by-produced NaCl, and then acetone was removed under reduced pressure to obtain 314 g of styrenated allylphenyl ether.

This styrenated allyl phenyl ether was charged in an autoclave and kept at 200 ° C. for 5 hours with stirring. A rearrangement reaction occurred at this stage, resulting in styrenated 1-propenylphenol. 290 g of this styrenated 1-propenylphenol was transferred to an autoclave, and 132 g (3 mol) of ethylene oxide (EO) was added under the conditions of a pressure of 147 kPa and a temperature of 130 ° C. using potassium hydroxide as a catalyst.

Next, 71 g (0.5 mol) of anhydrous phosphoric acid was added dropwise to 422 g (1 mol) of this styrenated 1-propenylphenol EO 3 mol adduct while cooling so as not to exceed 20 ° C., and 70 ° C. after completion of the addition. The temperature was raised to 5 and the reaction was carried out for 5 hours. By such a reaction, a polyoxyethylene (3 mol) styrenated 1-propenylphenyl ether phosphate monoester represented by the following formula (1-1-1) (hereinafter abbreviated as (A-1)) is obtained. rice field. In the formula, EO represents an oxyethylene group (the same applies hereinafter).

[Synthesis Example 2: Synthesis of Monomer (A-2)]
By performing the same operation as in Synthesis Example 1 except that the amount of anhydrous phosphoric acid used was 47 g (0.33 mol), the phosphoric acid monoester represented by the above formula (1-1-1) and the following Polyoxyethylene (3 mol) styrenated 1-propenylphenyl ether phosphoric acid sesquiester (hereinafter, (A)) which is a mixture (molar ratio 1: 1) with a phosphoric acid diester represented by the formula (1-2-1). -2)) was obtained.

[Synthesis Example 3: Synthesis of Monomer (A-3)]
By performing the same operation as in Synthesis Example 1 except that the amount of anhydrous phosphoric acid used was 36 g (0.25 mol), the polyoxyethylene (3 mol) represented by the above formula (1-2-1) was used. A styrenated 1-propenylphenyl ether phosphate diester (hereinafter abbreviated as (A-3)) was obtained.

[Synthesis Example 4: Synthesis of Monomer (A-4)]
Polyoxyethylene (5 mol) styrenated 1 represented by the following formula (1-1-2) by performing the same operation as in Synthesis Example 1 except that the amount of ethylene oxide used was 220 g (5 mol). -Propenylphenyl ether phosphate monoester (hereinafter abbreviated as (A-4)) was obtained.

[Synthesis Example 5: Synthesis of Monomer (A-5)]
By performing the same operation as in Synthesis Example 2 except that the amount of ethylene oxide used was 220 g (5 mol), the monoester represented by the above formula (1-1-2) and the following formula (1-2-2) were performed. Polyoxyethylene (5 mol) sterylated 1-propenylphenyl ether phosphate sesquiester (hereinafter abbreviated as (A-5)), which is a mixture with the diester represented by 2), was obtained.

[Synthesis Example 6: Synthesis of Monomer (A-6)]
Polyoxyethylene (5 mol) styrenated 1 represented by the above formula (1-2-2) by performing the same operation as in Synthesis Example 3 except that the amount of ethylene oxide used was 220 g (5 mol). -Propenylphenyl ether phosphate diester (hereinafter abbreviated as (A-6)) was obtained.

[Synthesis Example 7: Synthesis of Monomer (A-7)]
By reacting 49.3 g of the monomer (A-1) obtained in the same operation as in Synthesis Example 1 with 4.0 g of sodium hydroxide, polyoxyethylene (3 mol) styrenated 1-propenylphenyl ether phosphoric acid monoester (Hereinafter, abbreviated as (A-7)) was obtained.

[Synthesis Example 8: Synthesis of Monomer (A-8)]
Polyoxyethylene (3 mol) styrenated 1- by reacting 49.3 g of the monomer (A-1) obtained in the same operation as in Synthesis Example 1 with 6.8 g of 25% ammonium water and distilling off the water. An ammonium salt of propenylphenyl ether phosphoric acid monoester (hereinafter abbreviated as (A-8)) was obtained.

[Synthesis Example 9: Synthesis of Monomer (A-9)]
49.3 g of the monomer (A-1) obtained in the same operation as in Synthesis Example 1 and 6.1 g of monoethanolamine are reacted to form a monoester of polyoxyethylene (3 mol) styrenated 1-propenylphenyl ether phosphoric acid monoester. An ethanolamine salt (hereinafter abbreviated as (A-9)) was obtained.

(Monomer B)
The following (B-1) to (B-4) were prepared as the monomer B.
-(B-1): Butyl acrylate- (B-2): Methyl methacrylate- (B-3): Styrene- (B-4): Vinyl acetate

(Reactive emulsifier C)
As the reactive emulsifier (C), (C-1) to (C-9) shown below were prepared.
(C-1): "Aqualon KH-10" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
(C-2): ADEKA's "Adecaria Soap SR-10"
・ (C-3): "SINONATE LRS10" manufactured by Sino-Japan Chemical Co., Ltd.
(C-4): "Eleminol JS-20" manufactured by Sanyo Chemical Industry Co., Ltd.
・ (C-5): Kao Corporation "Latemuru PD-104"
(C-6): "Maxemul 6106" manufactured by Croda International.
-(C-7): "Aqualon KH-20" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
-(C-8): "Aqualon AN-20" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
・ (C-9): ADEKA's "Adecaria Soap ER-20"

(Other emulsifiers)
As a reactive emulsifier other than the reactive emulsifier (C), (c-1) shown below was prepared.
(C-1): "Aqualon BC-10" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

(Other monomers)
The following (a-1) to (a-3) were prepared as the other monomers (a).
-(A-1): Acrylic acid- (a-2): Hydroxyethyl methacrylate phosphoric acid monoester (Product name: Light ester P-1M, manufactured by Kyoeisha Chemical Co., Ltd.)

(Example 1)
As shown in Table 1 below, 2.5 parts by mass of (A-1) obtained in Synthesis Example 1 as the monomer (A) and 123.75 parts by mass of (B-1) as the monomer (B). By mixing 123.75 parts by mass of a mixture of parts and (B-2), 5 parts by mass of (C-1) as a reactive emulsifier (C), and 107.15 parts by mass of water and emulsifying. A preemulsion was obtained. Separately, a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser was charged with 117.11 parts by mass of water and 0.25 parts by mass of sodium hydrogen carbonate, and 36. 46 parts by mass was added, the temperature was raised to 80 ° C., and the mixture was mixed for 15 minutes. Next, an aqueous solution prepared by dissolving 0.38 part by mass of ammonium persulfate in 10 parts by mass of water as a polymerization initiator was added and reacted for 15 minutes, and then the remaining preemulsion was added dropwise over 3 hours and reacted for another 1 hour. .. Subsequently, an aqueous solution prepared by dissolving 0.12 parts by mass of ammonium persulfate in 10 parts by mass of water was added and reacted for 1 hour, cooled to 40 ° C., and adjusted to pH 8 with ammonia water as a neutralizing agent. An aqueous dispersion was obtained. By neutralizing with aqueous ammonia, the phosphoric acid ester of the monomer (A) in the constituent monomers of the polymer became an ammonium salt at the stage of the aqueous dispersion.

(Examples 2 to 8)
Example 1 except that the types and amounts (parts by mass) of the monomer (A), the monomer (B), the reactive emulsifier (C) and the other monomer (a) are changed to the formulations shown in Table 1 below. An aqueous dispersion was obtained in the same manner. In Example 7, since an aqueous sodium hydroxide solution was used as the neutralizing agent instead of aqueous ammonia, the phosphoric acid ester of the monomer (A) became a sodium salt in the constituent monomers of the polymer.

(Examples 9 to 16)
Example 1 except that the types and amounts (parts by mass) of the monomer (A), the monomer (B), the reactive emulsifier (C) and the other monomer (a) are changed to the formulations shown in Table 2 below. An aqueous dispersion was obtained in the same manner. In Example 9, since monoethanolamine was used as the neutralizing agent instead of aqueous ammonia, the phosphoric acid ester of the monomer (A) in the constituent monomers of the polymer became a monoethanolamine salt.

(Examples 17 to 23)
Example 1 except that the types and amounts (parts by mass) of the monomer (A), the monomer (B), the reactive emulsifier (C) and the other monomer (a) are changed to the formulations shown in Table 3 below. An aqueous dispersion was obtained in the same manner.

(Comparative Examples 1 to 5, Reference Example 1)
Example 1 and Example 1 except that the types and amounts (parts by mass) of the monomer (A), the monomer (B), the reactive emulsifier (C) and the other monomer (a) were changed to the formulations shown in Table 4 below. An aqueous dispersion was obtained in the same manner.

(Evaluation method)
The following adhesion 1, adhesion 2, water whitening resistance, rust resistance, abrasion resistance, wettability to the substrate, and weather resistance were evaluated for the water dispersions obtained in each Example, Comparative Example, and Reference Example. did.

<Adhesion 1>
The aqueous dispersion was applied to a stainless steel (SUS) plate so as to have a film thickness of 22 μm (wet), and dried at 105 ° C. for 10 minutes to obtain a test piece. Using this test piece, a grid test was carried out according to JIS K 5400-8.5, and a judgment was made based on the following criteria from the rate of peeling.
≪Judgment criteria≫
A: The rate of peeling is 0%
B: Peeling rate is more than 0% and less than 25% C: Peeling rate is 25% or more and less than 50% D: Peeling rate is 50% or more and less than 75% E: Peeling rate is 75% or more

<Adhesion 2>
The determination was made in the same manner as for Adhesion 1 except that the drying temperature after coating was changed to 60 ° C.

<Water whitening resistance>
The aqueous dispersion was applied to a glass plate so as to have a film thickness of 22 μm (wet), and the film obtained by drying at 105 ° C. for 10 minutes was immersed in water at 25 ° C. to evaluate the degree of whitening. A glass plate on which a film was formed was placed on the 10-point characters, and the distinctiveness of the characters seen through the film was judged according to the following criteria.
≪Judgment criteria≫
A: Letters can be seen even after soaking for 3 days.
B: The characters can be seen after soaking for 1 day, but the characters cannot be seen after soaking for 3 days.
C: No characters can be seen after soaking for 1 day.

<Rust prevention>
The aqueous dispersion was applied to a stainless steel (SUS) plate so that the film thickness was 22 μm (wet), and dried at 60 ° C. for 10 minutes. The film was obtained in accordance with the JIS K 5600-5-6 cross-cut method. And made a notch. The state after immersing this film in 3% by mass of salt water at 20 ° C. for 10 days was evaluated. The evaluation was performed on the condition of rust generation, and the judgment was made according to the following criteria.
≪Judgment criteria≫
A: No rust B: Rust is seen only in the cross-cut part C: Rust is seen in the whole

<Abrasion resistance>
The aqueous dispersion was applied to a stainless steel (SUS) plate so that the film thickness was 22 μm (wet), and dried at 60 ° C. for 10 minutes. Was measured. The ratio of the wear loss of each film was calculated based on the wear loss (g) of the film formed of the aqueous dispersion obtained in Comparative Example 1 (assuming 100%), and the determination was made according to the following criteria.
≪Judgment criteria≫
A: 50% or less B: 50-80%
C: 80% or more

<Wetability to the base material>
A sample for measurement is prepared by diluting the aqueous dispersion twice with water, and the surface tension (mN / m) at 25 ° C. is measured with a Wilhelmy type tensiometer using this sample according to the following criteria. The wettability with respect to the substrate was evaluated. The lower the surface tension, the higher the wettability with respect to the substrate.
≪Judgment criteria≫
〇: Surface tension is less than 40 mN / m ×: Surface tension is 40 mN / m or more

<Hou resistance>
A film obtained by applying an aqueous dispersion to a glass plate so as to have a thickness of 254 μm (wet) and drying at 60 ° C. for 60 minutes was used with an eye super UV tester SUV-W151 manufactured by Iwasaki Electric Co., Ltd. , Weather resistance was evaluated. The test conditions were: light source: metal halide lamp, UV intensity: 1000 w / m ² , temperature: 20 ° C., humidity: 40% RH, irradiation time: 200 hours. Before and after the test, the color difference ΔE * ab of the film was measured using a color difference meter (SD6000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) and evaluated based on the following criteria. The smaller the difference in color difference before and after the test, the higher the weather resistance of the film.
≪Judgment criteria≫
〇: ΔE * ab is less than 5.
X: ΔE * ab is 5 or more.

Tables 1 to 4 show the compounding conditions of the aqueous dispersion prepared in each Example, Comparative Example or Reference Example, and the evaluation results of the coating film obtained from the aqueous dispersion. In addition, in the compounding conditions of each table, the blank part means that the raw material is not used.

As can be seen from the comparison between the evaluation results shown in Tables 1 to 3 and the evaluation results shown in Table 4, the weight containing any of the specific phosphoric acid esters (A-1) to (A-9) as the constituent monomers. The aqueous dispersion containing the coalescence and the reactive emulsifier (C) has high wettability to metal and excellent coating property, and the coating film obtained from these aqueous dispersions has adhesion to metal (stainless steel) and weather resistance. In addition to being excellent in various performances of resistance and abrasion resistance, it was also excellent in water whitening resistance and rust prevention.

Claims (8)

A polymer containing a polyoxyalkylene styrenated propenylphenyl ether phosphate ester and / or a salt thereof (A) as a constituent monomer is contained.
An aqueous dispersion obtained by synthesizing the polymer using the reactive emulsifier (C) (excluding the polyoxyalkylene styrenated propenylphenyl ether phosphate ester and / or a salt thereof (A)). The aqueous dispersion according to claim 1, wherein the reactive emulsifier (C) contains an anionic reactive emulsifier. The aqueous dispersion according to claim 1, wherein the reactive emulsifier (C) contains a nonionic reactive emulsifier. The anionic reactive emulsifier is a compound having a polymerizable unsaturated group, a polyoxyalkylene group and an anionic group (provided that the polyoxyalkylene styrated propenylphenyl ether sulfate ester salt and the polyoxyalkylene alkyl propenylphenyl ether sulfate are used. The aqueous dispersion according to claim 2, which comprises (excluding ester salts). Any of claims 1 to 4, wherein the polymer further contains at least one monomer (B) selected from the group consisting of (meth) acrylic acid ester, aromatic vinyl compound and vinyl carboxylate as a constituent monomer. Or the aqueous dispersion according to item 1. The salt (A) of the polyoxyalkylene sylated propenylphenyl ether phosphate ester is at least one selected from the group consisting of an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an alkylammonium salt and an alkanolamine salt. The aqueous dispersion according to claim 1-5. A coating agent for metals, which comprises the aqueous dispersion according to any one of claims 1 to 6. A coating film obtained by using the aqueous dispersion according to any one of claims 1 to 6 or the metal coating agent according to claim 7.