WO2021246131A1

WO2021246131A1 - Aqueous dispersion, coating agent for metal, and coating film

Info

Publication number: WO2021246131A1
Application number: PCT/JP2021/018314
Authority: WO
Inventors: 拓郎木村; 亜沙子小笠原; 祐輝高町
Original assignee: 第一工業製薬株式会社
Priority date: 2020-06-02
Filing date: 2021-05-14
Publication date: 2021-12-09
Also published as: JP6852209B1; CN115698099A; JP2021187993A

Abstract

Provided are an aqueous dispersion that can form a coating film having remarkably excellent adhesion to metal while also having excellent abrasion resistance, a coating agent for metal that contains said aqueous dispersion, and a coating film. An aqueous dispersion according to the present invention contains a polymer that comprises, as component monomers thereof, a compound (A1) represented by general formula (1-1) and a compound (A2) represented by formula (1-2), wherein if the content ratio of the compound (A1) in terms of the total amount of the compound (A1) and the compound (A2) in the polymer is designated k(mol%), the value of k is 50<k<100.

Description

Water dispersions, metal coatings and coatings

The present invention relates to an aqueous dispersion, a metal coating agent and a coating film.

Known are sulfate esters (salts) and phosphate esters (salts), which are 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

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 on metals, for example. It has been desired to further improve the adhesion to the metal. In addition, it has been required to improve the wear resistance of the coating film in order to provide the coating film with excellent durability. Particularly in recent years, in applications for coating metals and the like, it has been required that the formed coating film adheres strongly to the metal and that the coating film has excellent wear resistance. From this viewpoint, the adhesion to the metal is required. There was an urgent need to develop an aqueous dispersion capable of forming a coating film having excellent wear resistance.

The present invention has been made in view of the above, and is an aqueous dispersion capable of forming a coating film having remarkably excellent adhesion to a metal and also excellent wear resistance, and a metal containing the aqueous dispersion. It is an object of the present invention to provide a coating agent for use and a coating film.

As a result of diligent research to achieve the above object, the present inventors have found that the above object can be achieved by including a constituent monomer having a specific structure in the polymer, and have completed the present invention.

That is, the present invention includes, for example, the subjects described in the following sections.
Item 1
As a constituent monomer, a polymer containing a compound (A1) represented by the following general formula (1-1) and a compound (A2) represented by the following formula (1-2) is contained.
When the content ratio of the compound (A1) to the total amount of the compound (A1) and the compound (A2) in the polymer is k (mol%), the value of k is 50 <k <100. Water dispersion.

(In formula (1-1) and formula (1-2), R represents a 1-propenyl group or an allyl group (that is, a 2-propenyl group), L represents a counter ion, and A represents 2 to 4 carbon atoms. Represents the alkylene group of, x is the number of substituents in the range of 1 to 3, y is the number of substituents in the range of 1 to 3, and n is the average number of added moles of the oxyalkylene group of 0 to 100. It is a range.)
Item 2
Item 2. The aqueous dispersion according to Item 1, 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. body.
Item 3
The L in the formula (1-1) and the L in the formula (1-2) are the same or different and consist of hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion, and organic ammonium ion. Item 2. The aqueous dispersion according to Item 1 or 2, which is at least one selected from the group.
Item 4
A coating agent for metals, which comprises the aqueous dispersion according to any one of Items 1 to 3.
Item 5
A coating film obtained by using the aqueous dispersion according to any one of Items 1 to 3 or the metal coating agent according to claim 4.

According to the aqueous dispersion according to the present invention, it is possible to form a coating film having excellent adhesion to metals and also excellent wear 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 compound (A1) represented by the following general formula (1-1) and a compound (A2) represented by the following formula (1-2) as constituent monomers. Contains the polymer it contains. In particular, when the content ratio of the compound (A1) to the total amount of the compound (A1) and the compound (A2) in the polymer is k (mol%), the value of k is 50 <k <100. be.

Here, in the formula (1-1) and the formula (1-2), R represents a 1-propenyl group or an allyl group (that is, a 2-propenyl group), L represents a counter ion, and A represents a carbon number of 2. Represents 4 alkylene groups, x is the number of substituents in the range of 1 to 3, y is the number of substituents in the range of 1 to 3, and n is the average number of moles of oxyalkylene groups added. It is in the range of 100.

According to the aqueous dispersion of the present invention, it is possible to form a coating film having remarkably excellent adhesion to a metal, and it is also possible to form a coating film having excellent wear resistance.

In the aqueous dispersion of the present invention, the polymer contains both the compound (A1) and the compound (A2) as constituent monomers. In the present specification, the compound (A1) and the compound (A2) are collectively abbreviated as "monomer (A)". Therefore, 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. ..

As can be seen from the formula (1-1), the compound (A1) is a phosphoric acid monoester, and as can be seen from the formula (1-2), the compound (A2) is a phosphoric acid diester. Therefore, the monomer (A) is a mixture of a phosphoric acid monoester and a phosphoric acid diester.

In the formula (1-1) and the formula (1-2), L represents a counterion, and the type thereof is not particularly limited. L in the formula (1-1) and L in the formula (1-2) are at least one selected from the group consisting of hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion, and organic ammonium ion. It is preferably a seed. In this case, the aqueous dispersion easily forms a coating film having excellent adhesion to a metal, and the synthesis of each compound is also easy. L in the formula (1-1) and L in the formula (1-2) may be the same or different. Further, the two Ls existing in the equation (1-1) may be the same or different.

In the formulas (1-1) and (1-2), when L is a hydrogen ion, the compound (A1) and the compound (A2) are acid-type phosphate esters. Further, in the formulas (1-1) and (1-2), when L is an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or an organic ammonium ion, it is in the form of a salt. Both compound (A1) and compound (A2) may be a mixture of an acid-type phosphoric acid ester and a salt thereof. That is, the polymer may have both an acid-type phosphoric acid ester and a salt thereof as a constituent monomer.

When L is an alkali metal ion, Na, K and the like are exemplified as the alkali metal, and when L is an alkaline earth metal ion, Mg, Ca and the like are exemplified as the alkaline earth metal. When L is an organic ammonium ion, examples of the organic ammonium include alkylammoniums such as monomethylammonium and dipropylammonium; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.

L is more preferably at least one selected from the group consisting of hydrogen ions, alkali metal ions, ammonium ions and alkanolammonium, in which case the aqueous dispersion has excellent adhesion to metals and wear resistance. It is possible to form a coating film which is also excellent in water whitening resistance.

For example, when L is an ammonium ion, most of the ammonia is eliminated when the aqueous dispersion is heated and dried. As a result, the compound (A1) and the compound (A2) can be the acid-type phosphoric acid ester described above, so that the polymer may contain the acid-type phosphoric acid ester as a constituent monomer in the state of the coating film described later.

In the formulas (1-1) and (1-2), R represents a 1-propenyl group or an allyl group (that is, a 2-propenyl group), and is preferably a 1-propenyl group. The substitution positions of R in the formulas (1-1) and (1-2) are preferably ortho-positions and / or para-positions, and more preferably the ortho-positions. The R in the formula (1-1) and the R in the formula (1-2) may be the same or different. Further, in the compound represented by the formula (1-2), the two Rs contained in the molecule may be the same or different.

In the formula (1-1) and the formula (1-2), x is the number of substituents in the range of 1 to 3, and is preferably 1. The x in the formula (1-1) and the x in the formula (1-2) may be the same or different. Further, in the compound represented by the formula (1-2), the two x's may be the same or different.

In the formula (1-1) and the formula (1-2), since A represents an alkylene group having 2 to 4 carbon atoms, the group represented by AO is an oxyalkylene group. 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 formulas (1-1) and (1-2), when AO is an alkylene oxide having 2 to 4 carbon atoms, the (AO) _n- chain moiety is ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran (1). , 4-Butylene oxide) or the like, or an addition polymer using two or more of them can be used. 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 (AO) n} chain moiety of the formula (1-1) and the formula (1-2), n represents the average number of moles of oxyalkylene group added and is in the range of 0 to 100. n is preferably a number 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.

R in the formula (1-1) and A in the formula (1-2) may be the same or different. Further, in the compound represented by the formula (1-2), the two A's in the molecule may be the same or different. Further, the R in the formula (1-1) and the _n of the (AO) n chain site in the formula (1-2) may be the same or different. Further, in the compound represented by the formula (1-2), the two ns may be the same or different.

In the formulas (1-1) and (1-2), y indicates the number of substituents of the α-methylbenzyl group, which is the number of substituents in the range of 1 to 3, and the average value is in the range of 1 to 3. , Preferably in the range of 1-2. The substitution position of the α-methylbenzyl group is preferably the ortho-position and / or the para-position. The y in the formula (1-1) and the y in the formula (1-2) may be the same or different. Further, in the compound represented by the formula (1-2), the two y's may be the same or different.

The content ratio (mol%) of the compound (A1) to the total amount (mol) of the compound (A1) and the compound (A2) in the polymer contained in the aqueous dispersion of the present invention is defined as k (mol%). If so, the value of k is 50 <k <100. As a result, the coating film obtained from the aqueous dispersion of the present invention has remarkably excellent adhesion to metals and the like, and also has excellent wear resistance.

The value of k is not particularly limited as long as it is within the above range. K is preferably 55 or more, more preferably 60 or more, further preferably 65 or more, and particularly preferably 70 or more, in that the adhesion to a metal or the like can be further improved. .. Further, k is preferably 99 or less, more preferably 95 or less, and particularly preferably 90 or less, in that the adhesion to a metal or the like can be further improved.

The method for producing the compound (A1) and the compound (A2) is not particularly limited, and for example, a known production method can be widely adopted. For example, compound (A1) and compound (A2) 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 above production method, for example, by adjusting the amount of the phosphorylating agent used, the amount of the polyoxyalkylene styrenated propenylphenyl ether used, the amount of water used, etc., and the reaction time, the reaction temperature, etc., the compound ( A mixture of A1) and compound (A2) can be obtained, or compound (A1) or compound (A2) can be obtained alone. Therefore, the monomer (A) containing the compound (A1) and the compound (A2) in a predetermined ratio can be produced by adjusting the amount of the phosphorylating agent used in the above production method. Of course, the monomer (A) can also be prepared by separately producing the compound (A1) and the compound (A2) and mixing them in a predetermined ratio.

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, (meth) decyl acrylate, (meth) dodecyl acrylate, (meth) tetradecyl 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 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.

In the aqueous dispersion of the present invention, the polymer can contain a monomer other than the monomer (B) as a constituent monomer. For example, when the polymer is produced in the presence of a reactive emulsifier, such a reactive emulsifier (C) may also be included as a constituent monomer. That is, the reactive emulsifier (C) is a component that can be copolymerized with a monomer component for forming a polymer such as the monomer (A). 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).

The type of the reactive emulsifier (C) is not particularly limited, and for example, known reactive emulsifiers can be widely used, and various anionic reactive emulsifiers and nonionic reactive emulsifiers can be mentioned.

For example, examples of the reactive emulsifier (C) include compounds having a polymerizable unsaturated group and a polyoxyalkylene group. Such a compound is hereinafter referred to as "compound (C1)".

In the compound (C1), 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 one of these is used. Alternatively, it may have two or more types.

In the compound (C1), 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 present. The polyoxyalkylene group preferably contains 50 to 100 mol% of an oxyethylene group, more preferably 70 to 100 mol%, and preferably a polyoxyethylene group.

Compound (C1) can also have an anionic hydrophilic group. In this case, it is possible to enhance the emulsifying effect at the time of emulsion polymerization for obtaining the aqueous dispersion described later. Examples of the anionic hydrophilic group include SO ₃ M group, COM group, PO ₃ M ₂ group, PO ₂ M group and the like, and one or more of these may be present. Here, M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium residue, an alkylammonium residue or an alkanolamine residue. Among these, the SO ₃ M group is preferable as the anionic hydrophilic group.

Specific examples of the compound (C1) include at least one selected from the group consisting of a polyoxyalkylene styrated propenylphenyl ether sulfate ester salt and a polyoxyalkylene alkyl propenylphenyl ether sulfate ester salt. More specifically, at least one selected from the group consisting of the sulfate ester salt represented by the following general formula (3-1) and the sulfate ester salt represented by the following general formula (3-2) can be mentioned.

In formulas (3-1) and (3-2), R ² and R ³ represent a 1-propenyl group or an allyl group (ie, a 2-propenyl group), preferably a 1-propenyl group. The substitution positions of R ² and R ³ are preferably ortho-position and / or para-position, and more preferably the ortho-position.

In the formulas (3-1) and (3-2), m1 indicates 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 formulas (3-1) and (3-2), R ⁴ represents an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 5 to 15 carbon atoms. The substitution position of R ⁴ is preferably ortho and / or para position, more preferably ortho.

In formulas (3-1) and (3-2), A ¹ and A ² have the same meaning as A in the formula (1-1), and represent alkylene groups having 2 to 4 carbon atoms, respectively. Therefore, the ^{oxyalkylene group represented by A 1} O and A ² O is preferably an oxyethylene group, respectively, and when two or more kinds of oxyalkylene groups are contained, one of them is preferably an oxyethylene group. The (A ¹ O) _n1 chain moiety and the (A ² O) _n2 chain moiety each preferably contain 50 to 100 mol% of an oxyethylene group, and more preferably 70 to 100 mol%.

In formulas (3-1) and (3-2), n1 and n2 each indicate the average number of moles of oxyalkylene group added, preferably in the range of 1 to 50, and more preferably 5 to 30. Is.

In formulas (3-1) and (3-2), M is an alkali metal atom such as sodium and potassium, an alkaline earth metal atom such as magnesium and calcium, an ammonium residue, an alkylammonium residue or an alkanolamine residue. Represents. Examples of the alkylammonium residue include a monomethylammonium residue, a dipropylammonium residue and the like, and examples of the alkanolamine residue include a monoethanolamine residue, a diethanolamine residue, a triethanolamine residue and the like. Can be mentioned.

Examples of the anionic reactive emulsifier (hereinafter, “Compound C2”) which is another example of the compound (C1) include a polymerizable unsaturated group and a polyoxyalkylene group (for example, the alkylene has 2 to 4 carbon atoms). Examples thereof include compounds having 1 to 20) oxyalkylene units and anionic groups, respectively. Specific examples of the compound C2 include polyoxyalkylene-1- (allyloxymethyl) alkyl ether sulfate ester and its salt, polyoxyalkylene-1- (allyloxymethyl) alkyl ether phosphoric acid ester and its salt, and polyoxyalkylene. -1-alkoxymethyl-2- (2-propenyloxy) ethyl ether sulfate ester and its salt, polyoxyalkylene-1-alkoxymethyl-2- (2-propenyloxy) ethyl ether phosphate ester and its salt, etc. One or more species selected from the group consisting of. Other examples of anionic reactive emulsifiers include alkylalkenyl sulfosuccinates and the like.

When the reactive emulsifier (C) contains a nonionic reactive emulsifier, the type thereof is not particularly limited as long as it has a polymerizable unsaturated group and is nonionic, for example, known nonionic. Reactive emulsifiers can be widely used. 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 a nonionic reactive emulsifier, the coating film formed from the aqueous dispersion has improved adhesion to metal and abrasion resistance. Cheap. 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 can contain other monomers as constituent monomers in addition to the monomers (A) and the monomers (B) and the reactive emulsifier (C), if necessary. 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 if necessary, the monomer (B), and further contains a reactive emulsifier (reactive emulsifier). C) and / or other monomers can also be included 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 also contain a non-reactive emulsifier, if necessary. 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 such non-reactive emulsifier is not particularly limited, and examples thereof include at least one emulsifier selected from the group consisting of known anionic emulsifiers and nonionic emulsifiers.

Among the non-reactive emulsifiers, 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 anionic emulsifiers include polyoxyalkylene alkyl ether sulfate ester and its salt, polyoxyalkylene alkyl phenyl ether sulfate ester and its salt, polyoxyalkylene alkenyl ether sulfate ester and its salt, and polyoxyalkylene alkenyl phenyl ether sulfate ester. And its salts, polyoxyalkylene styrene phenyl ether sulfate esters and their salts, polyoxyalkylene alkyl ether phosphoric acid esters and their salts, polyoxyalkylene alkenyl ether phosphoric acid esters and their salts, polyoxyalkylene alkyl phenyl ether phosphoric acid esters And its salts, polyoxyalkylene alkenyl phenyl ether phosphate and its salts, polyoxyalkylene styrene phenyl ether phosphate 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 esters and their salts, polyoxyalkylene alkenylphenyl ether acetate esters and their salts, polyoxyalkylene styrene phenyl ether acetate esters and their salts, alkylbenzene sulfonic acid and its salts, alkyl sulphates and their salts, and alkyl phosphates and their salts. The salt is exemplified. 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 includes polyoxyalkylene alkyl ether sulfate ester and its salt, polyoxyalkylene alkylphenyl ether sulfate ester and its salt, polyoxyalkylene alkenyl ether sulfate ester and its salt, and polyoxyalkylene. It is preferable to contain one selected from the group consisting of styrenated phenyl ether sulfate ester and a salt thereof.

Among the non-reactive emulsifiers, examples of the non-ionic emulsifier include compounds having a polyoxyalkylene moiety.

Specific nonionic emulsifiers include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkenyl phenyl ether, polyoxyalkylene styrene phenyl ether, polyoxyalkylene naphthyl ether, and poly. Oxyalkylene triblock polymers (eg, polyoxyethylene polyoxypropylene glycol, etc.) are exemplified. 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 70. It is by mass% or more, more preferably 80% by mass or more.

(Water dispersion)
The aqueous dispersion of the present invention contains the polymer, and may also contain a reactive emulsifier (C) that was not incorporated into the polymer when the reactive emulsifier (C) was used during the production of the polymer. Further, when a non-reactive emulsifier is used in the production of the polymer, such a non-reactive emulsifier is also included in the aqueous dispersion. For example, the non-reactive emulsifier is contained in an amount of 0.01 part by mass or more, preferably 0.05 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the polymer. It is particularly preferable that the amount is 0.2 parts by mass or more. Further, the non-reactive emulsifier is contained in an amount of 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and 5 parts by mass or less with respect to 100 parts by mass of the polymer. Is more preferable, and it is particularly preferable that the amount is 3 parts by mass or less.

The aqueous dispersion contains an aqueous solvent as a medium. 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, in 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 the non-reactive emulsifier as long as the effect of the present invention is 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.

(Manufacturing method of aqueous dispersion)
The method for producing the aqueous dispersion according to the present embodiment is not particularly limited, and for example, a known emulsion 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 a monomer (A), that is, a compound (A1) and a compound (A2). 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.

The emulsifier used in the method for producing an aqueous dispersion includes, for example, the reactive emulsifier (C) and / or a non-reactive emulsifier. When the reactive emulsifier (C) is used in combination, all or part of the reactive emulsifier may be copolymerized with the monomer (A) or the like and incorporated into the polymer, or a part thereof may be incorporated into the polymer. A part of it may remain as it is without being incorporated and may be contained in the aqueous dispersion as an emulsifier or dispersant.

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

In emulsion polymerization, for example, a known polymerization initiator used in emulsion polymerization can be widely used as the polymerization initiator used in the polymerization reaction. 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. In particular, by using the aqueous dispersion according to the present invention, it has excellent adhesion to metals and wear resistance. Since it can form an excellent coating film, it is suitable for use as a coating agent for metals.

(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 metals and excellent wear resistance. 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 has excellent adhesion to metals, excellent wear resistance, and also excellent 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: compound (A1) and compound (A2))
[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, 64.52 g (0.45 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 after completion of the addition. The temperature was raised to 70 ° C. and the reaction was carried out for 5 hours. By such a reaction, a mixture of the compound represented by the following formula (1-1-1) (compound (A1)) and the compound represented by (1-2-1) (compound (A2)) is converted into a monomer (A). Obtained as -1). In the formula, EO represents an oxyethylene group (the same applies hereinafter). When the content ratio k (mol%) of the compound (A1) to the total amount of the compound (A1) and the compound (A2) in the obtained monomer (A-1) ^{was confirmed by 31} P-NMR, it was 90 mol%. rice field.

[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 61.71 g (0.43 mol), the compound represented by the above formula (1-1-1) (compound (A1)). )) And A mixture of the compounds represented by (1-2-1) (compound (A2)) were obtained as the monomer (A-2). When the content ratio k (mol%) of the compound (A1) to the total amount of the compound (A1) and the compound (A2) in the monomer (A) ^{was confirmed by 31} P-NMR, it was 85 mol%.

[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 59.14 g (0.42 mol), the compound represented by the above formula (1-1-1) (compound (A1)). )) And a mixture of the compounds represented by (1-2-1) (compound (A2)) were obtained as the monomer (A-3). When the content ratio k (mol%) of the compound (A1) to the total amount of the compound (A1) and the compound (A2) in the monomer (A) ^{was confirmed by 31} P-NMR, it was 80 mol%.

[Synthesis Example 4: Synthesis of Monomer (A-4)]
By performing the same operation as in Synthesis Example 1 except that the amount of anhydrous phosphoric acid used was 56.78 g (0.40 mol), the compound represented by the above formula (1-1-1) (compound (A1)). )) And a mixture of the compounds represented by (1-2-1) (compound (A2)) were obtained as the monomer (A-4). When the content ratio k (mol%) of the compound (A1) to the total amount of the compound (A1) and the compound (A2) in the monomer (A) ^{was confirmed by 31} P-NMR, it was 75 mol%.

[Synthesis Example 5: Synthesis of Monomer (A-5)]
By performing the same operation as in Synthesis Example 1 except that the amount of anhydrous phosphoric acid used was 54.59 g (0.38 mol), the compound represented by the above formula (1-1-1) (compound (A1)). )) And a mixture of the compounds represented by (1-2-1) (compound (A2)) were obtained as the monomer (A-5). When the content ratio k (mol%) of the compound (A1) to the total amount of the compound (A1) and the compound (A2) in the monomer (A) ^{was confirmed by 31} P-NMR, it was 70 mol%.

[Synthesis Example 6: Synthesis of Monomer (A-6)]
By performing the same operation as in Synthesis Example 2 except that the amount of ethylene oxide used was 220 g (5 mol), the compounds represented by the following formula (1-1-2) (compound (A1)) and (1). A mixture of the compound represented by -2-2) (compound (A2)) was obtained as a monomer (A-6). When the content ratio k (mol%) of the compound (A1) to the total amount of the compound (A1) and the compound (A2) in the monomer (A) ^{was confirmed by 31} P-NMR, it was 85 mol%.

[Synthesis Example 7: Synthesis of Monomer (A-7)]
By reacting 48.3 g of the monomer (A-2) obtained in the same operation as in Synthesis Example 2 with 4.0 g of sodium hydroxide, a mixture of the sodium salt of the compound (A1) and the sodium salt of the compound (A2) ( Hereinafter, it is abbreviated as monomer (A-7)).

[Synthesis Example 8: Synthesis of Monomer (A-8)]
48.3 g of the monomer (A-2) obtained in the same operation as in Synthesis Example 2 was reacted with 6.8 g of 25% ammonia water, and the water was distilled off to distill off the ammonium salt of the compound (A1) and the compound (A2). A mixture of ammonium salts (hereinafter abbreviated as monomer (A-8)) was obtained.

[Synthesis Example 9: Synthesis of Monomer (A-9)]
48.3 g of the monomer (A-2) obtained in the same operation as in Synthesis Example 2 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.

[Synthesis Example 10: 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 39.43 g (0.28 mol), the compound represented by the above formula (1-1-1) (compound (A1)). )) And A mixture of the compounds represented by (1-2-1) (compound (A2)) were obtained as the monomer (a-2). When the content ratio k (mol%) of the compound (A1) to the total amount of the compound (A1) and the compound (A2) in the monomer (A) ^{was confirmed by 31} P-NMR, it was 20 mol%.

(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

(Emulsifier (C))
≪Reactive emulsifier≫
As the reactive emulsifier, (C-1) to (C-8) and (C-27) to (C-29) shown below were prepared.
-(C-1): "Aqualon AR-10" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
-(C-2): "Aqualon KH-10" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
(C-3): "Aqualon BC-10" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
・ (C-4): ADEKA's "Adecaria Soap SR-10"
-(C-5): "SINONATE LRS10" manufactured by Sino-Japan Chemical Co., Ltd.
-(C-6): "Eleminor JS-20" manufactured by Sanyo Chemical Industry Co., Ltd.
・ (C-7): Kao Corporation "Latemuru PD-104"
(C-8): "Maxemul 6106" manufactured by Croda International.
-(C-27): "Aqualon AN-20" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
-(C-28): "Aqualon KN-20" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
・ (C-29): ADEKA's "Adecaria Soap ER-20"

≪Non-reactive emulsifier≫
As the non-reactive emulsifier, the anionic emulsifiers (C-9) to (C-19) shown in Table 1 below and the nonionic emulsifiers (C-20) to (C-26) were prepared. All non-reactive emulsifiers were 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): Monomer obtained in Synthesis Example 10- (a-3): Hydroxyethyl methacrylate phosphoric acid monoester (Product name: Light ester P-1M, Kyoeisha Chemical Co., Ltd.) Made by Co., Ltd.)

(Example 1)
As shown in Table 2 below, 2.5 parts by mass of (A-1) obtained in Synthesis Example 1 as the monomer (A), 123.75 parts by mass of (B-1) as the monomer (B), and (B-2) A preemulsion is formed by mixing 123.75 parts by mass of a mixture, 5 parts by mass of a reactive emulsifier (C-1) as an emulsifier (C), and 107.15 parts by mass of water and emulsifying them. 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)
Same as in Example 1 except that the types and amounts (parts by mass) of the monomer (A), the monomer (B), the emulsifier (C) and the other monomer (a) are changed to the formulations shown in Table 2 below. An aqueous dispersion was obtained by the method. 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)
Same as in Example 1 except that the types and amounts (parts by mass) of the monomer (A), the monomer (B), the emulsifier (C) and the other monomer (a) are changed to the formulations shown in Table 3 below. An aqueous dispersion was obtained by the method. 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 24)
Same as in Example 1 except that the types and amounts (parts by mass) of the monomer (A), the monomer (B), the emulsifier (C) and the other monomer (a) are changed to the formulations shown in Table 4 below. An aqueous dispersion was obtained by the method.

(Examples 25 to 32)
Same as in Example 1 except that the types and amounts (parts by mass) of the monomer (A), the monomer (B), the emulsifier (C) and the other monomer (a) are changed to the formulations shown in Table 5 below. An aqueous dispersion was obtained by the method.

(Examples 33 to 40)
Same as in Example 1 except that the types and amounts (parts by mass) of the monomer (A), the monomer (B), the emulsifier (C) and the other monomer (a) are changed to the formulations shown in Table 6 below. An aqueous dispersion was obtained by the method.

(Examples 41 to 48)
Same as in Example 1 except that the types and amounts (parts by mass) of the monomer (A), the monomer (B), the emulsifier (C) and the other monomer (a) are changed to the formulations shown in Table 7 below. An aqueous dispersion was obtained by the method.

(Comparative Examples 1 to 6)
Same as in Example 1 except that the types and amounts (parts by mass) of the monomer (A), the monomer (B), the emulsifier (C) and the other monomer (a) are changed to the formulations shown in Table 8 below. An aqueous dispersion was obtained by the method.

(Evaluation method)
The water dispersions obtained in each Example and Comparative Example were evaluated for the following adhesion 1, adhesion 2, water whitening resistance, rust prevention and abrasion resistance.

<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 60 ° 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>
Judgment was made in the same manner as for Adhesion 1 except that the drying conditions after coating were changed to 25 ° C. for 30 minutes.

<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 25 ° C. for 30 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 25 ° C. for 30 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

Tables 2 to 8 show the compounding conditions of the aqueous dispersion prepared in each Example or Comparative 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 2 to 7 and the evaluation results shown in Table 8, any one of the specific phosphate esters (A-1) to (A-9) (that is, A-9) as a constituent monomer (that is, The coating film obtained from the aqueous dispersion containing the polymer having the compound (A1) and the compound (A2) having 50 <k <100 as a constituent monomer has extremely high adhesion to the metal (stainless steel). It was also excellent in abrasion resistance. Further, these coating films also have excellent water whitening resistance and rust prevention. In particular, from the comparison between Comparative Example 5 and each example, it was found that the adhesion of the coating film became remarkable when 50 <k <100.

Claims

As a constituent monomer, a polymer containing a compound (A1) represented by the following general formula (1-1) and a compound (A2) represented by the following formula (1-2) is contained in the polymer. When the content ratio of the compound (A1) to the total amount of the compound (A1) and the compound (A2) is k (mol%), the value of k is 50 <k <100, an aqueous dispersion.

(In formula (1-1) and formula (1-2), R represents a 1-propenyl group or an allyl group, L represents a counter ion, A represents an alkylene group having 2 to 4 carbon atoms, and x. Is the number of substituents in the range of 1 to 3, y is the number of substituents in the range of 1 to 3, and n is the average number of added moles of the oxyalkylene group, which is in the range of 0 to 100.)
The water according to claim 1, 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. Dispersion.
The L in the formula (1-1) and the L in the formula (1-2) are the same or different and consist of hydrogen ion, alkali metal ion, alkaline earth metal ion, ammonium ion, and organic ammonium ion. The aqueous dispersion according to claim 1 or 2, which is at least one selected from the group.
A coating agent for metals, which comprises the aqueous dispersion according to any one of claims 1 to 3.
A coating film obtained by using the aqueous dispersion according to any one of claims 1 to 3 or the metal coating agent according to claim 4.