JP5924536B2 - Metal surface treatment agent and metal material treated with the surface treatment agent - Google Patents

Description

  The present invention relates to a metal surface treatment agent that can be used for surface treatment of a metal material. More specifically, a surface treatment agent for metal that provides excellent durability, rust prevention, workability, etc., excellent in adhesion to a metal material and on the surface of the metal material, and a metal material treated with the surface treatment agent About.

Conventionally, chrome-treated steel sheets for primary rust prevention treatment that have been electroplated or hot-dip galvanized and further chrome-treated are used for metal workpieces such as building materials, automobiles, home appliances, transformers, and motors.
This chromium treatment is performed to improve the rust resistance of the steel sheet, but the chromate used has been pointed out to have environmental impacts, health problems, etc. Development is required.

On the other hand, various organic resins such as acrylic resins, from the improvement of workability, punchability, rust prevention, etc.
Surface treatment agents using urethane resins, olefin resins, epoxy resins and the like are also used. However, the surface treatment agent of these organic resins alone is insufficient in rust prevention, so that it is usually used in combination with the chromium treatment agent, and the transition to non-chromium is also required.

In response to these requirements, for example, a technique relating to a non-chromium steel surface treatment agent made of an organic resin and scaly silica particles and a non-chromium anticorrosive agent has been reported (for example, see Patent Document 1). .

However, since the surface treatment agent described in Patent Document 1 contains scaly silica,
There was a problem in the stability as a composition, and the antirust property was insufficient.

JP 2003-253462 A

The problem to be solved by the present invention is a non-chromium system that does not require the addition of a chromium-based compound such as chromate, exhibits excellent adhesion to metal materials, and is excellent in durability, rust prevention, workability, etc. And a metal material treated with the surface treatment agent.

  As a result of intensive studies, the present inventors have found that a two-component metal containing a composite resin in which a polysiloxane segment having an epoxy group and a vinyl polymer segment are bonded by a specific bond, and a polyisocyanate as a curing agent. A surface treatment agent for a metal surface wherein the mass ratio of the polysiloxane segment in the composite resin, the epoxy equivalent of the composite resin, the amount of hydroxyl group in the vinyl polymer segment, and the mass ratio of the polyisocyanate are within a specific range. Even if the treatment agent is non-chromic, it has excellent adhesion to the metal material, and can impart durability, rust prevention, workability, etc. excellent to the metal material. The metal material treated in this way was found to be excellent in durability, rust resistance and workability, and the present invention was completed.

  That is, the present invention provides a polysiloxane segment (a1) having a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, and an epoxy group. A composite resin (A) in which a vinyl polymer segment (a2) having an alcoholic hydroxyl group is bonded by a bond represented by the general formula (3), and a polyisocyanate (B) It is an agent, Comprising: The mass ratio of the said polysiloxane segment (a1) in solid content of the said composite resin (A) is 20-70 mass%, The epoxy equivalent of the solid content of the said composite resin (A) is 900- 17,000 g / eq, the hydroxyl group value of the vinyl polymer segment (a2) is 50 to 200 mgKOH / g, and the mass ratio of the polyisocyanate (B) is totally solid. To provide a metal surface treatment agent which is a 5 to 50 mass% in min.

(In the general formulas (1) and (2), R ¹ , R ² and R ³ are each independently -R ⁴ -CH = CH ₂ , -R ⁴ -C (CH ₃ ) = CH ₂ ,- A group having one polymerizable double bond selected from the group consisting of R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ and —R ⁴ —O—CO—CH═CH ₂ (provided that R ⁴ Represents a single bond or an alkylene group having 1 to 6 carbon atoms.), An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or 7 carbon atoms. Represents an aralkyl group of ˜12.)

（一般式（３）中、炭素原子は前記ビニル系重合体セグメント（ａ２）の一部分を構成し、酸素原子のみに結合したケイ素原子は、前記ポリシロキサンセグメント（ａ１）の一部分を構成するものとする）

(In the general formula (3), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1). To do)

  In addition, the present invention provides a metal material characterized by being treated with the metal surface treatment agent.

  The metal surface treatment agent of the present invention can easily apply a surface treatment excellent in durability, rust prevention and workability to a metal material.

  The metal surface treatment agent of the present invention has the structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, and an epoxy group. A composite resin (A) in which a polysiloxane segment (a1) and a vinyl polymer segment (a2) having an alcoholic hydroxyl group are bonded by a bond represented by the general formula (3); and a polyisocyanate (B) A metal surface treatment agent containing a solid content of the composite resin (A), wherein a mass ratio of the polysiloxane segment (a1) in the solid content of the composite resin (A) is 20 to 70% by mass. Epoxy equivalent is 900 to 17000 g / eq, the hydroxyl value of the vinyl polymer segment (a2) is 50 to 200 mg KOH / g, and the polyisocyanate ( Mass ratio of) are those wherein 5 to 50 mass% of the total solids.

(Composite resin (A))
The composite resin (A) used in the present invention comprises a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, an epoxy group, A polysiloxane segment (a1) having the following (hereinafter simply referred to as polysiloxane segment (a1)), a vinyl polymer segment (a2) having an alcoholic hydroxyl group (hereinafter simply referred to as vinyl polymer segment (a2)), and Is a composite resin bonded by a bond represented by the general formula (3).

A silanol group and / or hydrolyzable silyl group possessed by the polysiloxane segment (a1) described later and a silanol group and / or hydrolyzable silyl group possessed by the vinyl polymer segment (a2) described below undergo a dehydration condensation reaction. Thus, the bond represented by the general formula (3) is generated. Accordingly, in the general formula (3), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1). And
The form of the composite resin (A) is, for example, a composite resin having a graft structure in which the polysiloxane segment (a1) is chemically bonded as a side chain of the polymer segment (a2), or the polymer segment (a2). And a composite resin having a block structure in which the polysiloxane segment (a1) is chemically bonded.

(Composite resin (A) Polysiloxane segment (a1))
The polysiloxane segment (a1) in the present invention comprises a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, and an epoxy group. It has a segment.

(Structural unit represented by general formula (1) and / or general formula (2))
Specifically, R ¹ , R ² and R ³ in the general formulas (1) and (2) are each independently —R ⁴ —CH═CH ₂ , —R ⁴ —C (CH ₃ ) = A group having one polymerizable double bond selected from the group consisting of CH ₂ , —R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ , and R ⁴ —O—CO—CH═CH ₂ (provided that R ⁴ represents a single bond or an alkylene group having 1 to 6 carbon atoms.), An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or 7 to 7 carbon atoms. 12 aralkyl groups are represented.

Examples of the alkylene group having 1 to 6 carbon atoms in R ⁴ include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, and pentylene. Group, isopentylene group, neopentylene group, tert-pentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohexylene group, 1-methylpentylene Group, 2-methylpentylene group, 3-methylpentylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1,1, 2-trimethylpropylene group, 1,2,2-trimethylpropylene group, 1-ethyl-2-methyl Examples include a propylpropylene group and a 1-ethyl-1-methylpropylene group. Among these, R ⁴ is preferably a single bond or an alkylene group having 2 to 4 carbon atoms because of easy availability of raw materials.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and isopentyl. Group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl Group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2 , 2-trimethylpropyl group, 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group, and the like.
Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

Further, when at least one of R ¹ , R ² and R ³ is a group having the polymerizable double bond, it can be cured by active energy rays or the like, active energy rays, silanol groups and / or It is preferable from the viewpoint that a cured coating film having more excellent durability and scratch resistance can be formed by two curing mechanisms of improving the crosslinking density of the coating film by the condensation reaction of hydrolyzable silyl groups.
It is preferable that two or more groups having a polymerizable double bond exist in the polysiloxane segment (a1), more preferably 3 to 200, more preferably 3 to 50, A coating film having more excellent scratch resistance can be obtained. Specifically, if the content of the polymerizable double bond in the polysiloxane segment (a1) is 3 to 35% by mass, desired scratch resistance can be obtained. The polymerizable double bond here is a general term for groups capable of performing a growth reaction by free radicals among vinyl group, vinylidene group or vinylene group. Moreover, the content rate of a polymerizable double bond shows the mass% in the polysiloxane segment of the said vinyl group, vinylidene group, or vinylene group.
As the group having a polymerizable double bond, all known functional groups containing the vinyl group, vinylidene group, and vinylene group can be used. Among them, —R ⁴ —C (CH ₃ ) = The (meth) acryloyl group represented by CH ₂ or —R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ is rich in reactivity at the time of ultraviolet curing, and a vinyl polymer segment (described later) Good compatibility with a2).

  The structural unit represented by the general formula (1) and / or the general formula (2) is a three-dimensional network-like polysiloxane structural unit in which two or three of the silicon bonds are involved in crosslinking. Since a three-dimensional network structure is formed but a dense network structure is not formed, gelation or the like is not caused and storage stability is also improved.

(Composite resin (A) Epoxy group)
The said polysiloxane segment (a1) which comprises the composite resin (A) in this invention has an epoxy group, and the epoxy equivalent of the solid content of a composite resin (A) is 900-17000g / eq. Since it is excellent in long-term storage stability as it is 2500-6000 g / eq, it is especially preferable. When the epoxy equivalent of solid content is larger than 17000 g / eq, the composite resin (A) is easily gelled and cannot be stored for a long time. Moreover, when smaller than 900 g / eq, it is inferior to curability as a surface treating agent.

  In order to introduce an epoxy group into the polysiloxane segment (a1), a silane compound having an epoxy group may be used during the production of the composite resin (A) described later. Examples of the silane compound having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltriacetoxysilane, γ-glycidoxypropyldimethoxymethylsilane, γ-glycidoxypropyldiethoxymethylsilane, γ-glycidoxypropyldimethoxyethoxymethylsilane, γ-glycidoxypropyldia SE Xylmethylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyethoxymethylsilane , Β- (3,4-epoxycyclohexyl) ethyldiacetoxymethylsilane, γ-glycidoxypropyldimethoxyethylsilane, γ-glycidoxypropyldiethoxyethylsilane, γ-glycidoxypropyldimethoxyethoxyethylsilane, γ -Glycidoxypropyldiacetoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxyethylsilane, β- (3,4-epoxycyclohexyl) Shi ) Ethyldimethoxyethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyldiacetoxyethylsilane, γ-glycidoxypropyldimethoxyisopropylsilane, γ-glycidoxypropyldiethoxyisopropylsilane, γ-glycidoxypropyl Dimethoxyethoxyisopropylsilane, γ-glycidoxypropyldiacetoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldiacetoxyisopropylsilane, γ-glycidoxypropylmethoxy Sidimethylsilane, γ-glycidoxypropylethoxydimethylsilane, γ-glycidoxypropylmethoxyethoxydimethylsilane, γ-glycidoxypropylacetoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylacetoxydimethylsilane, γ-glycid Xylpropylmethoxydiethylsilane, γ-glycidoxypropylethoxydiethylsilane, γ-glycidoxypropylmethoxyethoxydiethylsilane, γ-glycidoxypropylacetoxydiethylsilane, β- (3,4-epoe Cycyclohexyl) ethylmethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethyl Acetoxydiethylsilane, γ-glycidoxypropylmethoxydiisopropylsilane, γ-glycidoxypropylethoxydiisopropylsilane, γ-glycidoxypropylmethoxyethoxydiisopropylsilane, γ-glycidoxypropylacetoxydiisopropylsilane, β- (3, 4-epoxycyclohexyl) ethylmethoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) ethylethoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) ) Ethylmethoxyethoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) ethylacetoxydiisopropylsilane, γ-glycidoxypropylmethoxyethoxymethylsilane, γ-glycidoxypropylacetoxymethoxymethylsilane, γ-glycidoxypropyl Acetoxyethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyacetoxymethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxyacetoxy Methylsilane, γ-glycidoxypropylmethoxyethoxyethylsilane, γ-glycidoxypropylacetoxymethoxyethylsilane, γ-glycidoxypropylacetoxyethoxyethyl Lan, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyacetoxyethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxyacetoxyethylsilane, γ-glycidoxypropylmethoxyethoxyisopropylsilane, γ-glycidoxypropylacetoxymethoxyisopropylsilane, γ-glycidoxypropylacetoxyethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxyisopropylsilane, β -(3,4-epoxycyclohexyl) ethylmethoxyacetoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethylethoxyacetoxyisopropylsilane, glycidoxy Methyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltrimethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltri Ethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltri Phenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltri Methoxysilane, γ-g Sidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltryptoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4 Epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethyl Methyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidyl Sidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ -Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylme Tildiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycyl Sidoxypropylvinyldiethoxysilane and the like can be mentioned.

(Composite resin (A) Silanol group and / or hydrolyzable silyl group)
In the present invention, the silanol group is a silicon-containing group having a hydroxyl group directly bonded to a silicon atom. Specifically, the silanol group is a silanol group formed by combining an oxygen atom having a bond with a hydrogen atom in the structural unit represented by the general formula (1) and / or the general formula (2). Preferably there is.

  In the present invention, the hydrolyzable silyl group is a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom, and specifically includes, for example, a group represented by the general formula (4). .

(In the general formula (4), R ⁵ is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R ⁶ is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, (It is a hydrolyzable group selected from the group consisting of an amino group, an amide group, an aminooxy group, an iminooxy group and an alkenyloxy group, and b is an integer of 0 to 2.)

Examples of the alkyl group in R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a tert group. -Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl Group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group and the like.
Moreover, as an aryl group, a phenyl group, a naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-vinylphenyl group, 3-isopropylphenyl group etc. are mentioned, for example.
Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

In R ⁶ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, and a sec-butoxy group.
Examples of the acyloxy group include formyloxy group, acetoxy group, propanoyloxy group, butanoyloxy group, pivaloyloxy group, pentanoyloxy group, phenylacetoxy group, acetoacetoxy group, benzoyloxy group, naphthoyloxy group Etc.
Examples of the aryloxy group include a phenyloxy group and a naphthyloxy group.
Examples of the alkenyloxy group include a vinyloxy group, an allyloxy group, a 1-propenyloxy group, an isopropenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, a 2-petenyloxy group, and a 3-methyl-3-butenyloxy group. , 2-hexenyloxy group and the like.

By hydrolyzing the hydrolyzable group represented by R ⁶ , the hydrolyzable silyl group represented by the general formula (4) becomes a silanol group. Among these, a methoxy group and an ethoxy group are preferable because of excellent hydrolyzability.
The hydrolyzable silyl group specifically includes an oxygen atom having a bond in the structural unit represented by the general formula (1) and / or the general formula (2) bonded to the hydrolyzable group. Or it is preferable that it is the hydrolyzable silyl group substituted.

Since the silanol group or the hydrolyzable silyl group undergoes a hydrolytic condensation reaction between the hydroxyl group in the silanol group or the hydrolyzable group in the hydrolyzable silyl group, the polysiloxane structure of the resulting coating film The crosslink density increases, and a coating film excellent in durability and the like can be formed.
Further, the polysiloxane segment (a1) containing the silanol group or the hydrolyzable silyl group is bonded to the vinyl polymer segment (a2) described later via the bond represented by the general formula (3). Use when.

In addition, examples of the structure in which at least one of R ¹ , R ^2, and R ³ is a group having the polymerizable double bond as the polysiloxane segment (a1) include the following structures.

  In this invention, it is important that the mass ratio of the said polysiloxane segment (a1) in solid content of the said composite resin (A) is 20-70 mass%, and, thereby, it was excellent as a surface treating agent. , Durability, adhesion, and rust prevention can be exhibited.

(Composite resin (A) vinyl polymer segment (a2))
The vinyl polymer segment (a2) in the present invention is a vinyl polymer segment such as an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, an aromatic vinyl polymer, and a polyolefin polymer. .

  The acrylic polymerizable segment is obtained by polymerizing or copolymerizing a general-purpose (meth) acrylic monomer. The (meth) acrylic monomer is not particularly limited, and vinyl monomers can also be copolymerized. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) Alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms such as acrylate and lauryl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; ω-alkoxyalkyl such as 2-methoxyethyl (meth) acrylate and 4-methoxybutyl (meth) acrylate ( ) Acrylates; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and other carboxylic acid vinyl esters; methyl crotonate, alkyl crotonate and other alkyl esters; dimethyl malate, di-n -Dialkyl esters of unsaturated dibasic acids such as butyl malate, dimethyl fumarate and dimethyl itaconate; α-olefins such as ethylene and propylene; vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene and the like Fluoroolefins; alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; N, N-dimethyl (meth) Acrylamide, N- (meth) acryloyl morpholine, N- (meth) acryloyl pyrrolidine, tertiary amide group-containing monomers such as N- vinylpyrrolidone and the like.

  There are no particular limitations on the polymerization method, solvent, or polymerization initiator for copolymerizing the monomers, and the vinyl polymer segment (a2) can be obtained by a known method. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-) can be obtained by various polymerization methods such as bulk radical polymerization, solution radical polymerization, and non-aqueous dispersion radical polymerization. Dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di- The vinyl polymer segment (a2) can be obtained by using a polymerization initiator such as tert-butyl peroxide, cumene hydroperoxide, diisopropyl peroxycarbonate or the like.

  As the number average molecular weight of the vinyl polymer segment (a2), it is possible to prevent thickening and gelation during the production of the composite resin (A), and to form a coating film having excellent durability and workability. In terms of number average molecular weight (hereinafter abbreviated as “Mn”), it is preferably in the range of 500 to 200,000, more preferably in the range of 700 to 100,000, and 1,000 to 50,000. The range of is particularly preferable.

  In addition, the vinyl polymer segment (a2) is a vinyl polymer segment (A1) in order to form a composite resin (A) bonded to the polysiloxane segment (a1) by a bond represented by the general formula (3). It has a silanol group and / or a hydrolyzable silyl group directly bonded to the carbon atom in a2). Since these silanol groups and / or hydrolyzable silyl groups become bonds represented by the general formula (3) in the production of the composite resin (A) described later, the composite resin (A) which is the final product. There is almost no vinyl polymer segment (a2). However, there is no problem even if a silanol group and / or a hydrolyzable silyl group remain in the vinyl polymer segment (a2), and when a coating film is formed by a curing reaction of the group having a polymerizable double bond, In parallel with the curing reaction, a hydrolytic condensation reaction proceeds between the hydroxyl group in the silanol group or the hydrolyzable group in the hydrolyzable silyl group. It is possible to form a coating film that is enhanced and has excellent durability and the like.

Specifically, the vinyl polymer segment (a2) having a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom includes the above-mentioned general-purpose monomer and a silanol group directly bonded to a carbon atom and / or It is obtained by copolymerizing a vinyl monomer having a hydrolyzable silyl group.
Examples of vinyl monomers having a silanol group and / or hydrolyzable silyl group directly bonded to a carbon atom include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri (2-methoxyethoxy) silane, Vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyl Examples include dimethoxysilane and 3- (meth) acryloyloxypropyltrichlorosilane. Among them, vinyltrimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane are preferable because the hydrolysis reaction easily proceeds and by-products after the reaction can be easily removed.

(Hydroxyl value of vinyl polymer segment (a2))
In order to cure the curable resin composition containing the composite resin (A) and the polyisocyanate (B), the vinyl polymer segment (a2) has an alcoholic hydroxyl group. It is important for the vinyl polymer segment (a2) to have a hydroxyl value of 50 to 200 mgKOH / g because it reacts with the polyisocyanate (B) and cures at room temperature, preferably in the range of 90 to 200 mgKOH / g. . When the hydroxyl value is less than 50 mgKOH / g, it is difficult to react with the polyisocyanate (B), so it does not cure at room temperature, and when the hydroxyl value is more than 200 mgKOH / g, gelation occurs during the synthesis of the composite resin (A). Is not preferable.

  The vinyl polymer segment (a2) having an alcoholic hydroxyl group can be obtained by copolymerizing a (meth) acrylic monomer having an alcoholic hydroxyl group. Specific examples of the (meth) acrylic monomer having an alcoholic hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl Monobutyl fumarate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, “Placcel FM” or “Placcel FA” (both are caprolactone-added mono products of Daicel Chemical Industries, Ltd.) Over) various such alpha, beta-hydroxyalkyl esters of ethylenically unsaturated carboxylic acid or an adduct thereof with ε- caprolactone, and the like. Of these, 2-hydroxyethyl (meth) acrylate is preferable because it is easy to react.

(Production method of composite resin (A))
Specifically, the composite resin (A) used in the present invention is produced by the methods shown in the following (Method 1) to (Method 3).

(Method 1) The general-purpose (meth) acrylic monomer and the silanol group directly bonded to the carbon atom by copolymerizing the vinyl monomer having a silanol group and / or a hydrolyzable silyl group directly bonded to the carbon atom. And / or the vinyl polymer segment (a2) having a hydrolyzable silyl group is obtained. This and a silane compound are mixed and hydrolytic condensation reaction is carried out. At this time, in order to introduce an epoxy group into the resulting polysiloxane, a silane compound having both a silanol group and / or a hydrolyzable silyl group and an epoxy group is simultaneously used. In addition, when there are other groups to be introduced, a silane compound having the group to be introduced is used in combination. For example, when an aryl group is introduced, a silane compound having both an aryl group and a silanol group and / or a hydrolyzable silyl group may be appropriately used in combination. When a group having a polymerizable double bond is introduced, a silane compound having both a group having a polymerizable double bond and a silanol group and / or a hydrolyzable silyl group may be used in combination.
In this method, a silanol group or a hydrolyzable silyl group of a silane compound, a silanol group directly bonded to a carbon atom and / or a vinyl polymer segment (a2) having a hydrolyzable silyl group, and / or Alternatively, a hydrolytic condensation reaction with a hydrolyzable silyl group forms a polysiloxane segment (a1) having the epoxy group, a polysiloxane segment (a1) having the epoxy group, and a vinyl polymer segment ( A composite resin (A) in which a2) is combined with the bond represented by the general formula (3) is obtained.

  (Method 2) In the same manner as in Method 1, a vinyl polymer segment (a2) having a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom is obtained. On the other hand, a silane compound (in order to introduce an epoxy group, a silane compound having both a silanol group and / or a hydrolyzable silyl group and an epoxy group is used. The polysiloxane segment (a1) having an epoxy group is obtained by hydrolytic condensation reaction. Then, the silanol group and / or hydrolyzable silyl group of the vinyl polymer segment (a2) and the silanol group and / or hydrolyzable silyl group of the polysiloxane segment (a1) having an epoxy group are hydrolyzed. A decomposition condensation reaction is performed.

  (Method 3) Similarly to Method 1, a vinyl polymer segment (a2) having a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom is obtained. On the other hand, in the same manner as in Method 2, a polysiloxane segment which may or may not have an epoxy group is obtained. Furthermore, in order to introduce an epoxy group into the polysiloxane segment, if there is a silane compound having both a silanol group and / or a hydrolyzable silyl group and an epoxy group, and another group to be introduced, if necessary, Then, a silane compound or the like having a group to be introduced is mixed and subjected to a hydrolytic condensation reaction to obtain a polysiloxane segment (a1) having an epoxy group.

  Further, as a silane compound having both a group having a polymerizable double bond and a silanol group and / or a hydrolyzable silyl group used when introducing a group having a polymerizable double bond, for example, vinyltrimethoxy Silane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrichlorosilane and the like are used in combination. Among them, vinyltrimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane are preferable because the hydrolysis reaction easily proceeds and by-products after the reaction can be easily removed.

  In addition, as general-purpose silane compounds used in the (Method 1) to (Method 3), for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n- Various organotrialkoxysilanes such as propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, methylcyclohexyldimethoxysilane, etc. Various diorganodialkoxysilanes; chlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, and diethyldichlorosilane . Of these, organotrialkoxysilanes and diorganodialkoxysilanes that can easily undergo a hydrolysis reaction and easily remove by-products after the reaction are preferable.

  In addition, a tetrafunctional alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane or tetra n-propoxysilane or a partial hydrolysis condensate of the tetrafunctional alkoxysilane compound may be used in combination as long as the effects of the present invention are not impaired. it can. When the tetrafunctional alkoxysilane compound or a partially hydrolyzed condensate thereof is used in combination, the silicon atoms of the tetrafunctional alkoxysilane compound are 20 with respect to the total silicon atoms constituting the polysiloxane segment (a1). It is preferable to use together so that it may become the range which does not exceed mol%.

  In addition, a metal alkoxide compound other than a silicon atom such as boron, titanium, zirconium, or aluminum can be used in combination with the silane compound as long as the effects of the present invention are not impaired. For example, it is preferable to use the metal alkoxide compound in combination within a range not exceeding 25 mol% with respect to all silicon atoms constituting the polysiloxane segment (a1).

  In the hydrolysis condensation reaction in the (Method 1) to (Method 3), a part of the hydrolyzable group is hydrolyzed under the influence of water or the like to form a hydroxyl group, and then the hydroxyl groups or the hydroxyl group and the hydrolysis are hydrolyzed. This refers to a condensation reaction that proceeds with a functional group. The hydrolysis-condensation reaction can be performed by a known method, but a method in which the reaction is advanced by supplying water and a catalyst in the production process is simple and preferable.

  Examples of the catalyst used include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; tetraisopropyl titanate , Titanates such as tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1 Compounds having various basic nitrogen atoms such as 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole; Methyl ammonium salt, tetrabutyl ammonium salt, dilauryl dimethyl ammonium Quaternary ammonium salts having chloride, bromide, carboxylate or hydroxide as a counter anion; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetate Examples thereof include tin carboxylates such as narate, tin octylate and tin stearate. A catalyst may be used independently and may be used together 2 or more types.

  The amount of the catalyst added is not particularly limited, but in general, it is preferably used in the range of 0.0001 to 10% by mass with respect to the total amount of each compound having the silanol group or hydrolyzable silyl group. , More preferably in the range of 0.0005 to 3% by mass, and particularly preferably in the range of 0.001 to 1% by mass.

The amount of water to be supplied is preferably 0.05 mol or more with respect to 1 mol of the silanol group or hydrolyzable silyl group of each compound having the silanol group or hydrolyzable silyl group, The above is more preferable, and particularly preferably 0.5 mol or more.
These catalyst and water may be supplied collectively or sequentially, or may be supplied by previously mixing the catalyst and water.

  The reaction temperature for carrying out the hydrolytic condensation reaction in the above (Method 1) to (Method 3) is suitably in the range of 0 ° C to 150 ° C, and preferably in the range of 20 ° C to 100 ° C. The reaction can be carried out under any conditions of normal pressure, increased pressure, or reduced pressure. Moreover, you may remove the alcohol and water which are the by-products which can be produced | generated in the said hydrolysis-condensation reaction by methods, such as distillation, as needed.

  The charging ratio of each compound in the (Method 1) to (Method 3) is appropriately selected depending on the desired structure of the composite resin (A) used in the present invention. Among them, it is important to obtain the composite resin (A) so that the content of the polysiloxane segment (a1) is 20 to 70% by mass because the obtained coating film is excellent in durability, adhesion, and rust prevention. 30 to 70% by mass is preferable.

  In the above (Method 1) to (Method 3), as a specific method for conjugating the polysiloxane segment and the vinyl polymer segment in a block shape, the above-mentioned silanol groups and the above-mentioned silanol groups at only one or both ends of the polymer chain may be used. For example, in the case of (Method 1), a silane compound is mixed with the vinyl polymer segment, and a hydrolyzable silyl group-containing vinyl polymer segment is used as an intermediate. The method of carrying out decomposition condensation reaction is mentioned.

  On the other hand, in the above (Method 1) to (Method 3), as a specific method of complexing the polysiloxane segment to the vinyl polymer segment in a graft form, the main chain of the vinyl polymer segment is The vinyl polymer segment having a structure in which silanol groups and / or hydrolyzable silyl groups are randomly distributed is used as an intermediate. For example, in the case of (Method 2), the vinyl polymer segment is Examples thereof include a method of subjecting the silanol group and / or hydrolyzable silyl group and the silane compound to a hydrolytic condensation reaction.

(Polyisocyanate (B))
The metal surface treating agent in the present invention contains the composite resin (A) and the polyisocyanate (B). At this time, it is important that the hydroxyl value of the vinyl polymer segment (a2) constituting the composite resin (A) is 50 to 200 mgKOH / g. Moreover, it is important that the mass ratio of the polyisocyanate (B) is 5 to 50% by mass in the total solid content of the metal surface treatment agent of the present invention. By including the polyisocyanate in this range, excellent durability and processability can be exhibited.

  There is no limitation in particular as polyisocyanate (B) to be used, A well-known thing can be used. For example, aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4′-diisocyanate; aralkyl diisocyanates such as meta-xylylene diisocyanate and α, α, α ′, α′-tetramethyl-meta-xylylene diisocyanate Polyisocyanates mainly composed of tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter abbreviated as “HDI”), 2,2,4- (or 2,4,4) 4-trimethyl-1,6-hexamethylene diisocyanate, lysine isocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,4-diisocyanate cyclohexane, 1,3-bi (Diisocyanate methyl) cyclohexane, aliphatic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate. Among them, aliphatic polyisocyanate from the viewpoint of durability is particularly preferred.

  Examples of the aliphatic polyisocyanate obtained from the aliphatic diisocyanate include allophanate type polyisocyanate, biuret type polyisocyanate, adduct type polyisocyanate, and isocyanurate type polyisocyanate, and any of them can be suitably used.

  In addition, as the above-described polyisocyanate, so-called blocked polyisocyanate compounds blocked with various blocking agents can be used. Examples of the blocking agent include alcohols such as methanol, ethanol and lactic acid esters; compounds having a phenolic hydroxyl group such as phenol and salicylic acid ester; amides such as ε-caprolactam and 2-pyrrolidone; acetone oxime, methyl ethyl ketoxime and the like Oximes: Active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone and the like can be used.

  The above various polyisocyanates may be used alone or in combination.

  It is preferable from the point of the workability of the cured coating film that the isocyanate group in the said polyisocyanate is 5-50 mass%. When the isocyanate group in the polyisocyanate is more than 50%, the molecular weight of the polyisocyanate becomes small, and the processability due to stress relaxation may not be exhibited. The reaction between the polyisocyanate and the hydroxyl group in the system (this is a hydroxyl group in the active energy ray-curable monomer having a hydroxyl group of the vinyl polymer segment (a2) or an alcoholic hydroxyl group described later) is particularly heated. It is not necessary, and it reacts gradually by leaving it at room temperature. If necessary, the reaction between the alcoholic hydroxyl group and the isocyanate may be promoted by heating at 80 ° C. for several minutes to several hours (20 minutes to 4 hours). In that case, you may use a well-known urethanation catalyst as needed. The urethanization catalyst is appropriately selected according to the desired reaction temperature.

(Long-term storage stability and film properties)
In the surface treatment agent for metal in the present invention, the mass ratio of the polysiloxane segment (a1) in the solid content of the composite resin (A) is 20 to 70% by mass, and the solid content of the composite resin (A) is The epoxy equivalent is 900-17000 g / eq, the hydroxyl value of the vinyl polymer segment (a2) is 50-200 mgKOH / g, and the mass ratio of the polyisocyanate (B) is 5-50 in the total solid content. When the content is% by mass, the composite resin (A) is excellent in storage stability and can exhibit excellent durability, adhesion, workability, and rust resistance as a surface treatment agent.

  When the epoxy equivalent of the solid content of the composite resin (A) is smaller than 900 g / eq, it is inferior in curability as a surface treatment agent. On the other hand, when the epoxy equivalent of solid content is larger than 17000 g / eq, the long-term storage stability of the composite resin (A) is not maintained.

  Moreover, when the hydroxyl value of the vinyl polymer segment (a2) is smaller than 50 mgKOH / g, the crosslinking density when the cured coating film is formed becomes insufficient, and the cured coating film has sufficient durability. Absent. On the other hand, when the hydroxyl value of the vinyl polymer segment (a2) is larger than 200 mgKOH / g, gelation occurs during the polymerization of the vinyl polymer segment (a2), and a composite resin cannot be obtained.

  As mentioned above, when the epoxy equivalent of solid content exists in the range of 900-17000 g / eq, sclerosis | hardenability is obtained as long-term storage stability of a composite resin (A) and a surface treating agent. Similarly, when the hydroxyl value of the vinyl polymer segment (a2) is in the range of 50 to 200 mg KOH / g, the cured coating film has excellent durability.

(Curing method)
The surface treatment agent for metals of the present invention, after mixing the composite resin (A) and the polyisocyanate (B), is allowed to stand at room temperature for about 1 to 10 days, more preferably about 3 to 10 days, and is dried. Thus, a highly practical cured film can be obtained.

  Alternatively, when faster curing is desired, a highly practical cured coating film can be obtained by baking within a temperature range of about 80 to 250 ° C. for about 30 seconds to 2 hours. Is possible.

(Other compounds)
The metal surface treatment agent of the present invention may use a dispersion medium for the purpose of adjusting the solid content and viscosity of the dispersion. Any liquid medium that does not impair the effects of the present invention may be used, and examples thereof include the above organic solvents and liquid organic polymers.

Moreover, although the metal surface treatment agent of the present invention can be cured at room temperature, it may be thermally cured by adding various catalysts. It is preferable to select each catalyst in consideration of the reaction temperature, reaction time, etc. of the urethanization reaction between an alcoholic hydroxyl group and an isocyanate.
Moreover, it is also possible to use a thermosetting resin together. Examples of the thermosetting resin include vinyl resins, unsaturated polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicon resins, and modified resins thereof.

  In addition, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, dyes, leveling agents, rheology control agents, UV absorbers, antioxidants, or as necessary Various additives such as a plasticizer can also be used.

(Coating and curing on base material)

  Such a metal surface treatment agent of the present invention can be easily applied to a metal material surface and cured to obtain a metal material excellent in durability, adhesion, rust prevention, and workability.

  The film thickness of the coating film formed using the metal surface treatment agent of the present invention is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 0.3 to 50 μm, It is especially preferable that it is 0.3-30 micrometers. If it is the film thickness in the said range, the crack which may arise in a cured coating film can be suppressed and the cured coating film which has the outstanding rust prevention property can be formed.

  Examples of the method for applying the metal surface treatment agent of the present invention to a metal material include, for example, a roller coating method, a spray coating method, a dip coating method, a flow coater coating method, a roll coater coating method, a brush coating method, and an electrodeposition method. Various coating methods such as a coating method can be applied.

  After applying the metal surface treatment agent of the present invention to the steel sheet surface by the coating method, it is allowed to stand at room temperature for about 1 to 10 days, or at a temperature range of 60 to 600 ° C. for about 10 seconds to 2 hours, preferably 80. By heating in a temperature range of ˜250 ° C. for 30 seconds to 2 hours, a metal material having a coating film excellent in durability, adhesion, rust prevention, workability and the like is obtained.

  Next, the present invention will be specifically described with reference to examples and comparative examples.

(Synthesis Example 1: Synthesis of polysiloxane (a-1-1))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, methyltrimethoxysilane (hereinafter abbreviated as “MTMS”) 1417.0 parts by mass, γ-glycidoxy 83.0 parts by mass of propyltrimethoxysilane (hereinafter abbreviated as “GPTMS”) was charged, and the temperature was raised to 60 ° C. while stirring under aeration of nitrogen gas. Next, a mixture consisting of 0.20 parts by mass of “Phoslex A-4” (normal butyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 211.1 parts by mass of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C. and stirred for 4 hours to carry out a hydrolysis condensation reaction, thereby obtaining a reaction product. By removing methanol and water contained in the obtained reaction product under conditions of 60 ° C. under reduced pressure of 1 to 30 kilopascals (kPa), the number average molecular weight is 1000 and the active ingredient is 75.2. % Polysiloxane (a-1-1) 1000 parts by mass was obtained.

The “active ingredient” is a value obtained by dividing the theoretical yield (parts by mass) when all the methoxy groups of the silane monomer used undergo hydrolysis condensation reaction by the actual yield (parts by mass) after hydrolysis condensation reaction, That is, it is calculated by the formula (theoretical yield when all the methoxy groups of the silane monomer undergo hydrolysis hydrolysis reaction (mass part) / actual yield after hydrolysis condensation reaction (mass part)).

  The number average molecular weight was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, Shodex GPC SYSTEM-21 (manufactured by Showa Denko KK) is used as the apparatus, Shodex Asahipak GF-7M HQ (manufactured by Showa Denko KK) is used as the GPC column, and 20 mM LiBr dimethylformamide solution is used as the GPC solvent. It was.

(Synthesis Examples 2 to 7: Synthesis of polysiloxanes (a-1-2) to (a-1-7))
1000 parts by mass of polysiloxanes (a-1-2) to (a-1-7) were obtained by operating in the same manner as in Synthesis Example 1 except that the composition was changed to the composition shown in Table 1 below.

  Table 1 shows the composition and property values of the polysiloxanes (a-1-1) to (a-1-7) obtained above.

ＧＰＭＤＭＳ：γ−グリシドキシプロピルメチルジメトキシシラン
ＥｐＣＨＥＴＭＳ：β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン

GPDMMS: γ-glycidoxypropylmethyldimethoxysilane EpCHETMS: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

(Synthesis Example 8: Synthesis of vinyl polymer (a-2-1))
In the same reaction vessel as in Synthesis Example 1, 23.2 parts by mass of phenyltrimethoxysilane (hereinafter abbreviated as “PTMS”), 28.0 parts by mass of dimethyldimethoxysilane (hereinafter abbreviated as “DMDMS”), 348.8 parts by mass of n-butyl acetate was added as an initial solvent, and the temperature was raised to 95 ° C. with stirring under aeration of nitrogen gas. Then, as a monomer, methyl methacrylate (hereinafter abbreviated as “MMA”) 125.2 parts by mass, n-butyl methacrylate (hereinafter abbreviated as “BMA”) 74.4 parts by mass, n-butyl acrylate ( Hereinafter, abbreviated as “BA”.) 91.6 parts by mass, methacrylic acid (hereinafter abbreviated as “MAA”) 4.0 parts by mass, 3-methacryloyloxypropyltrimethoxysilane (hereinafter, “MPTMS”) Abbreviated.) 12.0 parts by mass, 2-hydroxyethyl methacrylate (hereinafter abbreviated as “HEMA”) 92.8 parts by mass, 40.0 parts by mass of n-butyl acetate, tert-butylperoxy-2- Ethyl hexanoate (hereinafter abbreviated as “TBPOEH”) 30.0 parts by mass were mixed, and nitrogen was maintained at 95 ° C. with respect to the reaction vessel. Scan ventilation under, while stirring, was dropped in 4 hours. After further stirring for 2 hours at the same temperature, a mixture of 0.064 parts by mass of “Phoslex A-4” and 14.6 parts by mass of deionized water was dropped into the reaction vessel over 5 minutes, For 4 hours, the hydrolysis condensation reaction of PTMS, DMDMS, and MPTMS was advanced to obtain 884 parts by mass of a vinyl polymer (a-2-1). When the vinyl polymer (a-2-1) was analyzed by ¹ H-NMR, almost 100% of the trimethoxysilyl group of the silane monomer in the reaction vessel was hydrolyzed.

  The hydroxyl value of the vinyl polymer segment of the reaction product was estimated to be 100 mgKOH / g from the content of HEMA with respect to the total amount of monomers used.

(Synthesis Examples 9 to 11: Synthesis of vinyl polymers (a-2-2) to (a-2-4))
Vinyl polymers (a-2-2) to (a-2-4) were obtained by the same operation as in Synthesis Example 8 except that the composition was changed to the composition shown in Table 2 below.

(Synthesis Example 12: Synthesis of vinyl polymer (a-2-5))
In a reaction vessel similar to Synthesis Example 1, 22.8 parts by mass of PTMS, 27.6 parts by mass of DMDMS, and 345.6 parts by mass of n-butyl acetate were charged to 95 ° C. while stirring under aeration of nitrogen gas. The temperature rose. Subsequently, MMA 67.2 parts by mass, BMA 76.8 parts by mass, 2-ethylhexyl methacrylate (2-EHMA) 31.6 parts by mass, BA 4.0 parts by mass, MAA 4.0 parts by mass, MPTMS 12.0 parts by mass The mixture containing 20 parts by mass, 204.4 parts by mass of HEMA, 40.0 parts by mass of n-butyl acetate and 30.0 parts by mass of TBPOEH was introduced into the reaction vessel while stirring at the same temperature under aeration of nitrogen gas. It was dripped in 4 hours. When the mixture was stirred at the same temperature for 1 hour, the viscosity of the reaction solution increased rapidly and gelled within a few minutes.

  The hydroxyl value of the vinyl polymer segment of the reaction product that led to gelation was estimated to be 220 mgKOH / g from the content of HEMA with respect to the total amount of monomers used.

  Table 2 shows the compositions and property values of the vinyl polymers (a-2-1) to (a-2-5) obtained above.

２−ＥＨＭＡ：２−エチルヘキシルメタクリレート

2-EHMA: 2-ethylhexyl methacrylate

(Synthesis Example 13: Synthesis of Composite Resin (A-1))
In the same reaction vessel as in Synthesis Example 1, 512.4 parts by mass of the vinyl polymer (a-2-1) obtained in Synthesis Example 8 and polysiloxane (a-1-) obtained in Synthesis Example 1 were used. 1) Charge 107.0 parts by weight, stir for 5 minutes, add 34.9 parts by weight of deionized water, stir at 80 ° C. for 4 hours, and add vinyl polymer (a-2-1) and poly Hydrolytic condensation reaction of siloxane (a-1-1) was performed. The obtained reaction product was distilled at 60 ° C. for 2 hours under reduced pressure of 1 to 30 kPa to remove the produced methanol and water, and then propylene glycol monomethyl ether acetate (hereinafter “PGMAC”). 40.5 parts by mass, n-butyl acetate 143.3 parts by mass, a composite resin (A-1) having a polysiloxane segment and a vinyl polymer segment having a nonvolatile content of 55.1% 600 parts by mass were obtained.

  The epoxy equivalent (the molecular weight (g / eq) of the sample per epoxy group) of the obtained composite resin (A-1) was measured according to the following procedure in accordance with JIS K7236. First, a 5.0 g sample was weighed into a 100 cc beaker, and 10 ml of chloroform was added and dissolved by stirring. Thereafter, 20 ml of acetic acid and 10 ml of tetraammonium bromide acetic acid solution were added at room temperature, and about 2-3 drops of crystal violet was used as an indicator in an automatic titration apparatus AUT-701 (manufactured by Toa DKK Corporation). By titrating a 1 mol / L perchloric acid / acetic acid solution (N / 10), the equivalence point is automatically determined, and the epoxy equivalent (from the titration difference between the sample and blank test and the potential change) The calculated value of g / eq) was obtained. Here, the tetraammonium bromide acetic acid solution was prepared by dissolving 100 g of tetraammonium bromide in 400 ml of acetic acid. This revealed that the epoxy equivalent of the solid content of the composite resin (A-1) was 8800 g / eq.

  The hydroxyl value of the vinyl polymer segment (a-2-1) in the obtained composite resin (A-1) was measured by the following procedure. First, 2.5 g of the composite resin (A-1) was weighed into a 200 ml Meyer flask, and an acetylating agent obtained by mixing acetic anhydride and pyridine in a volume ratio of 1:19 was added with a whole pipette. Next, it was placed in a heating bath with a condenser tube adjusted to 115 ° C., and reacted for 1 hour while shaking water through the condenser tube. After completion of the reaction, the flask was removed from the heating bath, and about 5 cc of ion exchange water was added from the top of the condenser tube with a graduated cylinder and shaken. After allowing to cool to room temperature, several drops of phenolphthalein indicator were added, and a 0.5N potassium hydroxide-ethanol solution was titrated. The point where the pale red color lasted for 30 seconds was taken as the end point, and the dripping amount at that time was read. At the same time, a blank test was also performed. The hydroxyl value of the vinyl polymer segment in the composite resin (A-1) was calculated from the following two formulas.

Ｂ：空試験での滴下量（ｍｌ）
Ｔ：本試験での滴下量（ｍｌ）
Ｆ：０．５Ｎ水酸化カリウム−エタノール溶液の力価
Ｓ：複合樹脂（Ａ−１）の採取量（ｇ）
ＡＮ：複合樹脂（Ａ−１）の酸価

B: Drop amount in blank test (ml)
T: Drop amount in this test (ml)
F: Potency of 0.5N potassium hydroxide-ethanol solution S: Collected amount of composite resin (A-1) (g)
AN: Acid value of composite resin (A-1)

Ｃ：複合樹脂（Ａ−１）の水酸基価
Ｎ：複合樹脂（Ａ−１）の固形分率（質量％）
Ｐ：複合樹脂（Ａ−１）の固形分中のポリシロキサンセグメント（ａ−１−１）の 質量割合（質量％）

C: Hydroxyl value of composite resin (A-1) N: Solid fraction (mass%) of composite resin (A-1)
P: Mass ratio (mass%) of polysiloxane segment (a-1-1) in solid content of composite resin (A-1)

  From this, the hydroxyl value of the vinyl polymer segment in the composite resin (A-1) was calculated to be 100 mgKOH / g, and the vinyl polymer segment estimated from the HEMA content relative to the total amount of the monomers used was calculated. It was confirmed that the hydroxyl value coincided with the calculated value from the actual measurement value.

(Synthesis Examples 14-17: Synthesis of Composite Resins (A-2) to (A-5))
600 mass parts of composite resin (A-2)-(A-5) was obtained by operating like the synthesis example 13 except having changed into the composition shown in following Table 3, respectively.

  Table 3 shows the composition and property values of the composite resins (A-1) to (A-5) obtained above.

(Synthesis Example 18: Synthesis of Composite Resin (R-1))
In the same reaction vessel as in Synthesis Example 1, 512.4 parts by mass of the vinyl polymer (a-2-1) obtained in Synthesis Example 8 and polysiloxane (a-1-6) obtained in Synthesis Example 6 ) After charging 106.7 parts by weight and stirring for 5 minutes, 16.7 parts by weight of deionized water was added and stirred at 80 ° C. for 4 hours to obtain a vinyl polymer (a-2-1) and polysiloxane ( The hydrolysis condensation reaction of a-1-6) was performed. The obtained reaction product was distilled under reduced pressure of 1 to 30 kPa at 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 36.0 parts by mass of PGMAC, n-acetate -140.2 parts by mass of butyl was added to obtain 600 parts by mass of a comparative composite resin (R-1) composed of a polysiloxane segment and a vinyl polymer segment having a nonvolatile content of 55.0%.

(Synthesis Examples 19 to 22: Synthesis of Composite Resins (R-2) to (R-5))
600 mass parts of composite resins (R-2) to (R-5) were obtained in the same manner as in Synthesis Example 18 except that the composition was changed to the composition shown in Table 4 below.

(Synthesis Example 23: Synthesis of Composite Resin (R-6))
In the same reaction vessel as in Synthesis Example 1, 502.7 parts by mass of the vinyl polymer (a-2-1) obtained in Synthesis Example 8 and polysiloxane (a-1-5) obtained in Synthesis Example 5 106 .7 parts by mass and “BGE-R” (butyl glycidyl ether manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), which is an epoxy compound having no hydrolyzable silyl group, for comparison with a silane compound having an epoxy group 4.9 parts by mass, and after stirring for 5 minutes, 36.9 parts by mass of deionized water was added, and the mixture was stirred at 80 ° C. for 4 hours to obtain vinyl polymer (a-2-1) and polysiloxane (a The hydrolysis condensation reaction of -1-5) was performed. Here, the addition amount of BGE-R is determined by calculation so that the epoxy equivalent of the solid content of the finally obtained composite resin and epoxy compound mixture is 8800 g / eq. At this time, the produced reaction product was distilled under reduced pressure of 1 to 30 kPa at 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 36.0 parts by mass of PGMAC. Then, 143.2 parts by mass of n-butyl acetate was added to obtain 600 parts by mass of a composite resin (R-6) composed of a polysiloxane segment having a nonvolatile content of 55.2% and a vinyl polymer segment.

(Synthesis Example 24: Synthesis of Composite Resin (R-7))
In the same reaction vessel as in Synthesis Example 1, 497.4 parts by mass of the vinyl polymer (a-2-1) obtained in Synthesis Example 8 and polysiloxane (a-1-5) obtained in Synthesis Example 5 106 For comparison with .7 parts by mass and a silane compound having an epoxy group, “4HBAGE” (4-hydroxybutyl acrylate glycidyl ether manufactured by Nippon Kasei Co., Ltd.), which is an epoxy compound having no hydrolyzable silyl group. 7.5 parts by mass, and after stirring for 5 minutes, 36.9 parts by mass of deionized water was added, and the mixture was stirred at 80 ° C. for 4 hours. The vinyl polymer (a-2-1) and the polysiloxane ( The hydrolysis condensation reaction of a-1-5) was performed. Here, the amount of 4HBAGE added is determined by calculation so that the epoxy equivalent of the finally obtained composite resin (R) and epoxy compound mixture is 8800 g / eq. At this time, the produced reaction product was distilled under reduced pressure of 1 to 30 kPa at 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 36.0 parts by mass of PGMAC. Then, 143.6 parts by mass of n-butyl acetate was added to obtain 600 parts by mass of a composite resin (R-7) composed of a polysiloxane segment having a nonvolatile content of 55.3% and a vinyl polymer segment.

  Table 4 shows the composition and property values of the composite resins (R-1) to (R-7) obtained above.

(Evaluation)
The composite resins (A-1) to (A-5) and the composite resins (R-1) to (R-7) obtained above were evaluated as follows. That is, the “color tone”, “turbidity” and “storage stability” of the resin were evaluated.

<Color tone>
The color of the obtained Gardner color (the value measured by the color test method of chemical products specified in JIS K 0071-2) is visually colorimetric with the standard sample specified in JIS K0071-2. Determined by. The smaller the Gardner color number, the lighter the coloration, and it was determined that the Gardner color number was 1 or less and the resin was colorless.

<Turbidity>
The turbidity of the obtained resin is determined according to JIS K0101, using a precision photoelectric turbidimeter T-2600S (manufactured by Tokyo Denshoku Co., Ltd.), integrating sphere scattering photometry (change in forward scattered light due to formation of agglomerates) , Measured using an integrating sphere, and measured under optical conditions according to a method for comparing the ratio with transmitted light intensity). The smaller the turbidity, the higher the transparency. The turbidity was determined to be a highly transparent resin having a turbidity of 0.5 or less and no turbidity.

<Storage stability>
The storage stability of the obtained resin was evaluated based on the viscosity ratio with the viscosity (so-called viscosity with time) of what was stored at 40 ° C. for 30 days as the numerator and the initial viscosity as the denominator. The viscosity was measured at 30 ° C. using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The sample was stored by placing the obtained resin in a glass tube and allowing it to stand in an environment of 40 ° C. for 1 month. The closer this viscosity ratio is to 1, the better the storage stability, and the more excellent the storage stability with a viscosity ratio of 0.9 to 1.1. It was judged that there was.

  The respective evaluation results are shown in Tables 3 and 4.

As a result, the composite resins (A-1) to (A-5) obtained in Synthesis Examples 13 to 17 and the composite resins (R-1) to (R-2) obtained in Synthesis Examples 18 to 19 were used. Were found to have good color tone, turbidity and storage stability.
On the other hand, the composite resins (R-3) to (R-4) obtained in Synthesis Examples 20 to 21 are examples in which the epoxy equivalent of the composite resin is larger than 17000 g / eq, but the storage stability is inferior. did.
Moreover, although composite resin (R-5)-(R-7) obtained by the synthesis examples 22-24 is an example in which polysiloxane does not have an epoxy group, it became clear that storage stability was inferior.

(Example 1: Preparation of metal surface treatment agent (1))
25.0 parts by mass of composite resin (A-1) obtained in Synthesis Example 1, Barnock DN-980 (manufactured by Polyisocyanate DIC Corporation, the diluent solvent is ethyl acetate, and the non-volatile content is 75.3% by mass In addition, by mixing 4.5 parts by mass of NCO% of varnish (16.0% by mass) and 18.9 parts by mass of ethyl acetate, the surface treatment agent for metal having a nonvolatile content of 55.0% by mass (1 )

(Examples 2-5 and Comparative Examples 1-2)
Based on the formulation shown in Table 5 below, metal surface treatment agents (2) to (5) and comparative metal surface treatment agents (R1) to (R2) were prepared in the same manner as in Example 1.

(Evaluation)
Evaluation of the metal surface treatment agents (1) to (5) and the comparative metal surface treatment agents (R1) to (R2) obtained in Examples 1 to 5 and Comparative Examples 1 and 2 is as follows. went. That is, "color tone" of the surface treatment agent for metal, cured coating film X or Y for evaluation, "solvent resistance", "acid resistance", "adhesiveness", and processability indicators that are indicators of durability “Substrate followability” and “rust prevention” were evaluated.

<Color tone>
The Gardner color number (value measured by the color test method of chemical products specified in JIS K 0071-2) of the obtained surface treatment agent for metal was visually checked with a standard sample specified in JIS K0071-2. Determined by colorimetric. The smaller the Gardner color number, the lighter the coloration, and it was determined that the Gardner color number was 1 or less and the surface treatment agent was colorless.

(Evaluated cured coating X)
The surface coating agent for metal is applied on a 150 mm × 70 mm × 2 mm soft aluminum plate so that the dry film thickness is 10 μm, and dried for 10 minutes in an environment of 80 ° C., whereby a coating film is formed on the aluminum plate. A laminated test plate (1) was obtained.

(Evaluated cured coating Y)
On a 150 mm x 70 mm x 2 mm zinc (Zn) -iron (Fe) molten steel sheet (untreated surface), a metal surface treatment agent is applied to a dry film thickness of 2 μm and dried at 150 ° C. for 5 minutes. By doing, the test plate (2) by which the coating film was laminated | stacked on the said zinc (Zn) -iron (Fe) molten steel plate was obtained.

<Solvent resistance>
The test plates (1) to (2) obtained above were set in “RUBBING TESTER” manufactured by Ohira Rika Kogyo Co., Ltd., and rubbed back and forth 50 times with a load of 1 kg using felt impregnated with methyl ethyl ketone.
The state of the coating film before rubbing and after rubbing was confirmed by finger touch and visual observation, and evaluated according to the following evaluation criteria.
○: Softening and gloss reduction are not observed before and after rubbing.
Δ: Some softening or gloss reduction is observed before and after rubbing.
X: Significant softening or gloss reduction is observed before and after rubbing.

<Acid resistance>
After leaving the surfaces of the test plates (1) and (2) obtained above immersed in a 5% by mass sulfuric acid aqueous solution at a temperature of 25 ° C. for 24 hours, the coating film was washed with water and then dried. The surface state of the coating film was confirmed visually. The evaluation criteria are as follows.
○: There is no etching mark.
Δ: There is a slight etching mark.
X: Remarkable etching.

<Adhesion>
Using the test plates (1) to (2) obtained above, measurement was performed based on the JIS K-5600 cross cut test method. The evaluation criteria are as follows.
○: No peeling of coating film.
(Triangle | delta): The area which the coating film peeled is 1 to 64% of the total grid area.
X: The area where the coating film peeled is 65% or more of the total grid area.

<Substrate followability (bending test)>
The test plate (1) obtained above was used for evaluation based on the JIS K-5600 flexural resistance test method (mandrel diameter was 2 mm). The evaluation criteria are as follows.
○: No cracks are observed on the surface of the coating film at the bent portion.
Δ: Some cracks are observed in a very small part of the coating surface at the bent portion.
X: Generation | occurrence | production of a crack is seen in the whole coating-film surface of a bending part.

<Rust prevention>
It measured based on the JIS K-5600 9.1 salt spray resistance test using the test board (2) obtained above. Specifically, the coating plate surface of the test plate (2) is scratched with a cutter knife to a depth that reaches the base material (cross cut part), and salt spray tester (manufactured by Suga Test Instruments Co., Ltd.) Then, a salt spray test was conducted, and the rust generation area after 240 hours was visually determined and evaluated. The evaluation was performed separately for a flat portion not damaged by the cutter knife and a peripheral portion of the cross cut portion. The evaluation criteria are as follows.
<Plane>
(Double-circle): The area where the generation | occurrence | production of rust and the swelling and peeling of the coating film resulting from rust were less than 5% with respect to the whole plane part.
◯: The area where the occurrence of rust and the swelling or peeling of the coating film due to rust occurred was 5% or more and less than 30% with respect to the entire plane portion.
(Triangle | delta): The area where the generation | occurrence | production of rust and the swelling and peeling of the coating film resulting from rust were 30% or more and less than 60% with respect to the whole plane part.
X: The area where the occurrence of rust and the swelling and peeling of the coating film due to rust occurred was 60% or more with respect to the entire plane portion.
<The peripheral part of the crosscut part>
(Double-circle): Generation | occurrence | production of rust was not seen in the peripheral part of a crosscut part, and peeling of the coating film etc. resulting from rust was not seen.
◯: A very small amount of rust was observed in the periphery of the crosscut part, but no peeling or swelling of the coating film due to it was observed.
Δ: Rust was widely observed in the periphery of the crosscut portion, and although peeling or swelling of the coating film was observed due to this, no flow rust was observed.
X: Rust was widely generated in the periphery of the crosscut part, and peeling and swelling of the coating film due to the rust were observed. Further, contamination of the coating film due to flowing rust was observed.

  Each evaluation result is shown in Table 5.

As a result, the metal surface treating agents (1) to (5) evaluated in Examples 1 to 5 are all excellent in solvent resistance, acid resistance, adhesion, substrate follow-up properties, and rust prevention properties. was gotten.
The metal surface treatment agent (R1) evaluated in Comparative Example 1 is an example in which the epoxy equivalent of the composite resin is too small, but it has been found that the solvent resistance, adhesion, substrate follow-up property, and rust resistance are poor. .
The metal surface treatment agent (R2) evaluated in Comparative Example 2 is an example in which the hydroxyl value of the vinyl polymer segment is too small, but the solvent resistance, acid resistance, adhesion, substrate follow-up property, and rust resistance are low. It turned out to be inferior.

Claims (2)

A polysiloxane segment (a1) having a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, and an epoxy group, and an alcoholic hydroxyl group. The vinyl polymer segment (a2) having a composite resin (A) bonded by a bond represented by the general formula (3) and a polyisocyanate (B), a metal surface treatment agent, The mass ratio of the polysiloxane segment (a1) in the solid content of the composite resin (A) is 20 to 70 mass%, and the epoxy equivalent of the solid content of the composite resin (A) is 900 to 17000 g / eq, The hydroxyl group value of the vinyl polymer segment (a2) is 50 to 200 mgKOH / g, and the mass ratio of the polyisocyanate (B) is 5 to 50 mass in the total solid content. Metal surface treatment agent characterized in that it.

(In the general formulas (1) and (2), R ¹ , R ² and R ³ are each independently -R ⁴ -CH = CH ₂ , -R ⁴ -C (CH ₃ ) = CH ₂ ,- A group having one polymerizable double bond selected from the group consisting of R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ and —R ⁴ —O—CO—CH═CH ₂ (provided that R ⁴ Represents a single bond or an alkylene group having 1 to 6 carbon atoms.), An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or 7 carbon atoms. Represents an aralkyl group of ˜12.)

(In the general formula (3), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1). To do)   A metal material treated with the metal surface treatment agent according to claim 1.