WO2018097012A1 - Surface conditioning agent, coating material composition containing said surface conditioning agent, and coating film forming method - Google Patents

Abstract

A surface conditioning agent (A) which contains a copolymer (a) of monomers (a1)-(a4) having a weight average molecular weight within the range of from 1,000 to 50,000. The copolymer (a) uses, as copolymerization components, (a1) a tertiary amino group-containing polymerizable unsaturated monomer and/or a quaternary ammonium salt group-containing polymerizable unsaturated monomer, (a2) an N-substituted (meth)acrylamide having a molecular weight of less than 145, and (a3) a polysiloxane chain-containing polymerizable unsaturated monomer having a weight average molecular weight within the range of from 420 to 4,600; and the content ratio of the monomer (a1) to the monomer (a2), namely (a1)/(a2) is within the range of from 5/95 to 55/45 in terms of mass ratio.

Description

Surface conditioner, coating composition containing the surface conditioner, and coating film forming method

The present invention relates to a surface conditioner.

The base material used outdoors is generally coated with paint for the purpose of decoration or protection. The coating surface of such a coating substrate may be soiled by air pollutants such as dust, iron powder, rain, sunlight, and PM2.5 when exposed outdoors for a long period of time, resulting in a poor appearance. . Thus, as one of the methods for improving the stain resistance of the coating film by outdoor exposure, a technique for imparting hydrophilicity to the coating film surface has been proposed so far.

For example, Patent Document 1 discloses dimethyl (meth) acrylamides, acrylamide monomers that are diethyl (meth) acrylamides, one-terminal (meth) acryl-modified siloxy group-containing mono (meth) acrylate monomers, and specific functional groups A surface conditioner containing a copolymer obtained by copolymerizing a monomer in a specific amount is disclosed. According to this invention, a small amount of a surface conditioner is blended in the coating material forming the coating film, thereby preventing the cracks, which are bubble marks generated during baking due to the fine bubbles involved during coating, from being applied. It is possible to impart hydrophilicity to the film surface and impart antifouling properties. However, according to the method of Patent Document 1, although the stain resistance at the initial stage of outdoor exposure is improved, the hydrophilicity of the coating film surface is lowered and the desired stain resistance cannot be obtained in long-term outdoor exposure. Sometimes.

Patent Document 2 discloses a highly hydrophilic coating composition containing a water-soluble polymer copolymerized with 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof. According to the present invention, since the hydrophilic functional group derived from 2-acrylamido-2-methylpropane sulfonic acid having a sulfonic acid group or a salt thereof is contained in a high ratio, it exhibits very high hydrophilicity and is easily contaminated. However, the appearance defect and the stain resistance may be deteriorated.

Japanese Unexamined Patent Publication No. 2014-224219 Japanese Unexamined Patent Publication No. 2015-147852

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a surface conditioner that can impart stain resistance that can be maintained even in long-term exposure to a coating film. is there.

Under such circumstances, as a result of intensive studies, the present inventors have found that the above problems can be solved by using a surface conditioner containing a copolymer obtained by copolymerizing a specific monomer at a specific ratio.

That is, the present invention includes embodiments of the following surface conditioner, a coating composition containing the surface conditioner, and a coating film forming method.

Aspect 1. A surface conditioner (A) containing a copolymer (a) of the following monomers (a1) to (a4) having a weight average molecular weight in the range of 1,000 to 50,000,
The copolymer (a) is:
(A1) a tertiary amino group-containing polymerizable unsaturated monomer and / or a quaternary ammonium base-containing polymerizable unsaturated monomer,
(A2) N-substituted (meth) acrylamide having a molecular weight of less than 145, and (a3) a polysiloxane chain-containing polymerizable unsaturated monomer having a weight average molecular weight in the range of 420 to 4600, as a copolymerization component, and A surface conditioner (copolymer (a) in which the content ratio of the monomer (a1) and the monomer (a2) is in the range of (a1) / (a2) = 5/95 to 55/45 by mass ratio ( A).

Aspect 2. The copolymer (a) is a hydroxyl group-containing (meth) acrylate, an optionally blocked isocyanate group-containing (meth) acrylate, an alkyl (meth) acrylate compound, a polyoxyalkylene chain-containing (meth) acrylate compound, (meth) At least one polymerizable group selected from the group consisting of an acrylamide compound (excluding the monomer (a1) or monomer (a2)), a vinyl group-containing compound and a polymerizable unsaturated compound having a nitrogen atom-containing heterocyclic ring. The surface conditioning agent (A) of embodiment 1 further containing a saturated group monomer (a4).
Aspect 3. A coating composition containing the surface conditioning agent (A) according to aspect 1 or aspect 2.

Aspect 4. The surface conditioner (A) according to the first aspect or the second aspect, the hydroxyl group-containing resin (B), and the crosslinking agent (C) are contained, and the surface conditioner (A) is used as a resin solid content in the coating composition. The coating composition according to aspect 3, which contains 0.1 to 15 parts by mass based on 100 parts by mass.

Aspect 5. Furthermore, the coating composition of the aspect 3 or aspect 4 containing an anionic surfactant (D).

Aspect 6. The anionic surfactant (D) is an alkyldiphenyl ether disulfonate anionic surfactant (d1), a polyoxyethylene alkyl ether sulfate ester anionic surfactant (d2), or an alkylbenzene sulfonate. The coating composition according to aspect 5, wherein the coating composition is at least one anionic surfactant selected from the group consisting of an anionic surfactant (d3) based on a system and an anionic surfactant (d4) based on a sulfosuccinate .

Aspect 7. A coating film forming method comprising a step of coating a coating composition with the coating composition according to any one of Embodiments 3 to 6 to form a coating film.

The coating film formed from the coating composition containing the surface conditioner of the present invention is excellent in stain resistance and can exhibit sufficient stain resistance even after being exposed outdoors for a long time. .

Hereinafter, embodiments for carrying out the present invention will be described in detail.

The surface conditioner (A) of the present invention contains a specific copolymer (a) having a weight average molecular weight in the range of 1,000 to 50,000.

Copolymer (a)
The copolymer (a) contained in the surface conditioner (A) of the present invention contains the monomers (a1) to (a3) described later as essential components, and the remainder contains the monomer (a4) as a copolymerization component as necessary. In addition, the content ratio of the monomer (a1) and the monomer (a2) is in a range of (a1) / (a2) = 5/95 to 55/45 by mass ratio. That is, when the total of the monomer (a1) and the monomer (a2) is 100, the mass ratio is within the range from (a1) :( a2) = 5: 95 to (a1) :( a2) = 55: 45. It is.

Monomer (a1)
A tertiary amino group-containing polymerizable unsaturated monomer and / or a quaternary ammonium base-containing polymerizable unsaturated monomer (used as a copolymerization component in the copolymer (a) contained in the surface conditioner of the present invention ( a1) is a compound having a tertiary amino group and a polymerizable unsaturated group in one molecule, a compound having a quaternary ammonium base and a polymerizable unsaturated group in one molecule, or both. is there.

Specific examples of the tertiary amino group-containing polymerizable unsaturated monomer include compounds represented by the following general formula (I).

[In the formula (I), R ¹ represents hydrogen or a methyl group, n represents an integer of 1 to 8, Y represents an oxygen atom or —NH— group, and R ² represents a methyl group or an ethyl group. ]
Examples of the general formula (I) include amine derivatives of (meth) acrylic acid, dialkylamine derivatives of (meth) acrylamide, and the like. Specifically, amine derivatives of (meth) acrylic acid include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate. N, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminobutyl (meth) acrylate. Dialkylamine derivatives of (meth) acrylamide include [(meth) acryloylamino] ethyl-N, N-dimethylamine, [(meth) acryloylamino] ethyl-N, N-diethylamine, [(meth) acryloylamino] propyl Examples include [(meth) acryloylamino] alkyldialkylamines such as —N, N-dimethylamine, [(meth) acryloylamino] ethyl-N, N-dimethylamine, and N- (dimethylaminomethyl) acrylamide.

Here, the above (meth) acrylate means methacrylate or acrylate, and (meth) acryloyl means methacryloyl or acryloyl.

The monomer (a1) may be a quaternary ammonium salt of a tertiary amino group-containing polymerizable unsaturated monomer using a quaternary chlorinating agent. As quaternary chlorinating agents, alkylene halides such as methylene chloride and methylene bromide; alkyl halides such as methyl iodide; dialkyl sulfates such as dimethyl sulfate; dialkyl carbonates such as diethyl carbonate; benzyl chloride, benzyl bromide, And methyl sulfonate. The quaternary chlorination can be performed by a conventionally known method. For example, the tertiary amino group-containing polymerizable unsaturated monomer represented by the general formula (I) and the quaternary chlorinating agent 20 It can be obtained by reacting at a temperature in the range of ˜120 ° C. until the desired amount of salt product is obtained. This quaternary chlorination step may be carried out after obtaining the copolymer (a).

The resulting copolymer (a) has a quaternary ammonium salt group, and the concentration of the quaternary ammonium base in the copolymer (a) is preferably 3 to 30% by mass, more preferably It is in the range of 4 to 25% by mass, more preferably 10 to 20% by mass.

The concentration of the quaternary ammonium base can be quantified by, for example, potentiometric titration.

Specific examples of the quaternary ammonium base-containing polymerizable unsaturated monomer include compounds represented by the following general formula (II).

[In the formula (II), R ¹ , n, Y and R ² are the same as those described above for the formula (I), and R ³ is hydrogen, a linear, branched or fatty acid having 1 to 24 carbon atoms. cyclic alkyl group, or an aromatic ring having 1 to 24 carbon atoms, X ^- represents an inorganic anion or an organic anion].
Preferred examples of the linear, branched or alicyclic alkyl group having 1 to 24 carbon atoms for R ³ include a methyl group, an ethyl group, and a propyl group. Preferred examples of the aromatic ring having 1 to 24 carbon atoms of R ³ include a phenyl group and a benzyl group.

The above X ⁻ is not particularly limited, but halogen ions such as Cl ⁻ , Br ⁻ and I ⁻ , OH ⁻ , CH ₃ COO ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , HSO ₄ ⁻ , CH ₃ SO ₃ ⁻ , CH ₃ C ₆ H ₆ SO ₃ ⁻ , H ₂ PO ₄ ^{— and the} like can be mentioned. Preferred X ⁻ includes Cl ⁻ , CH ₃ SO ₃ ^{— and the} like.

Specific examples of the general formula (II) include [(meth) acryloyloxy] ethyltrimethylammonium chloride, [(meth) acryloyloxy] ethyltrimethylammonium bromide, [(meth) acryloyloxy] ethyltrimethylammonium dimethyl phosphate, [ [(Meth) acryloyloxy] alkyltrialkylammonium salts such as (meth) acryloyloxy] ethyltrimethylammonium methylsulfate; [(meth) acrylamide] propyltrimethylammonium chloride, [(meth) acrylamide] propyltrimethylammonium bromide, [ [(Meth) acrylamide] alkyltrialkyl such as (meth) acrylamide] propyltrimethylammonium methylsulfate Ammonium salts, and the like. These can be used alone or in combination of two or more. Here, the (meth) acrylamide refers to methacrylamide or acrylamide.

Among them, 2-[(meth) acryloyloxy] ethyltrimethylammonium chloride, 3-[(meth) acrylamide] propyltrimethylammonium chloride, 2-[(meth) acryloyloxy] ethyltrimethylammonium methylsulfate, 3-[( (Meth) acrylamide] propyltrimethylammonium methyl sulfate is preferred.

The content of the monomer (a1) is based on the total amount of monomer components constituting the copolymer (a) (hereinafter referred to as “copolymerization monomer component”) as a reference for contamination resistance and durability of contamination resistance. From the viewpoint, it is preferably in the range of 3 to 30% by mass, more preferably 4 to 25% by mass, and still more preferably 10 to 20% by mass.

Monomer (a2)
The monomer (a2) used as a copolymerization component of the copolymer (a) contained in the surface conditioner of the present invention is an N-substituted (meth) acrylamide monomer having a molecular weight of less than 145. The N-substituted (meth) acrylamide having a molecular weight of less than 145 is not particularly limited, but N-substituted (meth) acrylamide having a molecular weight of 80 or more and less than 145 is preferred. Here, N-substitution refers to either N, N-disubstitution or N-monosubstitution. However, a dialkylamine derivative of (meth) acrylamide having a molecular weight of less than 145 is excluded from the monomer (a2).

Specific examples of the monomer (a2) include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl ( N, N-dialkyl such as (meth) acrylamide or N-alkyl (meth) acrylamide, N-substituted alkoxyalkyl (meth) acrylamide such as N-methoxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- Examples include hydroxyl-containing (meth) acrylamide compounds such as methyl-N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N, N- or N-hydroxyethyl (meth) acrylamide. These monomers may be used alone or in combination of two or more.

Among these, N-substituted alkyl (meth) acrylamide is preferable from the viewpoint of stain resistance and coating film appearance, and N, N-dimethyl (meth) acrylamide is more preferable.

In the present invention, the content ratio of the monomer (a1) and the monomer (a2) is in the range of (a1) / (a2) = 5/95 to 55/45 by mass ratio. When the mass ratio is less than 5/95, the stain resistance becomes insufficient. When the mass ratio is larger than 55/45, the durability of the stain resistance is lowered. From the viewpoint of stain resistance and durability of stain resistance, preferably (a1) / (a2) = 10/90 to 40/60, more preferably (a1) / (a2) = 15/85 to 30/70. Is within the range.

The content of the monomer (a2) is from 10% by weight to 95% by weight, preferably from 35 to 87% by weight, more preferably from 50 to 75%, based on the total amount of the copolymerization monomer components, from the viewpoint of stain resistance. The range of mass% is preferred.

In particular, by containing the monomer (a1) and the monomer (a2) at a specific ratio and containing the monomer (a3) described later as a copolymerization component, the coating film has excellent appearance and stain resistance is effectively improved. It is possible to obtain a copolymer that is improved and has a persistent stain resistance.

Monomer (a3)
The polysiloxane chain-containing polymerizable unsaturated monomer (a3) used as a copolymerization component of the copolymer (a) contained in the surface conditioner of the present invention has one or more siloxane chains and one in the molecule. It is a compound having the above polymerizable unsaturated group.

The polymerizable unsaturated group is an unsaturated group capable of radical polymerization, and specifically includes, for example, acryloyl group, methacryloyl group, vinyl group, allyl group, propenyl group, isopropenyl group, maleimide group, vinyl ether group, Etc.

Among these polymerizable unsaturated groups, an acryloyl group and a methacryloyl group are preferable, and an acryloyl group is particularly preferable from the viewpoint of excellent reactivity.

The polysiloxane chain is a polymer having a siloxane bond (Si—O—Si) as a skeleton, and examples of the skeleton include branched or linear polysiloxane.

Examples of the polysiloxane chain-containing polymerizable unsaturated monomer (a3) include polymerizable unsaturated monomers represented by the following general formula (III).

[In formula (III), R ¹ has the same meaning as described above for formula (I). R ⁴ represents a hydrocarbon group having 2 to 10 carbon atoms, preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and R ⁵ are the same or different from each other, Represents an alkyl group of ˜4, a phenyl group or a trialkylsiloxy group, preferably an alkyl group of 1 to 4 carbon atoms, more preferably a methyl group and / or a trimethylsiloxy group, m is an integer, preferably an integer of 3 to 300 More preferably, it is an integer of 4 to 100. ]

Commercially available products of the above polysiloxane chain-containing polymerizable unsaturated monomer (a3) include, for example, Silaplane FM-0721, Silaplane FM-0711, Silaplane FM-0725 (manufactured by JNC, trade name); X -22-174ASX, X-22-174BX, KF-2012, X-22-2426, X-22-2404, X-22-2475 (above, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) .

The weight average molecular weight of the polysiloxane chain-containing polymerizable unsaturated monomer (a3) is preferably 420 to from the viewpoints of maintaining stain resistance, coating film appearance, ease of production of the copolymer (a), and the like. It is within the range of 4600, more preferably 600 to 4000, and still more preferably 800 to 3000.

The polysiloxane chain-containing polymerizable unsaturated monomer (a3) can be used alone or in combination of two or more.

The content of the polysiloxane chain-containing polymerizable unsaturated monomer (a3) in the copolymer (a) is determined from the viewpoint of stain resistance, stain resistance maintenance, coating film appearance, and the like. In the range of 2 to 20% by mass, preferably 3 to 15% by mass, more preferably 5 to 13% by mass, based on the total amount.

Monomer (a4)
The other polymerizable unsaturated group monomer (a4) is not particularly limited as long as it is a monomer having at least one polymerizable unsaturated group other than the monomers shown in components (a1) to (a3). For example, a hydroxyl group-containing (meth) acrylate, an optionally blocked isocyanate group-containing (meth) acrylate, an alkyl (meth) acrylate compound, a polyoxyalkylene chain-containing (meth) acrylate compound, the monomer (a1) or the monomer (a2 (Meth) acrylamide compounds other than), vinyl group-containing compounds, and polymerizable unsaturated compounds having a nitrogen atom-containing heterocyclic ring.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy- Examples thereof include 3-phenoxypropyl (meth) acrylate or monomers obtained by adding ε-caprolactone to (meth) acrylate having a hydroxyl group (for example, Plaxel FM series).

Examples of the isocyanate group-containing (meth) acrylate compound include 2-isocyanatoethyl (meth) acrylate. Examples of the blocking agent when the isocyanate group-containing (meth) acrylate compound is blocked with a blocking agent include ethyl alcohol, isopropyl alcohol, caprolactam, MEK-oxime, dimethylpyrazole, diethyl malonate and the like.

Examples of the alkyl (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, 2-acryloyloxyethyl- And succinic acid, 2-acryloyloxyethyl-phthalic acid, tetrahydrofurfuryl (meth) acrylate, and the like.

Examples of the polyoxyalkylene chain-containing (meth) acrylate compound include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene (propylene) glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and ethoxy polyethylene glycol. (Meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, methoxypolyethylene (propylene) glycol (meth) acrylate, ethoxypolyethylene (propylene) glycol (meth) acrylate, and the like. In the present specification, “polyethylene (propylene) glycol” means a copolymer of ethylene glycol and propylene glycol, and includes either or both of a block copolymer and a random copolymer. Also good.

(Meth) acrylamide compounds other than those classified as component (a2), such as diacetone acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, (meth) acrylamide-tert-butyl sulfonic acid And (meth) acrylamide alkyl sulfonic acid such as (meth) acrylamide-tert-butylsulfonic acid inorganic salt or the sulfonic acid salt thereof.

Examples of the vinyl group-containing compound include styrene; linear, branched or cyclic alkyl vinyl ether having 1 to 12 carbon atoms such as n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, and lauryl vinyl ether. Monomers; vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl laurate.

Examples of the polymerizable unsaturated compound having a nitrogen atom-containing heterocyclic ring include N-vinylpyridine, N-vinylpyrrolidone, N-vinylpyridine compound, vinylquinoline compound, vinylpiperidine compound, (meth) acryloylmorpholine and the like.

As the monomer (a4), it is preferable to use a crosslinking functional group-containing monomer as a part of the component. Examples of the cross-linking functional group include a hydroxyl group and an optionally blocked isocyanate group. Specifically, among the above, for example, a hydroxyl group-containing (meth) acrylate compound, a hydroxyl group-containing (meth) acrylamide compound, and a block At least one crosslinking functional group-containing monomer selected from isocyanate group-containing (meth) acrylate compounds that may be used is preferable.

Further, as the monomer (a4), it is preferable to use a polyoxyalkylene chain-containing (meth) acrylate compound as a part of its components. Thereby, a copolymer (a) can be manufactured stably and it is possible for the coating film containing this to ensure sufficient stain resistance.

The content of the monomer (a4) is preferably in the range of 0 to 55% by mass, more preferably in the range of 0 to 30% by mass, based on the total amount of the copolymerization monomer components.

As described above, the copolymer (a) contained in the surface conditioner of the present invention contains the above monomers (a1) to (a3) as essential components and, if necessary, the monomer (a4) as a copolymerization component. In addition, the content ratio of the monomer (a1) and the monomer (a2) is in the range of (a1) / (a2) = 5/95 to 55/45 by mass ratio.

The method for producing the copolymer (a) is not particularly limited, and a known polymerization method is suitably used, and examples thereof include a bulk polymerization method, a solution polymerization method, and a suspension polymerization method. . These polymerization methods can be used alone or in combination.

Specifically, the copolymer (a) comprises the above monomers (a1) to (a3) and, if necessary, the monomer (a4) as appropriate in a solvent, a polymerization initiator, and if necessary. It can be obtained by copolymerization in the presence of a chain transfer agent.

As the polymerization initiator and organic solvent used for the preparation of the copolymer (a), various known ones can be used.

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

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

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

The weight average molecular weight of the copolymer (a) obtained as described above is usually in the range of 1,000 to 50,000, preferably from the viewpoint of the appearance of the coating film and the stain resistance and durability of the stain resistance. Is in the range of 2000-20000, more preferably 2200-10000.

In addition, in this specification, the number average molecular weight or the weight average molecular weight is the retention time (retention capacity) measured using a gel permeation chromatograph (GPC). (Retention capacity) is a value obtained by converting to the molecular weight of polystyrene.

As the gel permeation chromatograph, “HLC8120GPC” (manufactured by Tosoh Corporation) was used. Four columns, “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL”, “TSKgel G-2000HXL” (both manufactured by Tosoh Corporation), are used as columns. Mobile phase: Tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 cc / min, detector: RI

Surface conditioner (A)
The surface conditioner (A) of the present invention contains the copolymer (a) described above.

The surface conditioning agent (A) of the present invention may consist of only the copolymer (a), or the copolymer (a) is dissolved or suspended in an inert solvent together with other components and diluted. Also good.

The inert solvent is capable of dissolving or suspending the copolymer (a). Specific examples of the inert solvent include hydrocarbon solvents such as xylene, toluene, and cyclohexane; ketone solvents such as cyclohexanone and methyl isobutyl ketone; methyl cellosolve, cellosolve, butylcellosolve, methyl carbitol, carbitol, and butyl carbitol. Ether solvents such as diethyl carbitol and propylene glycol monomethyl ether; ester solvents such as n-butyl acetate, isobutyl acetate, n-amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Alcohols such as butyl alcohol, sec-butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, 3-methyl-3-methoxybutanol Medium, and the like. These solvents may be used alone or in combination of two or more.

The surface conditioner (A) of the present invention obtained as described above can be blended in various coating compositions.

The solid content of the copolymer (a) in the surface conditioner is not particularly limited, but is preferably 1 to 70% by mass, more preferably 5 to 40% by mass.

Here, the solid content in the present specification was calculated by taking about 2.0 g of a sample in an aluminum foil cup having a diameter of about 5 cm and measuring the residue (g) after heating at 110 ° C. for 1 hour. Value.

When a coating composition is prepared by blending the surface conditioner (A), the desired performance can be achieved by simply mixing the surface conditioner (A) with a conventionally known coating composition simultaneously or in any order. The coating composition to be obtained can be obtained.

Although it does not restrict | limit especially as a coating composition, For example, a well-known thermosetting type coating composition, normal temperature curable coating composition, etc. are mentioned.

The form of these coating compositions is not particularly limited, and may be any form such as an organic solvent type, a non-aqueous dispersion type, an aqueous solution type, an aqueous dispersion (slurry) type, a high solid type, and a powder type. Things can be used. An organic solvent type and a non-aqueous dispersion type are particularly preferable.

The content of the surface conditioning agent (A) in the coating composition is based on 100 parts by mass of the resin solid content contained in the coating composition from the viewpoint of the stain resistance of the content of the copolymer (a). Is preferably adjusted to be in the range of preferably 0.1 to 15 parts by mass, more preferably 0.5 to 8.0 parts by mass.

Here, the resin solid content contained in the coating composition of the present invention is the solid content of all resins except the surface conditioner (A), and is a base resin to be described later and a cross-link for curing the same. When a coating composition containing an agent is used, it means the total resin solid content of all of the base resin and the crosslinking agent.

As the coating composition, in particular, a coating composition containing a base resin having a crosslinkable functional group and a cross-linking agent for cross-linking and curing the base resin is preferable from the viewpoint of the coating film appearance and stain resistance obtained. . Examples of the base resin include acrylic resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, epoxy / polyester resin, alkyd resin, polyurethane resin, and polyamide resin. Examples of the crosslinkable functional group include a hydroxyl group, an epoxy group, a carboxyl group, and a silanol group. These can be used alone or in combination of two or more. Among them, the base resin contains, as at least a part thereof, a coating composition containing a hydroxyl group-containing resin (B) and a crosslinking agent (C) that reacts with a hydroxyl group, and an acid group-containing resin and an epoxy group-containing resin. A coating composition is preferred.

Hydroxyl-containing resin (B)
As the resin of the hydroxyl group-containing resin (B), a hydroxyl group-containing acrylic resin and / or a hydroxyl group-containing polyester resin are preferable from the viewpoint of improving stain resistance, coating film hardness, and processability, and a hydroxyl group-containing polyester resin is particularly preferable. .

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

The hydroxyl group-containing polymerizable unsaturated monomer is a compound having at least one hydroxyl group and one polymerizable unsaturated bond in one molecule, and specifically includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Monoesterified products of (meth) acrylic acid such as propyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and dihydric alcohols having 2 to 8 carbon atoms; Ε-caprolactone modified product of monoesterified product of acrylic acid and dihydric alcohol having 2 to 8 carbon atoms; N-hydroxymethyl (meth) acrylamide; allyl alcohol, and further polyoxyethylene chain having a hydroxyl group at the molecular end A (meth) acrylate etc. can be mentioned.

Examples of other polymerizable unsaturated monomer copolymerizable with a hydroxyl group-containing polymerizable unsaturated monomer include, for example, alkyl or cycloalkyl (meth) acrylate; polymerizable unsaturated monomer having an isobornyl group; polymerization having an adamantyl group Polymerizable unsaturated monomer; Vinyl aromatic compound; Polymerizable unsaturated monomer having alkoxysilyl group; Perfluoroalkyl (meth) acrylate; Polymerizable unsaturated monomer having fluorinated alkyl group; Polymerizability having photopolymerizable functional group Unsaturated monomer; vinyl compound; carboxyl group-containing polymerizable unsaturated monomer; nitrogen-containing polymerizable unsaturated monomer; polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule; Saturated monomer; having a polyoxyethylene chain whose molecular end is an alkoxy group (Meth) acrylate; polymerizable unsaturated monomer having a sulfonic acid group; polymerizable unsaturated monomer having a phosphoric acid group; polymerizable unsaturated monomer having a UV-absorbing functional group; polymerizable unsaturated monomer compound having a carbonyl group These may be used alone or in combination of two or more.
Examples of the alkyl or cycloalkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (Meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (Meth) acrylate, stearyl (meth) acrylate, isostearyl acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, Rododeshiru (meth) acrylate.
Examples of the polymerizable unsaturated monomer having an isobornyl group include isobornyl (meth) acrylate.
Examples of the polymerizable unsaturated monomer having an adamantyl group include adamantyl (meth) acrylate.
Examples of the vinyl aromatic compound include styrene, α-methylstyrene, vinyltoluene and the like.

Examples of the polymerizable unsaturated monomer having an alkoxysilyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, and γ-meth) acryloyloxy. Examples thereof include propyltriethoxysilane.
Examples of the perfluoroalkyl (meth) acrylate include perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate.
Examples of the polymerizable unsaturated monomer having a fluorinated alkyl group include fluoroolefins.
Examples of the polymerizable unsaturated monomer having a photopolymerizable functional group include a maleimide group.
Examples of the vinyl compound include N-vinyl pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate and the like.
Examples of the carboxyl group-containing polymerizable unsaturated monomer include (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl (meth) acrylate, and the like.
Nitrogen-containing polymerizable unsaturated monomers include (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, and glycidyl (meth) acrylate. Examples include adducts with amine compounds.
Examples of the polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule include allyl (meth) acrylate and 1,6-hexanediol di (meth) acrylate.
Examples of the epoxy group-containing polymerizable unsaturated monomer include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, Examples include 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl ether, and the like.

Examples of the polymerizable unsaturated monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, styrenesulfonic acid sodium salt, sulfoethyl methacrylate and its sodium salt, ammonium salt and the like.
Examples of the polymerizable unsaturated monomer having a phosphoric acid group include 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate and the like.
Polymerizable unsaturated monomer having a UV-absorbing functional group; UV-stable polymerizable unsaturated monomers include 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- ( 3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3-acryloyloxy-2 -Hydroxypropoxy) benzophenone, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole and the like.
Examples of UV-stable polymerizable unsaturated monomers include 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetra Methylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6- Tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetra Methylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6 Tetramethylpiperidine, and the like.
Examples of the polymerizable unsaturated monomer compound having a carbonyl group include acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrol, and vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone). Vinyl ethyl ketone, vinyl butyl ketone) and the like.

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

The weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably 2000 to 30000, and particularly preferably has a weight average molecular weight in the range of 3000 to 25000, from the viewpoint of coating film hardness, workability, and finish of the obtained coating film. .

The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably in the range of 10 to 200 mgKOH / g, particularly 60 to 185 mgKOH / g, from the viewpoint of the coating film hardness and stain resistance of the resulting coating film.

The type of the hydroxyl group-containing polyester resin is not particularly limited, and examples thereof include a reaction product by an esterification reaction or a transesterification reaction with a polybasic acid component and a polyhydric alcohol component. As said polybasic acid component, an alicyclic polybasic acid component, an aliphatic polybasic acid component, an aromatic polybasic acid component, etc. can be used, for example.

As the polyhydric alcohol component, a polyhydric alcohol having two or more hydroxyl groups in one molecule can be suitably used. Examples of the polyhydric alcohol include alicyclic diols, aliphatic diols, aromatic diols, and trihydric or higher polyhydric alcohols.

Further, the hydroxyl group-containing polyester resin may be modified with a fatty acid, an oil, a fat, a monoepoxy compound, a monoalcohol compound, a polyisocyanate compound or the like during the preparation of the resin or after the esterification reaction or the transesterification reaction. Good.

The number average molecular weight of the hydroxyl group-containing polyester resin is preferably 2000 to 30000, and particularly preferably within the range of 3000 to 25000, from the viewpoints of coating film hardness, workability, and finish of the obtained coating film.

The hydroxyl value of the hydroxyl group-containing polyester resin is preferably in the range of 10 to 200 mgKOH / g, particularly 60 to 185 mgKOH / g, from the viewpoint of the coating film hardness and stain resistance of the resulting coating film. The acid value of the hydroxyl group-containing polyester resin is 30 mgKOH / g or less, preferably 1 to 20 mgKOH / g from the viewpoint of processability.

Cross-linking agent (C)
The crosslinking agent (C) can be used without particular limitation as long as it reacts with a hydroxyl group, and examples thereof include melamine resins, urea resins, guanamine resins, and polyisocyanate compounds that may be blocked.

The content of the crosslinking agent (C) can be appropriately adjusted so that the coating film is cured and has sufficient performance. From the viewpoint of curability of the resulting coating film, the ratio of the hydroxyl group-containing resin (B) / crosslinking agent (C) is preferably in the range of 85/15 to 50/50 by mass ratio. When a polyisocyanate compound is used as the cross-linking agent (C), the blending ratio thereof is usually such that the equivalent ratio (NCO / OH) between the isocyanate group of the polyisocyanate compound and the hydroxyl group of the hydroxyl group-containing resin in the coating composition is 0. The range of 0.5 to 2, preferably 0.7 to 1.8 is suitable.

Anionic surfactant (D)
The coating composition of the present invention can contain an anionic surfactant (D) in combination with the surface conditioner (A) for the purpose of improving stain resistance.

Examples of the anionic surfactant (D) include alkyldiphenyl ether disulfonate-based anionic surfactant (d1), polyoxyethylene alkyl ether sulfate-based anionic surfactant (d2), and alkylbenzene. Examples thereof include at least one anionic surfactant selected from the group consisting of a sulfonate anionic surfactant (d3) and a sulfosuccinate anionic surfactant (d4).

Alkyl diphenyl ether disulfonate anionic surfactant (d1)
The alkyldiphenyl ether disulfonate-based anionic surfactant (d1) (hereinafter sometimes abbreviated as anionic surfactant (d1)) is an alkyldiphenyl ether having the structural formula represented by the following formula (IV). A disulfonic acid or its metal salt can be mentioned. Among these, alkyl diphenyl ether disulfonic acid sodium salt is particularly preferable from the viewpoint of improving stain resistance.

[In the formula (IV), R represents an alkyl group having 1 to 15 carbon atoms, and M ⁺ represents H ⁺ , Na ⁺ , K ⁺ , Li ⁺ , NH ₄ ⁺ or an organic ammonium ion)
Examples of commercially available anionic surfactants (d1) include Perex SS-L, Perex SS-H (Kao Corporation), New Coal 261-A, New Coal 271-A (Nippon Emulsifier Co., Ltd.) and the like. It is done.

Polyoxyethylene alkyl ether sulfate anionic surfactant (d2)
The polyoxyethylene alkyl ether sulfate ester-based anionic surfactant (d2) (hereinafter sometimes abbreviated as anionic surfactant (d2)) is a structure represented by the following general formula (V) Mention may be made of the polyoxyethylene alkyl ether sulfates of the formula or their metal salts. Among these, polyoxyethylene alkyl ether sulfate sodium salt is particularly preferable from the viewpoint of improving stain resistance.

[R in the formula (V) is a hydrocarbon group having 1 to 50 carbon atoms, a represents 1 to 30, M ⁺ represents H ⁺ , Na ⁺ , K ⁺ , Li ⁺ , NH ₄ ⁺ or an organic ammonium ion. To express]
Commercially available products of the anionic surfactant (d2) include, for example, New Coal 707SN, New Coal 714SF, New Coal 2308SF, New Coal 2360SN (Nippon Emulsifier Co., Ltd.), Latem E-118B, Latem E-150, Latem WX, Laterum PD-140 (Kao Corporation) and the like.

Alkylbenzenesulfonate anionic surfactant (d3)
As the alkylbenzene sulfonate-based anionic surfactant (d3) (hereinafter sometimes abbreviated as anionic surfactant (d3)), an alkylbenzene sulfonic acid having a structural formula represented by the following formula (VI) Or the metal salt can be mentioned. Among these, alkylbenzenesulfonic acid sodium salt is particularly preferable from the viewpoint of improving the stain resistance.

[In the formula (VI), R represents a hydrocarbon group having 1 to 15 carbon atoms, and M ⁺ represents H ⁺ , Na ⁺ , K ⁺ , Li ⁺ , NH ₄ ⁺ or an organic ammonium ion)
Examples of commercially available anionic surfactants (d3) include New Coal 210, New Coal 220-L (Nippon Emulsifier Co., Ltd.), Neoperex G-15, Neoperex G-25 (Kao Co., Ltd.) and the like. It is done.

Sulfosuccinate anionic surfactant (d4)
The sulfosuccinate-based anionic surfactant (d4) (hereinafter sometimes abbreviated as anionic surfactant (d4)) is a dialkylsulfosuccinate having the structural formula represented by the following general formula (VII). An acid or its metal salt can be mentioned.

[R in formula (VII) is the same or different and each represents an alkyl group having 1 to 15 carbon atoms. M ⁺ represents H ⁺ , Na ⁺ , K ⁺ , Li ⁺ , NH ₄ ⁺ or an organic ammonium ion]
Specifically, for example, monoalkyl sulfosuccinic acid ester salt, dialkyl sulfosuccinic acid ester salt, sulfosuccinic acid alkyl disalt, polyoxyethylene alkyl sulfosuccinic acid disalt, alkylamine oxide bistridecyl sulfosuccinate sodium, dioctyl sulfosuccinate sodium, dihexyl Sodium sulfosuccinate, sodium dicyclohexylsulfosuccinate, sodium diamylsulfosuccinate, sodium diisobutylsulfosuccinate, disodium isodecylsulfosuccinate, N-octadecylsulfosuccinamide disodium, N- (1,2-dicarboxyethyl) -N- And octadecyl sulfosuccinamide tetrasodium. Among these, a dialkylsulfosuccinic acid sodium salt is particularly preferable from the viewpoint of improving stain resistance.

Commercially available products of the anionic surfactant (d4) include Perex OT-P, Perex TR, Perex CS, Perex TA (Kao Corporation), New Coal 290-A, New Coal 290-M, New Coal 291- M, New Coal 291-PG, New Coal 291-GL, New Coal 292-PG, New Coal 293 (Nippon Emulsifier Co., Ltd.), Neocoal SW-C, Neocoal YSK, Neocoal P (Daiichi Kogyo Seiyaku Co., Ltd.) It is done.

Also, the alkyldiphenyl ether disulfonate anionic surfactant (d1), the polyoxyethylene alkyl ether sulfate ester anionic surfactant (d2), and the alkylbenzene sulfonate anionic surfactant ( At least one anionic surfactant selected from the group consisting of d3) and at least one surfactant selected from the sulfosuccinate-based anionic surfactant (d4) are: [Anionic surfactant (d1) + anionic surfactant (d2) + anionic surfactant (d3)] / anionic surfactant (d4) = 20/80 to 75/25 (Mass ratio), preferably in the range of 44/56 to 70/30 (mass ratio), a coating film excellent in stain resistance, coating film hardness and workability is obtained. Desirable in order.

When the anionic surfactant (D) is blended in the coating composition of the present invention, the content thereof is 0.1 to 20 parts by weight, preferably 100 parts by weight based on the total resin solid content in the coating composition, The amount of 2 to 10 parts by weight, more preferably 2 to 6 parts by weight, is suitable from the viewpoint of obtaining a coating film excellent in stain resistance, coating film hardness and workability.

Other components In addition, the coating composition may include, as necessary, other components such as a lubricity imparting agent, a pigment such as a color pigment, an extender pigment, and a rust preventive pigment, a curing catalyst (for example, the crosslinking agent is an amino resin). In the case of a sulfonic acid compound or an amine neutralized product of a sulfonic acid compound, and in the case of a blocked polyisocyanate compound, examples include organometallic compounds such as tin octylate, dibutyltin dilaurate, and zinc octylate). , Pigment dispersants, ultraviolet absorbers, ultraviolet stabilizers, antifoaming agents, surface modifiers other than the surface modifier (A), cationic surfactants, fluorosurfactants, resin particles, silica fine powders, etc. It can contain known materials conventionally used in paints such as matting agents, diluting solvents and organic solvents. Moreover, a sensitizer, an antistatic agent, an antifoamer, a dispersing agent, a viscosity modifier, etc. may be mix | blended with a coating composition as needed.

Coating Film Forming Method The coating film forming method for the coating composition containing the surface conditioner (A) of the present invention is appropriately selected depending on the curing method of the resin of the applied coating composition. The article to which the coating composition containing the surface conditioner (A) of the present invention is applied is not particularly limited. For example, a metal substrate such as a steel plate, aluminum, tin, etc .; mortar, cement, plastic And other base materials such as glass and glass; those obtained by subjecting these base materials to surface treatment and / or film formation. Among these, metal substrates, particularly those using a steel plate as a base material, and plastics as a base material can be suitably used. Examples of the steel sheet include cold-rolled steel sheet, hot-dip galvanized steel sheet, electrogalvanized steel sheet, aluminum-plated steel sheet, stainless steel sheet, copper-plated steel sheet, tin-plated steel sheet, lead-tin alloy-plated steel sheet (turn sheet); iron-zinc, aluminum -Zinc, nickel-zinc and other zinc alloy plated steel sheets. Examples of the steel plate subjected to the surface treatment include a steel plate obtained by subjecting the steel plate to chemical conversion treatment such as phosphate treatment and chromate treatment.

A primer coating film may be formed on one side or both sides of the metal substrate.

As the primer of the present invention, known primers known in the colored color steel sheet coating field, industrial machine coating field, metal part coating field, and the like can be applied.

Examples of the method for applying the coating composition to which the present invention is applied include air spray, airless spray, rotary atomization, brush, roller, hand gun, universal gun, dipping, roll coater, curtain flow coater, roller curtain coater, die coater, etc. Can be selected as appropriate according to the application of the object to be coated, etc., and may be applied a plurality of times.

The coating film thickness is usually 5 to 100 μm, preferably 10 to 50 μm, more preferably 15 to 35 μm in terms of the cured film thickness.

The paint of the present invention may be cured at room temperature or heat.

The heating temperature and time in the case of heat curing can be appropriately selected according to the material to be applied. The ultimate temperature of the material is preferably 120 to 260 ° C. and about 15 seconds to 30 minutes. The heating temperature when applying a material that may be deformed by heating (for example, a plastic substrate) is preferably 30 to 100 ° C., and more preferably 35 to 90 ° C., for example. The heating time is, for example, preferably 5 to 120 minutes, more preferably 10 to 100 minutes.

Since the coating composition to which the present invention is applied is excellent in stain resistance, it is particularly suitable to be used as a top coating composition.

It may be processed after the coating composition to which the present invention is applied is applied.

The use of the object to be coated with the coating composition to which the present invention is applied is not particularly limited, and an article or part thereof requiring stain resistance is particularly preferable. Examples thereof include outdoor base materials such as buildings, display objects, guard fences, roofs, construction machinery, automobile and bicycle bodies and exterior parts, and home appliances.

The contamination resistance can be expressed in the obtained cured coating film by simply adding a small amount of the surface conditioner (A) containing the copolymer (a) of the present invention to the coating composition. In addition, the coating film formed from the coating composition containing the surface conditioner (A) of the present invention is excellent in stain resistance without deteriorating the appearance and physical properties of the resulting coating film, and has been exposed to the outdoors for a long time. Even afterwards, sufficient stain resistance can be exhibited, and the durability is excellent.

Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” indicate “part by mass” and “% by mass” unless otherwise specified.

Example 1
100 parts by weight of propylene glycol monomethyl ether was added to a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet, and the temperature was raised to 100 ° C. in a nitrogen gas atmosphere. The temperature of propylene glycol monomethyl ether was maintained at 100 ° C., and mixed solution 1 in which 1.0 part of V-59 (Note 12) was mixed in advance with the monomer composition and polymerization initiator shown in Table 1 was added for 2 hours using a dropping funnel. At a constant speed. After completion of the dropwise addition, the monomer solution was reacted for 2 hours while maintaining the temperature at 100 ° C. to obtain copolymer (a) No. 1 was obtained. This copolymer (a) No. The weight average molecular weight of 1 was 4200 in terms of polystyrene. This copolymer (a) No. No. 1 was adjusted with propylene glycol monomethyl ether to a solid content of 25%. It was set to 1.

(Examples 2, 3 and 5-18)
The copolymer (a) No. 1 was prepared in the same manner as in Example 1 except that the monomer composition and blending amount of each copolymer component in Example 1 were as shown in Table 1 below. Surface conditioning agent (A) No. 2 containing 2, 3 and 5-18 2, 3 and 5-18 were obtained. The solid content of the surface conditioner (A) was adjusted with propylene glycol monomethyl ether so that the solid content was 25%. The weight average molecular weight of each copolymer (a) is shown together in Table 1.

(Note 1) 3- (Acrylamide) propyltrimethylammonium chloride: quaternary ammonium base-containing polymerizable unsaturated monomer, compound represented by the following (a1-1), molecular weight 206.7

(Note 2) 2- (methacryloyloxy) ethyltrimethylammonium chloride: quaternary ammonium base-containing polymerizable unsaturated monomer, compound represented by the following (a1-2), molecular weight 207.7

(Note 3) N- [2- (acryloyloxy) ethyl] -N-benzyl-N, N-dimethylammonium chloride: a quaternary ammonium base-containing polymerizable unsaturated monomer, represented by the following (a1-3) Compound, molecular weight 269.8

(Note 4) 3- (acryloylamino) propyl-N, N-dimethylamine: tertiary amino group-containing polymerizable unsaturated monomer, compound represented by the following (a1-4), molecular weight 156.23

(Note 5) N, N-dimethylacrylamide: compound represented by the following (a2-1), molecular weight 99.13

(Note 6) N, N-diethylacrylamide: compound represented by the following (a2-2), molecular weight 127.19

(Note 7) N-isopropylacrylamide: a compound represented by the following (a2-3), molecular weight 113.16

(Note 8) Silaplane FM-0711: trade name, manufactured by JNC, one-end type methacryl-modified polydimethylsiloxane, linear polysiloxane chain-containing polymerizable unsaturated monomer, weight average molecular weight 1,000
(Note 9) X-22-2404: Trade name, manufactured by Shin-Etsu Chemical Co., Ltd., one-end type methacryl-modified polydimethylsiloxane, branched polysiloxane chain-containing polymerizable unsaturated monomer, weight average molecular weight 420, unsaturated functional group Equivalent 420

(Note 10) “Blemmer PME-400”: trade name, manufactured by NOF Corporation, methoxypolyethylene glycol methacrylate, number of oxyethylene repeating units≈9

(Note 11) 2-acrylamido-2-methylpropanesulfonic acid: other polymerizable unsaturated monomer

(Note 12) V-59: trade name, manufactured by Wako Pure Chemical Industries, Ltd., 2,2'-azobis (2-methylbutyronitrile), polymerization initiator

Example 4
100 parts by weight of propylene glycol monomethyl ether was added to a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet, and the temperature was raised to 100 ° C. in a nitrogen gas atmosphere. The temperature of propylene glycol monomethyl ether was maintained at 100 ° C., and 1.0 part of 2,2′-azobis (2-methylbutyronitrile) was previously added to the monomer composition and polymerization initiator described in the first stage column of Table 1. The mixed solution 1 was added dropwise at a constant rate over 2 hours using a dropping funnel. After completion of dropping, the monomer solution was reacted for 2 hours while maintaining at 100 ° C. to obtain a copolymer.
The solution was cooled to about 30 ° C., the dropping funnel was replaced with a methyl chloride introduction tube, and the reaction was carried out at 30 ° C. for 8 hours while introducing methyl chloride. After completion of the reaction, the reaction mixture was degassed under vacuum to drive off unreacted methyl chloride. 4 was obtained. Copolymer (a) No. No. 4 was adjusted with propylene glycol monomethyl ether to a solid content of 25%. It was set to 4. The weight average molecular weight of the copolymer (a) was 4200 in terms of polystyrene, and the concentration of the quaternary ammonium salt was 15% by mass. The quaternary ammonium salt concentration was determined by using a potentiometric automatic titrator (apparatus name: AT-310 manufactured by Kyoto Electronics Industry Co., Ltd.) using a sodium tetraphenylborate solution (manufactured by Kanto Chemical Co., Ltd.) having a concentration of 0.02 mol / L. Titration was performed for confirmation.

(Comparative Examples 1 to 8)
The copolymer (a) No. 1 was prepared in the same manner as in Example 1 except that the monomer composition and blending amount of each copolymer component in Example 1 were as shown in Table 2 below. Surface conditioning agent (A) No. 19 containing 19 to 26 19-26 were obtained. The solid content of the surface conditioner (A) was adjusted with propylene glycol monomethyl ether so that the solid content was 25%. The weight average molecular weight of each copolymer (a) is shown together in Table 2.

(Example 19) Coating composition No. 1
Surface conditioning agent (A) No. obtained in Example 1 No. 1 25% solution 24 parts (solid content 6 parts), hydroxyl group-containing resin No. 1 160 parts of a 50% solution of B-1 (Note 13) (80 parts of solid content), Cymel 303 (Note 15) as a cross-linking agent C-1 20 parts of solid content, and Taipei CR-95 (Note 19) as a pigment 120 Part, 0.5 part of dodecylbenzenesulfonic acid as a curing catalyst, 3.0 part of solid content of anionic surfactant Neucor 291-M (Note 14), organic solvent (cyclohexanone / swazol 1500 = 40/60 ( (Mass ratio) mixed solvent was added for dilution to obtain a coating composition No. 1.

(Examples 19 to 36 and Comparative Examples 9 to 17)
In Example 19, except that the blending of each component was changed to the blending shown in Table 3, in the same manner as in Example 19, the coating composition No. 2 to No. 27 was obtained. In addition, the compounding quantity of Table 3 shows the compounding quantity of solid content.

(Note 13) Hydroxyl-containing resin No. B-1: Hydroxyl group-containing polyester resin A reactor equipped with a thermometer, a stirrer, a heating device and a rectifying tower was charged with 1079 parts of isophthalic acid, 407 parts of adipic acid, 466 parts of neopentyl glycol and 802 parts of trimethylolpropane, The temperature was raised to 160 ° C., and the temperature was gradually raised from 160 ° C. to 230 ° C. over 3 hours. Next, after continuing the reaction at 230 ° C. for 30 minutes, the rectifying column was replaced with a water separator, and 124 parts of xylene was added to the contents, and xylene was also added to the water separator to azeotrope water and xylene. The condensed water was removed, the reaction was continued until the acid value reached 10 mgKOH / g, the mixture was cooled, and 855 parts of cyclohexanone was added to the reaction product to obtain a polyester resin solution having a solid content of 55%. The number average molecular weight of the obtained resin was 3400, and the hydroxyl value was 184 mgKOH / g.

(Note 14) Hydroxyl-containing resin No. B-2: A reaction vessel equipped with a hydroxyl group-containing acrylic resin thermometer, thermostat, stirrer, reflux condenser and dropping device was charged with 480 parts of butyl acetate, heated to 130 ° C. while blowing nitrogen gas, and then the temperature was adjusted. While being held, a mixed solution of 200 parts of styrene, 290 parts of methyl methacrylate, 250 parts of cyclohexyl methacrylate, 260 parts of 2-hydroxyethyl methacrylate and 50 parts of 22′-azobis (2-methylbutyronitrile) from the dropping device for 3 hours. It was dripped over. After completion of dropping, the reaction product was aged at 130 ° C. for 1 hour, and the solid content was adjusted with cyclohexanone to obtain an acrylic resin solution having a resin solid content of 55%. The obtained resin had a weight average molecular weight of 9000 and a hydroxyl value of 107 mgKOH / g.

(Note 15) Crosslinker C-1: Cymel 303, trade name, manufactured by Daicel Ornex, methyl etherified melamine resin (Note 16) Crosslinker C-2: Sumidur BL3175, trade name, Sumika Covestrourethane Co., Ltd. Made by company, solid content 75% by mass, HDI nurate oxime block, NCO%: 11.2%
(Note 17) Anionic surfactant D-1: Neucor 291-M, trade name, dialkyl succinate sulfonate Na salt, active ingredient 70%
(Note 18) Anionic surfactant D-2: New Coal 714-SF, trade name, polyoxyethylene polycyclic phenyl ether sulfate, active ingredient 30%
(Note 19) TIPAQUE CR-95: Product name, manufactured by Ishihara Sangyo Co., Ltd., titanium white, coloring component

<Creation of test coating plate>
The coating composition No. obtained in the above Examples and Comparative Examples was applied to the article 1 by a roll coater. 1 to 27 were each coated to a dry film thickness of 18 μm, and baked for 40 seconds under the condition that the maximum material arrival temperature was 220 ° C. to obtain each test plate. Table 3 shows the test results of each test plate according to the test conditions described later.

Coating object 1: A zinc-aluminum alloy plated steel plate (GL material, plate thickness 0.35 mm) formed with a primer coating film having a dry film thickness of 3 μm.

<Evaluation test>
The test methods and evaluation criteria for each evaluation item are as follows.

(Test item 1.) Initial appearance of painted surface:
A: There are no paint surface abnormalities such as repellency, dents or cloudiness on the paint surface.
B: Although paint surface abnormalities such as repellency and dent are not recognized, the paint surface is cloudy.
C: Abnormalities in the coating surface such as repellency and dents are observed on the coating surface.

(Test item 2.) Contact angle:
With reference to the test method described in JIS R3257 (1999), 2 μL of distilled water is dropped from a syringe onto the coating surface of each test plate in an atmosphere of 23 ° C. and 65% RH and left to stand. The contact angle 1 was measured using a “contact angle meter CA-X150 (trade name, manufactured by Kyowa Interface Science Co., Ltd.)”. Further, the distance between the tip of the syringe and the coating surface was maintained at 1 mm, 200 μL of water was squeezed out, and water was sucked up again, and the contact angle 2 of the remaining water droplets was measured using the same apparatus.
An average of three test tests with different test locations on the test coating plate, with contact angle 1 as the static contact angle (static drop method) and contact angle 2 as the dynamic contact angle (contact angle during contraction in the expansion / contraction method) The value was evaluated according to the following criteria. The lower the value of the contact angle, the more hydrophilic the coating film is.

(Static contact angle)
S: The static contact angle is less than 70 °,
A: The static contact angle is 70 ° or more and less than 75 °,
B: The static contact angle is 75 ° or more and less than 80 °,
C: The static contact angle is 80 ° or more.
(Dynamic contact angle)
S: Dynamic contact angle is less than 15 °,
A: The dynamic contact angle is 15 ° or more and less than 25 °,
B: The dynamic contact angle is 25 ° or more and less than 35 °,
C: The dynamic contact angle is 35 ° or more.

(Test item 3.) Hydrophilic sustainability:
Each test plate was immersed in deionized water at 20 ° C. for 24 hours. Thereafter, the contact angle was measured in the same manner as in Test Item 2 and evaluated according to the same criteria.

(Test item 4.) Contamination resistance 1: Carbon adhesion test
A 10 mass% aqueous dispersion of carbon pigment (FW-200, trade name, manufactured by Orion Engineer Carbons) was used as a model contaminated water on the surface of the coating film of each test plate, and 2 g of the contaminated water was spot-dropped. After baking at 30 ° C. for 30 minutes, after washing with a sponge lightly, the color difference ΔE between the initial non-contaminated part and the contaminated part was measured. For the measurement, a colorimeter SP-64 manufactured by X-rite was used.

S: ΔE is in the range of less than 1.
A: ΔE is within the range of 1 or more and less than 2.
B: ΔE is in the range of 2 or more and less than 5.
C: ΔE is 5 or more.

(Test item 5.) Contamination resistance 2: Outdoor exposure test
Each test plate cut to a size of 100 x 300 mm is used as a test plate for outdoor exposure, and each test plate for outdoor exposure is used as an installation table that models the eaves of the roof of Kansai Paint Co., Ltd. in Ota-ku, Tokyo. A mounting exposure test was conducted at an angle of 4 degrees from the vertical so that the coating faced north. In “1 month after the start of exposure” and “3 months after the start of exposure”, the color difference (ΔE) from the initial coated plate was measured using a multi-light source spectrocolorimeter MSC-5N manufactured by Suga Test Instruments Co., Ltd. Based on JIS-K5600-4-6, it was evaluated according to the following criteria.

S: ΔE is in the range of less than 1.
A: ΔE is within the range of 1 or more and less than 2.
B: ΔE is in the range of 2 or more and less than 5.
C: ΔE is 5 or more.

Claims (7)

1. A surface conditioner (A) containing a copolymer (a) having a weight average molecular weight in the range of 1,000 to 50,000,
   The copolymer (a) is:
   (A1) a tertiary amino group-containing polymerizable unsaturated monomer and / or a quaternary ammonium base-containing polymerizable unsaturated monomer,
   (A2) N-substituted (meth) acrylamide having a molecular weight of less than 145, and (a3) a polysiloxane chain-containing polymerizable unsaturated monomer having a weight average molecular weight in the range of 420 to 4600, as a copolymerization component, and A surface conditioner (copolymer (a) in which the content ratio of the monomer (a1) and the monomer (a2) is in the range of (a1) / (a2) = 5/95 to 55/45 by mass ratio ( A).
2. The copolymer (a) is a hydroxyl group-containing (meth) acrylate, an optionally blocked isocyanate group-containing (meth) acrylate, an alkyl (meth) acrylate compound, a polyoxyalkylene chain-containing (meth) acrylate compound, (meth ) At least one polymerizable selected from the group consisting of an acrylamide compound (excluding the monomer (a1) or monomer (a2)), a vinyl group-containing compound, and a polymerizable unsaturated compound having a nitrogen atom-containing heterocyclic ring. The surface conditioning agent (A) according to claim 1, further comprising an unsaturated group monomer (a4).
3. A coating composition containing the surface conditioner (A) according to claim 1 or 2.
4. The surface conditioning agent (A) according to claim 1 or 2, a hydroxyl group-containing resin (B), and a crosslinking agent (C) that reacts with a hydroxyl group, and the surface conditioning agent (A) is contained in the coating composition. The coating composition according to claim 3, comprising 0.1 to 15 parts by mass based on 100 parts by mass of the resin solid content.
5. Furthermore, the coating composition of Claim 3 or Claim 4 containing an anionic surfactant (D).
6. The anionic surfactant (D) is an alkyldiphenyl ether disulfonate anionic surfactant (d1), a polyoxyethylene alkyl ether sulfate ester anionic surfactant (d2), or an alkylbenzene sulfonate. 6. The coating composition according to claim 5, which is at least one anionic surfactant selected from the group consisting of an anionic surfactant (d3) based on a system and an anionic surfactant (d4) based on a sulfosuccinate. .
7. A coating film forming method comprising a step of coating a coating composition with the coating composition according to any one of claims 3 to 6 to form a coating film.