JP2006089589A - Water-dispersible resin treating agent for metal surface and surface-treated metal plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-dispersible resin-treating agent for metal surface, excellent in a rust-proofing property, adhesion, etc. to a metal, etc., and suitable for surface treatment and primer coating of steel plate, Galvalume(R) steel plate, etc., not requiring chromium. <P>SOLUTION: The water-dispersible resin treating agent for metal surface comprises (A) a water-dispersible resin composition containing a copolymer resin emulsion obtained by carrying out emulsion polymerization of an unsaturated monomer mixture composed of a polymerizable unsaturated monomer (a) not containing any one of an epoxy group, an acid group and a hydroxy group, a polymerizable unsaturated monomer (b) having an epoxy group, an acid group-containing polymerizable unsaturated monomer (c), a hydroxy group-containing polymerizable unsaturated monomer (d) and a cyclic ureido group-containing polymerizable unsaturated monomer (e) having a specific structure, (B) a zirconium compound and (C) a silane coupling agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a water-dispersible resin treatment agent for metal surfaces and a surface-treated metal plate. More specifically, the present invention relates to rust prevention, adhesion to metals, alkyd paint, foamed polyurethane as a building material insulation, adhesion to topcoat materials such as foamed polyethylene, water resistance, boiling water resistance, alkali resistance and resistance. The present invention relates to a water-dispersible resin treatment agent for metal surfaces and a surface-treated metal plate that are excellent in blocking properties and that do not contain chromic acid or chromate pigments and that are suitable for surface treatment of general steel plates, galvanized steel plates, galvalume steel plates and the like.

  Conventionally, pre-coating of undercoat paint for interior and exterior of buildings, metal furniture such as furniture, home appliance housing, agricultural vinyl house struts, roofing materials for livestock huts, automobile bodies, chassis, engine surroundings and cans Organic solvent alkyd phthalate paints, urethane paints, and epoxy resin paints have been used as undercoat paints for steel plates (pre-coated metals). However, in recent years, the use of water-based resin paints has been demanded in place of conventional organic solvent-based paints due to global environmental problems caused by organic solvents and the risk of fire. However, conventional water-based resin paints are inferior in rust prevention, adhesion to metals, adhesion to top coating materials, water resistance, boiling water resistance, alkali resistance, blocking resistance, slipping properties, etc. It was not enough to replace paint.

  Regarding the corrosion of the metal surface, for example, in the galvanized steel sheet, white rust is generated on the surface due to the oxidative corrosion of zinc by oxygen in the atmosphere. Also, in the case of the so-called Galvalume steel plate, which is a 55% aluminum / galvanized steel plate, it is used in large quantities without being painted as a building material, for example, due to its beautiful appearance, but it is exposed to the strong alkali of cement materials such as concrete. Then, aluminum is corroded by alkali and black rust is generated. In either of these cases, the appearance is remarkably deteriorated, and the durability is also adversely affected.

  Therefore, in order to improve the corrosion resistance and durability performance of these metal materials, a chromate treatment is generally performed in which the surface is treated with a treatment liquid containing chromic acid, dichromic acid or a salt thereof (for example, Japanese Patent No. 2097278). JP-A-7-251128 and JP-A-2000-5697). However, hexavalent chromium during the chromate treatment has a serious adverse effect directly on the human body, and it has remarkably receded from the viewpoint of global environmental ecology.

  Therefore, Japanese Patent Application Laid-Open No. 2003-201578 discloses a water-soluble urethane resin having a carboxyl group and an acid amide bond, N-methylpyrrolidone, a zirconium metal compound, and a silane coupling on the surface of an aluminum / zinc alloy-plated steel sheet. A surface treatment agent containing an agent has been reported. However, first of all, water-soluble urethane resins have very poor water resistance and are far from being able to withstand such demands. Even when the description of a water-soluble urethane resin is interpreted in a broad sense and used as an aqueous urethane dispersion, it generally has a drawback of being inferior in weather resistance and being expensive compared to an acrylic resin or the like. In addition, it contains N-methylpyrrolidone which is a high boiling point solvent, which is a problem from the viewpoint of environmental hygiene.

  Next, JP 2003-201579 A discloses a water-based resin having a carboxyl group and an acid amide bond —CONH—, specifically, a urethane resin or an acrylic resin, Al, Mg, Ca, Zn, Ni, Co, A surface treatment agent for metal plate materials containing a metal compound of Fe, Zr, Ti, V, W, Mn and Ce and a silicon compound has been introduced. Among these, the urethane resin has the drawbacks of weather resistance and economy, and the acrylic resin has a water-dispersible resin having an acid amide bond —CONH— that is too reactive with the above metal compound or silicon compound, Due to poor mixing stability and short life, workability is extremely poor, and there is a problem in industrial application.

  Thus, in the prior art, a water-dispersible resin treatment agent for metal surfaces that satisfies the above requirements and is suitable for surface treatment of galvalume steel plates and the like that do not contain chromium at all has not been obtained.

Japanese Patent No. 2097278 JP 7-251128 A JP 2000-5697 A JP 2003-151578 A JP 2003-201579 A

  The object of the present invention is to overcome the drawbacks of the conventional water-dispersible resin treatment agents for metal surfaces, and to provide anti-corrosion properties, adhesion to metals, alkyd paints, foamed polyurethane as a building material insulation, foamed polyethylene, and other top coating materials. Excellent metal adhesion, water resistance, boiling water resistance, alkali resistance and blocking resistance, and does not require chromic acid or chromate pigments. Suitable metal surface for surface treatment and undercoating of steel plates, galvalume steel plates, etc. An object of the present invention is to provide a water-dispersible resin treatment agent and a surface-treated steel sheet.

  As a result of extensive studies, the present inventor has obtained a water-dispersible resin composition containing a copolymer resin emulsion obtained by emulsion polymerization of an unsaturated monomer mixture having a specific composition as the component (A); The present invention has been accomplished by finding that the above object can be achieved by a water dispersible resin treating agent for metal surfaces containing a zirconium (Zr) compound as component (B) and a silane coupling agent as component (C). .

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は炭素数２〜１０の２価のアルキレン基を示し、Ｒ³は炭素数２又は３の２価のアルキレン基を示す）
で表される環状ウレイド基含有重合性不飽和モノマー（ｅ）とからなる不飽和単量体混合物が乳化重合された共重合体樹脂エマルジョンを含む水分散性樹脂組成物
（Ｂ）ジルコニウム化合物
（Ｃ）シランカップリング剤 That is, this invention provides the water-dispersible resin processing agent for metal surfaces containing the following (A) component, (B) component, and (C) component.
(A) Polymerizable unsaturated monomer (a) containing no epoxy group, acid group or hydroxyl group, polymerizable unsaturated monomer (b) having an epoxy group, and acid group-containing polymerizable unsaturated monomer (c) A hydroxyl group-containing polymerizable unsaturated monomer (d), and the following formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent alkylene group having 2 to 10 carbon atoms, and R ³ represents a divalent alkylene group having 2 or 3 carbon atoms)
A water-dispersible resin composition comprising a copolymer resin emulsion obtained by emulsion polymerization of an unsaturated monomer mixture comprising a cyclic ureido group-containing polymerizable unsaturated monomer (e) represented by (B) a zirconium compound (C )Silane coupling agent

  In the above component (A), the use amount of the polymerizable unsaturated monomer (b) having an epoxy group, the acid group-containing polymerizable unsaturated monomer (c), and the hydroxyl group-containing polymerizable unsaturated monomer (d) is respectively polymerizable. 0.1 to 10% by weight based on the total amount of unsaturated monomers (a), (b), (c), (d) and (e), and the cyclic ureido group-containing polymerizable unsaturated monomer (e). The amount used is preferably 0.1 to 5% by weight based on the total amount of the polymerizable unsaturated monomers (a), (b), (c), (d) and (e).

  In the component (A), the polymerizable unsaturated monomer (a) which does not contain any of an epoxy group, an acid group and a hydroxyl group is a (meth) acrylic acid alkyl ester (a-1) in which the alkyl group has 1 to 18 carbon atoms. ), Or (meth) acrylic acid alkyl ester (a-1) having 1 to 18 carbon atoms of the alkyl group, styrene monomer (a-2), (meth) acrylonitrile (a-3), hydrolysis A monomer mixture with at least one monomer selected from the group consisting of a polymerizable unsaturated monomer having a reactive silyl group (a-4) and a polyfunctional vinyl group-containing polymerizable unsaturated monomer (a-5) Preferably used.

  Examples of the cyclic ureido group-containing polymerizable unsaturated monomer (e) include at least one monomer selected from the group consisting of methacrylamide ethyl ethylene urea, methacrylamide ethyl propylene urea, acrylamide ethyl ethylene urea, and acrylamide ethyl propylene urea. Can be used.

  The copolymer resin emulsion in component (A) has a reaction of 0.3 to 6% by weight with respect to the total amount of polymerizable unsaturated monomers (a), (b), (c), (d) and (e). It is preferably a copolymer resin emulsion in which the unsaturated monomer mixture is emulsion-polymerized in the presence of the surfactant (f).

  The copolymer resin emulsion in component (A) is preferably a core / shell type resin emulsion. The amount of the solid component (B) used is preferably in the range of 0.1 to 20% by weight based on the solid content of the water-dispersible resin composition (A). Moreover, it is preferable that the solid content usage-amount of (C) component is the range of 0.1-10 weight% with respect to solid content of the water-dispersible resin composition which is (A) component. The metal surface water-dispersible resin treatment agent preferably contains substantially no chromium.

  The present invention also provides a surface-treated metal plate in which the surface of the metal plate is treated with the water-dispersible resin treatment agent for a metal surface.

The solid content adhesion amount of the water-dispersible resin treatment agent for metal surface on the metal plate surface is, for example, 0.2 to 10 g / m ² .

  The water-dispersible resin treatment agent for metal surfaces of the present invention has rust prevention, adhesion to metals, adhesion to topcoat materials such as alkyd paints, foamed polyurethane and foamed polyethylene, water resistance, boiling water resistance, alkali resistance, Excellent blocking resistance and slipperiness. Further, it does not require addition of chromic acid or chromate pigments, and is excellent from the viewpoint of protecting the global environment. The surface-treated metal plate of the present invention has a metal plate surface that has been treated with a treatment agent having the above-described excellent characteristics, and therefore is not easily rusted and has excellent durability.

  Component (A) (water-dispersible resin composition) in the water-dispersible resin treatment agent for metal surface of the present invention is an emulsification of monomer components (a), (b), (c), (d) and (e). A copolymer resin emulsion obtained by polymerization is included.

  As a typical example of the polymerizable unsaturated monomer (a) containing neither an epoxy group, an acid group nor a hydroxyl group, a (meth) acrylic acid alkyl ester (a) having 1 to 18 carbon atoms in the alkyl group is used. -1), styrenic monomer (a-2), (meth) acrylonitrile (a-3), polymerizable unsaturated monomer having hydrolyzable silyl group (a-4), polyfunctional vinyl group-containing polymerizable unsaturated And monomer (a-5). The polymerizable unsaturated monomer (a) can be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid alkyl ester (a-1) having 1 to 18 carbon atoms in the alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ( N-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, (meth) Examples include decyl acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. These 1 type (s) or 2 or more types are used in combination as appropriate. Among them, (meth) acrylic acid alkyl ester having 1 to 10 carbon atoms in the alkyl group is preferable.

  Examples of the styrene monomer (a-2) include α-methylstyrene, vinyltoluene and the like in addition to styrene. These monomers can be used alone or in combination of two or more.

  Examples of the polymerizable unsaturated monomer (a-4) having a hydrolyzable silyl group include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, and γ- (meth). Examples thereof include monomers containing an alkoxysilyl group such as acryloxypropylmethyldiethoxysilane and γ- (meth) acryloxypropyltriethoxysilane.

  Examples of the polyfunctional vinyl group-containing polymerizable unsaturated monomer (a-5) include divinylbenzene, ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and allyl (meth). In addition to divinyl compounds such as acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) An acrylate etc. are mentioned. These may be used alone or in combination of two or more.

  As the polymerizable unsaturated monomer (a) which does not contain any of an epoxy group, an acid group and a hydroxyl group, in order to obtain good film formability and high film hardness, at least the (meth) acrylic acid alkyl ester (a- It is preferable to use 1), and it is particularly preferable to use the (meth) acrylic acid alkyl ester (a-1) and the styrene monomer (a-2) in combination. Further, together with the (meth) acrylic acid alkyl ester (a-1), or the (meth) acrylic acid alkyl ester (a-1) and the styrenic monomer (a-2), (meth) acrylonitrile (a-3), It is also preferable to use at least one monomer selected from a polymerizable unsaturated monomer (a-4) having a hydrolyzable silyl group and a polyfunctional vinyl group-containing polymerizable unsaturated monomer (a-5).

  When (meth) acrylonitrile (a-3) is used as a copolymerization monomer, a dense and tough resin film is formed by the orientation and crystallization effect of the cyano group in the polymer, which adversely affects water and rust prevention. Permeation of components is suppressed, and rust prevention is further improved. Further, since the film hardness is increased, the blocking resistance and the slipping property are also improved.

  When a polymerizable unsaturated monomer (a-4) having a hydrolyzable silyl group is used as a copolymerization monomer, a water-dispersible resin composition containing a copolymer resin emulsion and a water-dispersible resin treatment for metal surfaces using the same The water resistance of the agent is increased, and as a result, the rust prevention power is improved. Moreover, blocking resistance and slipperiness are also improved by crosslinking. Furthermore, the adhesion is improved by the silane coupling effect of the hydrolyzable silyl group and the affinity of the silane group for the metal substrate. Moreover, it shows high crosslinking reactivity with the silane coupling agent which is the component (C) blended in the present invention, and a highly crosslinked structure by silanol bond is formed. Therefore, a resin film having higher rust prevention power and water resistance, particularly excellent alkali resistance can be obtained.

  When the polyfunctional vinyl group-containing polymerizable unsaturated monomer (a-5) is used as a copolymerization monomer, crosslinking within the emulsion particles is promoted, and the blocking resistance, abrasion resistance, and slipping property of the resin film are improved. It also has an effect of improving water resistance and alkali resistance.

  The amount of the (meth) acrylic acid alkyl ester (a-1) is, for example, 20 to 100% by weight, preferably 30 to 80% by weight, more preferably, based on the total amount of the polymerizable unsaturated monomer (a). It is about 35 to 70% by weight. The amount of the styrenic monomer (a-2) is, for example, 0 to 80% by weight, preferably 20 to 70% by weight, more preferably 30 to 60% by weight, based on the total amount of the polymerizable unsaturated monomer (a). Degree. The amount of (meth) acrylonitrile (a-3) is usually 0 to 20% by weight (for example 1 to 20% by weight), preferably 0 to 10%, based on the total amount of the polymerizable unsaturated monomer (a). It is about weight% (for example, 1 to 10 weight%). Moreover, the quantity of the polymerizable unsaturated monomer (a-4) which has a hydrolyzable silyl group is 0-10 weight% normally (for example, 1-10 weight) with respect to the total amount of the said polymerizable unsaturated monomer (a). %), Preferably about 0 to 5% by weight (for example, 0.5 to 5% by weight). The amount of the polyfunctional vinyl group-containing polymerizable unsaturated monomer (a-5) is usually 0 to 10% by weight (for example, 1 to 10% by weight) based on the total amount of the polymerizable unsaturated monomer (a). Preferably, it is about 0 to 5% by weight (for example, 1 to 5% by weight).

  Examples of the polymerizable unsaturated monomer (b) having an epoxy group include monomers having a glycidyl group such as glycidyl acrylate, glycidyl methacrylate (GMA), glycidyl chlorate, glycidyl allyl ether, β-glycidyl methacrylate, (3 , 4-epoxychlorohexyl) methyl methacrylate, 3-epoxychloro-2-hydroxypropyl methacrylate and the like. Usually, glycidyl methacrylate is often used.

  By using the polymerizable unsaturated monomer (b) having an epoxy group, the affinity of the epoxy group to the metal surface and the adhesion of the acid group-containing polymerizable unsaturated monomer (c) to the metal surface Due to the synergistic effect, adhesion to the metal is further promoted, and a great effect is exhibited in further improving the rust prevention effect. Furthermore, a three-dimensional network structure is formed by a cross-linking reaction between an epoxy group and a carboxyl group in the resin composition, and the resin composition has the effect of imparting water resistance, boiling water resistance, alkali resistance, blocking resistance, and slipperiness. Demonstrated.

  The amount of the polymerizable unsaturated monomer (b) having an epoxy group is, for example, 0.1 to 10 weights based on the total amount of the monomer components (a), (b), (c), (d) and (e). %, Preferably 1 to 7% by weight. When the amount of the polymerizable unsaturated monomer (b) having an epoxy group is set within this range, a resin film containing a copolymer resin emulsion is used as a water-dispersible resin treatment agent for metal surfaces. As a result, the affinity to the metal surface is increased, the adhesion is improved, and at the same time, an excellent rust preventive power is obtained. If the said usage-amount of an epoxy-group-containing polymerizable unsaturated monomer (b) is less than 0.1 weight%, the rust prevention power of a resin film is weak, and water resistance, boiling water resistance, and blocking resistance will fall easily. On the other hand, if the amount exceeds 10% by weight, the internal structure of the resin film will be microgel-like inhomogeneous, causing cracks due to strain, water permeation, and chlorine ions and sulfate ions that are catalyst components for rusting. Since the permeation of the resin film is promoted, the rust preventive power is weak, and the strength of the resin film tends to be lowered.

  As the acid group-containing polymerizable unsaturated monomer (c), for example, an ethylenically unsaturated compound having in the molecule thereof at least one acid group selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like can be used.

  Among the acid group-containing polymerizable unsaturated monomers (c), examples of the carboxyl group-containing polymerizable unsaturated monomers include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, α-ethylacrylic acid, β-ethylacrylic acid, Examples thereof include β-propylacrylic acid, β-isopropylacrylic acid, itaconic acid, maleic anhydride and fumaric acid. Examples of the sulfonic acid group-containing polymerizable unsaturated monomer include p-vinylbenzenesulfonic acid, p-acrylamidepropanesulfonic acid, t-butylacrylamidesulfonic acid and the like. Examples of the phosphoric acid group-containing polymerizable unsaturated monomer include phosphoric acid monoester of 2-hydroxyethyl acrylate, phosphoric acid monoester of 2-hydroxypropyl methacrylate, etc., and these are trade names “Light Ester PM” (Kyoeisha). (Available from Chemical Co., Ltd.). The acid group-containing polymerizable unsaturated monomer (c) can be used alone or in combination of two or more.

  By using the acid group-containing polymerizable unsaturated monomer (c) as a copolymerization component, the storage stability of the resin composition containing the copolymer resin emulsion and the water-dispersible resin treatment agent for metal surfaces using the same, mechanical Various stability such as stability and stability against freezing can be obtained. In addition, since the adhesion to the metal substrate during the resin film formation is strong, water enters the interface between the metal substrate and the resin film, promotes the formation of rust, and exerts a catalytic effect such as chloride ions and sulfate ions. Therefore, it is possible to obtain a high rust preventive power. Further, by using the acid group-containing polymerizable unsaturated monomer (c) as a copolymerization component, a zirconium compound as the curing agent component (B) blended in the present invention, a silane coupling agent as the component (C), and A cross-linking reaction is performed, and a coating film having higher rust prevention ability and excellent alkali resistance is obtained.

  The amount of the acid group-containing polymerizable unsaturated monomer (c) is, for example, 0.1 to 10% by weight based on the total amount of the monomer components (a), (b), (c), (d) and (e). The amount is preferably 1 to 7% by weight. When the amount of the acid group-containing polymerizable unsaturated monomer (c) used is less than 0.1% by weight, the polymerization stability of the copolymer emulsion and the various stability deteriorates, and the adhesion of the resin film to the metal surface and Rust prevention power tends to be weak. On the other hand, when it exceeds 10% by weight, the polymerization stability of the copolymer resin emulsion and the above-mentioned various stability deteriorate, and the water resistance and alkali resistance of the obtained resin film tend to be weak.

  The hydroxyl group-containing polymerizable unsaturated monomer (d) is not particularly limited as long as it is an unsaturated monomer having a hydroxyl group. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy methacrylate Examples thereof include hydroxyl-containing acrylic monomers such as propyl, hydroxybutyl acrylate, hydroxybutyl methacrylate, and ε-caprolactone-modified acrylic monomer. These 1 type (s) or 2 or more types are used in combination. As the ε-caprolactone-modified acrylic monomer, trade names “Placcel FA-1”, “Placcel FA-2”, “Placcel FA-3”, “Placcel FA-4”, “Placcel FA” manufactured by Daicel Chemical Industries, Ltd. −5 ”,“ Plaxel FM-1 ”,“ Plaxel FM-2 ”,“ Plaxel FM-3 ”,“ Plaxel FM-4 ”,“ Plaxel FM-5 ”and the like are preferably used.

  By using the hydroxyl group-containing polymerizable unsaturated monomer (d) as a copolymerization component, the hydrophilicity and hydrogen bond-forming property of a resin composition containing a copolymer resin emulsion and a water-dispersible resin treatment agent for metal surfaces using the same. After the resin film is formed, the affinity with a top coating material such as foamed polyurethane or foamed polyethylene as a building material heat insulating material is increased, and adhesion is promoted. Moreover, the crosslinking reaction with the silane coupling agent which is (C) component mix | blended by this invention also occurs, and the coating film which has higher rust prevention power and the outstanding alkali resistance is obtained.

  The amount of the hydroxyl group-containing polymerizable unsaturated monomer (d) is, for example, 0.1 to 10% by weight based on the total amount of the monomer components (a), (b), (c), (d) and (e), Preferably it is 1 to 7 weight%. When the amount of the hydroxyl group-containing polymerizable unsaturated monomer (d) used is less than 0.1% by weight, the affinity with the top coating material is poor and the adhesion tends to be insufficient. On the other hand, if it exceeds 10% by weight, the hydrophilicity is too strong and the water resistance of the resin film tends to be weak.

The cyclic ureido group-containing polymerizable unsaturated monomer (e) is represented by the formula (1). In formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² is a divalent alkylene group having 2 to 10 carbon atoms (preferably a divalent alkylene group having 2 to 3 carbon atoms from the viewpoint of obtaining raw materials. R ³ represents a divalent alkylene group having 2 or 3 carbon atoms.

Examples of the divalent alkylene group having 2 to 10 carbon atoms in R ² include ethylene, propylene, dimethylethylene, trimethylene, 2,2-dimethyltrimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene and octamethylene. And linear or branched C _2-10 alkylene groups such as nonamethylene and decamethylene groups. The divalent alkylene group having 2 or 3 carbon atoms in R ³ includes ethylene, propylene and trimethylene groups.

As typical examples of the cyclic ureido group-containing polymerizable unsaturated monomer (e), methacrylamide ethyl ethylene urea (MAEEEU) (R ¹ = methyl group, R ² = ethylene group, R ³ = ethylene group), methacrylamide ethyl Propylene urea (R ¹ = methyl group, R ² = ethylene group, R ³ = propylene group), acrylamide ethyl ethylene urea (R ¹ = hydrogen atom, R ² = ethylene group, R ³ = ethylene group), and acrylamide ethyl propylene Examples include urea (R ¹ = hydrogen atom, R ² = ethylene group, R ³ = propylene group).

  By using the cyclic ureido group-containing polymerizable unsaturated monomer (e), an effect of improving the adhesion of the resin composition to a substrate such as a metal surface, particularly to a wet surface is exhibited. Furthermore, the compatibility with the top coating material, especially the alkyd coating material, the foaming polyurethane as the building material heat insulating material, the foaming polyethylene, and the adhesive property are remarkably improved. Regarding the mechanism for these excellent effects, the scientific basis in the strict sense is not necessarily clear, but it is estimated as follows.

  First, polar interactions are possible. The amide group and cyclic ureido group of the cyclic ureido group-containing polymerizable unsaturated monomer (e) contribute to the adhesion of the resin composition to the base material and the topcoat material by acting on the base material and the topcoat material. Gives a bipolar interaction. The dipole moment of the cyclic ureido group is as large as 4.5 Debye, and it is considered that a strong interaction is formed with the alkyd resin surface in particular. In addition, the contribution of hydrogen bonds with hydroxyl groups, carboxyl groups, and the like is also conceivable.

  Secondly, a wetting phenomenon can be considered. The cyclic ureido group-containing polymerizable unsaturated monomer (e) reduces the interfacial tension, thereby improving the wettability of the base material and the top coating material, making the resin composition easy to wet, and developing a strong interaction between the two. It becomes easy.

  Third, the contribution of the spacer group can be considered. For example, when the cyclic ureido group-containing polymerizable unsaturated monomer (e) is MAEEU, an amide group and an ethylene chain exist as a spacer group between the main chain and the ethylene urea group, and this spacer group is a polymer of the ethylene urea group. Well separated from the main chain. For this reason, the freedom degree of an ethylene urea group becomes large and it becomes easy to exert an interaction with the base-material surface and topcoat material.

  The amount of the cyclic ureido group-containing polymerizable unsaturated monomer (e) used is 0.1 to 5% by weight based on the total amount of the monomer components (a), (b), (c), (d) and (e). Is preferable, and 0.5 to 3 weight% is more preferable. When the amount of the cyclic ureido group-containing polymerizable unsaturated monomer (e) is set within this range, the resin composition containing the copolymer resin emulsion is used as a water-dispersible resin treatment agent for metal surfaces. The wettability and affinity for the material, particularly the wet surface, are increased, and the adhesion is improved and the rust prevention power is improved. Further, the adhesion with the top coating material and the top coating material, particularly the alkyd coating material is improved. When the amount of the cyclic ureido group-containing polymerizable unsaturated monomer (e) used in the copolymer resin is less than 0.1% by weight, the adhesion to the substrate and the rust preventive power are likely to be lowered. On the other hand, if it exceeds 5% by weight, the water resistance of the resin film tends to decrease.

  The emulsifier used in the emulsion polymerization of the present invention may be a general non-reactive emulsifier, but for the reason described later, the reactive surfactant (f) is used for the performance of the water-dispersible resin treatment agent for metal surfaces. This is advantageous.

  Although it does not restrict | limit especially as a non-reactive general emulsifier, For example, a hydrocarbon group which has a C6 or more carbon atom, carboxylate, sulfonate, sulfate partial ester, phosphate An anionic or nonionic (nonionic) emulsifier selected from micelle compounds having a hydrophilic moiety such as a phosphate partial ester in the same molecule; micelle compounds having a polyoxyalkylene group in the molecule Used. Among these, as an anionic emulsifier, alkali metal salt or ammonium salt of sulfuric acid half ester of alkoxyphenols or higher alcohols; alkali metal salt or ammonium salt of alkyl or allyl sulfonate; polyoxyethylene alkylphenyl ether, polyoxyethylene Examples thereof include alkali metal salts or ammonium salts of alkyl ether or polyoxyethylene allyl ether sulfate half ester. Examples of nonionic emulsifiers include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene allyl ether. These non-reactive emulsifiers can be used alone or in combination of two or more. These general-purpose anionic and nonionic emulsifiers have radical polymerizable unsaturated double bonds in the molecule described below, that is, groups such as acrylic, methacrylic, propenyl, allyl, allyloxy, and maleic acid groups. Various anionic and nonionic reactive surfactants are used in appropriate combination.

  The reactive surfactant (f) is not particularly limited, and exhibits a surfactant activity such as a group containing a reactive group such as a polymerizable unsaturated group and a nonionic hydrophilic group or an anionic hydrophilic group. Any reactive surfactant having a group may be used. Examples of the group containing a reactive group such as a polymerizable unsaturated group include a vinyl group, an allyl group, a methacryl group, an allyloxy group, a methallyloxy group, an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group. It is done.

  Representative reactive surfactants (f) include, for example, compounds represented by the following formula (2), (3), (4), (5), (6), (7) or (8) Is included.

（式中、Ａ¹は炭素数２〜４の置換若しくは無置換のアルキレン基、Ｒ⁴は水素原子又はメチル基、Ｒ⁵は炭素数７〜２４の炭化水素基又は炭素数７〜２４のアシル基、Ｘは水素原子、又はノニオン系若しくはアニオン系の親水基、ｍは０〜１００の整数を示す）

(In the formula, A ¹ is a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group having 7 to 24 carbon atoms or an acyl having 7 to 24 carbon atoms. Group, X is a hydrogen atom, or a nonionic or anionic hydrophilic group, m represents an integer of 0 to 100)

（式中、Ａ²は炭素数２〜４の置換若しくは無置換のアルキレン基、Ｒ⁶は炭素数１〜１８の炭化水素基、Ｒ⁷は水素原子又は炭素数１〜１８の炭化水素基、ｐは２〜２００の整数、Ｍはアルカリ金属又はＮＨ₄を示す）

(In the formula, A ² is a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, R ⁶ is a hydrocarbon group having 1 to 18 carbon atoms, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, p is an integer of 2 to 200, M represents an alkali metal or NH ₄ )

（式中、Ａ³は炭素数２〜４の置換若しくは無置換のアルキレン基、Ｒ⁸は水素原子又はメチル基、Ｒ⁹は水素原子又はアルキル基、ｑは０〜１００の整数、Ｍはアルカリ金属又はＮＨ₄を示す）

(In the formula, A ³ is a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, R ⁸ is a hydrogen atom or a methyl group, R ⁹ is a hydrogen atom or an alkyl group, q is an integer of 0 to 100, and M is an alkali. Represents metal or NH ₄ )

（式中、Ｒ¹⁰は置換基を有していてもよい炭化水素基、Ｒ¹¹は水素原子又はメチル基、Ｍはアルカリ金属又はＮＨ₄を示す）

(In the formula, R ¹⁰ is a hydrocarbon group which may have a substituent, R ¹¹ is a hydrogen atom or a methyl group, M is an alkali metal or NH ₄ )

（式中、Ｒ¹²は置換基を有していてもよい炭化水素基、Ｒ¹³は水素原子又はメチル基、Ｍはアルカリ金属又はＮＨ₄を示す）

(Wherein R ¹² represents a hydrocarbon group which may have a substituent, R ¹³ represents a hydrogen atom or a methyl group, and M represents an alkali metal or NH ₄ )

（式中、Φは多官能フェニル基、Ａ⁴、Ａ⁵は、それぞれ炭素数２〜４の置換若しくは無置換のアルキレン基、Ｒ¹⁴は水素原子又はメチル基、ｒ、ｓは、それぞれ１〜１００の整数、Ｍはアルカリ金属又はＮＨ₄を示す）

(Wherein Φ is a polyfunctional phenyl group, A ⁴ and A ⁵ are each a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, R ¹⁴ is a hydrogen atom or a methyl group, and r and s are each 1 to 1. An integer of 100, M represents an alkali metal or NH ₄ )

（式中、Ａ⁶は炭素数２〜４の置換若しくは無置換のアルキレン基、Ｒ¹⁵は水素原子又はメチル基、Ｍはアルカリ金属又はＮＨ₄を示す）

(In the formula, A ⁶ represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, R ¹⁵ represents a hydrogen atom or a methyl group, M represents an alkali metal or NH ₄ )

In the formula (2), examples of the substituted or unsubstituted alkylene group having 2 to 4 carbon atoms in A ¹ include ethylene, propylene, trimethylene, tetramethylene groups, and halogen atoms (fluorine atoms, chlorine atoms). Etc.), an alkylene group to which a substituent such as a hydroxyl group or an alkoxy group (C _1-4 alkoxy group such as methoxy or ethoxy group) is bonded. Examples of the hydrocarbon group having 7 to 24 carbon atoms in R ⁵ include alkyl groups such as octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl groups; alkenyl groups such as octenyl and decenyl groups; 4-methylphenyl, Examples thereof include alkylaryl groups such as 4-propylphenyl, 4-octylphenyl, 4-nonylphenyl, 4-decylphenyl, 4-dodecylphenyl, 4-tetradecylphenyl and 4-hexadecylphenyl groups. Examples of the acyl group having 7 to 24 carbon atoms in R ⁵ include aliphatic, alicyclic or aromatic acyl groups such as octanoyl, nonanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl and 4-nonylbenzoyl groups. Is mentioned. m is preferably an integer of about 0 to 50.

（式中、Ａ⁷は炭素数２〜４の置換若しくは無置換のアルキレン基、Ｍはアルカリ金属又はＮＨ₄、ｎは０〜１００の整数を示す）
で表される基が例示される。Ａ⁷における炭素数２〜４の置換若しくは無置換のアルキレン基としては、前記Ａ¹における炭素数２〜４の置換若しくは無置換のアルキレン基と同様のものが挙げられる。Ｍにおけるアルカリ金属としては、例えば、ナトリウム、カリウムなどが挙げられる。ｎは、好ましくは０〜３０程度の整数である。 Examples of the nonionic or anionic hydrophilic group in X include various groups including a polyoxyalkylene group, a sulfonic acid group, and a carboxyl group. As a representative group, the following formula (9)

(In the formula, A ⁷ represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, M represents an alkali metal or NH ₄ , and n represents an integer of 0 to 100)
The group represented by these is illustrated. Examples of the substituted or unsubstituted alkylene group having 2 to 4 carbon atoms in A ⁷ include the same as the substituted or unsubstituted alkylene group having 2 to 4 carbon atoms in A ¹ . Examples of the alkali metal in M include sodium and potassium. n is preferably an integer of about 0 to 30.

In the formula (3), the substituted or unsubstituted alkylene group having 2 to 4 carbon atoms for A ^2, are the same as those of the substituted or unsubstituted alkylene group having 2 to 4 carbon atoms in the A ^1. Examples of the hydrocarbon group having 1 to 18 carbon atoms in R ⁶ and R ⁷ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, nonyl, decyl, dodecyl, Alkyl groups such as hexadecyl and octadecyl groups; alkenyl groups such as vinyl, allyl, hexenyl, octenyl, nonenyl and decenyl groups; aralkyl groups such as benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl groups It is done. Among these, a hydrocarbon group having 4 to 18 carbon atoms is particularly preferable. The alkali metal in M is the same as described above. p is preferably an integer of about 2 to 50.

In formula (4), examples of the substituted or unsubstituted alkylene group having 2 to 4 carbon atoms in A ³ include the same as the substituted or unsubstituted alkylene group having 2 to 4 carbon atoms in A ¹ . Examples of the alkyl group in R ⁹ include about 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, nonyl, decyl, dodecyl, and hexadecyl groups. And the like. q is preferably an integer of about 0 to 50. The alkali metal in M is the same as described above.

In the formulas (5) and (6), examples of the hydrocarbon group optionally having a substituent in R ¹⁰ and R ¹² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, alkyl groups such as t-butyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl groups; alkenyl groups such as vinyl, allyl, hexenyl, octenyl, decenyl groups; cycloalkyl groups such as cyclohexyl groups; phenyl groups, etc. Aryl groups; aralkyl groups such as benzyl and 2-phenylethyl; or a halogen atom (fluorine atom, chlorine atom, etc.), hydroxyl group, alkoxy group (C _1-4 alkoxy group such as methoxy, ethoxy group, etc.), etc. And a hydrocarbon group to which the substituents are bonded. M is the same as described above.

In formula (7), the substituted or unsubstituted alkylene group having 2 to 4 carbon atoms in A ⁴ and A ⁵ is the same as the substituted or unsubstituted alkylene group having 2 to 4 carbon atoms in A ¹ . Can be mentioned. r and s are preferably integers of about 1 to 50. The alkali metal in M is the same as described above. As the reactive surfactant represented by the formula (6), a trade name “Antox MS-60” manufactured by Nippon Emulsifier Co., Ltd. is commercially available.

In formula (8), examples of the substituted or unsubstituted alkylene group having 2 to 4 carbon atoms in A ⁶ include the same as the substituted or unsubstituted alkylene group having 2 to 4 carbon atoms in A ¹ . The alkali metal in M is the same as described above.

  The reactive surfactant (f) is copolymerized or grafted with the monomer components (a), (b), (c), (d) and (e), and after the polymerization, a high molecular weight polymer is formed. Present as a unit. For this reason, non-reactive general emulsifiers remain in the water phase in the water phase in the low molecular weight form after polymerization, and the cast film of the resin dispersion finally obtained is therefore water and boiling resistant. The cast film of the resin dispersion obtained using a reactive surfactant, while having poor alkali resistance, rust resistance, solvent resistance and adhesion, has high water resistance, boiling water resistance, Demonstrates alkali resistance, rust prevention, solvent resistance and adhesion.

  The amount of the reactive surfactant (f) used in the emulsion polymerization is, for example, 0.3 to 6 with respect to the total amount of the monomer components (a), (b), (c), (d) and (e). % By weight. When the amount used is less than 0.3% by weight, the stability of emulsion polymerization is poor, and grit is likely to occur during the polymerization, and the stability of the resin dispersion obtained after the polymerization is poor and the commercial value is poor. It is easy to become a thing. On the other hand, if it exceeds 6% by weight, water resistance, boiling water resistance, alkali resistance, rust resistance, solvent resistance and adhesiveness may be hindered, and there may be a problem in economy. Is not preferable.

  In the present invention, in addition to the monomer components (a), (b), (c), (d) and (e), as long as the properties such as rust prevention, adhesion, water resistance and alkali resistance are not impaired, Alternatively, in addition to these and the reactive surfactant (f), other polymerizable unsaturated monomers may be copolymerized. The amount of the polymerizable unsaturated monomer used is, for example, 20% by weight or less, preferably 10% with respect to the total amount of the monomer components (a), (b), (c), (d) and (e). % Or less, more preferably 5% by weight or less.

  In the present invention, the copolymer resin emulsion is particularly preferably a core / shell type resin emulsion. Here, as the definition of the core / shell, in the emulsion polymerization, when the polymerization is performed in multiple stages (for example, two stages), the resin component that is the core formed in the first stage polymerization is referred to as the core, and the second A resin component that becomes a shell formed on the surface of the core in the polymerization after the step is referred to as a shell. For example, when the monomer is dropped in two stages and the polymerization is performed, the monomer is dropped in the first stage, the resin component formed by the polymerization corresponds to the core, and after the core formation, the monomer in the second stage The resin component formed by polymerization corresponds to the shell.

  In the core-shell type synthetic resin emulsion, the ratio of the core part to the shell part is 20% by weight to 95% by weight, preferably 30% by weight to 90% by weight, based on the total weight, It is desirable that the shell portion is in the range of 5 wt% to 80 wt%, preferably 10 wt% to 70 wt%. The core part and the shell part are respectively formed from the monomer components (a), (b), (c), (d) and (e) (or these components and the reactive surfactant (f)). It only has to be.

  The reason why the core / shell type synthetic resin emulsion is particularly preferable in the present invention is that it is advantageous in blocking resistance and slipping property because a tougher and harder resin film can be obtained as compared with a homogeneous polymerization emulsion. Such a feature is difficult to obtain in any case outside the range of the ratio of the core portion and the shell portion.

  In the emulsion polymerization, the monomer components (a), (b), (c), (d) and (e) are used in an aqueous liquid, using a radical polymerization initiator, and a general emulsifier and / or a reactive surfactant. It can carry out by heating with stirring in the presence of (f). The reaction temperature is preferably about 30 to 100 ° C. and the reaction time is preferably about 1 to 10 hours, for example. The reaction temperature may be adjusted by batch addition of the monomer mixed solution or monomer pre-emulsified solution or temporary dropwise addition to a reaction vessel charged with water and a general emulsifier and / or reactive surfactant (f).

  As the radical polymerization initiator, known initiators usually used in emulsion polymerization of acrylic resins can be used. Specifically, as a water-soluble free radical polymerization initiator, for example, potassium persulfate, sodium persulfate, ammonium persulfate, a water-soluble azo initiator in the form of an aqueous solution, an oil-soluble azo initiator, a peroxide Benzoyl oxide alone is used, and so-called redox initiators in combination with oxidizing agents such as hydrogen peroxide and reducing agents such as sodium bisulfite, sodium thiosulfate, Rongalite and ascorbic acid are used in the form of an aqueous solution. Is done.

  In addition, in the emulsion polymerization, the use of an auxiliary agent (chain transfer agent) for adjusting the molecular weight such as a mercaptan compound or a lower alcohol can be used from the viewpoint of promoting the emulsion polymerization and, for example, smooth and uniform formation of a resin film. Is often preferred from the viewpoint of promoting adhesion, improving adhesion to the substrate, and improving rust prevention, and is carried out depending on the situation as appropriate.

  Emulsion polymerization methods include any one of the following, such as the usual one-stage continuous monomer uniform dropping method, the core-shell polymerization method which is a multistage monomer feed method, and the power feed polymerization method in which the monomer composition fed continuously during the polymerization is changed. Can be legal.

  Thus, the copolymer resin emulsion in the present invention is prepared. The weight average molecular weight of the copolymer resin is not particularly limited, but is generally about 50,000 to 1,000,000, preferably about 100,000 to 800,000.

  The water-dispersible resin composition in the present invention is mainly composed of the copolymer resin emulsion and may further contain an additive such as a basic compound. As the basic compound, ammonia, various amines, alkali metal compounds such as alkali metal salts, and the like are used. By adding a basic compound, a part or all of the acid contained in the copolymer resin emulsion is neutralized, and the stability of the copolymer resin emulsion is ensured.

  In the present invention, the zirconium compound as the component (B) is an acid group-containing polymerizable unsaturated monomer (c) (such as an unsaturated carboxylic acid) copolymerized in the component (A) and an acid group (such as a carboxyl group). Crosslinking reaction gives the coating film excellent rust resistance, alkali resistance, water resistance and solvent resistance. In particular, the contribution to alkali resistance is significant.

  The zirconium compound is not particularly limited as long as it is a compound containing zirconium (Zr) in the molecule. Is mentioned. A zirconium compound is used individually or in combination of 2 or more types.

  The solid content of the zirconium compound is preferably about 0.1 to 20% by weight, more preferably 0.3 to 15% by weight, based on the solid content of the water dispersible resin composition (A). More preferably, it is in the range of 0.5 to 10% by weight. If it is less than 0.1% by weight, the crosslinking effect of the resin by the zirconium compound is poor, and it is difficult to obtain desirable alkali resistance and rust prevention power. When it is more than 20% by weight, a problem is likely to occur in the film-forming property, and it is disadvantageous in terms of economy.

  In the present invention, the silane coupling agent which is the component (C) has a crosslinking reaction with an acid group (carboxyl group, etc.), a hydroxyl group and a hydrolyzable silyl group (alkoxysilyl group, etc.) in the component (A). A cross-linking reaction between the coupling agents and the metal material also occurs, improving the adhesion, and imparting excellent rust prevention power, alkali resistance, water resistance, and solvent resistance to the coating film.

  The silane coupling agent to mix | blend is not specifically limited, A well-known silane coupling agent can be used. Examples of silane coupling agents include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxysilane), and phenyl. Trimethoxysilane, diphenyldimethoxysilane, vinyltriacetoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ -(Meth) acryloxypropylmethyldiethoxysilane, glycidoxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, N- (β- Minoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, mercaptopropylenetrimethoxysilane, It is selected from those which are relatively stable in an aqueous solution such as mercaptopropylene triethoxysilane.

  The solid content of the silane coupling agent is preferably about 0.1 to 10% by weight, more preferably 0.3 to 8%, based on the solid content of the water dispersible resin composition (A). % By weight, and more preferably in the range of 0.5 to 5% by weight. If the amount is less than 0.1% by weight, the crosslinking effect of the resin with the silane coupling agent is poor, so a dense film cannot be obtained, and the coupling effect to the metal substrate is poor, the adhesiveness is poor, and the desired alkali resistance. Rust prevention power cannot be obtained. When the amount is more than 10% by weight, a problem occurs in the film-forming property, and it is disadvantageous in terms of economy.

  The water-dispersible resin treatment agent for metal surfaces of the present invention comprises the water-dispersible resin composition as the component (A), the zirconium compound as the component (B), and the silane coupling agent as the component (C). It can be prepared by mixing and stirring. The component (B) and the component (C) may be used for mixing as they are, but may be used for mixing in the form of a solution or dispersion dissolved or dispersed in a solvent such as water. Mixing and stirring can be performed by known or conventional methods.

  The water-dispersible resin treatment agent for metal surface of the present invention is applied as it is to form a clear film as a coating agent on the surface of a metal plate (especially a steel plate such as a galvalume steel plate) as it is. The surface-treated metal plate is protected on the surface and maintains the original beautiful appearance as it is, so that the commercial value is remarkably increased.

  In the present invention, the surface slipperiness can be increased by adding molybdenum disulfide, graphite, fluorine resin, polyolefin wax emulsion or the like as a lubricant to the water-dispersible resin treatment agent for metal surfaces. Furthermore, it is also possible to color with a coloring pigment. In addition, it is possible to add appropriate additives such as resin dispersions such as aqueous urethane resin dispersions, antifoaming agents, and leveling agents as long as the original performance is not impaired.

  The solid content in the metal surface water-dispersible resin treatment agent can be appropriately set according to the use, but is generally about 10 to 70% by weight. In the actual application by a coater or the like, it is necessary to adjust the viscosity in consideration of workability, and it is desirable to dilute appropriately according to the situation. Therefore, the solid content concentration at the time of actual application is preferably 15 to 40% by weight, for example. Even if the water-dispersible resin treatment agent for metal surfaces of the present invention does not contain any chromium compound, it significantly improves the corrosion resistance and durability performance of the metal material.

  Although it does not specifically limit as a method of processing the surface of a metal plate (especially steel plates, such as a Galvalume steel plate) using the water-dispersible resin processing agent for metal surfaces of this invention, For example, it paints by arbitrary methods, such as a urethane rubber roll. Is possible. Drying after coating is preferably performed by drying within 60 seconds until the plate temperature reaches about 80 ° C. using, for example, a jet dryer.

The coating amount of the water-dispersible resin treatment agent for a metal surface of the present invention on a metal plate such as a galvalume steel plate is not particularly limited, but is usually in the range of 0.5 to 10 μm in terms of dry film thickness. A range of 5 μm is preferable. When the coating amount is less than 0.5 μm, the surface protection function is poor, which is not preferable. On the other hand, if it exceeds 10 μm, the appearance may become cloudy, which is not preferable from the viewpoint of economy. Moreover, generally the solid content adhesion amount of the water-dispersible resin treatment agent for metal surfaces on the metal plate surface is about 0.2-10 g / m < ² >. When the solid content is less than 0.2 g / m ² , the surface protection function is small, and when the solid content is greater than 10 g / m ² , the appearance is liable to deteriorate.

  Surface-treated metal sheets such as surface-treated galvalume steel plates obtained in this way are used for building materials, roofing materials and exterior wall materials for buildings, pillars for agricultural vinyl houses, furniture, home appliances, housings for industrial equipment, guardrails, soundproof walls. It can be used as civil engineering products such as drainage grooves, automobile body, chassis, engine surroundings and pre-coated steel plates (pre-coated metal) for metal structures such as cans.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples. In the examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified.

Example 1 (one-stage polymerization)
In a reaction vessel for producing a normal acrylic resin emulsion equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 400 parts of water and a general emulsifier [trade name “New Coal 707SF”, manufactured by Nippon Emulsifier Co., Ltd .; Polyoxyethylene polycyclic phenyl ether sulfate ester salt, 30% aqueous solution] was charged, and the temperature was raised to 75 ° C. Separately, a mixed liquid of the following monomer, emulsifier and water was uniformly emulsified using a high-pressure homogenizer, and charged into a dropping funnel as a monomer emulsion.
(Monomer emulsion)
General emulsifier [trade name “Newcol 707SF”] 13 parts MMA (methyl methacrylate) (a1) 57 parts SM (styrene) (a2) 177 parts 2EHA (2-ethylhexyl acrylate) (a3) 99 parts GMA (glycidyl methacrylate) ) (B1) 25 parts MAA (methacrylic acid) (c1) 12 parts 2HEMA (2-hydroxyethyl methacrylate) (d1) 12 parts Cyclic ureido group-containing polymerizable unsaturated monomer [trade name “Cypomer WAM-II”, methacrylamide 1: 1 mixture of ethylethyleneurea MAEEU (e1) and MAA (c1), manufactured by Rhodia Nikka Co., Ltd.] 20 parts Water 197 parts In addition, the following dropping initiator aqueous solution was charged into another dropping funnel.
(Initiator aqueous solution for dripping)
Potassium persulfate 1 part Water 50 parts Next, 5% of the monomer emulsion is added to the reaction vessel and heated to 75 ° C., and then 5% of the dropping initiator aqueous solution is added thereto for 10 minutes. A polymerization reaction was performed. During this time, the internal temperature of the reaction vessel automatically increased to 80 ° C. Thereafter, the remaining monomer emulsion and the dropping initiator aqueous solution were dropped into the reaction vessel at a constant rate at 80 ° C. over 3 hours. After completion of the dropwise addition, the reaction was aged for 1 hour while maintaining at 80 ° C., cooled to room temperature, and then 4 parts of ammonia water (25%) was put into the reaction vessel to prepare a water-dispersible resin composition (synthetic resin emulsion). Got.
To 100 g of the obtained water-dispersible resin composition, 15 g of a 20% aqueous solution of ammonium zirconium carbonate as a zirconium compound and a mixed solution of 2 g of phenyltrimethoxysilane and 20 g of water as a silane coupling agent are added to a propeller stirrer. The mixture was thoroughly stirred to prepare a water-dispersible resin treatment agent for metal surfaces.

Example 2
In Example 1, the same operation as in Example 1 was carried out except that the same amount of mercaptopropylenetrimethoxysilane was used instead of the silane coupling agent phenyltrimethoxysilane. Was prepared.

（式中、Ｒはアルキル基を示す）
で表される反応性界面活性剤［商品名「アデカリアソープＳＲ−１０」、旭電化工業（株）製］（f1）１．５部を用いるとともに、モノマー乳化液における一般乳化剤（商品名「ニューコール７０７ＳＦ」）１３部及び水１９７部の代わりに、前記式（10）で表される反応性界面活性剤［商品名「アデカリアソープＳＲ−１０」、旭電化工業（株）製］（f1）４部及び水２０９部を用いた以外は、すべて実施例１と同様にて、金属表面用水分散性樹脂処理剤を得た。 Example 3
In Example 1, in place of 5 parts of the initially prepared general emulsifier (trade name “New Coal 707SF”), the following formula (10)

(Wherein R represents an alkyl group)
In addition to using 1.5 parts of a surfactant (trade name “ADEKA rear soap SR-10” manufactured by Asahi Denka Kogyo Co., Ltd.) (f1), a general emulsifier (trade name “ (New Coal 707SF ") In place of 13 parts and 197 parts of water, a reactive surfactant represented by the above formula (10) [trade name" Adekaria Soap SR-10 ", manufactured by Asahi Denka Kogyo Co., Ltd.] ( f1) Except that 4 parts and 209 parts of water were used, all were the same as in Example 1 to obtain a water-dispersible resin treating agent for metal surfaces.

Example 4
In Example 3, the same operation as in Example 3 was performed except that the same amount of mercaptopropylenetrimethoxysilane was used instead of the silane coupling agent phenyltrimethoxysilane. Was prepared.

で表される反応性界面活性剤［商品名「アクアロンＨＳ−１０」、第一工業製薬（株）製］（f2）を用いた以外は、すべて実施例３と同様にして重合を行い、水分散性樹脂組成物を得、同様にして金属表面用水分散性樹脂処理剤を調製した。 Example 5
In Example 3, instead of the reactive surfactant (trade name “ADEKA rear soap SR-10”) (f1), the same amount of the following formula (11)

Polymerization was carried out in the same manner as in Example 3 except that the reactive surfactant represented by the formula [trade name “AQUALON HS-10”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] (f2) was used. A dispersible resin composition was obtained, and a water-dispersible resin treatment agent for metal surfaces was prepared in the same manner.

Example 6 (two-stage polymerization)
In a reaction vessel for production of an ordinary acrylic resin emulsion equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 470 parts of water and a general emulsifier [trade name “New Coal 707SF”, manufactured by Nippon Emulsifier Co., Ltd .; Polyoxyethylene polycyclic phenyl ether sulfate ester salt, 30% aqueous solution] was charged, and the temperature was raised to 75 ° C. Separately, the following mixture of monomers, emulsifier and water was uniformly emulsified using a high-pressure homogenizer, and charged into the dropping funnel as a first-stage monomer emulsion.
(First stage monomer emulsion)
General emulsifier [trade name “New Coal 707SF”] 13 parts MMA (methyl methacrylate) (a1) 28 parts SM (styrene) (a2) 90 parts 2EHA (2-ethylhexyl acrylate) (a3) 60 parts MAA (methacrylic acid) ) (C1) 9 parts 2HEMA (2-hydroxyethyl methacrylate) (d1) 9 parts Cyclic ureido group-containing polymerizable unsaturated monomer [trade name “Cypomer WAM-II”, methacrylamide ethyl ethylene urea MAEEU (e1) and MAA ( c1) 1: 1 mixture, Rhodia Nikka Co., Ltd.] 20 parts Water 127 parts Separately, the monomer mixture shown below was charged into the dropping funnel as the second stage monomer.
(Second stage monomer)
MMA (methyl methacrylate) (a1) 29 parts SM (styrene) (a2) 87 parts 2EHA (2-ethylhexyl acrylate) (a3) 39 parts MAA (methacrylic acid) (c1) 3 parts 2HEMA (2-hydroxyethyl methacrylate) ) (D1) 3 parts GMA (glycidyl methacrylate) (b1) 25 parts In addition, the following initiator solution for dropping was separately charged in another dropping funnel.
(Initiator aqueous solution for dripping)
Potassium persulfate 1 part Water 50 parts Next, 5% of the first-stage monomer emulsion is added to the reaction vessel, heated to 75 ° C., and then 5% of the dropping initiator aqueous solution is added. A prepolymerization reaction was performed for 10 minutes. During this time, the internal temperature of the reaction vessel automatically increased to 80 ° C. Thereafter, the remaining first-stage monomer emulsion was dropped into the reaction vessel at a constant rate over 2 hours at 80 ° C. and the initiator aqueous solution for dropping over 3.5 hours at 80 ° C. After completion of dropping of the first-stage monomer emulsion, aging reaction was carried out for 0.5 hours while maintaining at 80 ° C., and the second-stage monomer was added dropwise over 1 hour. Thereafter, the mixture was kept at 80 ° C. for 1 hour, matured, cooled to room temperature, and then 4 parts of ammonia water (25%) was put into the reaction vessel to prepare a water-dispersible resin composition (synthetic resin emulsion; core-shell type). Emulsion).
To 100 g of the obtained water-dispersible resin composition, 15 g of a 20% aqueous solution of ammonium zirconium carbonate as a zirconium compound and a mixed solution of 2 g of phenyltrimethoxysilane and 20 g of water as a silane coupling agent are added to a propeller stirrer. The mixture was thoroughly stirred to prepare a water-dispersible resin treatment agent for metal surfaces.

Example 7
In Example 6, instead of 470 parts of initially charged water and 5 parts of a general emulsifier [trade name “New Coal 707SF”] initially charged, 482 parts of water, a reactive surfactant (trade name “ADEKA rear soap SR- 10 ”) (f1) and 1.5 parts of a general surfactant (trade name“ New Coal 707SF ”) in the first stage monomer emulsion, 13 parts of a reactive surfactant (trade name“ Adekalia ”) Except for using 4 parts of soap SR-10 ") (f1), polymerization was conducted in the same manner as in Example 6 to obtain a water-dispersible resin composition (synthetic resin emulsion; core-shell type emulsion). Thus, a water-dispersible resin treatment agent for metal surfaces was prepared.

Comparative Example 1
In Example 1, instead of MMA 57 parts and MAA 12 parts, except for MMA 69 parts and MAA 0 parts, emulsion polymerization was carried out in the same manner as in Example 1 to obtain a water-dispersible resin composition, and in the same manner, a zirconium compound And the silane coupling agent was mixed and the water-dispersible resin processing agent for metal surfaces was prepared.

Comparative Example 2
In Example 1, instead of MMA 57 parts and 2 HEMA 12 parts, except for MMA 69 parts and 2 HEMA 0 parts, emulsion polymerization was performed in the same manner as in Example 1 to obtain a water-dispersible resin composition, and a zirconium compound and a silane cup A ring agent was mixed to prepare a water-dispersible resin treatment agent for metal surfaces.

Comparative Example 3
In Example 1, instead of 57 parts of MMA and 20 parts of the trade name “Cypomer WAM-II”, emulsion polymerization was carried out in the same manner as in Example 1 except that 77 parts of MMA and 0 part of the trade name “Cypomer WAM-II” were used. A water dispersible resin composition was obtained, and a zirconium compound and a silane coupling agent were mixed to prepare a metal surface water dispersible resin treatment agent.

Comparative Example 4
In Example 1, emulsion polymerization was carried out in the same manner as in Example 1 except that MMA 82 parts and GMA 0 parts were used instead of MMA 57 parts and GMA 25 parts to obtain a water-dispersible resin composition. A ring agent was mixed to prepare a water-dispersible resin treatment agent for metal surfaces.

Comparative Example 5
In Example 1, except that the zirconium compound ammonium zirconium carbonate was not used, the same operation as in Example 1 was carried out to prepare a metal surface water-dispersible resin treatment agent.

Comparative Example 6
In Example 1, except for not using phenyltrimethoxysilane as a silane coupling agent, the same operation as in Example 1 was performed to prepare a water-dispersible resin treatment agent for metal surfaces.

Comparative Example 7
In Example 1, except that zirconium zirconium ammonium carbonate as a zirconium compound and phenyltrimethoxysilane as a silane coupling agent were not used, the same operation as in Example 1 was performed to prepare a water-dispersible resin treatment agent for metal surfaces. .

Performance evaluation test To each of the water-dispersible resin treatment agents for metal surfaces obtained in Examples and Comparative Examples, an aqueous butyl cellosolve solution was added so that the MFT was 20 ° C. or less, and the dry film thickness was 1 μm on the surface of the galvalume steel plate. Then, after coating with a # 4 bar coater, the plate temperature reached 80 ° C., dried for 10 seconds, air-cooled, allowed to stand for 24 hours, and then measured for the following characteristics. The results are shown in Table 1.

(1) Normal adhesion The 100-scale gobang tape test of the coating film was performed at room temperature to measure the normal adhesion. It was displayed as a fraction of the number of galvanic eyes (numerator) remaining without peeling with respect to the number of galvanic eyes 100 (denominator).

(2) Adhesiveness to foamed polyurethane After the polyurethane foam was heat-sealed on the coating film, it was peeled off, and the adhesion state was observed and evaluated by a five-point method.
5: 100% of the polyurethane foam part was cohesive failure at the time of peeling 4; 90% or more and less than 100% of the polyurethane foam part was cohesive failure at the time of peeling 3; Cohesive failure, the remainder peeled off at the interface 2; 20% or more and less than 50% of the foamed polyurethane part peeled off at the time of peeling, and the remainder peeled off at the interface 1;

(3) Corrosion resistance (SS resistance)
The salt spray resistance test (SST) of the coated steel sheet was conducted for 240 hours with a salt spray tester, and the blisters and the peeled state of the coated surface were observed.
○: Blister, peeling, etc. were scarce and good. Δ: Blister, peeling, etc. occurred in 1/3 or more and less than 2/3 of the coated surface. X: Blister, peeling, etc. were 2/3 or more of the coated surface. Or occurred all over

(4) Blocking resistance The coated surfaces were put together and overlapped, and a load of 200 Kg / cm ² (= 19.6 MPa) was applied at 40 ° C. After leaving for 7 days, they were peeled off and the fixed state was observed.
○: Not fixed △; Slightly fixed ×: Fixed

(5) Boiling-resistant water The parts other than the coated surface of the coated plate were sealed with paraffin, and then immersed in hot water at 95 ° C. for 96 hours, and the appearance such as the softened state of the coated surface and the state of occurrence of blisters was visually determined.
○: There is no blister, etc., and the appearance is good. Δ: Although blisters are generated, the film is in close contact with the metal. ×: A large amount of blisters are generated, and the film is peeled off from the metal surface.

(6) Alkali resistance After the parts other than the coated surface of the coated plate are sealed with paraffin, they are immersed in a 1% aqueous sodium hydroxide solution at 20 ° C. for 5 hours to change the appearance of the painted surface, particularly before dark coating. And was evaluated by the 5-point method.
5: Good with no change in appearance 4: About 20% of the entire coating surface is dark 3: About 50% of the entire coating surface is dark 2: About 50-80% of the entire coating surface is dark 1 The whole paint surface is darkened

Claims (11)

A water-dispersible resin treating agent for metal surfaces containing the following component (A), component (B) and component (C).
(A) Polymerizable unsaturated monomer (a) containing no epoxy group, acid group or hydroxyl group, polymerizable unsaturated monomer (b) having an epoxy group, and acid group-containing polymerizable unsaturated monomer (c) A hydroxyl group-containing polymerizable unsaturated monomer (d), and the following formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent alkylene group having 2 to 10 carbon atoms, and R ³ represents a divalent alkylene group having 2 or 3 carbon atoms)
A water-dispersible resin composition comprising a copolymer resin emulsion obtained by emulsion polymerization of an unsaturated monomer mixture comprising a cyclic ureido group-containing polymerizable unsaturated monomer (e) represented by (B) a zirconium compound (C )Silane coupling agent   In the component (A), the use amounts of the polymerizable unsaturated monomer (b) having an epoxy group, the acid group-containing polymerizable unsaturated monomer (c), and the hydroxyl group-containing polymerizable unsaturated monomer (d) are not polymerizable. 0.1 to 10% by weight based on the total amount of the saturated monomers (a), (b), (c), (d) and (e), the amount of the cyclic ureido group-containing polymerizable unsaturated monomer (e) used is The water-dispersible resin for metal surfaces according to claim 1, which is 0.1 to 5% by weight based on the total amount of the polymerizable unsaturated monomers (a), (b), (c), (d) and (e). Processing agent.   In the component (A), the polymerizable unsaturated monomer (a) which does not contain any of an epoxy group, an acid group and a hydroxyl group is a (meth) acrylic acid alkyl ester (a-1) in which the alkyl group has 1 to 18 carbon atoms. ), Or (meth) acrylic acid alkyl ester (a-1) having 1 to 18 carbon atoms of the alkyl group, styrene monomer (a-2), (meth) acrylonitrile (a-3), hydrolysis A monomer mixed with at least one monomer selected from the group consisting of a polymerizable unsaturated monomer having a reactive silyl group (a-4) and a polyfunctional vinyl group-containing polymerizable unsaturated monomer (a-5) The water-dispersible resin treatment agent for metal surfaces according to claim 1.   The cyclic ureido group-containing polymerizable unsaturated monomer (e) is at least one monomer selected from the group consisting of methacrylamide ethyl ethylene urea, methacrylamide ethyl propylene urea, acrylamide ethyl ethylene urea and acrylamide ethyl propylene urea. Item 8. A water-dispersible resin treatment agent for metal surfaces according to Item 1.   The copolymer resin emulsion in the component (A) has a reaction of 0.3 to 6% by weight with respect to the total amount of the polymerizable unsaturated monomers (a), (b), (c), (d) and (e). The water-dispersible resin treatment agent for metal surfaces according to claim 1, which is a copolymer resin emulsion obtained by emulsion polymerization of an unsaturated monomer mixture in the presence of a water-soluble surfactant (f).   The water-dispersible resin treatment agent for metal surfaces according to claim 1 or 5, wherein the copolymer resin emulsion in component (A) is a core-shell type resin emulsion.   The solid content of component (B) is in the range of 0.1 to 20% by weight based on the solid content of the water-dispersible resin composition as component (A). The water dispersible resin treatment agent for metal surfaces as described in 2.   The amount of the solid content of the component (C) is in the range of 0.1 to 10% by weight with respect to the solid content of the water-dispersible resin composition as the component (A). The water dispersible resin treatment agent for metal surfaces as described in 2.   The water-dispersible resin treatment agent for metal surfaces according to any one of claims 1 to 8, which contains substantially no chromium.   A surface-treated metal plate, wherein the surface of the metal plate is treated with the water-dispersible resin treatment agent for a metal surface according to any one of claims 1 to 9. Surface-treated metal sheet according to claim 10, wherein the solid content adhesion quantity of the metal surface water dispersible resin treatment agent in the metal plate surface is 0.2 to 10 g / m ^2.