JP2006070149A - Water-dispersible resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-dispersible resin composition having excellent efflorescence resistance, water resistance, alkali resistance, adhesiveness to inorganic substrate, adhesiveness to top coat, etc. <P>SOLUTION: The water-dispersible resin composition contains a copolymer resin emulsion produced by the emulsion polymerization of an unsaturated monomer mixture composed of (a) a polymerizable unsaturated monomer free from acid group and hydrolyzable silyl group, (b) a polymerizable unsaturated monomer containing a specific amount of an acid group, (c) a polymerizable unsaturated monomer having a hydrolyzable silyl group and (d) a polymerizable unsaturated monomer containing a cyclic ureide group and expressed by formula (1) (R<SP>1</SP>is a hydrogen atom or a methyl group; R<SP>2</SP>is a 2-10C bivalent alkylene group; and R<SP>3</SP>is a 2-3C bivalent alkylene group) in the presence of (e) a specific amount of a reactive surfactant. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a water-dispersible resin composition useful as an inorganic material undercoat paint or the like. More specifically, the present invention can be applied to the inorganic material before curing the autoclave, so that the overcoating after the autoclave curing can be omitted. Further, the efflorescence resistance, water / alkali resistance, and inorganic properties required for the undercoat paint Excellent adhesion to base materials, excellent adhesion to top coatings, especially fluorine / acrylic resin coatings, which are particularly difficult to adhere, only in two steps: undercoating just before curing in autoclave and top coating of fluorine / acrylic resin coating The present invention relates to a water dispersible resin composition that enables a process-saving coating system in which all coating is completed.

  Conventionally, in the ceramics building material coating plate manufacturing process, in the process-saving coating where the undercoat paint is applied before curing the autoclave, and the overcoat paint, especially the fluorine / acrylic resin paint that is difficult to adhere, is applied directly without overcoating after the autoclave curing. Since the above severe performance is required, organic solvent resin coatings have been used exclusively. However, in recent years, the use of water-based resin paints has been demanded from the viewpoint of safety and ecology.

  The production of inorganic pre-painted boards used for the outer walls of buildings is made by first molding the inorganic material into a plate shape, followed by primary curing, then applying the primary undercoat, drying, autoclave curing, cutting, preheating Then, another second undercoat paint is applied and dried, and then a top coat paint is applied and dried. The undercoat paint is usually applied once or several times before and after the autoclave curing in consideration of the impregnation to the substrate, adhesion, and topcoat adhesion. Such an undercoat with autoclave curing, and therefore a binder resin used therefor, is required to have efflorescence resistance, adhesion to an inorganic base material and topcoat, water resistance / alkali resistance, and the like.

  In particular, recent building exterior wall materials are required to be maintenance-free due to high weather resistance, and the high weather resistance can be obtained by using acrylic / silicone resin paints, silicon resin paints, fluorine / acrylic resin paints and the like as top coatings. . In this case, the undercoat paint is required to have a high degree of adhesion to the base material and the top coat, and particularly the adhesion is particularly difficult when the top coat is a fluorine / acrylic resin paint. Further, even when the topcoat fluorine / acrylic resin paint adheres well to the undercoat paint, the undercoat paint must be applied once or several times before and after the autoclave curing, and there is a difficulty in the number of coating processes. Therefore, undercoating before autoclave curing is sufficient, and after autoclave curing there is no need for repeated overcoating, and fluorine / acrylic resin coating is applied as it is as a top coating, providing sufficient adhesion, water and alkali resistance There were almost no water-based undercoat paint compositions for inorganic materials having coating film properties.

JP 2001-181605 A

  Therefore, the object of the present invention is to overcome the disadvantages of the conventional water-dispersible undercoating composition described above, apply to an inorganic material before curing the autoclave, omit the overcoating after curing the autoclave, and further demand for the undercoating paint. Excellent adhesion to efflorescence resistance, water / alkali resistance, inorganic substrate adhesion, top coating, especially fluorine / acrylic resin coating, which is particularly difficult to adhere, and also from an ecological point of view, safety Another object of the present invention is to provide a water-dispersible resin composition that is useful as an undercoat for an inorganic material having a high coating quality.

  As a result of extensive studies, the present inventor has found that a polymerizable unsaturated monomer containing neither an acid group nor a hydrolyzable silyl group, an acid group-containing polymerizable unsaturated monomer, and a polymer having a hydrolyzable silyl group. A water-dispersible resin composition containing a copolymer resin emulsion obtained by emulsion polymerization of a polymerizable unsaturated monomer and a cyclic ureido group-containing polymerizable unsaturated monomer having a specific structure using a reactive surfactant, The inventors have found that the above object can be achieved and have completed the present invention.

（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（ｄ）とからなる不飽和単量体混合物が、反応性界面活性剤（ｅ）の存在下で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であって、前記酸基含有重合性不飽和モノマー（ｂ）の使用量が、前記重合性不飽和モノマー（ａ）、（ｂ）、（ｃ）及び（ｄ）の総量に対して０．１〜１０重量％であり、前記加水分解性シリル基を有する重合性不飽和モノマー（ｃ）の使用量が、前記重合性不飽和モノマー（ａ）、（ｂ）、（ｃ）及び（ｄ）の総量に対して０．１〜５重量％であり、前記反応性界面活性剤（ｅ）の使用量が前記重合性不飽和モノマー（ａ）、（ｂ）、（ｃ）及び（ｄ）の総量に対して０．３〜６重量％である水分散性樹脂組成物を提供する。 That is, the present invention relates to a polymerizable unsaturated monomer (a) containing neither an acid group nor a hydrolyzable silyl group, an acid group-containing polymerizable unsaturated monomer (b), and a polymerizable compound having a hydrolyzable silyl group. Unsaturated monomer (c) and 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)
The unsaturated monomer mixture comprising the cyclic ureido group-containing polymerizable unsaturated monomer (d) represented by the formula (1) includes a copolymer resin emulsion that is emulsion-polymerized in the presence of the reactive surfactant (e). A water-dispersible resin composition, wherein the acid group-containing polymerizable unsaturated monomer (b) is used in a total amount of the polymerizable unsaturated monomers (a), (b), (c) and (d). The amount of the polymerizable unsaturated monomer (c) having a hydrolyzable silyl group is 0.1 to 10% by weight based on the polymerizable unsaturated monomer (a), (b), (c ) And (d) is 0.1 to 5% by weight, and the amount of the reactive surfactant (e) used is the polymerizable unsaturated monomer (a), (b), (c). And the water dispersible resin composition which is 0.3 to 6 weight% with respect to the total amount of (d) is provided.

  As the polymerizable unsaturated monomer (a) containing neither the acid group nor the hydrolyzable silyl group, for example, a (meth) acrylic acid alkyl ester (a-1) having an alkyl group having 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), amide bond-containing polymerization Unsaturated monomer (a-4), hydroxyl group-containing polymerizable unsaturated monomer (a-5), epoxy group-containing polymerizable unsaturated monomer (a-6), and polyfunctional vinyl group-containing polymerizable unsaturated monomer (a -7) can be used as a mixed monomer with at least one monomer selected from the group consisting of:

  As the cyclic ureido group-containing polymerizable unsaturated monomer (d), for example, at least one monomer selected from the group consisting of methacrylamide ethyl ethylene urea, methacrylamide propylene urea, acrylamide ethyl ethylene urea and acrylamide ethyl propylene urea is used. it can.

  The amount of the cyclic ureido group-containing polymerizable unsaturated monomer (d) used is, for example, 0.1 to 5 weights based on the total amount of the polymerizable unsaturated monomers (a), (b), (c) and (d). %.

  The water-dispersible resin composition is useful as, for example, a resin composition for an inorganic material undercoat.

  The water-dispersible resin composition of the present invention can be applied to an inorganic material before curing the autoclave, so that the overcoating after the autoclave curing can be omitted, and the efflorescence resistance, water resistance / resistance It has excellent alkalinity and adhesion to inorganic substrates, and also has excellent adhesion to topcoat paints, especially to fluorine / acrylic resin paints that are particularly difficult to adhere. It is also excellent from an ecological point of view.

  The water-dispersible resin composition of the present invention comprises a copolymer emulsion obtained by emulsion polymerization using the reactive surfactant (e) of the monomer components (a), (b), (c) and (d). Contains.

  The polymerizable unsaturated monomer (a) containing neither an acid group nor a hydrolyzable silyl group may be any monomer as long as it does not contain an acid group and a hydrolyzable silyl group. Examples include (meth) acrylic acid alkyl ester (a-1) having 1 to 18 carbon atoms in the alkyl group, styrene monomer (a-2), (meth) acrylonitrile (a-3), amide bond Polymerizable unsaturated monomer (a-4), hydroxyl group-containing polymerizable unsaturated monomer (a-5), epoxy group-containing polymerizable unsaturated monomer (a-6), and polyfunctional vinyl group-containing polymerizable unsaturated monomer ( a-7). The polymerizable unsaturated polymer (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 amide bond-containing polymerizable unsaturated monomer (a-4) include acrylamide, methacrylamide, α-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylacrylamide, N- Examples thereof include at least one monomer selected from the group consisting of methyl methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide, methylene bis acrylamide, methylene bis methacrylamide and N-vinyl pyrrolidone.

  Examples of the hydroxyl group-containing polymerizable unsaturated monomer (a-5) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate. And ε-caprolactone-modified acrylic monomers. These hydroxyl group-containing polymerizable unsaturated monomers can be used alone or in combination of two or more. 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 "," Placcel FM-1 "," Placcel FM-2 "," Placcel FM-3 "," Placcel FM-4 "," Placcel FM-5 "and the like.

  Examples of the epoxy group-containing polymerizable unsaturated monomer (a-6) include polymerizable unsaturated monomers having a glycidyl group such as glycidyl acrylate, glycidyl methacrylate (GMA), glycidyl crotonate, glycidyl allyl ether, and β-glycidyl methacrylate. Etc. These monomers can be used alone or in combination of two or more. Usually, glycidyl methacrylate is often used.

  The polyfunctional vinyl group-containing polymerizable unsaturated monomer (a-7) is not particularly limited as long as it is a monomer having a plurality of polymerizable unsaturated groups such as vinyl group, (meth) allyl group, and (meth) acryloyl group. For example, divinylbenzene, ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, allyl (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di ( Divinyl compounds such as (meth) acrylate (bifunctional vinyl group-containing polymerizable unsaturated monomer); trifunctional or more such as pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate The multifunctional bi Etc. Le-containing polymerizable unsaturated monomers. These polyfunctional vinyl group-containing polymerizable unsaturated monomers can be used alone or in combination of two or more.

  As the polymerizable unsaturated monomer (a) containing neither an acid group nor a hydrolyzable silyl group, at least the (meth) acrylic acid alkyl ester ( a-1) is preferably used, and the (meth) acrylic acid alkyl ester (a-1) and the styrene monomer (a-2) are also preferably used 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), Amide bond-containing polymerizable unsaturated monomer (a-4), hydroxyl group-containing polymerizable unsaturated monomer (a-5), epoxy group-containing polymerizable unsaturated monomer (a-6), or polyfunctional vinyl group-containing polymerizable unsaturated It is also preferable to use a monomer (a-7).

  When (meth) acrylonitrile (a-3) is used as a copolymerization monomer, a dense, tough and highly barrier film is formed due to the orientation and crystallization effect of the cyano group in the polymer. The water resistance and efflorescence resistance required for paints are further improved. Moreover, since the coating film hardness is increased, the blocking resistance is also improved. When the amide bond-containing polymerizable unsaturated monomer (a-4) is used as a copolymerization monomer, a newtonian viscosity is imparted to the emulsion, which improves the leveling and workability of the paint. The uniformity of the thickness is increased, and the occurrence of efflorescence from a thin portion can be prevented.

  When the hydroxyl group-containing polymerizable unsaturated monomer (a-5) is used as a copolymerization monomer, the hydrophilicity of the resin composition containing the copolymer resin emulsion and the water-based paint using the same increases, Affinity increases and adhesion improves. When an epoxy group-containing polymerizable unsaturated monomer (a-6) is used as a copolymerization monomer, a three-dimensional network structure is formed in the resin composition by a cross-linking reaction between an epoxy group and a carboxyl group, and the resin composition has water resistance. The effect of imparting alkali resistance and blocking resistance is exhibited. When the polyfunctional vinyl group-containing polymerizable unsaturated monomer (a-7) is used as a copolymerization monomer, crosslinking within the emulsion particles is promoted, and the hardness and strength of the coating film are increased, and at the same time, the blocking resistance is 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, 30 to 100% by weight, preferably 50 to 99% by weight, more preferably, based on the total amount of the polymerizable unsaturated monomer (a). It is about 60 to 98% by weight. The amount of the styrene monomer (a-2) is, for example, 0 to 60% by weight, preferably 0 to 40% by weight, more preferably 0 to 30% 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%). The amount of the amide bond-containing polymerizable unsaturated monomer (a-4) is usually 0 to 20% by weight (for example 1 to 20% by weight), preferably 0, based on the total amount of the polymerizable unsaturated monomer (a). It is about 10 to 10 weight% (for example, 1 to 10 weight%).

  The amount of the hydroxyl group-containing polymerizable unsaturated monomer (a-5) is usually 0 to 20% by weight (for example 1 to 20% by weight), preferably based on the total amount of the polymerizable unsaturated monomer (a). It is about 0 to 10% by weight (for example, 1 to 10% by weight). The amount of the epoxy group-containing polymerizable unsaturated monomer (a-6) is usually 0 to 20% by weight (eg 1 to 20% by weight), preferably 0, based on the total amount of the polymerizable unsaturated monomer (a). It is about 10 to 10 weight% (for example, 1 to 10 weight%). The amount of the polyfunctional vinyl group-containing polymerizable unsaturated monomer (a-7) is usually about 0 to 5% by weight (for example, 1 to 5% by weight) with respect to the total amount of the polymerizable unsaturated monomer (a). It is preferably about 0 to 3% by weight (for example, 0.5 to 3% by weight).

  As the acid group-containing polymerizable unsaturated monomer (b), 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 (b), 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 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 (b) can be used alone or in combination of two or more.

  The amount of the acid group-containing polymerizable unsaturated monomer (b) is 0.1 to 10% by weight, preferably 0 based on the total amount of the monomer components (a), (b), (c) and (d). 0.5 to 8% by weight, more preferably 1 to 7% by weight. By setting the amount of the acid group-containing polymerizable unsaturated monomer (b) within this range, the storage stability of the resin composition containing the copolymer resin emulsion and the aqueous paint using the same, the mechanical stability, and Various stability such as stability against freezing is obtained, and adhesion with an inorganic base material at the time of coating film formation becomes strong. When the amount of the acid group-containing polymerizable unsaturated monomer (b) used is less than 0.1% by weight, the polymerization stability of the resin and the various stability are deteriorated, and the adhesion of the coating film to the surface of the inorganic substrate is weak. Become. On the other hand, when it exceeds 10% by weight, the polymerization stability of the resin and the above-mentioned various stability deteriorate, and the water resistance and alkali resistance of the obtained coating film become weak.

  Among the acid group-containing polymerizable unsaturated monomers (b), a carboxyl group-containing polymerizable unsaturated monomer is preferable from the viewpoints of improving the stability and imparting adhesion. The amount of the carboxyl group-containing polymerizable unsaturated monomer is preferably 50% by weight or more, more preferably 80% by weight or more based on the total amount of the acid group-containing polymerizable unsaturated monomer (b).

  Examples of the polymerizable unsaturated monomer (c) having a hydrolyzable silyl group include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acrylic. Monomers containing an alkoxysilyl group such as loxypropylmethyldiethoxysilane and γ- (meth) acryloxypropyltriethoxysilane may be mentioned, but the invention is not limited thereto. As the polymerizable unsaturated monomer (c) having a hydrolyzable silyl group, a compound generally known as a silane coupling agent can be suitably used. The polymerizable unsaturated monomer (c) having a hydrolyzable silyl group can be used alone or in combination of two or more.

  The amount of the polymerizable unsaturated monomer (c) having a hydrolyzable silyl group is 0.1 to 5% by weight based on the total amount of the monomer components (a), (b), (c) and (d). , Preferably 0.2 to 4.5% by weight, more preferably 0.5 to 4% by weight. By setting the amount of the polymerizable unsaturated monomer (c) having a hydrolyzable silyl group within this range, the water resistance of the resin composition containing the copolymer resin emulsion and the water-based coating film using the resin composition is increased. As a result, the efflorescence resistance is improved. Moreover, the affinity with the inorganic base material is excellent, and the adhesion is improved. Furthermore, the coating film hardness, strength and blocking resistance are also improved by crosslinking. If the said usage-amount of the polymerizable unsaturated monomer (c) which has a hydrolyzable silyl group is less than 0.1 weight%, the water resistance of a coating film is weak and adhesive force is inferior. On the other hand, when it exceeds 5% by weight, the polymerization stability of the copolymer resin emulsion is deteriorated.

The cyclic ureido group-containing polymerizable unsaturated monomer (d) 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 triethylene groups.

As typical examples of the cyclic ureido group-containing polymerizable unsaturated monomer (d), 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 (d), the effect of improving the adhesion of the resin composition to the inorganic substrate, particularly to the wet surface is exhibited. Furthermore, the affinity with and adhesion to top coating materials, particularly alkyd coating materials, acrylic / silicone resin coatings, silicon resin coatings and fluorine / acrylic resin coatings are 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 (d) act on the base material and the pigment, thereby causing a bipolar interaction that contributes to the adhesion of the resin composition to the base material. give. The dipole moment of the cyclic ureido group is as large as 4.5 Debye, which is considered to exert a strong interaction with various top coat surfaces. 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. When the cyclic ureido group-containing polymerizable unsaturated monomer (d) lowers the interfacial tension, the wettability of the base material and the pigment is improved, and the resin composition is easily wetted by the base material and the pigment. The effect is easily manifested.

  Third, the contribution of the spacer group can be considered. For example, when the cyclic ureido group-containing polymerizable unsaturated monomer (d) 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.

  The amount of the cyclic ureido group-containing polymerizable unsaturated monomer (d) used is preferably 0.1 to 5% by weight based on the total amount of the monomer components (a), (b), (c) and (d). More preferred is 5 to 3% by weight. By setting the amount of the cyclic ureido group-containing polymerizable unsaturated monomer (d) within this range, when a resin composition containing a copolymer resin emulsion is used as an undercoat, it is particularly suitable for a substrate, particularly a wet surface. The wettability and affinity are increased, the adhesion is improved and the efflorescence resistance is improved. Furthermore, the adhesiveness with the top coating, especially the fluorine / acrylic resin coating is improved. When the amount of the cyclic ureido group-containing polymerizable unsaturated monomer (d) used in the copolymer resin is less than 0.1% by weight, the adhesion to the base material and the top coat tends to be lowered. On the other hand, if it exceeds 5% by weight, the water resistance of the coating film tends to decrease.

  The reactive surfactant (e) used in the emulsion polymerization of the present invention is not particularly limited, and includes a group containing a reactive group such as a polymerizable unsaturated group, a nonionic hydrophilic group or an anionic hydrophilic group. Any reactive surfactant having a group that exhibits a surfactant activity such as, for example, 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 methallyl 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 include, for example, compounds represented by the following formula (2), (3), (4), (5), (6), (7) or (8). .

（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 (e) is copolymerized or grafted with the monomer components (a), (b), (c) and (d), and exists as a constituent unit of a high molecular weight polymer after polymerization. . For this reason, non-reactive general emulsifiers are present in the low-molecular form in the aqueous phase even after polymerization in the form of free water-soluble substances, and the final cast film of the resin dispersion is therefore water and water resistant. In contrast, the cast film of the resin dispersion obtained by using a reactive surfactant has a high level of the above-mentioned performance (while it is inferior in moisture and heat resistance, hot water resistance, alkali resistance, efflorescence resistance and adhesion) Exhibits water resistance.

  The amount of the reactive surfactant (e) used in the emulsion polymerization is 0.3 to 6% by weight based on the total amount of the monomer components (a), (b), (c) and (d). 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 will be a thing. If it exceeds 6% by weight, water resistance, moist heat resistance, hot water resistance, alkali resistance, efflorescence resistance, adhesiveness, etc. 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 the reactive surfactant (e), as long as the properties such as water resistance and alkali resistance are not impaired. The polymerizable unsaturated monomer may be copolymerized. The amount of the polymerizable unsaturated monomer used is, for example, 20% by weight or less, preferably 10% by weight or less, based on the total amount of the monomer components (a), (b), (c) and (d). Preferably it is 5 weight% or less.

  In the emulsion polymerization, the monomer components (a), (b), (c) and (d) are heated in an aqueous liquid with stirring in the presence of a radical polymerization initiator and a reactive surfactant (e). Can be implemented. 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 adding a monomer mixed solution or monomer pre-emulsified solution all at once to a reaction vessel charged with water and a reactive surfactant.

  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, hydrogen peroxide and the like, and these oxidizing agents, sodium bisulfite, sodium thiosulfate, Rongalite, A so-called redox initiator combined with a reducing agent such as ascorbic acid is used in the form of an aqueous solution.

  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, from the viewpoint of promoting the emulsion polymerization, and the smooth and uniform formation of the coating film. In many cases, it is preferable from the viewpoint of promoting and improving the adhesion to the base material, and this is appropriately carried out according to the situation.

  In addition, as the emulsion polymerization method, any one of the usual one-stage continuous monomer uniform dropping method, the core-shell polymerization method which is a multi-stage monomer feed method, the power feed polymerization method which continuously changes the monomer composition fed during the polymerization, etc. The polymerization method can be used.

  In this way, a copolymer resin emulsion 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, for example, about 100,000 to 800,000.

  The water-dispersible resin composition of the present invention may contain an additive such as a basic compound, mainly based on the copolymer resin emulsion. As the basic compound, ammonia, various amines, 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.

  The water-dispersible resin composition of the present invention can be used as it is for forming a clear film as a coating material as it is, but usually, the resin composition is colored pigment, extender pigment, water-soluble resin, colloidal. Dispersion, organic solvent, film-forming aid, plasticizer, dispersant, curing agent, wetting agent, thickener, surface tension modifier, preservative, anti-settling agent, antifoaming agent, colloidal silica, zinc phosphate, Various additives such as aluminum tripolyphosphate can be blended and used as a paint. The water-dispersible resin composition of the present invention or a paint using the same is particularly suitable for use as an inorganic material undercoat.

  As the color pigment, titanium oxide, red rust (iron oxide), ocher, carbon black and the like are used. As extender pigments, barium sulfate, calcium carbonate, clay, mica, talc and the like are used. As the curing agent, an epoxy resin or an isocyanate resin is used. The blending amount when blending these pigments is usually about 0.01 to 50 parts by weight for the color pigment and about 1 to 200 parts by weight for the extender pigment with respect to 100 parts by weight of the copolymer resin emulsion. .

  Although content of copolymer resin in a water-dispersible resin composition can be suitably set according to a use, generally it is about 10 to 70 weight%.

  The water-dispersible resin composition of the present invention is made by, for example, making or pressing a compound containing a cement as a main component, a reinforcing fiber such as pulp or rock wool, a siliceous material such as silica sand, or an inorganic filler. After molding by molding, it can be applied as an undercoat paint to an inorganic base material (for example, calcium silicate board, asbestos cement board, wood chip cement board, pulp cement board, lightweight cellular concrete board) produced by water curing.

The water-dispersible resin composition of the present invention is preferably used as an undercoat paint to be applied before curing an inorganic base material in an autoclave. There is no restriction | limiting in particular in autoclave curing, It can carry out on the conditions (for example, 150-180 degreeC, 8-10 atmospheres, 8-10 hours) normally employ | adopted with respect to the ceramic-type inorganic base material. For example, after an undercoat paint 100 g / m ² (dry film thickness 30 to 40 μm) is applied to an inorganic substrate, it is not dried, or is dried for 30 to 60 seconds with a jet (air blow) dryer at 150 to 170 ° C. Then, it is cured in an autoclave under the above conditions, and then a top coating such as a fluorine / acrylic resin coating is applied.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. In the following, “part” and “%” are all based on weight unless otherwise specified.

で表される反応性界面活性剤［商品名「アデカリアソープＳＥ−１０Ｎ」、旭電化工業（株）製］（e1）３部を仕込み、７５℃に昇温した。別途、次に示すモノマー、乳化剤及び水の混合液を高圧ホモジナイザーを用いて均一に乳化し、モノマー乳化液として滴下ロートに仕込んだ。
（モノマー乳化液）
反応性界面活性剤（e1） １０部
ＭＭＡ（メタクリル酸メチル）（a1） ２６０部
２ＥＨＡ（アクリル酸２−エチルヘキシル）（a2） １３０部
ＭＡＡ（メタクリル酸）（b1） ８部
加水分解性シリル基含有重合性不飽和モノマー［商品名「Ａ−１７４」、γ−メタクリロキシプロピルトリメトキシシラン、日本ユニカー（株）製］（c1） ３部
環状ウレイド基含有重合性不飽和モノマー［商品名「サイポマーＷＡＭ−II」、メタクリルアミドエチルエチレン尿素ＭＡＥＥＵ（d1）とＭＡＡ（b1）の１：１混合物、ローディア日華（株）製］ １０部
水 １４０部
また、別途、次に示す滴下用開始剤水溶液を別の滴下ロートに仕込んだ。
（滴下用開始剤水溶液）
過硫酸カリウム １部
水 ７５部
次に、前記反応容器内に、前記モノマー乳化液の５％を添加し、７５℃に加熱後、前記滴下用開始剤水溶液の５％を投入し、１０分間プレ重合反応を行った。この間反応容器の内温は自動的に８０℃に上昇した。その後、残りのモノマー乳化液及び滴下用開始剤水溶液を８０℃で３時間かけて一定速度で同反応容器内に滴下した。滴下終了後８０℃に保持して１時間熟成反応を行い、室温に冷却した後、アンモニア水（２５％）４部を反応容器内に投入し、樹脂組成物（水性樹脂分散液）を得た。この樹脂組成物の固形分濃度は４２．３重量％、ｐＨは８．２であった。
次に、上記で得られた樹脂組成物１００重量部に造膜助剤としてブチルセロソルブ４重量部と水４重量部の混合液を添加後、分散剤［商品名「ＳＭＡレジン１４４０−２０」、スチレン−マレイン酸ソーダ系樹脂、川原油化（株）製］１．４重量部、黒色着色顔料［商品名「Toda Color KN-320」、戸田工業社製］１１．５重量部、黄色着色顔料［商品名「Toda Color TSY-1」、戸田工業社製］２．９重量部、水１５重量部を添加、混合し、よく練り、下塗り塗料とした。 Example 1
In a normal reaction vessel for producing an acrylic resin emulsion equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 356 parts of water and the following formula (10)

3 parts of a surfactant (trade name “ADEKA rear soap SE-10N” manufactured by Asahi Denka Kogyo Co., Ltd.) (e1) represented by the formula: 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)
Reactive surfactant (e1) 10 parts MMA (methyl methacrylate) (a1) 260 parts 2EHA (2-ethylhexyl acrylate) (a2) 130 parts MAA (methacrylic acid) (b1) 8 parts Hydrolyzable silyl group-containing Polymerizable unsaturated monomer [trade name “A-174”, γ-methacryloxypropyltrimethoxysilane, manufactured by Nippon Unicar Co., Ltd.] (c1) 3 parts Cyclic ureido group-containing polymerizable unsaturated monomer [trade name “Sypomer WAM -II ", 1: 1 mixture of methacrylamide ethyl ethylene urea MAEEU (d1) and MAA (b1), manufactured by Rhodia Nikka Co., Ltd.] 10 parts Water 140 parts Charged to another dropping funnel.
(Initiator aqueous solution for dripping)
Potassium persulfate 1 part Water 75 parts Next, 5% of the monomer emulsion is added into the reaction vessel, heated to 75 ° C., and then 5% of the dropping initiator aqueous solution is added. 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 dropping, the mixture was kept at 80 ° C. for 1 hour, cooled to room temperature, and then 4 parts of ammonia water (25%) was put into the reaction vessel to obtain a resin composition (aqueous resin dispersion). . This resin composition had a solid content concentration of 42.3% by weight and a pH of 8.2.
Next, after adding a mixture of 4 parts by weight of butyl cellosolve and 4 parts by weight of water as a film-forming aid to 100 parts by weight of the resin composition obtained above, a dispersant [trade name “SMA Resin 1440-20”, styrene -Sodium maleate resin, manufactured by Kawa Crude Chemical Co., Ltd.] 1.4 parts by weight, black colored pigment [trade name “Toda Color KN-320”, manufactured by Toda Kogyo Co., Ltd.] 11.5 parts by weight, yellow colored pigment [ Product name “Toda Color TSY-1” (manufactured by Toda Kogyo Co., Ltd.) 2.9 parts by weight and 15 parts by weight of water were added, mixed, kneaded well, and used as an undercoat paint.

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］（e2）を用いた以外は、すべて実施例１と同様にして乳化重合を行い、樹脂組成物（水性樹脂分散液）を得た。この樹脂組成物の固形分濃度は４２．４重量％、ｐＨは８．２であった。次に、実施例１と同様の配合で下塗り塗料を得た。 Example 2
In Example 1, instead of the reactive surfactant (trade name “ADEKA rear soap SE-10N”) (e1), the same amount of the following formula (11)

In the same manner as in Example 1 except that the reactive surfactant represented by the formula [trade name “AQUALON HS-10”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] (e2) was used, A resin composition (aqueous resin dispersion) was obtained. The resin composition had a solid content concentration of 42.4% by weight and a pH of 8.2. Next, an undercoat paint was obtained with the same formulation as in Example 1.

（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−２０」、旭電化工業（株）製］（e3）を用いた以外は、すべて実施例１と同様にして乳化重合を行い、樹脂組成物（水性樹脂分散液）を得た。この樹脂組成物の固形分濃度は４２．３重量％、ｐＨは８．０であった。次に、実施例１と同様の配合で下塗り塗料を得た。 Example 3
In Example 1, instead of the reactive surfactant (trade name “ADEKA rear soap SE-10N”) (e1), the same amount of the following formula (12)

(Wherein R represents an alkyl group)
Emulsion polymerization was carried out in the same manner as in Example 1 except that the reactive surfactant represented by the formula [trade name “ADEKA rear soap SR-20” manufactured by Asahi Denka Kogyo Co., Ltd.] (e3) was used. A resin composition (aqueous resin dispersion) was obtained. This resin composition had a solid content concentration of 42.3% by weight and a pH of 8.0. Next, an undercoat paint was obtained with the same formulation as in Example 1.

で表される反応性界面活性剤［商品名「ラテムルＳ−１８０Ａ」、花王（株）製］（e4）を用いた以外は、すべて実施例１と同様にして乳化重合を行い、樹脂組成物（水性樹脂分散液）を得た。この樹脂組成物の固形分濃度は４１．５重量％、ｐＨは８．１であった。次に、実施例１と同様の配合で下塗り塗料を得た。 Example 4
In Example 1, instead of the reactive surfactant (trade name “ADEKA rear soap SE-10N”) (e1), 2.5 times the following formula (13)

In the same manner as in Example 1 except that the reactive surfactant represented by the formula [trade name “Latemul S-180A”, manufactured by Kao Corporation] (e4) was used, emulsion polymerization was carried out in the same manner as in Example 1. (Aqueous resin dispersion) was obtained. This resin composition had a solid content concentration of 41.5% by weight and a pH of 8.1. Next, an undercoat paint was obtained with the same formulation as in Example 1.

（式中、Φは多官能フェニル基、ｒ、ｓは１〜１００の整数、Ｍはアルカリ金属又はＮＨ₄を示す）
で表される反応性界面活性剤［商品名「アントックスＭＳ−６０」、ビス（ポリオキシエチレン多官能フェニルエーテル）メタクリレート硫酸エステル塩、日本乳化剤（株）製］（e5）を用いた以外は、すべて実施例１と同様にして乳化重合を行い、樹脂組成物（水性樹脂分散液）を得た。この樹脂組成物の固形分濃度は４２．３重量％、ｐＨは８．０であった。次に、実施例１と同様の配合で下塗り塗料を得た。 Example 5
In Example 1, instead of the reactive surfactant (trade name “ADEKA rear soap SE-10N”) (e1), the same amount of the following formula (14)

(Wherein Φ is a polyfunctional phenyl group, r and s are integers of 1 to 100, and M is an alkali metal or NH ₄ )
Except that the reactive surfactant [trade name “ANTOX MS-60”, bis (polyoxyethylene polyfunctional phenyl ether) methacrylate sulfate, manufactured by Nippon Emulsifier Co., Ltd.] (e5) is used. In the same manner as in Example 1, emulsion polymerization was performed to obtain a resin composition (aqueous resin dispersion). This resin composition had a solid content concentration of 42.3% by weight and a pH of 8.0. Next, an undercoat paint was obtained with the same formulation as in Example 1.

Comparative Example 1
In Example 1, instead of the reactive surfactant (trade name “Adekaria Soap SE-10N”) (e1), the same amount of the non-reactive surfactant [trade name “Hitenol 08E”, Daiichi Kogyo Emulsion polymerization was carried out in the same manner as in Example 1 except that (manufactured by Pharmaceutical Co., Ltd.) (e ′) was used to obtain a resin composition (aqueous resin dispersion). The resin composition had a solid content concentration of 42.4% by weight and a pH of 8.3. Next, an undercoat paint was obtained with the same formulation as in Example 1.

Comparative Example 2
In Example 1, a hydrolyzable silyl group-containing polymerizable unsaturated monomer [trade name “A-174”, γ-methacryloxypropyltrimethoxysilane, manufactured by Nippon Unicar Co., Ltd.] (c1) 3 parts as a monomer In addition, emulsion polymerization was carried out in the same manner as in Example 1 except that 3 parts of MMA (a1) was used to obtain a resin composition (aqueous resin dispersion). The resin composition had a solid content concentration of 42.4% by weight and a pH of 8.2. Next, an undercoat paint was obtained with the same formulation as in Example 1.

Comparative Example 3
Example 1 is the same as Example 1 except that 10 parts of MMA (a1) was used in place of 10 parts of a cyclic ureido group-containing polymerizable unsaturated monomer (trade name “Cypomer WAM-II”) as a monomer. Similarly, emulsion polymerization was performed to obtain a resin composition (aqueous resin dispersion). The resin composition had a solid content concentration of 42.4% by weight and a pH of 8.1. Next, an undercoat paint was obtained with the same formulation as in Example 1.

Performance Evaluation Test Each undercoat aqueous coating composition obtained in the examples and comparative examples was subjected to a performance evaluation test as an inorganic material undercoat paint as follows. The test results are shown in Table 1. As the topcoat fluororesin, acrylic acid ester (MMA) is seeded with a fluororesin of VdF (vinylidene fluoride) / TFE (tetrafluoroethylene) / CTFE (chlorotrifluoroethylene) = 75/15/10 (molar ratio). / BA (butyl acrylate) = 50/50) was used as a resin composition (solid content concentration 45%, pH 7).

(Preparation of test paint plate)
Apply the above-mentioned undercoat paint to a JIS flex plate so that the application amount is 100 g / m ^2, and after curing for 10 hours at 160 ° C. and 10 atm (1.01 MPa), apply the above-mentioned top coat fluororesin at 100 g / m ^2. And dried for 40 seconds at 160 ° C. with a jet dryer. Then, the side and the back surface of the coated plate were sealed with aluminum foil and epoxy resin to obtain a test coated plate.

(Temperature and humidity resistance test)
Whitening:
The test plate was left for 14 days in an atmosphere of 50 ° C. and 99% RH, and after taking out, the whitening state of the coated plate was evaluated in five stages (5: no whitening at all, 1; whitening on the entire surface).

Adhesion:
The above test plate is left for 1 day in an atmosphere of 50 ° C. and 99% RH. After taking out, the surface water of the coating plate is wiped off with a cloth, and the adhesion test of the coating film is performed with Nichiban cello tape (registered trademark). And evaluated in the following five stages.
5: No peeling at all.
4: Less than 20% of the total area peeled.
3: Less than 20 to 50% of the total area is peeled off.
2: Less than 50 to 80% of the total area is peeled off.
1: 80 to 100% of the total area is peeled off.

Blister:
The test plate was left in an atmosphere of 50 ° C. and 99% RH for 14 days, and after taking out, the blister condition of the plate was evaluated in the following five stages.
5; No blister at all.
4: The generation state of blisters is less than 20% of the total area.
3: The blister generation state is less than 20 to 50% of the total area.
2: The generation state of blisters is less than 50 to 80% of the total area.
1: The generation state of blisters is 80 to 100% of the total area.

(Hot water resistance test)
Whitening:
The test coating plate was immersed in warm water at 60 ° C. for 5 days, and after taking out, the whitening state of the coating plate was evaluated in five stages (5: no whitening at all, 1; whitening on the entire surface).

Adhesion:
The test coating plate is immersed in warm water at 60 ° C. for 1 day, and after taking out, the surface water of the coating plate is wiped off with a cloth, and the adhesion test of the coating film is performed with Nichiban cello tape (registered trademark). Evaluation was made in 5 stages.
5: No peeling at all.
4: Less than 20% of the total area peeled.
3: Less than 20 to 50% of the total area is peeled off.
2: Less than 50 to 80% of the total area is peeled off.
1: 80 to 100% of the total area is peeled off.

Blister:
The test coating plate was immersed in warm water at 60 ° C. for 5 days, and after taking out, the blister condition of the coating plate was evaluated in the following five stages.
5; No blister at all.
4: The generation state of blisters is less than 20% of the total area.
3: The blister generation state is less than 20 to 50% of the total area.
2: The generation state of blisters is less than 50 to 80% of the total area.
1: The generation state of blisters is 80 to 100% of the total area.

  As shown in Table 1, the undercoat paint using the resin composition of the present invention showed excellent results in all test items.

Claims (5)

A polymerizable unsaturated monomer (a) containing neither an acid group nor a hydrolyzable silyl group, an acid group-containing polymerizable unsaturated monomer (b), and a polymerizable unsaturated monomer having a hydrolyzable silyl group (c ) 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)
The unsaturated monomer mixture comprising the cyclic ureido group-containing polymerizable unsaturated monomer (d) represented by the formula (1) includes a copolymer resin emulsion that is emulsion-polymerized in the presence of the reactive surfactant (e). A water-dispersible resin composition, wherein the acid group-containing polymerizable unsaturated monomer (b) is used in a total amount of the polymerizable unsaturated monomers (a), (b), (c) and (d). The amount of the polymerizable unsaturated monomer (c) having a hydrolyzable silyl group is 0.1 to 10% by weight based on the polymerizable unsaturated monomer (a), (b), (c ) And (d) is 0.1 to 5% by weight, and the amount of the reactive surfactant (e) used is the polymerizable unsaturated monomer (a), (b), (c). And the water dispersible resin composition which is 0.3 to 6 weight% with respect to the total amount of (d).   The polymerizable unsaturated monomer (a) containing neither an acid group nor a hydrolyzable silyl group is a (meth) acrylic acid alkyl ester (a-1) in which the alkyl group has 1 to 18 carbon atoms, or the alkyl (Meth) acrylic acid alkyl ester (a-1) having 1 to 18 carbon atoms, styrene monomer (a-2), (meth) acrylonitrile (a-3), amide bond-containing polymerizable unsaturated Monomer (a-4), hydroxyl group-containing polymerizable unsaturated monomer (a-5), epoxy group-containing polymerizable unsaturated monomer (a-6), and polyfunctional vinyl group-containing polymerizable unsaturated monomer (a-7) The water-dispersible resin composition according to claim 1, which is a mixed monomer with at least one monomer selected from the group consisting of:   The cyclic ureido group-containing polymerizable unsaturated monomer (d) is at least one monomer selected from the group consisting of methacrylamide ethyl ethylene urea, methacrylamide propylene urea, acrylamide ethyl ethylene urea and acrylamide ethyl propylene urea. 1. The water dispersible resin composition according to 1.   The amount of the cyclic ureido group-containing polymerizable unsaturated monomer (d) used is 0.1 to 5% by weight based on the total amount of the polymerizable unsaturated monomers (a), (b), (c) and (d). The water dispersible resin composition according to claim 1. The water-dispersible resin composition according to any one of claims 1 to 4, which is a water-dispersible resin composition for an inorganic material undercoat paint.