WO2006077751A1 - Low-staining coating composition, and low-staining coating film produced from the same - Google Patents

Abstract

A low-staining coating composition comprising: a coating composition which comprises (A) a coating film-forming resin, (B) a hydrophilizing agent having a hydrolyzable group and (C) an organic solvent capable of dissolving or dispersing therein the resin (A) and the hydrophilizing agent (B); and (D) a hydrolysis-promoting catalyst dispersion, blended into the coating composition, which comprises an organic transition metal compound (D-1) capable of promoting the hydrolysis by the hydrophilizing agent (B) and an organic solvent (D-2) having a carbonyl group as well as a carbonyl group and/or a hydroxyl group and having a catalyst blocking property against the organic transition metal compound (D-1). By using this coating composition, the surface hydrophilization of the coating film by the hydrophilizing agent can be expressed with high efficiency and with effective timing and a coating film having low staining property can be formed early in the course of the film formation process.

Description

 Specification

 Low stain coating composition and low stain coating obtained therefrom

 Technical field

 [0001] The present invention relates to a low-fouling coating composition containing a hydrophilization-promoting catalyst capable of rapidly developing low-fouling property on the surface of a coating film, and a low-fouling coating film obtained therefrom. Background art

 [0002] It is well known to prevent adhesion of dirt (especially hydrophobic dirt) by making the surface of the coating film hydrophilic, and a hydrolyzable group is added to make the coating film surface hydrophilic. It is also well known to add a hydrophilic glaze having the same (for example, WO 94Z06870 pamphlet, WO 96Z26254 pamphlet, JP 2000-160103 A).

 [0003] Further, it is also known to add a hydrophilization promoting catalyst in order to promote the hydrolysis action of the hydrophilizing agent (for example, JP-A-8-12921, JP-A-8-12922). .

 [0004] As such a hydrophilization promoting catalyst, in addition to various inorganic acids, organometallic compounds (alkoxide, chelate, ester) such as aluminum, titanium, tin, zinc, zirconium, and silicon have been proposed. (JP-A-8-12921, JP-A-8-12922). However, it is only a specific aluminum chelate compound such as aluminum acetylacetonate bisethylacetoacetate that has actually been confirmed to have a hydrophilic effect.

 [0005] Further, in the curable coating composition, a compound similar to the above-mentioned hydrophilization promoting catalyst is used as the curing catalyst (for example, International Publication No. 94Z06870, International Publication No. 96Z26254, etc.) .

 Disclosure of the invention

 [0006] The hydrophilization promoting catalyst essentially promotes hydrolysis of the hydrolyzable group of the hydrophilizing agent to make the hydrophilizing agent hydrophilic, and such hydrophilization (hydrolysis) If it does not occur on the surface of the paint film, it cannot achieve the ability to prevent contamination of the paint film (low contamination).

[0007] However, conventional hydrophilization promoting catalysts have high catalytic activity, and in some cases, hydrolysis or condensation reactions are promoted inside the coating film before the hydrophilizing agent appears on the surface in the process of forming the coating film. However, gelling may be caused and the surface hydrophilicity may not be achieved. On the other hand, if the catalyst activity is low, contaminants may adhere to the surface of the coating film before it becomes hydrophilic, even after the coating film is formed.

 [0008] As described above, in order to realize low contamination with an early force, it is most effective to control the hydrolyzing agent so that hydrolysis occurs promptly when it appears on the surface of the coating film. However, it has been difficult to control with conventional hydrophilization promoting catalysts.

[0009] An object of the present invention is to provide a coating composition that can be controlled so that hydrolysis occurs promptly when the hydrophilizing agent appears on the surface of the coating film, thereby promptly reducing contamination. It is to achieve.

 [0010] The coating composition of the present invention capable of solving such problems includes (A) a resin for forming a coating film, (B) a hydrophilizing agent having a hydrolyzable group, and (C) the resin (A). And a coating composition containing an organic solvent capable of dissolving or dispersing the hydrophilizing agent (B), (D) an organic transition metal compound (D-1) having a hydrolysis promoting action of the hydrophilizing agent (B) And a solvent (D-2) having a carbonyl group and an organic solvent having a carbonyl group and Z or a hydroxyl group and having a catalytic blocking property to the organic transition metal compound (D-1) The present invention relates to a low-fouling coating composition obtained by combining a catalyst dispersion.

 [0011] Hereinafter, for the purpose of classification, the paint composition comprising components (A), (B), and (C) is referred to as “paint composition (Π)”, and this is a low composition containing component (D). The staining paint composition is referred to as “paint composition (I)”.

 [0012] The coating film forming resin (A) includes various types of coating films such as fluorine resin, acrylic resin, urethane resin, polyester resin, alkyd resin, epoxy resin, and silicone resin. Although rosin can be used, low contamination is particularly effective when the fluorinated resin is easily contaminated with hydrophobic contaminants.

 [0013] The coating film forming resin (A) may be a curable resin or a thermoplastic resin, but the mechanical properties of the coating film are suitable for weather resistance, heat resistance, and the like. If you need an excellent coating, use a curable resin.

[0014] As the hydrophilizing agent (B), conventionally known hydrophilizing agents can be used, but organosilicates, particularly non-fluorinated organosilicates whose hydrolyzable groups are non-fluorinated organic groups are hydrolyzed. The effect of controlling the degradation to make the surface hydrophilic is particularly remarkable.

 [0015] As a transition metal of the organic transition metal compound (D-1) in the hydrophilization promoting catalyst dispersion (D), zirconium! :), tin (Sn) and titanium (Ti) are preferred. These transition metals form organic transition metal compounds in the form of alkoxides, esters, chelate compounds, organic acid salts and the like. As the organic zirconium compound, in particular, a zirconium alkoxide or a zirconium chelate compound is easily available, the solvent solubility, the pot life at the time of coating, and the point strength with good low contamination of the resulting coating film are also preferable. Among the organic tin compounds, alkyltin ester compounds such as dibutyltin dilaurate and alkyltin halides such as dichlorodibutyltin are easy to obtain, have good solvent solubility, and low contamination of the coating film. preferable.

 [0016] The solvent (D-2) having a catalyst blocking property is an organic solvent having a carbonyl group and a carbo group and Z or a hydroxyl group in addition to the carbonyl group, and catalyzes the organic transition metal compound (D-1). It is a solvent having block properties.

 [0017] The catalyst-blocking solvent (D-2) is at least one selected from the group consisting of a diketone solvent, a keto ester solvent, a hydroxyl group-containing carboxylic acid ester solvent, and a keto alcohol solvent. , Preferable from the point of good catalyst blocking.

 [0018] The solvent (D-2) having the catalyst blocking property is added to the coating composition (Π) containing the organic solvent (C) capable of dissolving or dispersing the resin (A) and the hydrophilizing agent (B). You can also add ヽ.

 [0019] As the diketone solvent, from the viewpoint of affinity with the organic transition metal compound (D-1), affinity with the organic solvent contained in the coating composition, and availability, 8-diketones Compound is preferred.

 [0020] The present invention is also a coating film formed by applying the coating composition (I) of the present invention to a substrate, wherein the content of transition metal atoms is at the free surface portion from the center of the coating film. Also related to high and low contamination coatings.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0021] The coating composition of the present invention comprises (A) a resin for forming a coating film, (B) a hydrophilic agent having a hydrolyzable group, and (C) the resin (A) and a hydrophilic agent (B ) Is dissolved or dispersed in a coating composition (Π) having an action of promoting the hydrolysis of (D) the hydrophilizing agent (B). This is a low-fouling paint composition (I) comprising a hydrophilization promoting catalyst dispersion composed of an organic transition metal compound (D-1) and a catalyst blocking solvent (D-2).

[0022] As the coating composition (ii), a conventionally known low-contamination specification coating composition containing a hydrophilizing agent can be used. Hereinafter, each component of the coating composition (II) will be described.

[0023] (A) Resin for coating film formation

 As the coating film forming resin (A), various conventionally known coating film forming resins can be used, which may be curable or thermoplastic. However, the mechanical properties of the coating film are weather resistant. When a coating film having excellent properties such as heat resistance and heat resistance is required, it is preferable to use a curable resin.

[0024] The curable resin for forming a coating film includes a hydroxyl group, an epoxy group, an amino group, a carboxyl group (or a derivative thereof), a nitrile group, a silanol group, a hydrolyzable silyl group, a mercapto group, and the like. Examples of the resin having a functional group.

[0025] Examples of the hydroxyl-containing curable resin include fluorine-based curable resins such as hydroxyl-containing fluorine-containing resins; hydroxyl-containing acrylic resins (including modified acrylic resins), and hydroxyl-containing ester resins. Non-fluorinated curable resins such as hydroxyl group-containing alkyd resins and hydroxyl group-containing silicone resins.

[0026] Among these, it is particularly effective in the case of curable fluorine resin that is easily contaminated with hydrophobic contaminants because the coating film is rich in hydrophobicity.

As the hydroxyl group-containing fluorine-containing resin, conventionally known resins can be used. For example, International Publication No. 94Z06870 pamphlet, JP-A-8-12921, JP-A-10-72569, JP-A-10-72569 Examples include hydroxyl-containing fluorine-containing resins described in Japanese Patent Publication No. 4-275379, International Publication No. 97/11130, International Publication No. 96Z26254, and the like.

[0028] More specific and non-limiting examples include, for example, fluorephrine, hydroxyl-containing radically polymerizable unsaturated monomers, and, if necessary, other radical polymerization properties copolymerizable therewith. Fluoroolefin-based fluorinated resin obtained by copolymerization with unsaturated monomer; has perfluoroalkyl group or perfluoroalkyl group at one end and ethylenic double bond at the other end A fluorine-containing acrylic obtained by copolymerizing a monomer having a hydroxyl group, a hydroxyl group-containing acrylate, and, if necessary, another radical polymerizable unsaturated monomer capable of being copolymerized therewith Examples include greaves.

 [0029] Fluoroolefins include, for example, tetrafluoroethylene (TFE), black trifluoroethylene (CTFE), trifluoroethylene (TrFE), vinylidene fluoride (VdF), fluorinated bur ( VF), hexafluoropropylene (HFP), etc., one or more of them are listed, and in particular, the solvent solubility of the fluorolephine-based fluorine resin obtained from these strengths and the resulting coating film However, TFE, CTFE, VdF, etc. are preferable because they are excellent in weather resistance, heat resistance, chemical resistance, and the like.

 [0030] Examples of the hydroxyl group-containing radically polymerizable unsaturated monomer include those having a radically polymerizable unsaturated double bond and a hydroxyl group capable of radical copolymerization with fluorephrine. Preferable specific examples include hydroxyalkyl butyl ethers such as hydroxyethyl vinyl ether, hydroxypropenorevinino reetenole, hydroxybutinorevinino reetenole, hydroxypentino levinore ether; ethylene glycol monoallyl Hydroxylyl ethers such as ether, diethyleneglycolmonomonolinoleether, triethyleneglycolmonomonolinole ether, glycerin monoallyl ether, and the like; Examples include adducts with ratatones such as force prolatatanes and y valerolatatanes.

[0031] Other radically polymerizable unsaturated monomers that can be copolymerized can be selected from conventionally known monomers according to the required coating film performance. Specifically, for example, etholein such as ethylene, propylene, isobutylene, butylene 1, and black mouth plane; ethinolevino reetenole, isobutino levino reetenore, butino levino reetenole, cyclohe Butyl ethers such as xinolev-norethenore, propinolev-norethenore, isopropyleno-bi-norethenore, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether; vinyl ether, o-, m-, p Any allyl butyl ether; acetate, lactate, butyrate, isobutyrate, caproate, isocaproate, pivalate, versatate (eg CH = CHOC = OC H

 2 8 17, CH = CHOC = OC H, etc.), bibenzoate

 2 9 19

Examples thereof include carboxylic acid butyl esters such as benzene; fatty acid isopropyl esters such as acetic acid isopropyl and propionic acid isopropyl. [0032] The hydroxyl group-containing fluorine-containing resin may further contain a carboxyl group. The carboxyl group can be introduced, for example, by addition reaction of a part of the hydroxyl group in the hydroxyl group-containing fluorine-containing resin with a polybasic acid anhydride (for example, itaconic anhydride, succinic anhydride, etc.). .

 [0033] As a monomer having a perfluoroalkyl group or a perfluoroalkyl group at one end and an ethylenic double bond at the other end in the fluorine-containing acrylic resin, it is preferable to use perfluoro Examples thereof include chlorobutyl methacrylate, perfluorooctyl methacrylate, perfluoroiso-ruethyl methacrylate, and perfluorodecyl methacrylate.

 [0034] Preferable examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and hydroxypropyl methacrylate.

 [0035] Other radical polymerizable unsaturated monomers copolymerizable with these in the fluorinated acrylic resin are preferably methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate. Hexyl acrylate, octyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate (Meth) acrylic acid alkyl esters such as lauryl methacrylate; ethylenically unsaturated carboxylic acids such as acrylic acid and methacrylic acid; butyl aromatic monomers such as styrene, α-methylstyrene and butyltoluene; Amidation of acrylic acid Compounds and their derivatives; acrylonitriles such as acrylonitrile and meta-tallow-tolyl are included.

 [0036] The number average molecular weight of the hydroxyl group-containing fluorine-containing resin is about 2,000 to 100,000, preferably about 5,000 to 80,000. It can maintain the durability and stain resistance of the coating film it has, and can maintain good paint storage stability that is compatible with the curing agent, hydrophilizing agent, and Sarakoko, a hydrophilic catalyst. .

[0037] The hydroxyl value is preferably in the range of about 20 to 200 mg KOHZg, preferably about 50 to 150 mg KOHZg. If the hydroxyl value is too low or too high, the durability of the coating film Contamination resistance may decrease, curability may decrease, hardness may decrease, mechanical strength may be insufficient, and chemical resistance and water resistance may decrease.

 [0038] As other curable fluorine-containing resin, JP-A-8-231919, JP-A-10

 Examples include fluorofluorin copolymers described in JP-A-265731, JP-A-10-204374, JP-A-8-12922, and the like.

 [0039] Examples of commercially available curable fluorine-containing resin include Lumiflon (Asahi Glass Co., Ltd., trade name, the same shall apply hereinafter), Cefral Coat (Central Glass Co., Ltd.), Zaflon (Toa Gosei Co., Ltd.), Zeffle (Daikin Industries Co., Ltd.), Fluonate (Dainippon Ink Industries Co., Ltd.), Floren CFSR Co., Ltd., and Kyner (Attoina).

 [0040] In the present invention, the curable resin for forming a coating film may be a non-fluorinated curable resin. Non-fluorinated curable resins include, for example, those containing silanol groups and Z or hydrolyzable silyl groups described in JP-A-10-72569, epoxy resins, and hydroxyl group-containing silicone resins. Contains hydrolyzable silyl groups as described in JP-A-2000-160103, such as oils, hydroxyl group-containing acrylic resins, hydroxyl group-containing polyester resins, hydroxyl group-containing alkyd resins, and hydroxyl group-containing polyester-modified acrylic resins. Acrylic resin, hydroxyl group-containing acrylic resin having a hydrolyzable silyl group described in JP-A-2000-160120, hydroxyl group, epoxy group, hydrolysis described in JP-A-10-204374 Examples thereof include cocoa butter containing a functional silyl group. Among these non-fluorinated curable resins, they are excellent in solvent affinity, coating properties, curability, weather resistance, chemical resistance, coating film hardness, availability, etc., so silanol groups and Z Or a resin containing a hydrolyzable silyl group, a hydroxyl group-containing acrylic resin, or a hydroxyl group-containing silicone resin is preferable.

[0041] In the present invention, the resin-forming resin (A) may not be curable! As the thermoplastic resin that does not contain such a crosslinkable group, those that have been conventionally used as a coating film forming resin can be used. Non-limiting examples of preferred paints include, for example, fluororesin paints containing vinylidene fluoride homopolymers and / or vinylidene fluoride copolymers, and cellulose derivative paints (nitrocellulose lacquer, acetyl cellulose). Lacquer, acetinorebutenoresenorelose lacquer, ethinoresenorelose lacquer, etc.), Atari Lubricant-based paint, urethane-based resin, vinyl chloride-based resin, fluorine-based resin, alkyd-based resin, vinyl-acetate-based resin, styrene-butadiene-based resin, salted butyl organo Examples include sol paints, and coating film forming resins used for these paints can be used.

 [0042] Among these, in the case of fluorine resin, which is easily contaminated by hydrophobic contaminants because the coating film is rich in hydrophobicity, regardless of whether it is curable or non-curable, It is preferable because it can produce the effect of early hydrophilization.

 Next, the hydrophilizing agent (B) having a hydrolyzable group will be described.

 [0044] As the hydrophilizing agent (B) used in the present invention, a conventionally known compound (hydrophilizing agent) that can achieve hydrophilization of the coating film by utilizing hydrolysis can be used.

 [0045] Non-fluorine organosilicates described in, for example, WO94Z06870 pamphlet, JP-A-8-12921, JP-A-2000-160103, JP-A-11-209690, etc. Fluorine-containing organosilicates described in the 96Z26254 pamphlet and the International Publication No. 97/11130 pamphlet are preferably listed.

 As the non-fluorinated organosilicate, for example, the formula (1):

Si (OR ¹ )

 Four

(Wherein, R ¹ is the same or different and is a non-fluorinated hydrocarbon group having 1 to 10 carbon atoms) or a functional silicate represented by the following formula (2):

(R ² ) Si (OR ² )

 n 4-n

(Wherein R ² is the same force or different and is a non-fluorinated hydrocarbon group having 1 to 10 carbon atoms; n is 1 or 2) or a trifunctional silicate or oligomer thereof, and further a tetrafunctional onoreganosilicate And co-condensates (co-oligomers) of 2- to 3-functional organosilicates.

 [0047] These non-fluorinated organosilicates or co-oligomers thereof (hereinafter simply referred to as organosilicates) may be used alone or in combination of two or more. However, since they are excellent in hydrolyzability (surface hydrophilization ability), at least A tetrafunctional organosilicate is preferably used.

[0048] Of R ¹ and R ^{2 represented by} the formulas (1) and (2), a non-fluorinated hydrocarbon group having 1 to L0 carbon atoms (hereinafter simply referred to as “hydrocarbon group”. It also has fluorine. The hydrocarbon group is “fluorinated coal. Examples of the “hydride group”, which is classified, include a C1-CLO alkyl group, a C6-C10 aryl group, and the like. When the number of carbon atoms in R ¹ and R ² exceeds 10, the hydrolysis rate becomes slow and the surface hydrophilicity of the coating film tends to be insufficient in terms of time and degree.

[0049] The alkyl group having 1 to 10 carbon atoms may be linear or branched, for example, methyl, ethinole, n-propinole, iso-propinole, n-butinole, iso-butinole, tert-butinole, n-pentinole And isopentinoles, neopentinoles, n-hexinoles, isohexinoles, n-octyl, and the like. Lower alkyl groups having 1 to 3 carbon atoms are particularly suitable because of their good hydrolyzability. The aryl group having 6 to C carbon atoms may be monocyclic or polycyclic, and examples thereof include substituted or unsubstituted phenyl, tolyl, xylyl, and naphthyl.

 [0050] Preferable examples of non-fluorinated organosilicates include, for example, tetrahydroxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, dimethoxydiethoxysilane, One or more of monomethoxytriethoxysilane, trimethoxymonoethoxysilane and the like; one or more (co) condensates thereof may be mentioned. Of these, different types of hydrolyzable leaving groups, for example, a methoxy group and an alkoxy group having a carbon number of 2 to L0, are exemplified in the molecule as exemplified in JP-A-11 209690. Among them, those having both a methoxy group and an alkoxy group having 2 to 5 carbon atoms are particularly preferred because of their good surface concentrating properties and quick hydrolyzability. The condensation degree of the organosilicate condensate is preferably 2 to L00, particularly 3 to 20. If the degree of condensation is too large, the effect of contamination resistance tends to be reduced.

 [0051] As the fluorine-containing organosilicate, the formula (3):

(Rf'O) Si (OR ³ )

 m 4 ~ m

(In the formula, Rf ¹ is the same force or different and the fluorine-containing hydrocarbon group having 1 to 10 carbon atoms; R ³ is the same or different and the hydrocarbon group having 1 to 10 carbon atoms; m is an integer of 1 to 4) Tetrafunctional fluorine-containing organosilicates or oligomers thereof represented by the formula (4):

(R ⁴ ) Si (ORf ² ) (OR ⁴ )

 (P q 4 ~ »+ q)

(Wherein, Rf ² is the same force or different, a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms; or R ⁴ is the same Or different from 1 to: hydrocarbon group of LO; p is 1 or 2; q is 1 to 3; p + q = 4) 2 to 3 functional fluorine-containing organosilicate or oligomer thereof, Examples thereof include co-condensates (co-oligomers) of tetrafunctional fluorine-containing organosilicates with 2 to 3 functional fluorine-containing organosilicates, and optionally 2 to 4 functional non-fluorinated organosilicates.

As the hydrocarbon groups R ³ and R ⁴ represented by the formulas (3) and (4), the same groups as the R ¹ and R ² described in the formulas (1) and (2) are adopted.

[0053] Rf ¹ and Rf ² may have ^one or all of hydrogen atoms substituted by fluorine atoms or fluorine atoms and chlorine atoms, and may have 1 to L000 carbon atoms, preferably 1 to 20 carbon atoms. This is a monovalent fluorine-containing organic group. This fluorine-containing organic group may contain an oxygen atom, a nitrogen atom, and a Z or silicon atom.

 [0054] Specifically, for example, — (CH 2) described in the pamphlet of WO 97Z11130.

 2 m

H, -CH (CH), -C (= 0) (CH) H, one (CH) (CF) F, — CH (CF), one (C

 3 2 2 m 2 m 2 n 3 2

H) (CF) H, 1 C (= 0) (CH) (CF) F, 1 C (= 0) (CH) (CF) H, 1 N ((

2 m 2 n 2 m 2 n 2 m 2 n

CH) (CF) F), N ((CH (CF))), N ((CH) (CF) H), C (C = 0) CF

2 m 2 n 2 3 2 2 2 m 2 n 2

 (CF) (CF (CF) CF O) 0 (CF) F, 1 N = C ((CH) (CF) F), 1 N = C ((CH

3 3 2 m 2 2 m 2 n 2

(CF)), 1 N = C ((CH) (CF) H), 1 NR ³ C (= 0) (CH) (CF) F, 1 NR ³

3 2 2 2 m 2 n 2 2 m 2 n

C (= 0) (CH) (CF) H, one C (= CH) (CH) (CF) F, one C (= CH) (CH) (

 2 m 2 n 2 2 m 2 n 2 2 m

CF) H, 1 C (= CF) (CH) (CF) F, 1 C (= CF) (CH) (G) 11 (where 111

2 n 2 2 m 2 n 2 2 m 2 n is an integer from 0 to 6, n is an integer from 1 to 10, R ³ represents an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear or branched And)) fluoroalkyl group, fluorocarbonyl group, fluoroether group and the like. Of these, for example, —CH (CF) H, —CH (CF) H, —CH (CF) H,

 2 2 2 2 2 3 2 2 4 1 CHFCF CF H, 1 CH CF, 1 CH CF CF, 1 CH (CF) CF, 1 CH CH (

 2 2 2 3 2 2 3 2 2 2 3 2 2

CF) CF, one CH CH (CF) CF, one C = OCF, one C = OCF CF, one C = 0 (CF

2 3 3 2 2 2 7 3 3 2 3 2

) CF, 1 C = 0 (CF) CF, etc. are particularly preferred.

 6 3 2 7 3

[0055] Preferable specific examples of the fluorinated organosilicate include, for example, one of the above fluorinated organosilicates having a fluorinated organic group described in WO96Z26254 pamphlet and WO97Z11130 pamphlet. 2 or more; these 1 Species or two or more (co) condensates.

 [0056] Examples of the hydrophilizing agent (B) having a hydrolyzable group other than the organosilicate include Ti, B, which are described in, for example, International Publication No. 97Z11130 pamphlet, Japanese Patent Application Laid-Open No. 10-237364, etc. Metals such as Ga, In, Sc, Y, La, Ac, Ge, Sn, Pb, Hf, As, Sb, Bi ゝ V, Nb, Ta, Mo, W, Cr, Mn, Fe, Co, Pd, Pt And other hydrolyzable group-containing metal compounds and oligomers thereof.

 [0057] This hydrophilizing agent (B) has the property of floating on the surface of the coating film when the coating film is formed, and the surface can be hydrophilized even with a relatively small amount.

 [0058] The blending ratio of the hydrophilizing agent (B) is 0.1 parts by mass or more, preferably 1 part by mass or more, particularly 2 parts by mass or more with respect to 100 parts by mass of the resin-forming resin. From the viewpoint of effectively exhibiting low contamination. The upper limit is about 50 parts by weight, preferably 40 parts by weight, particularly preferably 30 parts by weight, with respect to 100 parts by weight of the film forming resin. Care must be taken because coating defects such as deterioration may occur.

 [0059] The organic solvent (C) is capable of dissolving or dispersing the coating-forming resin (A) and the hydrophilizing agent (B).

 [0060] The organic solvent (C) is selected according to the types of the resin-forming resin (A) and the hydrophilizing agent (B). 1S Specifically, hexane, heptane, octane, mineral spirit, coal tar naphtha, Aliphatic hydrocarbon solvents such as Solvesso 100 and Solvesso 200; Aromatic hydrocarbon solvents such as xylene, toluene, benzene, and trimethylbenzene; Alcohol solvents such as propanol, butanol and pentanol Glycol ether solvents such as cetyl solvate, butinorecerosonolev, diethylene glycol monoethyl ether; ketone solvents such as acetonitrile, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone; ethyl acetate, acetic acid Propyl, butyl acetate, cellosolve acetate, isobutyl acetate, diethylene glycol acetate Ether acetate diethylene glycol methyl ether, and ester solvents such as propylene glycol methyl ether acetate can be used.

[0061] The organic solvent (C) is blended so that the solid content concentration is 10 to 95% by weight, preferably 20 to 70% by weight, so that the coating property and the surface concentrating property of the hydrophilizing agent are good. Point power is preferable [0062] The low-fouling coating composition (I) of the present invention is obtained by blending a specific hydrophilization promoting catalyst dispersion (D) with the coating composition (II).

 [0063] In the hydrophilization promoting catalyst dispersion (D), the organic transition metal compound (D-1) having a hydrolysis promoting action of the hydrophilizing agent (B) is dissolved or dissolved in the catalyst blocking solvent (D-2). Dispersed solution or dispersion.

 As the organic transition metal compound (D-1), for example, as described later, zirconium alkoxide titanium alkoxide is known as a curing catalyst (F) for a curing agent (E) for curable resin. However, in the present invention, it promotes the hydrolysis reaction of the hydrophilizing agent (B), which is not used to promote the curing reaction of the curable resin, and its action and effects are different. Of course, it differs also in composition as a composition.

 That is, in the present invention, the organic transition metal compound (D-1) is always blended as a dispersion of the catalyst blocking solvent (D-2), not by itself. This catalytic blocking solvent (D-2) effectively blocks the catalytic activity of the organic transition metal compound (D-1) and is curable in the low-fouling coating composition (I) before the coating is formed. Does not catalyze the curing of the resin-forming resin. Although the catalyst blocking mechanism of the catalyst blocking solvent (D-2) is halfway studied, at least the organoaluminum compound (for example, aluminum chelate), which is currently widely used as a curing catalyst and also used as a hydrophilization promoting catalyst. The blocking effect cannot be obtained for organometallic compounds other than transition metals, such as organic compounds and the like, which are known as curing agents or hydrophilizing agents.

 [0066] The estimated hydrophilization-promoting action in the present invention is described as follows. Catalyst blocking solvent (D

-The organic transition metal compound (D-1) blended as the dispersion (D) of 2) is present in a relatively stable state in the low-fouling paint composition (I) of the present invention, When coating and coating start to form, the catalyst block solvent (D-2) moves to the surface of the coating in a blocked state, and then the catalyst block solvent (D-2) evaporates to form an organic transition metal compound. When the catalytic activity block of (D-1) is released, the hydrolysis reaction of the hydrophilizing agent (B) that also floats on the coating film surface is promoted near the coating film surface, and the coating film surface is quickly It becomes hydrophilic and exhibits an early low contamination effect. [0067] On the other hand, when the organic transition metal compound (D-1) alone is preliminarily blended in the coating composition (Π), the curing reaction of the curable resin can be quickly performed by adding the curing agent (E). When it is severe, adding a curing agent (E) may cause gelling immediately. Further, even if the gelling is not carried out, the hydrolysis of the hydrophilizing agent (B) proceeds in the coating composition, so that the hydrophilization of the surface is inhibited.

 [0068] In addition, the effect of the low-fouling coating composition (I) of the present invention using the hydrophilization promoting catalyst dispersion (D) is that the coating-forming resin (A) is non-curable. It can be demonstrated as if it were curable.

 [0069] Examples of the transition metal of the organic transition metal compound (D-1) used in the present invention include Zr, Sn, Ti, Ni, etc. In particular, Zr, Sn U, who prefers, Sn, Ti. In addition, aluminum (A1), silicon (Si), zinc (Zn), copper (Cu), lead (Pb), and alkali metals and alkaline earth metals do not enter transition metals. These transition metals form organic transition metal compounds in the form of alkoxides, chelating compounds, salts, esters, and the like. As an organic zirconium compound, zirconium alkoxide or zirconium chelates compound is preferred because it is easily available, has good solvent solubility, pot life during coating, and low contamination of the coating film.

[0070] Zirconium alkoxide includes a compound represented by the general formula Zr (OR) (R is a hydrogen atom)

 Four

 A part or all of the children are alkyl groups having 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms which may be substituted with halogen atoms, and these contain sulfur, nitrogen, silicon or oxygen atoms. May be good). Specific examples include, for example, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetrabutoxide, dinolecum-dimethoxymethoxide, dinoleco-um monomethoxytriethoxide, zirconium trimethoxymonoethoxide. It is done. Of these, ease of availability, ease of control of catalyst activity, affinity for the catalyst blocking solvent (D-2) and solubility in the organic solvent (C), and low contamination of the coating film Zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetrabutoxide, etc. are preferred because of their good adhesion.

[0071] Zirconium chelate compounds include compounds represented by the general formula Zr (OR) (X) (

n 4-n n is an integer from 0 to 3, and R is a part of or all of the hydrogen atoms replaced by halogen atoms! May be an alkyl group having 1 to 50 carbon atoms, preferably 1 to L0, which may contain a sulfur atom, a nitrogen atom, a silicon atom or an oxygen atom; and X is a hydrogen atom. And an acyl acetonate group having 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms, which may be partially or fully substituted with a halogen element. Specific examples include, for example, zirconium tetraacetyl acetonate, zirconium trimethoxy acetyl acetonate, zirconium triethoxy cetino lacetonate, dinorecum dimethoxy dicetino lacetonate, zirconium diethoxy diacetate. Cetinoreacetonate, dinoleconium dipropoxydiacetylenoacetonate, dinoreconium dibutoxydiacetylenoacetonate, dinoreconium methoxytriacetylacetonate, zirconium ethoxytriacetylacetonate, zirconium butoxy Triacetinoreacetonate, Dinoreconium tribubutoxyacetinoreacetonate, Dinoreconium propoxytriacetinoreacetonate, Dinoreconium tripropoxyacetinoreacetonate, etc. It is. Among these, the availability, the controllability of the catalyst activity, the affinity for the catalyst blocking solvent (D 2) and the dispersibility in the organic solvent (C), and the low contamination adhesion of the coating film are particularly high. Zirconium trimethoxyacetylacetonate, dinoleco-trimethylacetinoreacetonate, dinoleco-dimethoxydiacetylenoacetonate, zirconium jetoxydiacetylacetonate, etc. are preferred because of their good points. ! /.

In addition, as an ester compound of zirconium, for example, a compound represented by the general formula Z OR ¹ ) (OCOR ² ) (R ¹ is a halogen atom, a sulfur atom, a nitrogen atom,

4-n

1 to 50 carbon atoms which may contain a silicon atom or an oxygen atom, preferably 1 to: an alkyl group of L0; n is an integer of 1 to 3, R ² is 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms And a saturated or unsaturated hydrocarbon group which may contain a halogen atom, sulfur atom, nitrogen atom, silicon atom or oxygen atom in addition to a hydrogen atom. Specific examples thereof include, for example, zirconium acylates, and examples thereof include zirconium trimethoxy stearate, zirconium tritoxate, zirconium tripropoxy systemate, zirconium tributoxy systemate, zirconium trimethoxy laurate, Zirco-mutriethoxy laurate, Zirconium tripropoxy laurate, Zirconium tributoxy laurate, Zirconium trimethoxy acetate, Dinoleco-mutriethoxyacetate And zirconium tripropoxyacetate and zirconium tributoxyacetate. Among these, particularly easy availability, easy control of catalyst activity, affinity for the catalyst blocking solvent (D2) and dissolution and dispersion in the organic solvent (C), and low contamination adhesion of the coating film are good. From the viewpoint, zirconium trimethoxy stearate, zirconium triethoxy stearate, zirconium tripropoxy stearate, and zirconium tributoxy stearate are preferable.

 [0073] Organic tin compounds include alkyltin esters such as dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin maleate, dibutyltin maleate, dibutinoles diacetate, trityltin monostearate, etc. Alkyl tin halides such as dioctyl dibutyl sulphate are readily available, and the point power of solvent solubility and low contamination of the coating film is also preferred.

 [0074] Examples of the organic titanium compound include alkoxytitanium compounds such as tetraisopropoxy titanium, tetrabutoxy titanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxy titanium; diisopropoxy bis (ethyl). Titanium chelate compounds such as cetatoacetate) titanium and diisopropoxy'bis (acetinoreacetonate) titanium; titanium ester compounds such as titanium stearate, tri-n-butoxytitanium monostearate, diisopropoxytitanium distearate Examples include compound. In particular, titanium chelate compounds such as diisopropoxy bis (ethinoreacetoacetate) titanium and diisopropoxy bis (acetylacetonate) titanium; titanium ester compounds such as titanium stearate are readily available, and solvents Preference is also given to good affinity, ease of control of catalytic activity, and low contamination of the coating film.

 [0075] The solvent (D-2), which is a dispersion medium for the organic transition metal compound (D-1), blocks the catalytic activity of the organic transition metal compound (D-1) and migrates to the surface. After that, those that can evaporate quickly are preferred. As such a catalyst blocking solvent (D-2), at least one kind selected from a group strength consisting of a diketone solvent, a ketoester solvent, a hydroxyl group-containing carboxylic acid ester solvent and a keto alcohol solvent is preferable.

 Of these, examples of the diketone solvent (D-2) include those represented by the formula:

χ'ο (= ο) -Y ¹ -C (= O) Z ¹ (Wherein X ¹ and z ¹ are the same force or different, and a carbon atom which may contain an oxygen atom, a sulfur atom, a nitrogen atom, or the like in which some or all of the hydrogen atoms may be substituted with a halogen atom is 1 to 10, preferably 1 to 6 organic groups; Y ¹ is an alkylene group represented by —C (A) —

 2

 A force in which both A are hydrogen atoms, one or all of which may be substituted with a halogen atom, and may contain an oxygen atom, sulfur atom, nitrogen atom, etc. 6-diketone solvent, which may be substituted with 6 organic groups, or

 Formula:

X ² C (= O) C (= O) Y ²

(Wherein χ ² and Y ² are the same force or different, and an organic group which may contain an oxygen atom, a sulfur atom, a nitrogen atom, etc., in which some or all of the hydrogen atoms may be substituted with halogen atoms) A-diketone solvent indicated

 1 type or 2 types or more.

 [0077] Specific examples of β-diketone solvents include, for example, 2,4 pentanedione; 3 substituted 1,2,4 pentanediones (eg, 3-methyl 2,4 pentanedione, 3 ethyl 2,4 pentanedione, 3 phenol). -1, 2, 4 pentanedione, etc.); 5 alkyl-substituted 1, 2, 4 pentanedione, etc.

 [0078] Specific examples of a-diketone solvents include 2,3 butanedione, 2,3 pentanedione, 2,3 hexanedione, 3,4 hexanedione, 2,3 heptanedione, 4-methyl-2,3 pentanedione. Examples thereof include one or more of 4-methyl-2,3 hexanedione, 5-methyl-2,3 hexanedione, 2-methyl-2,3 hexanedione, and the like.

 [0079] Of these, β-diketone solvents are preferred from the viewpoint of good catalytic activity blocking action, and boiling points suitable for rapid and forceful evaporation or forced drying after transfer to the surface (usually about 80 to Because it has a range of 280 ° C, 2,4-pentanedione and 3-methyl-2,4-pentanedione are preferred!

 [0080] Examples of keto ester solvents include those represented by the formula:

Y ³ — CO— (X ³ ) — COO— Z ³ (Wherein x ³ is an alkylene group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms which may have a functional group or a halogen element; Y ³ and Z ³ may be the same or different, and both are carbon atoms. And an organic group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

[0081] Preferably, specific examples include acetoacetate esters such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, isopropyl acetoacetate, butyl acetoacetate, isobutyl acetoacetate and pentyl acetate; acetopropionic acid Examples include acetocarboxylic acid esters such as methyl and acetopropionate; and other acyl carboxylic acid esters in which Y ³ is an organic group having 2 to 10 carbon atoms. Of these, acetoacetic acid is particularly preferred because of its moderate transpiration after coating and boiling point suitable for forced drying, good miscibility in the composition, easy availability, and relatively low material costs. Methyl, propyl acetoacetate and isopropyl acetoacetate are preferred.

 [0082] Examples of the hydroxyl group-containing carboxylic acid ester solvent include those represented by the formula:

Y ⁴ CX ⁴ (OH) COO Z ⁴

(Wherein X ⁴ is a hydrogen atom, a hydroxyl group or an optionally substituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms; Y ⁴ and Z ⁴ are the same or different, Any of these include compounds represented by an organic group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

 [0083] Preferable examples include, for example, lactate esters such as methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, and pentyl lactate; Malates such as dimethyl malate and decyl malate; citrate esters such as trimethyl taenoate and triethyl citrate; salicylic acid esters such as methyl salicylate and ethyl salicylate. Of these, lactic acid is particularly suitable because it has a suitable transpiration after coating and a boiling point suitable for forced drying, good miscibility with the composition, availability, and relatively low material costs. Lactic acid esters such as methyl and lactic acid ethyl are preferred.

 [0084] Examples of keto alcohol solvents include those represented by the formula:

Y ⁵ -CY ⁶ (OH)-X ⁵ -CO-Z ⁵

(Wherein X ⁵ is an optionally substituted alkylene group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms; Y ⁵ Y ⁶ and Z ⁵ are the same or different and both are carbon atoms. Number 1 to 10, preferably And an organic group having 1 to 6 carbon atoms).

[0085] Preferable specific examples include alkylhydroxy such as 4-hydroxy-4-methyl-2 pentanone (generic name: diacetone alcohol), 4 hydroxy1-2 pentanone, 4 hydroxy1-2 heptanone, 4-hydroxy-4-methyl-2-heptanone, etc. Examples include pentanones and alkylhydroxyheptanones. Among these, the transpiration after coating, the boiling point suitable for forced drying, good miscibility with the composition, easy availability, and relatively low material costs are particularly important. Acetone alcohol, 4-hydroxy 2-heptanone, etc. are preferred!

[0086] These may be used alone or in combination of two or more.

 [0087] In order to facilitate transpiration or to adjust the concentration, other solvents may be used in combination. Other solvents include organic solvents (C) used in coating compositions (組成).

 [0088] The blending ratio of the organic transition metal compound (D-1) to the catalyst blocking solvent (D-2) is as follows: per mole of the organic transition metal compound (D-1), the catalyst blocking solvent (D-2) Is at least 1.5 mol or more, preferably 2.0 mol or more, and more preferably 10 mol or more. Point power to improve the blocking effect of the catalytic activity is preferable. If the amount of the catalyst blocking solvent (D 2) relative to the organic transition metal compound (D-1) is small, and depending on the type of the organic transition metal compound, the storage stability may be reduced and the effect may be lost. The upper limit of the catalyst block solvent (D-2) in the dispersion (D) is not particularly limited. Further, from the viewpoint of the solid content concentration of the dispersion (D), it is 0.1% by mass or more, more preferably 0.5% by mass or more and 80% by mass or less, and further 50% by mass or less. The point power at which the dispersion or dissolution stability and storage stability of (D) are good is also preferred.

 [0089] The low-contamination paint composition (I) may be prepared by mixing the components (A), (B), (C) and (D) all together or sequentially or in any order. Alternatively, the component (D) may be added after preparing the coating composition (Π) comprising the components (A), (B) and (C).

[0090] The catalyst blocking solvent (D-2) described in the present invention is added to the coating composition (I) together with the organic transition metal compound as the organic transition metal compound dispersion (D). However, if there is concern over the inhibition of the catalytic activity blocking effect due to the effects of various paint additives and coating conditions described below, one or more of the catalyst blocking solvents (D-2) are used. The organic Aside from the transition metal compound dispersion (D), it may be added to the coating composition (I)! / ヽ.

[0091] In the hydrophilization promoting catalyst dispersion (D), the organic transition metal compound (D-1) contained is 0.001 part by mass or more, preferably 0.02 with respect to 100 parts by mass of the hydrophilizing agent (B). It is also preferable to add such an amount that it is not less than part by mass, and more preferably not less than 0.03 part by mass, because it has a good effect of promoting hydrophilization (hydrolysis). The amount of the organic transition metal compound (D-1) is 20 parts by mass or less, preferably 10 parts by mass or less, and further 2 parts by mass or less with respect to 100 parts by mass of the hydrophilizing agent (B). This is preferable because it is easy to adjust the pot life during coating and the material cost is advantageous.

[0092] If the amount of the hydrophilization promoting catalyst dispersion (D) added is too large, it will be difficult to adjust the solid content concentration of the low-fouling coating composition (I), Since precipitation may occur and the pot life during coating may be shortened, the amount of the hydrophilization promoting catalyst dispersion (D) added is about 0.1 to 100 parts by weight of the hydrophilizing agent (B). Not less than 0.2 parts by mass, preferably not less than 0.2 parts by mass, more preferably not less than 1 part by mass, and the upper limit is 80 parts by mass, preferably 40 parts by mass, more preferably 30 parts by mass. Is preferably added.

[0093] The low-fouling coating composition (I) of the present invention may be blended with various additives usually used in coating compositions in a range of amounts that do not impair the effects of the present invention. Yo ... Examples of additives include curing agents, curing catalysts, ultraviolet absorbers, leveling agents, pigments, dyes, fillers, light stabilizers, sagging inhibitors, antifoaming agents, antioxidants, pigment wetting and dispersing agents, and lubricants. Agents and coupling agents.

 [0094] In particular, as described above, when the coating-forming resin (A) is a curable resin, it may be cured by an active energy ray such as ultraviolet rays, but the curing agent (E) and, if necessary, Accordingly, in order to catalyze the curing reaction of the curable resin, it is desirable to add a known curing catalyst (F) to the low-fouling coating composition (I). The blending time is preferably just before the start of coating since the curing reaction starts to progress when these are blended. However, the curing catalyst (F) that does not promote hydrolysis of the hydrophilizing agent (B) may be blended in advance with the low-fouling paint composition (I).

[0095] The curing agent (E) may be appropriately selected from known curing agents according to the type and curing system of the curable coating-forming resin. [0096] As specific examples, for example, when the curable resin for forming a coating film has a hydroxyl group, an aminoblast curing agent, an isocyanate curing agent, a polybasic acid curing agent, a polyvalent amine curing agent, or the like is used. Is done.

 [0097] As the aminoplast type curing agent, methylol melamines, methylol guanamines, methylol ureas and the like can be used. Examples of methylol melamines include methylol melamine etherified with a lower alcohol such as butylated methylol melamine and methylated methylol melamine, and epoxy-modified methylol melamine. As methylol ureas, alkylated methylol ureas such as methylated methylol urea and ethylated methylol urea can also be used. In the case of using an aminoblast type curing agent, an acid catalyst described later is usually used to accelerate the curing reaction.

 [0098] Examples of isocyanate curing agents include polyvalent isocyanate compounds and blocked products thereof. The polyvalent isocyanate compound is a compound having two or more isocyanate groups, and may be a modified product thereof or a compound having two or more isocyanate groups that are multi-functional.

 [0099] The polyvalent isocyanate compounds include aliphatic polyvalent isocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, hexamethylene triisocyanate, and lysine diisocyanate; Alicyclic polyvalent isocyanate compounds such as isocyanate, dicyclohexylmethane diisocyanate, and diisocyanate methylcyclohexane; non-yellowing aromatic polyvalent isocyanate compounds such as xylylene diisocyanate .

 [0100] Examples of modified and multimeric polyvalent isocyanate compounds include urethane modified products, urea modified products, isocyanurate modified products, burette modified products, allophanate modified products, force rubodiimide modified products, and the like. In particular, isocyanurate-modified products that are trimers are preferably urethane-modified products that are reaction products with polyhydric alcohols such as trimethylolpropane.

[0101] When an isocyanate curing agent having a free isocyanate group is used, the resulting low-fouling coating composition can be cured at room temperature, and is particularly advantageous for painting in the field. Isocyanate-based curing agents with blocked isocyanate groups are other As in the case of the curing agent, a heat curable coating composition is usually obtained. When using an isocyanate curing agent, an organometallic curing catalyst described later is usually used.

 [0102] The compounding amount of the curing agent (E) is 0.1 to 1 with respect to 100 parts by mass of the curable resin-forming resin (A).

00 parts by mass, particularly 1 to 50 parts by mass is preferred.

[0103] The curing catalyst (F) may be an appropriate one selected from known organometallic curing catalysts and inorganic curing catalysts depending on the curing system.

[0104] Examples of such an organometallic curing catalyst include metal alkoxides such as aluminum, zirconium, titanium, tin, calcium, and sodium: a keto'enol tautomer can be formed on the metal alkoxides. Chelate compounds and the like can be preferably used. Among these, metal chelate compounds are preferred, and diisopropoxy cetyl acetate aluminum, tris (ethyl acetate acetate) aluminum, isopropoxy bis (ethyl acetate acetate) aluminum, mono Acetylacetonate 'bis (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (n-butynoacetoacetate) anoleum, monoethinoreacetoacetate'bis (acetylacetate) Aluminum chelate compounds such as aluminum, tris (acetylacetate) aluminum, tris (propiolacetonate) aluminum, acetylethylacetate 'bis (propio-lucacetonate) aluminum; diisopropoxy' Bi (Ethyleneacetate acetate) Titanium, diisopropoxy'bis (acetinoreacetonato) titanium and other titanium chelate compounds, titanium ester compounds such as titanium stearate; zirconium tetraacetylacetonate, Zirconium trimethoxyacetyl acetonate, Zirconium triethoxy acetyl acetonate, Zirconium dimethoxy dicetino acetonate, Dino REC Mudibutoxy diacetylenoacetonate, zirconium methoxytriacetylacetonate, zirconium ethoxytriacetylacetonate, zirconium butoxytriacetylacetonate, zirconium Zirconium chelating compounds such as mutributoxy acetylacetonate, zirconium propoxytriacetylacetonate, zirconium tripropoxyacetylylacetonate; dibutyls zujilaurate, dioctinoles dilaurate, dioctinoles Maleate, Djibutinoles Organic tin compounds such as alkyltin ester compounds such as alkyltin ester compounds such as dizulaleate, dibutyltin diacetate and triethyltin monostearate are also preferred.

 [0105] Examples of inorganic curing catalysts include: A1C1, A1 (C H) Cl, TiCl, ZrCl, SnCl,

 3 2 5 2 4 4 4

Lewis acids such as FeCl, BF, BF: (OC H); metasulfonic acid, benzenesulfonic acid

4 3 3 2 5 2

 P-Toluenesulfonic acid and other organic proton acids; phosphoric acid, phosphorous acid, phosphinic acid, sulfuric acid and other inorganic proton acids or esters thereof; compounds having a Si—O—A1 bond such as aluminum silicate Can be given.

 [0106] The mixing ratio of the curing catalyst (F) is 0.01 to 30 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the curable resin-forming resin (A). .

 [0107] When an isocyanate curing agent is used, it is particularly preferable that the curing catalyst (F) is easy to obtain, is solvent-soluble but can be easily mixed into a coating composition, In view of good curing acceleration between A) and the curing agent, the above examples include aluminum chelate compounds (for example, diisopropoxy cetylacetoacetate aluminum, tris (ethinoreacetoacetate) anoleminium. Isopropoxy bis (ethinoreacetoacetate) aluminum, monoacetyl cetateate bis (ethylacetoacetate aluminum), etc .; titanium chelate compounds (eg diisopropoxy bis (ethyl) Acetoacetate) titanium, diisopropoxy 'bis (acetyl cetate) titanium, etc.); Compound (for example, zirconium tetraacetylacetonate, zirconium trimethoxy caseino acetonate, dinolecum triethoxy caseino acetonate, dinolecum dimethoxy dicetino acetonate, dinoleconone Organic tin compounds (eg dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin maleate, dibutyltin maleate); organic protonic acids (eg p-toluenesulfonic acid, benzene) Examples thereof include sulfonic acid.

[0108] It should be noted that these curing catalysts (F) have a catalytic activity blocked with a catalyst blocking solvent, so that they do not float on the coating surface when the curing agent (E) is added and mixed. The resin for forming a coating film is quickly cured at the time of coating film formation, and as a result, it is present almost uniformly in the coating film even after curing. [0109] The coating film can be formed by a conventionally known method! For example, apply to the substrate by roller coating method, brush coating method, dip coating method, spray coating method, gravure coating method, coil coating method, curtain flow coating method, etc. To form a coating film. When the coating film forming resin is a curable resin, depending on the type of curing system, curing agent, coating amount, solvent type used, etc. In the case of a heat-curable coating that can be left for about 10 days, it is usually desirable to heat and cure at about 50 to 200 ° C for about 1 to 180 minutes. In addition, even when the coating film forming resin is a thermoplastic resin having a cured part, the room temperature drying type paint should be left at ambient temperature for about 1 hour to 10 days like the above room temperature curing type paint. It is also desirable to heat dry the paint at about 50 to 250 ° C for about 1 to 180 minutes. It should be noted that, regardless of whether the coating film forming resin is curable or thermoplastic, the drying or heating time of the coating film may be appropriately selected according to the purpose, coating conditions, etc., and is not limited to the above examples only. .

 [0110] As the base material, inorganic base materials such as glass, slate, concrete, etc .; metals such as aluminum, steel, zinc, tin, copper, stainless steel, etc., metal, steel with zinc, tin, chromium, etc. plated on the steel surface Metal base materials such as metals whose surfaces have been treated with chromic acid, phosphoric acid, etc .; plastic base materials such as polyethylene, polychlorinated butyl, polypropylene, ABS resin; poly salt butyl, polyethylene terephthalate, aluminum, etc. Examples of the tape include a base film provided with an adhesive layer and a pressure-sensitive adhesive layer, and a base material obtained by applying a known primer intermediate coating or top coating to these base materials.

 [0111] The organic transition metal compound (D-1) blocked with the catalyst blocking solvent (D-2) and the hydrophilizing agent (B) do not react while the coating film is formed! Because the film floats in the direction of the free surface of the coating on the opposite side of the substrate, the resulting coating has a transition metal atom content higher at the free surface than at the center of the coating! And On the other hand, when the organic transition metal compound (D-1) is not blended in the form of the dispersion (D), the organic transition metal compound (D-1) is hydrophilic in the coating composition and further during film formation. The hydrolysis of the agent (B) is promoted, and the agent is almost uniformly dispersed in the coating film.

[0112] It should be noted that the concept of the “free surface part” of the coating film is not numerically expressed in terms of thickness (depth). At least, the distribution of transition metal atoms from the center of the coating film toward the free surface opposite to the substrate side increases, so it can be identified by the portion closer to the free surface than the center.

 [0113] The content of the transition metal refers to the organic transition metal compound (D

 Not only the transition metal of 1) but the total content of the same or different transition metals contained in the curing catalyst (F) and other additives. For example, even if an organic zirconium compound is used as the curing catalyst (F) and an organic zirconium compound is used as the organic transition metal compound (D-1), the coating is performed depending on the characteristics of the organic transition metal compound (D-1). Since the distribution of transition metal atoms increases from the center of the film toward the free surface opposite to the substrate side, the coating film of the present invention can be easily identified.

 [0114] The film thickness of the coating film may be appropriately determined depending on the purpose of use and purpose of use, but it is usually 1 to 500 μm, preferably 10 to about LOO μm.

 Example

 [0115] Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

 [0116] Synthesis Example 1 (Synthesis of non-fluorinated organosilicate as hydrophilizing agent (B))

Two-liter four-necked eggplant-shaped flask with 500 g of ethyl silicate 40 (an oligomer of tetraethoxysilane manufactured by Colcoat Co.), aluminum chelate D (aluminum monoacetyl cetate bis manufactured by Kawaken Fine Chemical Co., Ltd. chill § 76 mass _^0/0 isopropanol solution Seth acetate)) 3. a mixture of 66g and water 14. 5 g of methanol 500g in example mosquitoes卩stirring to distill off volatile components by heating under reflux for 3 hours, non-fluorinated 374 g of organosilicate HB1) was obtained. This was analyzed by 1H-NMR. As a result, methyl group Z (methyl group + ethyl group) (number ratio) was 0.45. The number average molecular weight by GPC was 4800.

 [0117] Preparation Example 1 (Preparation of hydrophilization promoting catalyst dispersion (D))

 A hydrophilization promoting catalyst dispersion (D1 to D5) having a concentration of 1% by mass was prepared by combining the organic transition metal (D-1) shown in Table 1 and the dispersion solvent (D-2).

 [0118] Example 1

Hydroxyl group-containing tetrafluoroethylene copolymer (Zeffle GK-570 white paint, manufactured by Daikin Industries, Ltd., hydroxyl group-containing tetrafluoroethylene copolymer) White paint obtained by dispersing titanium oxide in butyl acetate solution. 25 parts of butyl acetate was added to 100 parts (parts by mass, the same applies hereinafter) of 100% by weight of the solids of resin and 32% by mass of the pigments. The hydrophilizing agent synthesized in Synthesis Example 1 was added to the hydrophilization promoting catalyst dispersion (D) in V ヽ in an amount of 20% by mass with respect to the hydrophilizing agent B1. 5.9 g of (B1) and 8.4 g of curing agent (E1) (Desmodur N3300. Hexamethylene diisocyanate curing agent manufactured by Bayer) (NCOZ resin OH ratio: 1.0) The paint composition was obtained by stirring well. This was applied to an AM-713 chemical conversion treated aluminum plate and then dried at room temperature for 3 days to prepare a coated plate having a thickness of about 30 m, and the following tests were conducted. The results are listed in Table 2.

 [0119] Contact angle to water (initial and aging hydrophilicity):

 After measuring the water contact angle immediately after coating with a contact angle meter (CA-DT'A type, manufactured by Kyowa Interface Science Co., Ltd.) The water contact angle is measured in the same way after 12 days and after 20 days.

 [0120] Antifouling adhesion:

 Continue to expose the same coated plate as above and evaluate the antifouling property after 3 months. In other words, the difference between the initial lightness of the coated plate and the lightness after exposure (lightness difference Δ L *) is measured with a color difference meter, and when AL * is 0 or more and less than 2, A is when it is 2 or more and less than 4. B, C is greater than 4 and less than 8, and D is greater than 8.

 [0121] Example 2

 A coating composition was prepared in the same manner as in Example 1 except that the hydrophilization promoting catalyst dispersion (D2) shown in Table 1 was used, and the coating plate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0122] Example 3

 A coating composition was prepared in the same manner as in Example 1 except that the hydrophilization promoting catalyst dispersion (D3) shown in Table 1 was used, and the coating plate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0123] Example 4

 A coating composition was prepared in the same manner as in Example 1 except that the hydrophilization promoting catalyst dispersion (D4) shown in Table 1 was used, and the coated plate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0124] Example 5

Hydroxyl group-containing chloroethylene copolymer (Lumi) as a resin-forming resin (A2) Freon LF—200. Asahi Glass Co., Ltd. In the same manner as in Example 1, except that the white paint was prepared in the same manner using a xylene solution and the hydrophilization promoting catalyst dispersion (D2) was added in an amount of 20% by mass relative to the hydrophilizing agent B1. A composition was prepared, and the coated plate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0125] Example 6

 A coating composition was prepared in the same manner as in Example 5 except that the hydrophilization promoting catalyst dispersion (D3) shown in Table 1 was used, and the coated plate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0126] Example 7

 A white paint was prepared in the same manner using a hydroxyl group-containing acrylic resin (Atalidic A-801. Manufactured by Dainippon Ink & Chemicals, Inc.) as the coating film forming resin (A3). A coating composition was prepared in the same manner as in Example 1 except that (D2) was added in an amount of 20% by mass relative to the hydrophilizing agent B1, and the coated plate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0127] Example 8

 A coating composition was prepared in the same manner as in Example 7 except that the hydrophilization promoting catalyst dispersion (D5) shown in Table 1 was used, and the coating plate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0128] Example 9

 Non-crosslinkable fluorinated resin solution consisting of vinylidene fluoride copolymer and acrylic resin as coating film forming resin (A4) (Zeffle LC-974, manufactured by Daikin Industries, Ltd .: Solid resin 38 parts by mass) Into 100 parts, 150 parts of a mixed solvent having a mass ratio of 1 Z1 of butyl acetate Ztoluene was added. Thus, the hydrophilization promoting catalyst dispersion (D2) was added in an amount of 20% by mass with respect to the hydrophilizing agent B1, and 5.7 g of the hydrophilizing agent (non-fluorinated organosilicate) was added thereto and stirred well. Thus, a coating composition was obtained. This coating composition was applied to an AM-713 chemical conversion treated aluminum plate previously coated with a white fluorine paint by spray coating, and then dried at 80 for 1 hour to prepare a coating plate having a thickness of about 30 m. The coated plate was evaluated in the same manner as in Example 1 using this coated plate. The results are listed in Table 2.

[0129] Example 10

A coating composition was prepared in the same manner as in Example 9 except that the hydrophilization promoting catalyst dispersion (D5) shown in Table 1 was used, and the coated plate was evaluated in the same manner as in Example 1. The results are shown in Table 2. [0130] Example 11

 Thermoplastic acrylic resin for coatings (Paraloid B-44 white coating. Made by Rohm & Haas Co., Ltd .: Methylmetatalylate Z ethyl acrylate copolymer is dissolved in xylene. In addition, 100 parts of butyl acetate was added to 100 parts of a solid dispersion of acid titanium. Next, the hydrophilization promoting catalyst dispersion (D2) is added in an amount of 20% by mass with respect to the hydrophilizing agent B1, and 2 g of the hydrophilizing agent (non-fluoroorganosilicate) is added thereto and stirred well to form a coating composition. Got. This coating composition was brushed on an AM-713 conversion treated aluminum plate and then dried at room temperature for 3 days to prepare a coated plate having a thickness of about 30 m. The coated plate was evaluated in the same manner as in Example 1 using this coated plate. The results are shown in Table 2.

[0131] Example 12

 A coating composition was prepared in the same manner as in Example 11 except that the hydrophilization promoting catalyst dispersion (D5) shown in Table 1 was used, and the coated plate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0132] Comparative Examples 1 to 3

 In each of Examples 1 to 3, each of the examples except that the dispersion solvent (D2) used for the hydrophilization promoting catalyst dispersion (D1 to D3) was replaced with the diketone solvent described above and the deviation was changed to butyl acetate. A coating composition for comparison was prepared in the same manner as described above, and the coated plate was evaluated in the same manner as in Example 1. The results are shown in Table 2. Comparative Example 1 corresponds to Example 1, Comparative Example 2 corresponds to Example 2, and Comparative Example 3 corresponds to Example 3.

[0133] [Table 1]

table 1

[] ^

Table 2

 [0135] As shown in Table 2, in the coating compositions of Examples 1 to 12 in which the hydrophilization-promoting catalyst dispersion (D) using a diketone solvent was blended, the coating film was clearly more than Comparative Examples 1 to 3. Good hydrophilicity in a short period of time and excellent antifouling properties.

 [0136] Experimental Examples 1-3 and Comparative Experimental Examples 1-3

The diketone solvent, which is the dispersion solvent (D-2) used in the hydrophilization promoting catalyst dispersion (D) according to the present invention, has a catalytic activity of the organic transition metal compound (D-1) that is a hydrophilization promoting catalyst. The fact that it contributes to the block was verified by thickening during coating of the coating composition. That is, the viscosities of the coating compositions used in Examples 1 to 3 and Comparative Examples 1 to 3 in which all the constituent materials were completely prepared were measured using a B-type rotational viscometer immediately after preparation, after 4 hours and after 8 hours. (Room temperature), the specific force increase viscosity of the viscosity after aging with respect to the initial viscosity was determined. The gel gel of the paint was visually observed. The results are shown in Table 3 as Experimental Examples 1 to 3 and Comparative Experimental Examples 1 to 3. [0137] [Table 3] Table 3

 [0138] As shown in Table 3, when the hydrophilization promoting catalyst dispersion (D) using a diketone solvent was blended, the viscosity increase with time of the coating composition was suppressed compared to the comparative experimental example, and the hydrophilization was promoted. It is presumed that the diketone solvent described in the present invention contributes to the catalytic activity block of the catalyst (D-1).

 [0139] Experimental Examples 4-6

 In the coating composition of Example 3, instead of 3-methyl-2,4-pentanedione, methyl acetoacetate (Example 13 = Experimental Example 4), which is a ketoester solvent, carboxylic group-containing carboxylic acid ester solvent Except for using methyl lactate (Example 14 = Experimental Example 5) and diacetone alcohol (Example 15 = Experimental Example 6), which is a keto alcohol solvent, respectively, immediately after the preparation, 4 hours. The viscosity was measured after and after 8 hours (room temperature), and the increase in viscosity was determined from the ratio of the viscosity after aging to the initial viscosity. In addition, the gel time of the paint was visually observed. The results are shown in Table 4.

[0140] [Table 4] Table 4

[0141] As shown in Table 4, in any hydrophilization promoting catalyst dispersion, thickening was suppressed and gel time could be extended.

 Industrial applicability

[0142] According to the low-fouling paint composition of the present invention, the hydrophilicity of the coating film hydrophilizing agent can be efficiently and effectively performed. Can be formed.

Claims

The scope of the claims

 [1] (A) a resin-forming resin, (B) a hydrophilizing agent having a hydrolyzable group, and (C) the resin (A) and the hydrophilizing agent (B) can be dissolved or dispersed. A coating composition containing an organic solvent has (D) an organic transition metal compound (D-1) having a hydrolysis promoting action of the hydrophilizing agent (B), a carbonyl group and a carbonyl group and z or a hydroxyl group in addition to the carbonyl group. A low-fouling paint composition comprising an organic solvent and a hydrophilization promoting catalyst dispersion containing a solvent (D-2) having a catalyst blocking property with respect to the organic transition metal compound (D-1) .

[2] The solvent composition (D-2) having a catalyst blocking property is also contained in a coating composition containing a resin (A), a hydrophilizing agent (B), and an organic solvent (C). The coating composition according to item 1.

[3] The catalyst-blocking solvent (D-2) is a diketone solvent or a ketoester solvent.

The coating composition according to claim 1 or 2, which is at least one selected from the group consisting of a hydroxyl group-containing carboxylic acid ester solvent and a keto alcohol solvent.

[4] The film forming resin (A) is a curable resin or a thermoplastic resin.

The coating composition according to any one of Items 1 to 3.

[5] Fluorine resin, talyl resin, urethane resin S, polyester resin, alkyd resin, epoxy resin S or the like, wherein the coating film-forming resin (A) is soluble or dispersible in an organic solvent. 5. The coating composition according to any one of claims 1 to 4, which is a silicone rosin.

[6] The coating composition according to any one of claims 1 to 4, wherein the coating film-forming resin (A) is a fluorine resin that is soluble or dispersible in an organic solvent.

[7] The paint according to any one of claims 1 to 6, wherein the hydrophilizing agent (B) is a non-fluorine-based organosilicate whose hydrolyzable group is a non-fluorine-based organic group. Composition.

[8] The organic transition metal compound (D-1) is an organic zirconium compound or an organic tin compound.

The coating composition according to any one of claims 1 to 7, which is an organic titanium compound.

 9. The coating composition according to claim 8, wherein the organic zirconium compound is a zirconium alkoxide, a chelate compound, or an ester compound.

[10] The coating composition according to claim 8, which is an organic tin compound compound or an alkyl tin ester compound or an alkyl tin cyanogen compound.

[11] The coating composition according to any one of claims 3 to 10, wherein the diketone solvent is a didiketone compound.

[12] A coating film formed by applying the coating composition according to any one of claims 1 to 11 to a substrate, wherein the transition metal atom content of the coating film is A low-pollution coating with a higher free surface area than the center.