JP2000198963A - Coating for precoated metal plate having low toxicity and high corrosion resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating for precoating having a low toxicity and a corrosion resistance comparable to that obtained using a chromium anticorrosive pigment, without using a chromium anticorrosive pigment. SOLUTION: A coating contains, as film-forming resin materials, (1) a polyester polyol having at least three functional groups, (2) a compound prepared by adding a lactone compound or alkylene oxide to an epoxy resin having at least one secondary hydroxyl group and (3) a blocked product of an organic polyisocyanate or a blocked product of a prepolymer having NCO groups at the terminus which is obtained by allowing an organic polyisocyanate to react with an active hydrogen compound, and, as non-chromium anticorrosive agents, a phosphate ion source which releases phosphate ions in the presence of water and oxygen and a vanadate ion source which releases vanadate ions in the presence of water and oxygen. The phosphate ion source and the vanadate ion source may be anticorrosive pigments.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint for a pre-coated metal sheet having low toxicity and high corrosion resistance, which is used for home electric appliances and building materials.

[0002]

2. Description of the Related Art In the fields of building materials, home appliances, sundries, automobiles, etc., a pre-painted metal plate (pre-coated metal plate: PCM) is used instead of the conventional post-coating method of forming and assembling and painting a metal plate. ) Is preformed and formed into a product by joining.

[0003] Furthermore, since PCM is required to have corrosion resistance, at present, rust-preventing power is increased mainly by including a chromium-based rust-preventive pigment in a primer (undercoat).
However, pollution due to elution of highly toxic chromium has become a concern.

On the other hand, conventionally, Japanese Patent Application Laid-Open No. 52-438
No. 30, JP-A-52-128979, JP-A-56-80454, JP-A-56-113383, etc., as a pollution-free paint, molybdate, phosphoric acid Salts, barium metaborate and the like have been reported. Further, as disclosed in Japanese Patent Application Laid-Open No. Hei 5-84466, an original plate is plated with iron,
There is also a method of applying a primer containing a phosphate-based rust preventive pigment and silica.

[0005]

However, even if the above-mentioned molybdate, phosphate, barium metaborate and the like are contained in the primer layer, the corrosion resistance is not comparable to that of the chromium pigment. Further, the method of applying an iron-based plating to a base plate and then applying a primer containing a phosphate-based rust preventive pigment and silica involves the complexity of applying an iron-based plating.

An object of the present invention is to solve the above-mentioned problems and to provide a low-toxic precoat paint having corrosion resistance comparable to that obtained by using a chromium pigment without using an iron-plated original plate. Aim.

[0007]

Means for Solving the Problems In order to achieve the above-mentioned object, the present inventors have prepared paints in which various resin raw materials and a non-chromium-based rust inhibitor are combined, and precoated steel sheets coated with the paints. By examining the corrosion resistance of
The present inventors have found a combination of a resin and a rust inhibitor capable of ensuring both corrosion resistance and completed the present invention.

[0008] The present invention provides a method for forming a film-forming resin material, comprising:
A polyester polyol having at least 3 functional groups,
(2) a product obtained by adding a lactone compound or an alkylene oxide to an epoxy resin having at least one secondary hydroxyl group; and (3) a product obtained by reacting a blocked organic polyisocyanate or an organic polyisocyanate with an active hydrogen compound. A phosphate ion source that contains a blocked prepolymer having an NCO group at its terminal and releases phosphate ions in an environment where water and oxygen are present, and A pre-coated metal sheet paint having low toxicity and excellent corrosion resistance, characterized by containing a vanadate ion source which releases vanadate ions in an existing environment. The phosphate ion source and the vanadate ion source may be rust preventive pigments. As the rust preventive pigment, a phosphorus compound containing a phosphorus compound, a vanadium compound and, if necessary, a mixture containing one or both of a network modifying ion source and a glassy substance, which is baked and pulverized, or a phosphorus compound which releases phosphate ions And mixtures of vanadium compounds that release vanadate ions.

[0009] RTECS (collection of toxicity data of chemical substances by a public organization in the United States) states that vanadium pentoxide and phosphate are lower in acute toxicity and chronic toxicity than chromic acid. .

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a film-forming resin will be described. The pre-coated metal plate requires high workability because the coating film is processed together with the metal. As a polyol component,
A polyester polyol having at least 3 functional groups,
When a product obtained by adding a lactone compound or an alkylene oxide to an epoxy resin having at least one secondary hydroxyl group and a blocked product of an organic polyisocyanate or a blocked product of an organic polyisocyanate and an active hydrogen compound is used in combination, A coating film having good bending properties, high hardness, and excellent chemical resistance and stain resistance can be obtained.

[0011] used in the resin used in the present invention,
The polyester polyol having at least 3 functional groups of (1) includes dicarboxylic acid, glycol and at least 3
It is obtained by esterifying a polyol having two OH groups. Examples of the dicarboxylic acid used in the production of the polyester polyol include succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dodecane diacid, maleic acid, maleic anhydride, fumaric acid,
Aliphatic systems such as itaconic acid and dimer acid, such as phthalic acid, phthalic anhydride, isophthalic acid, dimethyl isophthalate, terephthalic acid, dimethyl terephthalate, 2,6-naphthalenedicarboxylic acid, hexahydrophthalic anhydride, and tetrahydroacid Aromatic and alicyclic compounds such as phthalic anhydride, cyclohexanedicarboxylic acid, dimethyl cyclohexanedicarboxylate, methylhexahydrophthalic anhydride, hymic anhydride, and methylhymic anhydride are mentioned. Examples of the glycol include ethylene glycol, diethylene glycol, propylene glycol,
1,3-butylene glycol, 1,4-butylene glycol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, neopentyl glycol ester of hydroxyvivalic acid, triethylene glycol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2,
2,4-trimethyl-1,3-pentanediol, 2-
Ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, polycaprolactone diol, polypropylene glycol, polytetramethylene ether glycol, polycarbonate diol, 2-
n-butyl-2-ethyl-1,3-propanediol,
Aliphatic ones such as 2,2-diethyl-1,3-propanediol, for example, cyclohexanedimethanol,
Cyclohexanediol, 2-methyl-1,1-cyclohexanedimethanol, xylylene glycol, bishydroxyethyl terephthalate, 1,4-bis (2-hydroxyethoxy) benzene, hydrogenated bisphenol A,
Alicyclic or aromatic compounds such as an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A are mentioned. At least 3
Examples of polyols having two OH groups include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, diglycerin, ethylene oxide adducts using these polyols as initiators, propylene Oxide adducts and ε-caprolactone adducts are exemplified.

The esterification reaction is carried out by charging a polyol component in excess of the acid component and distilling off the condensate by a usual method. However, since the product is polyfunctional, if the reaction is advanced too much, gelation occurs. Because of the risk of
Usually, it is preferable to stop at an acid value of 0.1 to 50, especially 1 to 20. As a specific production method, for example, dicarboxylic acid is charged in excess of the number of moles of glycol, and
Condensed water is distilled off while blowing nitrogen gas at a temperature of 0 to 260 ° C., reacting to a predetermined acid value, and C
A polyester having an OOH group is obtained. Next, a polyol having at least three OH groups is charged so that the terminal of the polyester compound becomes an OH group, and condensed water is distilled off in the same manner, and the acid value is 50 or less, preferably 1 to 3.
There is a method of stopping in the range of 20. When a dimethyl ester of a dicarboxylic acid is used, a larger amount of the glycol is charged, the condensate is distilled off under the same conditions as above, and a polyester compound having a methyl ester group at both ends is obtained. And a transesterification reaction is carried out under the same conditions as described above to obtain a polyester polyol.

When an acid anhydride is used in combination, dicarboxylic acid is first charged in a smaller amount than the number of moles of glycol, and a condensate is distilled off under the same conditions as described above. First, a polyester having OH groups at both ends is obtained. Then, a dicarboxylic anhydride is added, and a polyester having COOH groups at both terminals is obtained by this ring opening reaction. Then at least three O
There is a method in which a polyol having an H group is charged and a reaction is performed in the same manner as described above to obtain a polyester polyol. The polyester polyol used in the present invention preferably has a functional group number of 3 to 7, particularly 4 to 6, a number average molecular weight of 600 to 3500, and a hydroxyl value of 80 to 460, and the functional group number is less than 3 , The hardness of the cured coating film decreases and the chemical resistance deteriorates.

On the other hand, if it has more than 7 functions, the bending resistance of the coating film may deteriorate. When the number average molecular weight is less than 600, the gloss of the cured coating film is deteriorated, and when it exceeds 3500, the viscosity becomes high, which may cause problems in coating workability and deteriorate the stain resistance. If the hydroxyl value is less than 80, the cured coating film may have poor chemical resistance and stain resistance. On the other hand, if the hydroxyl value exceeds 460, the coating may have poor bending resistance.

[0015] The secondary hydroxyl group of (2), which is the other component of the polyol component used in the present invention, has at least one secondary hydroxyl group.
Examples of the product obtained by adding a lactone compound or an alkylene oxide to an epoxy resin having a plurality of epoxy resins include a product obtained by adding a lactone compound or an alkylene oxide to an epoxy resin represented by the following general formula by a method known per se.

[0016]

Embedded image

In the formula, X represents a phenylene group or a cyclohexylene group which may be substituted with halogen, and n represents 0.5 to 12.0.

The addition amount of the lactone compound or alkylene oxide is about 5 to 40 parts by weight based on about 95 to 60 parts by weight of the epoxy resin. In particular, the lactone compound or alkylene oxide is preferably used in an amount of about 10 to 30 parts by weight based on about 90 to 70 parts by weight of the epoxy resin. In the epoxy resin represented by the above general formula, X is preferably a p-phenylene group, and n is preferably 2 to 9. Examples of the halogen include bromine and chlorine. The number of the substituents is usually about 1 to 3, and the position may be any position of a phenylene group or a cyclohexylene group.

Examples of the lactone compound include β-propiolactone, butyrolactone, γ-valerolactone, γ-caprolactone, δ-valerolactone, δ-caprolactone, and ε-caprolactone. -Caprolactone is preferred. Examples of the alkylene oxide include ethylene oxide, propylene oxide, styrene oxide, glycidyl methacrylate, epichlorohydrin and the like, with ethylene oxide being particularly preferred.

The proportion of the epoxy resin having at least one secondary hydroxyl group to which a lactone compound or an alkylene oxide is added is about 10% in the polyol component.
About 70% by weight, especially about 10 to 60% by weight.
It is preferable to use in the range of. When the compounding ratio is less than 10% by weight, among the stain resistances, particularly the mustard resistance may deteriorate. On the other hand, if the content exceeds 70% by weight, the stain resistance is improved, but the hardness may be extremely reduced.

(3) used for the resin used in the present invention
Examples of the blocked product include compounds having at least two NCO groups, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate,
1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 2,6-diisocyanate Aliphatic diisocyanates such as methylcaproate; for example, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, , 4'-methylenebis (cyclohexyl isocyanate), methyl-
2,4-cyclohexane diisocyanate, methyl-
2,6-cyclohexane diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, 1,4-
Bis (isocyanatomethyl) cyclohexane, 1,3
Cycloalkylene diisocyanates such as -bis (isocyanatomethyl) cyclohexane and trans-cyclohexane-1,4-diisocyanate;
Phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate,
1,5-naphthalenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6
-Tolylene diisocyanate, 4,4'-toluidine diisocyanate, dianisidine isocyanate, 4,
Aromatic diisocyanates such as 4'-diphenyl ether diisocyanate and naphthalene diisocyanate, for example, ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate 1,4-
Diethylbenzene, α, α, α ′, α′-tetramethylmetaxylylene diisocyanate, α, α, α ′, α ′
Araliphatic diisocyanates such as tetramethyl paraxylylene diisocyanate, for example triphenylmethane-4,4 ', 4 "-triisocyanate,
5-triisocyanate benzene, 2,4,6-triisocyanate toluene, ω-isocyanate ethyl-
Triisocyanates such as 2,6-diisocyanatocaproate, for example, blocked products of tetraisocyanates such as 4,4'-diphenyldimethylmethane-2,2 ', 5,5'-tetraisocyanate, dimers,
Trimers, burettes, allophanates, carbodiimides, polymethylene polyphenyl polyisocyanates (crude MDI, c-MDI, polymeric MD
Blocked products of derivatives from isocyanate compounds such as I) and crude TDI, and blocked products of prepolymers having an NCO group at a terminal obtained by reacting them with an active hydrogen compound.

When used as PCM, weather resistance is required. Therefore, among the compounds having an NCO group, hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,4-bis Isocyanate compounds such as (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4'-methylenebis (cyclohexylisocyanate), α, α, α ', α'-tetramethylmetaxylylene diisocyanate It is preferable to use

The prepolymer having a terminal NCO group obtained by the reaction between the isocyanate compound and the active hydrogen compound is obtained by reacting the isocyanate monomer with the active hydrogen compound in an excess of isocyanate groups. . Active hydrogen compounds used to produce this prepolymer include, for example, ethylene glycol, propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, Dihydric alcohols such as neopentyl glycol, neopentyl glycol hydroxybivalate, triethylene glycol, hydrogenated bisphenol A, xylylene glycol, 1,4-butylene glycol, for example, glycerin, trimethylolethane, trimethylolpropane, Low molecular weight polyols such as trihydric alcohols such as 2,2,6-hexanetriol, for example, tetrahydric alcohols such as pentaerythritol, and propylene oxide of the above polyols. Are high molecular weights such as polyether polyols such as ethylene oxide adducts, polytetramethylene ether glycol, polyester polyols obtained by reacting the aforementioned low molecular weight polyols with dicarboxylic acids, and those modified with fatty acids when producing polyester polyols. Polyols. These polyols may be used alone or as a mixture.

The prepolymer is generally composed of NCO groups / OH
The equivalent ratio with the group is about 2.0-15, preferably about 4-8
After the reaction is carried out usually at 40 to 140 ° C., preferably 70 to 100 ° C., if necessary, unreacted isocyanate monomer is obtained by removing it by a thin film distillation method or an extraction method which is usually carried out. Can be. In this reaction, an organometallic catalyst such as a tin-based, lead-based, zinc-based, or iron-based catalyst may be used.

The above-mentioned blocked isocyanate monomer or prepolymer thereof can be obtained by reacting the isocyanate monomer or prepolymer thereof with a blocking agent by a known method. As the blocking agent used in this reaction, there are known blocking agents that can be used for blocking an isocyanate, for example, phenol-based, lactam-based, active methylene-based, alcohol-based, mercaptan-based, acid amide-based, and imide-based blocking agents. ,
Amine-based, imidazole-based, urea-based, carbamate-based, imine-based, oxime-based, or sulfite-based blocking agents can be used, and in particular, phenol-based, oxime-based, lactam-based, imine-based, etc. Blocking agents are advantageously used. The following are specific examples of the blocking agent.

Phenolic blocking agents: phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, p-hydroxydiphenyl, t-butylphenol, o-isopropylphenol, o-sec-butylphenol, p-nonylphenol, p-t -Octylphenol, hydroxybenzoic acid, hydroxybenzoic acid esters and the like.

Lactam blocking agents: ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam and the like.

Active methylene blocking agents: diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone and the like.

Alcohol-based blocking agents: methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol
-Amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, distyrene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, methoxy methanol, glycolic acid, glycolic acid Methyl, ethyl glycolate, glycolic acid esters such as butyl glycolate, lactic acid, methyl lactate, lactate esters such as ethyl lactate, butyl lactate, methylol urea, methylol melamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromhydrin, 1,3-dichloro-2
-Propanol, ω-hydroperfluoroalcohol, acetocyanhydrin and the like.

Mercaptan blocking agents: butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol,
Ethylthiophenol and the like.

Acid amide blocking agent: acetanilide,
Acetanisidide, acetoloid, acrylamide,
Methacrylamide, acetate amide, stearamide,
Benzamide and the like.

Imide blocking agent: succinimide,
Phthalic imide, maleic imide and the like.

Amine-based blocking agent: diphenylamine,
Phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine,
Butylamine, dibutylamine, butylphenylamine and the like.

Imidazole-based blocking agents: imidazole, 2-ethylimidazole and the like.

Urea-based blocking agents: urea, thiourea, ethylene urea, ethylene thiourea, 1,3-diphenyl urea and the like.

Carbamate blocking agents: phenyl N-phenylcarbamate, 2-oxazolidone and the like.

Imine blocking agents: ethyleneimine, propyleneimine and the like.

Oxime blocking agents: formamidoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexanone oxime and the like.

Bisulfate blocking agent: sodium bisulfite,
Potassium bisulfite and the like.

As a specific method of the reaction between the isocyanate monomer or the prepolymer thereof and the blocking agent, for example, the isocyanate monomer or the prepolymer thereof and the blocking agent are combined with the NCO group / blocking agent in the NCO group / blocking agent. A method in which the reaction is carried out at an equivalent ratio of active hydrogen groups = about 0.9 to 1.0, preferably about 0.95 to 1.0, wherein an isocyanate monomer and a blocking agent are reacted with NCO groups / active hydrogen groups in the blocking agent. Equivalent ratio of about 1.1 to 3.0, preferably about 1.
After reacting at 2 to 2.0, a method of reacting a low-molecular-weight polyol, high-molecular-weight polyol, water or a lower amine as used in the production of the above-mentioned prepolymer, or an isocyanate monomer and a low-molecular-weight polyol NC, high molecular weight polyol, water or lower amine
After the reaction at an equivalent ratio of O group / active hydrogen group = about 1.6 to 10.0, preferably about 2.0 to 7.0, a method of reacting a blocking agent with the reaction may be used. Each of the above reactions is carried out in a solvent having no active hydrogen group (eg, aromatic solvents such as benzene, toluene, and xylene, petroleum solvents such as Solvesso-100 and Solvesso-200, and ester solvents such as ethyl acetate and butyl acetate; For example, the reaction is performed by a known method in the absence of a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and an ether such as tetrahydrofuran, or the like. In the reaction, a known catalyst such as a tertiary amine or an organic metal may be used. The film-forming resin raw materials used in the present invention are the above-mentioned polyols (1) and (2) and the blocked product (3), and the blending ratio of the polyol and the blocked product is OH group / regenerated NCO
The equivalent ratio of the groups is about 1/2 to 2/1, especially 1 / 0.8 to 1 /
1.2 is preferred.

Next, the chromium-free rust preventive will be described. By including the phosphate ion source and the vanadate ion source in the paint, the oxidizer function, which is insufficient with the phosphate ion alone, is supplemented by the vanadate ion. That is, the non-chromium rust inhibitor constituting the present invention is a phosphate ion source that releases phosphate ions in an environment where water and oxygen are present, and releases vanadate ions in an environment where water and oxygen are present. It is a vanadate ion source.

In order to exhibit the rust-preventive effect of the paint, it is sufficient that phosphate ions and vanadate ions coexist in the paint. Even if phosphate ions and vanadate ions are present as they are, water and oxygen are present. It may contain a substance that releases phosphate ions and vanadate ions in an environment. Phosphate ions rarely exist alone in an aqueous solution, and exist in various forms, for example, as a condensate. In such cases, it is understood that the phosphate ion is included in the concept of “phosphate ion” in the present specification. Is done. Further, the vanadate ion is understood as a concept including a condensed vanadate ion. The phosphate ion source and the vanadate ion source are mainly provided as rust preventive pigments, and contain a phosphorus compound and a vanadium compound, and if necessary, calcine and pulverize a mixture containing the network modifying ion source and / or a glassy substance. It can be obtained by:

Phosphorus compounds used in the rust preventive pigment include orthophosphoric acid, condensed phosphoric acid, orthophosphates or condensed phosphates of various metals, phosphorus pentoxide, phosphate minerals, commercially available composite phosphate pigments, Or a mixture thereof. The monohydrogen salt thereof in the orthophosphate here (HPO ₄ ^2-salt), dihydrogenphosphate (H ₂ PO ₄ ^- salt) is also included. The hydrogen phosphate is also included in the condensed phosphate. The condensed phosphates include metaphosphates, and include ordinary polyphosphates and polymetaphosphates. Specific examples of the phosphorus compound include phosphate minerals, such as monetite, tolfillite, witrockite, xenotime, starcolite, struvite, ornite, and the like.
Commercially available composite phosphate pigments, such as silica polyphosphate,
Complex phosphoric acid such as pyrophosphoric acid, metaphosphoric acid, complex phosphate such as metaphosphate, tetrametaphosphate, hexametaphosphate, pyrophosphate, acid pyrophosphate, tripolyphosphate, or a mixture thereof . The metal species forming the phosphate is not particularly limited, and examples thereof include alkali metals, alkaline earth metals, metal species of other typical elements, and transition metals. Examples of preferred metal species include magnesium, calcium, strontium, barium, titanium, zirconium, manganese, iron,
Examples include cobalt, nickel, zinc, aluminum, lead, and tin. In addition, oxo cations such as vanadyl, titanyl, and zirconyl are also included. Particularly preferred are calcium and magnesium. The use of large amounts of alkali metals is not preferred. When an alkali metal phosphate is used, the calcined product tends to be too soluble in water. However, when an alkali metal phosphate is used, it may be used if the solubility in water can be controlled at the time of producing the rust preventive or at another time. Such control includes, for example, use of a matrix material (particularly, a glassy substance) for prevention of solubility in water, or various modes such as coating.

The vanadium compound used for the rust preventive pigment is a compound having a valence of vanadium of 0, 2, 3, 4 or 5, or 2 or more thereof.
Hydroxides, oxyacid salts of various metals, vanadyl compounds, halides, sulfates, metal powders and the like. They decompose during heating or in the presence of water and react with oxygen to be upgraded. For example, metal powder or a divalent compound is finally changed to any of trivalent, tetravalent and pentavalent compounds. Those containing a pentavalent vanadium compound as one component are preferred. Zero-valent, for example, vanadium metal powder can be used for the above reasons, but is not practically preferable because of problems such as insufficient oxidation reaction. The pentavalent vanadium compound has a vanadate ion and easily reacts with a phosphate ion by heating to form a heteropolymer. Specific examples of the vanadium compound include vanadium (II) compounds such as vanadium oxide (I
I), vanadium (II) hydroxide, vanadium (III) compounds such as vanadium (III) oxide, vanadium (I
V) compounds, such as vanadium (IV) oxide, vanadyl halide, etc., vanadium (V) compounds, such as vanadium (V) oxide, vanadates, for example, orthovanadate, metavanadate or pyrovanadate of various metals Salts, vanadyl halides, and the like, or mixtures thereof. The metal species of vanadate may be the same as those shown for phosphate. This means that vanadium oxide and various metal oxides, hydroxides, carbonates, etc.
It may be made by firing at a temperature of 00 ° C. or more. In this case, too, alkali metals are not preferred because of their solubility in water, but they can be used if the solubility is controlled by appropriate treatment described for phosphates. Also halides,
The same applies to sulfates.

The network modifying ion used in the rust preventive pigment means a metal ion species added for modifying a network structure formed by a fired product of a phosphorus compound and a vanadium compound, and specifically includes various metal ions. Examples of ionic species include alkali metal ions, alkaline earth metal ions, metal ions of other typical elements, and transition metal ions. Examples of preferred network modifying ions include metal salts of phosphoric acid. Examples of the network modifying ion source include oxides, hydroxides, carbonates, nitrates, organic acid salts, silicates, borates, sulfates and chlorides of the above-mentioned metal species, and most preferably oxides, water Oxides and carbonates. When an alkali metal is used among the metal ion species, or when a sulfate or a chloride is used as the ion source, these compounds tend to be excessively dissolved in water. In such a case, as described above, appropriate measures such as the use of a matrix material or the coating of particles may be used to control the solubility in water.

The glassy substance used in the rust preventive pigment includes not only matrix-forming glasses such as silicate glass and borate glass, but also those containing a metal element such as a network modifying ion. The corresponding glassy substances are silica (quartz) glass, silicate glass such as soda-lime silicate glass, lead-silicate glass, aluminosilicate glass, borosilicate glass, lead-borate glass. (Commonly called solder glass), alumino-borophosphate glass, alumino-borate glass, alumino-phosphate glass, and the like. Examples of preferred glassy substances include soda-lime (C glass), for example, glass flake (CCF-150) manufactured by Nippon Glass Fiber Co., Ltd., and aluminosilicate glass (E glass), for example, glass flake (CEF) manufactured by Nippon Glass Fiber Co., Ltd. -150), borosilicate glass, for example, Pyrex manufactured by Corning Incorporated. It is preferable that the conductivity of the liquid obtained by dispersing and suspending 1 g of the fine powder of the glassy substance in 100 ml of water is 500 μS / cm or less. If it exceeds 500 μS / cm, the rust-preventing ability is reduced.

Phosphorus compounds, vanadium compounds and furthermore
If necessary, a mixture consisting of a glassy substance and a network-modified ion source
The compound is baked, cooled, and ground for use in the present invention.
A rust preventive pigment to be used is obtained. As needed in the mixture
Other inorganic substances such as a matrix material may be mixed.
No. Calcination is the melting of the calcination product of the mixture consisting of the above components
Temperature (T1) or more, specifically 600 ° C. or more,
Preferably at least 1000 ° C., more preferably the above T1
It is carried out above the higher melting temperature of the vitreous substance.
You. If the temperature is lower than this, the reaction becomes insufficient and each component
Remain simply mixed. In such a case,
Deterioration of rust prevention performance. Phosphorus and vanadium compounds
The amount is P_TwoO_Five/ V_TwoO_FiveConverted to the molar ratio of 0.3
-100, preferably 1-10. Network modifying ion
The amount of the source added should be all metals of the rust preventive used in the rust preventive composition.
The amount of the cation (M) is determined in the form of an oxide (M
O, M_TwoO_Three, M_ThreeO_Four, MO_TwoOr M_TwoO)
And V_TwoO_FiveAnd P_TwoO_FiveLess than 3 times the sum of the number of moles of
Or 0 to 2.0 times. M takes
When M is a monovalent metal, the form of the oxide is M_TwoO and M are divalent
MO if metal, M if M is trivalent metal_TwoO_Three, M
If is tetravalent, MO_Two, And M is a mixture of divalent and trivalent materials
Valence (for example, Mn is divalent or trivalent under the condition of firing)
The thing is M _ThreeO_FourAnd will be represented as Gala
Phosphorus compounds, vanadium compounds and mesh repair
5 to 500 times in total, preferably 10 to 10 times the decoration ion source
It is blended in an amount of 0 times. Sufficient rust prevention when exceeding the above range
Cannot be obtained.

As described above, the film-forming resin used in the present invention;
The non-chromium rust inhibitor has been described. By applying a paint obtained by mixing these to a precoated metal plate, it is possible to obtain low toxicity and high corrosion resistance. The mixing amount is 0.1 to 5 in total for both the phosphate ion source and the vanadate ion source with respect to 100 parts by weight of the total solid content of the paint.
0 parts, preferably 0.5 to 20 parts. If the amount is less than 0.1 part by weight, a sufficient rust-preventing effect is not exhibited. If the amount exceeds 50 parts by weight, the cohesive strength of the cured coating film is reduced and sufficient coating film strength cannot be obtained.

The film-forming resin raw material used in the present invention can be sufficiently formed by heating as it is. However, when forming a coating, in addition to the polyol and the blocked product, for example, ethyl acetate, butyl acetate, methyl acetoacetate, Esters such as 2-ethoxyethyl acetate, aromatics such as xylene and toluene, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as diethylene glycol dimethyl ether,
Petroleum-based organic solvents such as Solvesso-100 and Solvesso-200, for example, color pigments and extender pigments, silicon-based, amine-based, polyether-based, polyester-based,
Castor oil-based, synthetic wax-based, pentonite-based dispersants, defoamers, leveling agents, thixotropic agents, benzotriazole-based, hindered amine-based, hindered phenol-based stabilizers, tin-based, lead-based, zinc If necessary, reaction catalysts such as iron-based and iron-based catalysts, and UV inhibitors may be added. After the coating material of the present invention thus obtained is applied to a metal plate, the temperature of the reached plate (hereinafter sometimes referred to as PMT) is about 15 μm.
By heating at 0 to 350 ° C. for a heating time of about 20 to 120 seconds, the blocking agent contained in the blocked product is dissociated to regenerate NCO groups, and the regenerated NCO groups react with OH groups in the polyol. To give a cured coating.

The paint of the present invention may be used by coating one coat on a metal plate. However, when the paint is used as a primer for PCM having two or more coats, it shows a great effect.

As the metal plate to which the paint of the present invention is applied,
For example, hot rolled steel sheet, cold rolled steel sheet, electrogalvanized steel sheet,
Hot-dip galvanized steel sheet, alloyed hot-dip galvanized steel sheet, zinc alloy-coated steel sheet, aluminum-plated steel sheet, chromium-plated steel sheet, nickel-plated steel sheet, copper-plated steel sheet, etc., stainless steel sheet, aluminum sheet, copper sheet, aluminum alloy sheet, etc. A known metal plate or alloy plate may be used. In addition, by performing pre-coating treatment with these metal plates with chromate, phosphate, silane coupling agent, tannic acid, vanadic acid, thiourea, etc., higher corrosion resistance,
Coating adhesion is obtained. However, performing chromate treatment is not preferable in terms of toxicity and should be avoided as much as possible.

[0052]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference examples and examples. However, the present invention is not limited to these examples. In addition, the part or% shown without a reference shows a weight part or weight%, respectively.

The following Reference Examples 1 to 7 illustrate the production of a polyol. Reference Example 1 364.9 parts (1.52 mol) of hydrogenated bisphenol A, 441.6 parts of adipic acid (3.02 parts)
Mol) in a reaction vessel, heated to 220 ° C. and blown with nitrogen gas to react while distilling off the condensed water generated. When the acid value reached 250.0, trimethylolpropane (hereinafter referred to as TMP) 304 was prepared. .1 copy (2.27
Mol), and reacted while distilling off condensed water in the same manner to obtain a polyester polyol having an acid value of 2.6, a hydroxyl value of 187.2, a number of functional groups of 5, and a number average molecular weight of 1478.
A product obtained by adding 20 parts by weight of ε-caprolactone to 600 parts by weight of this polyester polyol and 80 parts by weight of an epoxy resin of the following formula (Placcel G-402 (manufactured by Daicel Chemical Industries, Ltd.)), hydroxyl value 119, epoxy equivalent 1
250) and 400 parts of cyclohexanone to give a solution having a solid content of 40%. The properties of this solution are shown in Table 1.

[0054]

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Reference Example 2 A product obtained by adding 20 parts by weight of ε-caprolactone to 800 parts by weight of the polyester polyol obtained in Reference Example 1 and 80 parts by weight of an epoxy resin represented by the following formula (Placcel G-702 (Daicel Chemical Industries, Ltd.) Industrial Co., Ltd.
20) having a hydroxyl value of 140 and an epoxy equivalent of 2710)
0 parts was dissolved in 1500 parts of cyclohexanone, and the solid content was 4 parts.
A 0% solution was obtained. The properties of this solution are shown in Table 1.

[0056]

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Reference Example 3 1,6-hexanediol 2
05.8 parts (1.74 mol), 670.1 parts (3.45 mol) of dimethyl isophthalate and 0.1 g of zinc acetate were charged into a reaction vessel, heated to 220 ° C. and blown with nitrogen gas to produce methanol. Was distilled off, and when 121 ml of methanol was distilled off, TMP 347.2 was obtained.
(2.59 mol), and the reaction was carried out while distilling off methanol in the same manner to obtain an acid value of 1.4, a hydroxyl value of 193.6,
A polyester polyol having 5 functional groups and a number average molecular weight of 1438 was obtained. 600 parts of this polyester polyol and 400 parts of Praxel G-402 of Reference Example 1 were dissolved in 1500 parts of cyclohexanone to prepare a solution having a solid content of 40%. The properties of this solution are shown in Table 1.

Reference Example 4 A reaction vessel was charged with 245.3 parts (2.08 mol) of 3-methyl-1,5-pentanediol and 541.6 parts (3.71 mol) of adipic acid.
The mixture was heated to 20 ° C. and nitrogen gas was blown thereinto to cause a reaction while distilling off generated condensed water. When the acid value reached 280.0, 372.9 parts (2.78 mol) of TMP and 0.1 part of dibutyltin dilaurate were added. And the reaction was carried out in the same manner while distilling off the condensed water to obtain an acid value of 1.6 and a hydroxyl value of 216.
A polyester polyol having 0, 5 functional groups, and a number average molecular weight of 1289 was obtained. This polyester polyol 800
And 200 parts of Praxel G-402 of Reference Example 1 were dissolved in 1500 parts of cyclohexanone to prepare a solution having a solid content of 40%. The properties of this solution are shown in Table 1.

Reference Example 5 Ethylene glycol 151.
8 parts (2.45 mol), 550.0 parts of succinic acid (4.6
6 mol), and reacted under the same conditions as in Reference Example 1.
When the acid value reached 420.0, 159.3 parts (1.17 mol) of pentaerythritol was charged, and the esterification reaction was continued. When the acid value reached 165.0, 159.3 parts of pentaerythritol (159.3 parts) was added. 1.17 mol)
And 157.0 parts (1.17 mol) of TMP were charged, and the condensation water was distilled off to obtain a polyester polyol having an acid value of 3.8, a hydroxyl value of 447.8, a number of functional groups of 7, and a number average molecular weight of 870. 800 parts of this polyester polyol and 200 parts of Praxel G-402 of Reference Example 1 were dissolved in 1500 parts of cyclohexanone to obtain a solution having a solid content of 40%. The properties of this solution are shown in Table 1.

Reference Example 6 325.9 parts (1.28 mol) of bishydroxyethyl terephthalate, sebacic acid 5
13.8 parts (2.54 mol) were charged and reacted under the same conditions as in Reference Example 1. When the acid value reached 184.4, 256.7 parts (1.91 mol) of TMP were charged and condensed water was added. Was distilled off to obtain a polyester polyol having an acid value of 8.0, a hydroxyl value of 168.3, a number of functional groups of 5, and a number average molecular weight of 15,91. 800 parts of this polyester polyol and 200 parts of Praxel G-402 of Reference Example 1 were dissolved in 1500 parts of cyclohexanone to obtain a solution having a solid content of 40%. The properties of this solution are shown in Table 1.

Reference Example 7 Ethylene glycol 183.
4 parts (2.95 mol), 664.7 parts of succinic acid (5.6
3 mol), and reacted under the same conditions as in Reference Example 1.
When the acid value becomes 420.0, TMP 189.4
Parts (1.41 mol), and the esterification reaction was continued.
When the acid value reached 170.0, 183.4 parts (2.95 mol) of ethylene glycol was further charged, and condensed water was distilled off to obtain an acid value of 1.5, a hydroxyl value of 215.5, a number of functional groups of 3, A polyester polyol having a number average molecular weight of 776 was obtained. 800 parts of this polyester polyol and 200 parts of Praxel G-702 of Reference Example 2 were mixed with cyclohexanone 1
It was dissolved in 500 parts to obtain a solution having a solid content of 40%. The properties of this solution are shown in Table 1.

In the following Reference Examples 8 to 13, the production of blocked products will be described. Reference Example 8 241.6 parts of 1,3-bis (isocyanatomethyl) cyclohexane was dissolved in Solvesso-100 40
Dissolved in 0.0 part of methyl ethyl ketoxime 180.6
Part is dropped in 1 hour. 1 hour after dropping 75 ~
Heat to 80 ° C. Next, dibutyltin dilaurate 0.6
Part and polyester polyol (adipic acid 876.6)
Parts, 186.3 parts of ethylene glycol, TMP 20
An acid value of 3.5 and a hydroxyl value of 17 obtained by condensing 1.2 parts and 402.3 parts of dipropylene glycol by a conventional method.
2.0, solid content 100%)
React at 0 ° C. for 6 hours. Thus, a blocked solution having a regenerated isocyanate group content of 8.5% and a solid content of 60% was obtained. Table 2 shows the properties of this solution.

Reference Example 9 A solution of TMP-3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate adduct (Takenate D-140N (manufactured by Takeda Pharmaceutical Co., Ltd.)) was placed in a 2-liter 4-diameter flask. , 751.2% solids, 10.78% isocyanate content, 801.2 parts ethyl acetate solution) and cellosolve acetate 3
16.1 parts are charged, and the internal temperature is 60 in a nitrogen gas atmosphere.
Keep methyl ethyl ketoxime at 18
2.7 parts was gradually added dropwise, and after the addition was completed, the temperature was maintained at the above temperature for about 4 hours to obtain a blocked solution having a solid content of 60% and a regenerated isocyanate group content of 6.64%. Table 2 shows the properties of this solution.

REFERENCE EXAMPLE 10 309.1 parts of ω, ω'-diisocyanate-1,3-dimethylbenzene were dissolved in 519.1 parts of Solvesso-100 and methyl ethyl ketone 1
Dissolved in 29.7 parts, methyl ethyl ketoxime 237.
2 parts are added dropwise in about 2 hours. 1 hour after dropping 7
Heat to 5-80 ° C. Next, 0.3 parts of dibutyltin dilaurate and 232.4 parts of the polyester polyol used in Reference Example 8 are added and reacted at 75 to 80 ° C. for 6 hours.
Thus, a blocked solution having a regenerated isocyanate group content of 8.02% and a solid content of 55% was obtained. Table 2 shows the properties of this solution.

REFERENCE EXAMPLE 11 A 2-liter 4-diameter flask was charged with TMP-hexamethylene diisocyanate adduct (Takenate D-160N (manufactured by Takeda Pharmaceutical Co., Ltd.), solid content 75%, isocyanate content 13.2%). 760.
7 parts and cellosolve acetate (325.6 parts) were charged, and 213.7 parts of methyl ethyl ketoxime was gradually dropped under a nitrogen gas atmosphere so that the internal temperature was maintained at 60 to 70 ° C. Solids 6 when kept at temperature
A blocked solution of 0% and a regenerated isocyanate group content of 7.77% was obtained. Table 2 shows the properties of this solution.

REFERENCE EXAMPLE 12 228.6 parts of 4,4'-methylenebis (cyclohexyl isocyanate) was dissolved in 160.0 parts of toluene and 160.0 parts of cyclohexanone, and 126.5 parts of methyl ethyl ketoxime was dissolved in about 16.5 parts.
Drop in time. 75-80 ° C for 1 hour after dropping
Heat to Next, 1,1,3,3-tetra n-butyl-
0.48 parts of 1,3-diacetoxydistannoxane and 123.92 parts of a polyester polyol (the same as the polyester polyol used in Reference Example 8) are added and reacted at 75 to 80 ° C. for 8 hours. Thus, a blocked solution having a regenerated isocyanate group content of 7.6% and a solid content of 60% was obtained. Table 2 shows the properties of this solution.

REFERENCE EXAMPLE 13 A 2-liter 4-diameter flask was equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a condenser for reflux cooling, and TMP and α, α, α ′, α′-tetramethylmetaxylylene diisocyanate were added. (Solid at room temperature, isocyanate content of 13.3%), 500 parts of ethyl acetate, 427.1 parts of ethyl acetate and 1,1,3,
0.19 parts of 3-tetra-n-butyl-1,3-diacetoxydistannoxane was charged, and 1 part of methyl ethyl ketoxime was added under a nitrogen gas atmosphere such that the internal temperature was maintained at 60 to 70 ° C.
40.5 parts were gradually added dropwise, and after the addition was completed, the temperature was maintained at the above temperature for about 4 hours to obtain a blocked solution having a solid content of 60% and a regenerated isocyanate group content of 6.20%. Table 2 shows the properties of this solution.

In the following Reference Examples 14 to 17, the production of a rust preventive will be described. [Reference Example 14] The components shown in Table 3 were mixed to obtain rust preventive agents 14a to 14d.

REFERENCE EXAMPLE 15 The components shown in Table 4 were fired, cooled and pulverized under the conditions shown in Table 4 to obtain rust preventive agents 15a to 15i.

REFERENCE EXAMPLE 16 The components shown in Table 5 were fired, cooled and pulverized under the conditions shown in Table 5 to obtain rust preventive agents 16a to 16e.

REFERENCE EXAMPLE 17 The components shown in Table 6 were mixed, melted at 140 ° C., cooled and pulverized to obtain rust preventive agents 17a to 17d.

Next, examples of the present invention and comparative examples will be described. In this embodiment, as film-forming resins, resins formed by various combinations of the polyols of Reference Examples 1 to 7 and the blocked products of Reference Examples 8 to 13 and, as non-chromium rust inhibitors, Reference Examples 14 to The rust inhibitor prepared in 17 (rust inhibitor 14)
a to 14d, 15a to 15i, 16a to 16e, 17a
And 17d) were examined for the performance of paints produced by various combinations of the above. In Comparative Examples, melamine alkyd resin (Nippon Paint Co., Ltd. Olga Select 100) and epoxy nylon resin (Toagosei Co., Ltd. FS75SZ) were used as comparative resins. In addition, comparative rust preventives were strontium chromate, dibasic magnesium phosphate, 2CaO.V ₂ O ₅ fired product, and no rust preventive added.

Example 1 43.4 parts of the polyol solution obtained in Reference Example 1 and 24.5 parts of the blocked product of Reference Example 8 were charged (NCO / OH equivalent ratio = 1.0). A mixture of the phosphorus compound and the vanadium compound of 14a
Prepare 0.0 parts. Further, 0.024 part of 1,1,3,3-tetra-n-butyl-1,3-diacetoxydistannoxane was added as a catalyst, and the mixture was sufficiently kneaded by a paint conditioner to obtain an enamel solution for PCM primer. This solution was subjected to a zinc phosphate treatment (adhesion amount: 2 g / m ² per side) as a pretreatment, and a 0.6 mm thick hot-dip galvanized steel sheet (zinc adhesion amount: 60 g / per side).
m ² ), coated with a bar coater to a dry film thickness of 5 μm and PMT 210 in a hot air oven.
After baking and water-cooling at 45 ° C. for 45 seconds, a high-molecular polyester paint (FL100HQ manufactured by Nippon Paint Co., Ltd.) was applied as a top coat to a dry film thickness of 16 μm.
Apply with a bar coater so that it becomes P
Baking under the condition of MT 230 ° C., arrival time 45 seconds,
Water cooled. On the opposite side (back side), a melamine alkyd-based paint was applied with a dry coat having a thickness of 7 μm using a bar coater, and baked under the conditions of PMT 230 ° C. and arrival time of 45 seconds.

[Examples 2 to 35] Using the composition shown in Table 7, kneading was carried out under the same conditions as in Example 1 to obtain an enamel solution for a primer, and baked and cooled under the same conditions as in Example 1. Each number in the column of “polyol” and “blocked product” in Table 7 indicates the number of the reference example in which the polyol and the blocked product used in each example were prepared.

[Comparative Examples 1 to 23] Enamel solutions for primers were obtained by kneading with the composition shown in Table 8, and baked and cooled with water under the same conditions as in Example 1. "Polyol" in Table 8
And each number in the column of "blocked product" indicates the number of the polyol used in each example and the reference example in which the blocked product was prepared.

The corrosion resistance of each Example and Comparative Example was evaluated for the coating film on the front side, and SST (JIS Z 237)
1 Based on salt spray test method) 240 hours and HCT
(Moisture resistance test: 50 ° C., 98% relative humidity) Judgment was made based on the swelling width from the cut surface of the steel sheet, the swelling width from the cross cut portion, and the degree of blister in the flat portion for 500 hours. These were rated based on the following criteria.

Swelling width from cut surface な し No swelling 最大 Maximum swelling width is less than 3 mm △ Maximum swelling width is 3 mm or more and less than 10 mm × Maximum swelling width is 10 mm or more

Bulging width from cross cut portion ◎ No swelling ○ Maximum swelling width is less than 1 mm △ Maximum swelling width is 1 mm or more and less than 3 mm × Maximum swelling width is 3 mm or more

Blister in flat part ◎ No blister ○ Blister area is less than 0.5% of the whole △ Blister area is 0.5% or more and less than 2% of the whole × Blister area is 2% or more of the whole

Regarding toxicity, those using chromium were regarded as toxic, and those not using chromium were regarded as non-toxic.

Table 7 shows the results of the examples, and Table 8 shows the results of the comparative examples. In the examples, it can be seen that since no chromium is used, toxicity is low and various corrosion resistances are good. On the other hand, in Comparative Examples 1 to 16, the resin shown in the Reference Example was used, but some problem occurred because an appropriate rust preventive was not used. That is, Comparative Examples 1 to 9 and 13 contain only the vanadate ion source, and Comparative Examples 10 and 14 do not have sufficient corrosion resistance because they contain only the phosphate ion source. In Comparative Examples 12 and 16, no corrosion resistance was obtained because no rust inhibitor was added. Comparative Examples 11 and 15 are excellent in corrosion resistance because of using strontium chromate, but are toxic. In Comparative Examples 17 and 18, the ones shown in Reference Examples were used as the rust preventives, but they were inferior in corrosion resistance because they did not use an appropriate resin. In Comparative Examples 19 to 23, neither the resin nor the rust preventive is suitable, and there is a problem in corrosion resistance or toxicity.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

[0088]

[Table 7]

[0089]

[Table 8]

[0090]

The PCM coated with the paint of the present invention has low toxicity and excellent corrosion resistance. Therefore, it can be advantageously used for home electric appliances and the like that may touch human hands or come into contact with food.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroshi Kanai 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corporation Technology Development Division (72) Inventor Kohei Ueda 20-1 Shintomi, Futtsu-shi, Chiba Made in New Japan (72) Inventor Akira Takahashi 1 Kimitsu, Kimitsu City, Chiba Prefecture Nippon Steel Corporation Kimitsu Works (72) Inventor Hiromasa Nomura 20-1 Shintomi, Futtsu City, Chiba Prefecture Nippon Steel Corporation (72) Inventor Hideaki Miyabayashi 2-17-85 Jusanhoncho, Yodogawa-ku, Osaka-shi, Osaka Prefecture, Japan Inside the Chemicals Company, Takeda Pharmaceutical Company Limited (72) Inventor Fumiaki Hirata, Yodogawa, Osaka-shi, Osaka 2-17-85, Jusanhoncho, Ward Takeda Pharmaceutical Co., Ltd. Chemicals Company F-term (reference) 4J038 DB471 DG111 DG301 GA03 HA066 HA126 HA216 HA246 HA 376 HA396 HA416 HA426 KA08 NA03 NA27 PB05 PB09 PC02 4K026 AA02 AA07 AA13 AA22 BA04 BA12 BB08 CA16 CA23 CA30 CA37 CA38 EB08

Claims (5)

[Claims] 1. A film-forming resin material comprising: (1) a polyester polyol having at least 3 functional groups; (2) an epoxy resin having at least one secondary hydroxyl group to which a lactone compound or an alkylene oxide is added; (3) containing a blocked product of an organic polyisocyanate or a blocked prepolymer having a terminal NCO group obtained by the reaction of an organic polyisocyanate with an active hydrogen compound, and water as a non-chromium rust preventive agent; Low-toxicity, comprising a phosphate ion source that releases phosphate ions in an environment where oxygen and oxygen are present, and a vanadate ion source that releases vanadate ions in an environment where water and oxygen are present. Pre-coated metal sheet paint with excellent corrosion resistance. 2. The prepainted metal plate paint according to claim 1, wherein the phosphate ion source and the vanadate ion source are rust preventive pigments. 3. The rust preventive pigment according to claim 1, wherein a mixture containing a phosphorus compound and a vanadium compound, and if necessary, a mixture containing at least one of a network modifying ion source and a glassy substance is baked and pulverized. Item 3. The paint for a precoated metal sheet according to Item 2. 4. The prepainted metal plate paint according to claim 2, wherein the rust-preventive pigment is a mixture of a phosphorus compound that releases phosphate ions and a vanadium compound that releases vanadate ions. 5. A polyester polyol having at least 3 functional groups and (2) at least one secondary hydroxyl group.
A product obtained by adding a lactone compound or an alkylene oxide to an epoxy resin having two or more (3) a blocked product of an organic polyisocyanate or N
The precoated metal sheet paint according to claim 1, wherein the blocked product of the prepolymer having a CO group is a one-part thermosetting resin composition.