JP3113017B2 - Water-soluble coating resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition used for preparing a low-temperature baking type water-soluble coating resin composition and a water-soluble coating resin composition. More specifically, the present invention relates to a low-temperature baking type water-soluble coating resin composition having excellent adhesion, water resistance, corrosion resistance, solvent resistance, and storage stability.

[0002]

2. Description of the Related Art In recent years, in the paint industry, from the viewpoints of resource saving, prevention of air pollution, prevention of fire and danger to the human body, development of water-dispersion paints and water-soluble resin paints using water as a solvent paint has been developed. Is widely used, and its use range is expanding.

[0003] Alkyd resins, acrylated alkyd resins, acrylic resins, epoxy ester resins and the like are known as water-dispersed paints and water-soluble resin paints generally used in the past. A type obtained by emulsion polymerization of a monomer in the presence of a surfactant or the like, or obtained by forcibly emulsifying a resin polymerized to a high molecular weight using an emulsifier. However, these types do not use the emulsifier, the surfactant or the like, or contain a hydrophilic component in the resin skeleton, so that neither of them has sufficient water resistance and corrosion resistance.

As a method for improving water resistance and corrosion resistance, a method of reacting a phosphoric acid with an epoxy resin to form a water-soluble coating composition is disclosed in JP-B-51-143620 and JP-B-52-136227.
No., JP-B-55-60567, JP-B-56-100824, JP-B-6
It is disclosed in 1-1171774. A method of reacting a phosphoric acid, a fatty acid and an epoxy resin to obtain a water-soluble coating composition is disclosed in Japanese Patent Publication No. 58-191764.

[0005]

However, in these methods, the temperature at the time of curing is higher than 140 ° C.
When the curing temperature is low, there is a disadvantage that the curing time is prolonged.

As described above, it is possible to bake at a low temperature for a short time, and it is excellent in the adhesiveness, water resistance, corrosion resistance, and solvent resistance of the original epoxy resin, and has a long-term stability at room temperature to 50 ° C. or lower. The coating resin composition has not been put to practical use yet.

An object of the present invention is to provide a water-soluble coating resin composition which has solved the above problems.

[0008]

Means for Solving the Problems The phosphorus-containing polyol of the present invention is provided.
The method for producing an alkali-neutralized resin-unsaturated compound is as follows:
It contains two or more epoxy groups in one molecule and has a molecular weight of 2
A phosphate (II) having at least two or more active hydrogens in an epoxy group-containing resin (I) of from 2000 to 2000;
Is reacted with one epoxy group at a ratio of 2.0 or more active hydrogens to obtain a phosphorus- containing polyol resin (A) .
Phosphorus-containing polyol resin (A) and isocyanate-containing prepolymer compound (III) having an unsaturated bond at a terminal
Preparative and reacted at a ratio of 0.1 to 2.0 mole phosphorus-containing polyol resin - give unsaturated compound (B), then, phosphorous
Active hydrogen groups in the polyol resin-unsaturated compound (B)
Neutralized with alkali and phosphorus-containing polyol resin-unsaturated compound
Characterized in that an alkali neutralized product (C) is obtained .

Furthermore, the water-soluble coating resin composition of the present invention comprises a method for producing the above-mentioned phosphorus-containing polyol resin-unsaturated compound.
-Containing polyol resin obtained by the method-unsaturated compound
Neutralized product (C) of urea-formaldehyde condensation
And / or melamine-formaldehyde condensate
(D) and water .

[0010]

The phosphorus-containing polyol resin used in the present invention
The unsaturated compound (B) is obtained by reacting the epoxy group-containing resin (I) with phosphate (II) having at least two or more active hydrogens at a ratio of 2.0 or more active hydrogens to one epoxy group. Is obtained by reacting the isocyanate-containing prepolymer compound (III) having an unsaturated bond at a terminal with the phosphorus-containing polyol resin (A) obtained at a rate of 0.1 to 2.0 mol.

The epoxy group-containing resin used in the present invention
As (I), those containing two or more epoxy groups in one molecule and having a molecular weight of 200 to 2,000, preferably 350 to 1,000 are suitable. The following are examples of such an epoxy group-containing resin (I).

An epoxy resin obtained from epichlorohydrin or β-methyl epichlorohydrin and bisphenol A, bisphenol F or bisphenolsulfone, polyglycidyl ether of novolak resin, polyglycidyl ether of ethylene oxide or propylene oxide adduct of bisphenol A,
Polypropylene glycol, neopentyl glycol,
Polyglycidyl ethers of polyhydric alcohols such as 1,6-hexanediol, glycerin, trimethylolpropane, etc .; polyglycidyl esters of polycarboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid and dimer acid; polyglycidyl Amines and the like. Further, an epoxy resin obtained by modifying the above epoxy resin with a polyphenol such as bisphenol A or bisphenol F or a polycarboxylic acid such as adipic acid or sebacic acid can be used.

The phosphate (II) having at least two or more active hydrogens used in the present invention includes phosphoric acid, phosphoric acid monoester, phosphoric acid monohydrochloride and the like. The phosphoric acids, phosphoric acid, pin pyrophosphate,
Phosphoric acid esters such as diphosphoric acid and polyphosphoric acid include monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monomethyl pyrophosphate and dimethyl pyrophosphate. Phosphates include monosodium dihydrogen phosphate, phosphorus Examples thereof include potassium dihydrogen acid, monoammonium dihydrogen phosphate, and monosodium trihydrogen pyrophosphate.

Of such phosphates (II) having two or more active hydrogens, phosphoric acid, pyrophosphate monoesters and pyrophosphate monosalts having three active hydrogens are preferred.

The phosphorus-containing polyol resin used in the present invention
(A) is obtained by adding at least 2 to the epoxy group-containing resin (I).
It is obtained by reacting a phosphate (II) having two or more active hydrogens. In the reaction, the active hydrogen equivalent of the phosphate (II) having at least two or more active hydrogens is 2.0 to 4.0 with respect to 1 equivalent of the epoxy group of the epoxy group-containing resin (I).
It is preferable to perform the reaction in an equivalent amount (preferably 2.0 to 3.0 equivalents). If the active hydrogen equivalent of the phosphate (II) is less than 2.0 equivalents per 1 equivalent of the epoxy group, the solubility and dispersibility of the obtained product in water are undesirably reduced. On the other hand, if the equivalent of the active hydrogen of the phosphate (II) is 4.0 equivalents or more per equivalent of the epoxy group, free phosphate is generated and the water resistance and corrosion resistance are lowered, which is not preferable. The reaction is preferably performed at 80 to 150 ° C.

Next, the isocyanate-containing prepolymer compound (III) having an unsaturated bond at the terminal of the present invention includes propylene oxide adduct of unsaturated fatty acid, ethylene oxide adduct of unsaturated fatty acid, allyl alcohol, allyl alcohol Propylene oxide adduct and aliphatic polyisocyanates such as hexamethylene diisocyanate, ethylene diisocyanate, butyl diisocyanate, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2
-Cyclohexane diisocyanate, cycloalkylene diisocyanate such as isophorone diisocyanate,
m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate,
Aromatic diisocyanates such as 1,5-naphthalenediisocyanate, 4,4'-diphenylenemethane diisocyanate, 2,4-ditoluene diisocyanate, 2,6-
Reaction with an aliphatic-aromatic isocyanate such as ditoluene diisocyanate or a mixed diisocyanate thereof, an isocyanate group derived from a polyfunctional isocyanate such as a dimer or trimer modification of toluene diisocyanate, or a dimer or trimer modification of hexamethylene diisocyanate. A prepolymer and the like can be exemplified.

An isocyanate-containing prepolymer compound having a terminal unsaturated bond in the phosphorus-containing polyol resin (A)
The reaction of adding (III) is a phosphorus-containing polyol resin (A)
The reaction is carried out at a ratio of 0.1 to 2.0 mol (preferably 0.5 to 1.5 mol) of the urethane prepolymer compound (III) having an unsaturated bond at a terminal per 1 mol. preferable. The reaction is preferably performed at 100 to 150 ° C.

When the viscosity of the reaction system is high, an appropriate solvent is preferably used. Examples of such a solvent include those which are inert to free isocyanate groups and are soluble in water, for example, ethyl acetate, acetic acid Butyl, cellosolve acetate, methyl ethyl ketone, dimethylformamide, dioxane and the like are preferred.

The composition for a coating resin obtained as described above is neutralized with an alkali to neutralize active hydrogen groups in the composition to give an alkali neutralized product (water-soluble coating resin) (C). I do.

Examples of the alkali used here include ammonia and dimethylaminoethanolamine.
The amount of the alkali used is 1.0 to 1.2 equivalents per equivalent of active hydrogen groups in the resin, and neutralized with ion-exchanged water to a non-volatile content of 20 to 40%. At this time the pH
Is preferably 9 to 10.

The alkali neutralized product (water-soluble coating resin) (C) of the present invention can be cured at room temperature by using a dryer which is a salt of an organic acid such as cobalt, lead, zinc, zirconium or manganese. It is possible.

On the other hand, the alkali-neutralized product (water-soluble coating resin) (C) of the present invention comprises another water-dispersible or water-soluble resin (D).
Can be used in combination with

The mixing ratio of the components (C) and (D) is (C)
The proportion of component (D) is 5 to 50 parts, preferably 10 to 30 parts, per 100 parts of component.

Further, a dryer which is a salt of the organic acid such as cobalt, lead, zinc, zirconium, manganese or the like can be used in combination.

Examples of the water-dispersible or water-soluble resin of the component (D) include condensation products of an amino compound and an aldehyde compound. For example, there are a urea-formaldehyde condensate and a melamine-formaldehyde condensate.

[0027]

EXAMPLES Preparation Example 1 Preparation of phosphorus-containing polyol resin "ADEKARESIN EP-4100" having an epoxy equivalent of 190
(Bisphenol A epichlorohydrin type epoxy resin manufactured by Asahi Denka Kogyo Co., Ltd.) 190 parts (parts by weight, the same applies hereinafter)
Was mixed with 115 parts of 85% phosphoric acid and stirred at 80 ° C. for 3 hours to obtain a phosphorus-containing polyol resin (A-1). Acid value is 3
65.

Production Example 2 Preparation of phosphorus-containing polyol resin "ADEKARESIN EP-5100" having an epoxy equivalent of 500
(Bisphenol A epichlorohydrin type epoxy resin manufactured by Asahi Denka Kogyo Co., Ltd.) 500 parts of monomethyl pyrophosphate (194 parts) and cellosolve acetate (297 parts) were blended and mixed at 80 ° C.
For 3 hours to obtain a phosphorus-containing polyol resin (A-2). The acid value was 170.

Production Example 3 Preparation of phosphorus-containing polyol resin "ADEKARESIN EP-4901" having an epoxy equivalent of 175
(Bisphenol F epichlorohydrin type epoxy resin manufactured by Asahi Denka Kogyo Co., Ltd.) 175 parts, bisphenol A: 50 parts, dimethylbenzylamine 2 parts were mixed, and 1
After reacting at 50 ° C. for 3 hours, monosodium phosphate 31 was added.
Were added, and 110 parts of cellosolve acetate was added, followed by stirring at 12 ° C. for 5 hours to obtain a phosphorus-containing polyol resin (A-3).
The acid value was 70.

Production Example 4 Preparation of phosphorus-containing polyol resin 152 parts of pyrophosphoric acid was mixed with 240 parts of a hydrogenated bisphenol A type epoxy resin having an epoxy equivalent of 240,
For 3 hours to obtain a phosphorus-containing polyol resin (A-4). The acid value was 355.

Production Example 5 Preparation of phosphorus-containing polyol resin "ADEKARESIN EP-4000" having an epoxy equivalent of 320
To 320 parts of bisphenol A propylene oxide adduct (Asahi Denka Kogyo Co., Ltd.) was mixed 55 parts of bisphenol A and reacted at 150 ° C. for 5 hours to obtain an epoxidized product having an epoxy equivalent of 750. Further, 180 parts of cellosolve acetate was added, the temperature was cooled to 80 ° C, 60 parts of monosodium phosphate was blended, and the mixture was stirred at 80 ° C for 3 hours to obtain a phosphorus-containing polyol resin (A-5). The acid value was 129.

Production Example 6 Prepolymer containing isocyanate
Preparation of 2,4-toluene diisocyanate (174 parts), allyl alcohol (58 parts) and ethyl acetate (110 parts) were added, and the mixture was stirred and reacted at 80 ° C. for 3 hours under nitrogen.
% Of an isocyanate-containing prepolymer (III-
6) was obtained.

Production Example 7 Prepolymer containing isocyanate
Preparation of Compounds 174 parts of 2,4-toluene diisocyanate, 130 parts of hydroxypropyl acrylate, and 130 parts of cellosolve acetate were added, and the mixture was stirred and reacted at 80 ° C. for 3 hours under nitrogen. The isocyanate-containing prepolymer (III-7) was obtained.

Example 1 Preparation of phosphorus-containing polyol resin-unsaturated compound The phosphorus-containing polyol resin (A-1) 30 obtained in Production Example 1
0 parts, 342 parts of the isocyanate-containing prepolymer (III-6) obtained in Production Example 6, and 140 parts of ethyl acetate were stirred and reacted at 80 ° C. for 3 hours under nitrogen to obtain a non-volatile content of 70%.
To obtain a phosphorus-containing epoxy resin-unsaturated adduct (B-1).
The acid value was 144.

Example 2 Preparation of phosphorus-containing polyol resin-unsaturated compound The phosphorus-containing polyol resin (A-2) 50 obtained in Production Example 2
0 parts and 342 parts of the isocyanate-containing prepolymer obtained in Production Example 7 were added, and the mixture was stirred at 80 ° C. for 3 hours under nitrogen.
The reaction was conducted to obtain a phosphorus-containing epoxy resin-unsaturated adduct (B-2) having a nonvolatile content of 70%. The acid value was 100.

Example 3 Preparation of Phosphorus-Containing Polyol Resin-Unsaturated Compound The phosphorus-containing polyol resin (A-3) 25 obtained in Production Example 3
0 parts and 200 parts of the isocyanate-containing prepolymer (III-6) obtained in Production Example 6 was stirred and reacted at 80 ° C. for 3 hours under nitrogen to react with a phosphorus-containing epoxy resin having a nonvolatile content of 70% -unsaturated adduct ( B-3) was obtained. The acid value was 39.

Example 4 Preparation of phosphorus-containing polyol resin-unsaturated compound The phosphorus-containing polyol resin (A-4) 40 obtained in Production Example 4
0 parts and 645 parts of the isocyanate-containing prepolymer obtained in Production Example 7 were added, and the mixture was stirred at 80 ° C. for 3 hours under nitrogen.
The reaction was performed to obtain a phosphorus-containing epoxy resin-unsaturated adduct (B-4) having a nonvolatile content of 70%. The acid value was 136.

Example 5 Preparation of phosphorus-containing polyol resin-unsaturated compound The phosphorus-containing polyol resin (A-5) 61 obtained in Production Example 5
5 parts and 430 parts of the isocyanate-containing prepolymer obtained in Production Example 7 were added, and the mixture was stirred at 80 ° C. for 3 hours under nitrogen.
The reaction was performed to obtain a phosphorus-containing epoxy resin-unsaturated adduct (B-5) having a nonvolatile content of 70%. The acid value was 76.

Example 6 Phosphorus-containing epoxy resin obtained in Example 1-unsaturated adduct
(B-1) 100 parts was mixed with 33 parts of 28% aqueous ammonia, and further diluted with ion-exchanged water.
Thus, an aqueous solution (C-1) was obtained. And Cymel-303
(Melamine-formaldehyde condensate) (Mitsui Toatsu) 1
The aqueous clear resin obtained by adding 5 parts was treated with sandpaper (# 360) and then degreased with acetone according to JIS G-31.
41 was applied on a steel plate and baked at 100 ° C. for 10 minutes to obtain a coating film. The test results of the coating film performance are shown in Table 1.

Example 7 The phosphorus-containing epoxy resin-unsaturated adduct (B-2) obtained in Example 2 was subjected to the same operation as in Example 6 to obtain a nonvolatile matter 2
An aqueous solution (C-2) of 5%, pH = 10 was obtained. (C-
2) An aqueous clear resin obtained by adding 10 parts of Cymel-303 to 100 parts was subjected to the same operation as in Example 6 to obtain a coating film. The test results of the coating film performance are shown in Table 1.

Example 8 The phosphorus-containing epoxy resin-unsaturated adduct (B-3) obtained in Example 3 was subjected to the same operation as in Example 6 to obtain a nonvolatile matter 2
An aqueous solution (C-3) having a pH of 5% and a pH of 10 was obtained. (C-
3) An aqueous clear resin obtained by adding 10 parts of Cymel-370 (melamine-formaldehyde condensate) (manufactured by Mitsui Toatsu Co.) to 100 parts was subjected to the same operation as in Example 6 to obtain a coating film. . The test results of the coating film performance are shown in Table 1.

Example 9 The phosphorus-containing epoxy resin-unsaturated adduct (B-4) obtained in Example 4 was subjected to the same operation as in Example 6 to obtain a nonvolatile matter 2
An aqueous solution (C-4) of 5% and pH = 10 was obtained. (C-
3) An aqueous clear resin obtained by adding 150 ppm of cobalt naphthenate to 100 parts was subjected to the same operation as in Example 6 to obtain a coating film. The test results of the coating film performance are shown in Table 1.

Example 10 The phosphorus-containing epoxy resin-unsaturated adduct (B-5) obtained in Example 5 was subjected to the same operation as in Example 6 to obtain a nonvolatile matter 2
An aqueous solution (C-5) of 5%, pH = 10 was obtained. (C-
3) An aqueous clear resin obtained by adding 370: 10 parts of Cymel to 100 parts and 150 ppm of cobalt naphthenate was subjected to the same operation as in Example 6 to obtain a coating film. The test results of the coating film performance are shown in Table 1.

Comparative Example 1 "ADEKARESIN EP-5100" having an epoxy equivalent of 500
(Bisphenol A epichlorohydrin type epoxy resin manufactured by Asahi Denka Kogyo Co., Ltd.)
5 parts and 265 parts of cellosolve acetate were added and stirred at 100 ° C. for 3 hours to obtain a phosphorus-containing polyol resin having a nonvolatile content of 70%. The acid value was 128. 2 in 100 parts of the obtained resin
28 parts of 8% aqueous ammonia was mixed and further diluted with ion-exchanged water to obtain an aqueous solution having a nonvolatile content of 25 % and pH = 10.
The same operation as in Example 6 was performed on the aqueous clear resin obtained by adding 15 parts of Cymel-303 to obtain a coating film. The test results of the coating film performance are shown in Table 1.

Comparative Example 2 "ADEKARESIN EP-4100" having an epoxy equivalent of 190
(Bisphenol A epichlorohydrin type epoxy resin manufactured by Asahi Denka Kogyo Co., Ltd.) Monobutyl phosphate 1 in 190 parts
Ten parts and 130 parts of ethyl acetate were mixed and stirred at 85 ° C. for 3 hours to obtain a phosphorus-containing polyol resin. The acid value was 265. The same procedure as in Example 6 was carried out on the aqueous clear resin obtained by adding 35 parts of Cymel-303 to obtain a coating film. The test results of the coating film performance are shown in Table 1.

Comparative Example 3 "ADEKARESIN EP-5100" having an epoxy equivalent of 500
(Bisphenol A epichlorohydrin type epoxy resin manufactured by Asahi Denka Kogyo KK) 250 parts of cellosolve acetate 1
30 parts, 70 parts of dehydrated castor oil fatty acid and 0.3 parts of dimethylbenzylamine were added and stirred at 150 ° C. for 3 hours to react. When the acid value became 1 or less, the temperature was lowered to 120 ° C.
5 parts were added and the mixture was further stirred at 120 ° C. for 3 hours to be reacted. A reaction product having an acid value of 55 was obtained. 45 parts of dimethylethanolamine was added to obtain an alkali neutralized product. Obtained resin 1
An aqueous clear resin obtained by adding 25 parts of Cymel-303 to 00 parts was subjected to the same operation as in Example 6 to obtain a coating film. The test results of the coating film performance are shown in Table 1.

Comparative Example 4 "ADEKARESIN EP-5100" having an epoxy equivalent of 500
(Bisphenol A epichlorohydrin type epoxy resin manufactured by Asahi Denka Kogyo KK) 250 parts of cellosolve acetate 1
30 parts, 70 parts of dehydrated castor oil fatty acid and 0.3 parts of dimethylbenzylamine were added and stirred at 150 ° C. for 3 hours to react. When the acid value became 1 or less, the temperature was lowered to 120 ° C.
5 parts were added and the mixture was further stirred at 120 ° C. for 3 hours to be reacted. A reaction product having an acid value of 55 was obtained. 45 parts of dimethylethanolamine was added to obtain an alkali neutralized product. Obtained resin 1
An aqueous clear resin obtained by adding 25 parts of Cymel-303 to 00 parts and 150 ppm of cobalt naphthenate was subjected to the same operation as in Example 6 to obtain a coating film. The test results of the coating film performance are shown in Table 1.

Comparative Example 5 "ADEKARESIN EP-5100" having an epoxy equivalent of 500
(Bisphenol A epichlorohydrin type epoxy resin manufactured by Asahi Denka Kogyo KK) 250 parts of cellosolve acetate 1
30 parts, 70 parts of dehydrated castor oil fatty acid and 0.3 parts of dimethylbenzylamine were added and stirred at 150 ° C. for 3 hours to react. When the acid value became 1 or less, the temperature was lowered to 120 ° C.
5 parts were added and the mixture was further stirred at 120 ° C. for 3 hours to be reacted. A reaction product having an acid value of 55 was obtained. 45 parts of dimethylethanolamine was added to obtain an alkali neutralized product. Obtained resin 1
An aqueous clear resin obtained by adding 25 parts of Cymel-303 to 00 parts and 150 ppm of cobalt naphthenate was subjected to the same operation as in Example 6 to obtain a coating film. The test results of the coating film performance are shown in Table 1.

[0049]

[Table 1]

[0050]

The water-soluble resin composition for coating of the present invention can be cured at a low temperature of room temperature to 100 ° C. for a short time.
The storage stability at temperatures below ℃ is also very good.
Therefore, metal, slate board, mortar board, and various plastics can be used as they are in the form of clear or colored with coloring agents such as pigments and dyes by spraying, brushing, electrodeposition coating, dip coating, etc. , Can be used as a low-temperature baking type coating agent for thermoplastic materials such as rubber.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenji Furusho Asahi Denka Kogyo Co., Ltd. 7-2-35 Higashiogu, Arakawa-ku, Tokyo (56) References JP-A-2-84469 (JP, A) JP-A Sho 60-258269 (JP, A) JP-A-3-195739 (JP, A) JP-A-4-67314 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 1/00 -201/10 C08K 3/00-13/08 C08L 1/00-101/16 C08G 18/00-18/87 C08G 71/00-71/04

Claims (2)

(57) [Claims] 1. Contains two or more epoxy groups in one molecule
Then, a phosphate (II) having at least two or more active hydrogens is reacted with the epoxy group-containing resin (I) having a molecular weight of 200 to 2,000 at a ratio of 2.0 or more active hydrogens to one epoxy group. the resulting phosphorus-containing polyol resin (a) Te, then the phosphorus-containing polyol resin (a), an isocyanate-containing prepolymer compound having an unsaturated bond at the terminal (III) and 0.1 to 2.0 molar proportions of in reacted with a phosphorus-containing polyol resin - unsaturated compound (B)
And then the phosphorus-containing polyol resin-unsaturated compound (B)
Phosphorus-containing polyol by neutralizing active hydrogen groups in the alkali with alkali
Obtaining alkali-neutralized product (C) of resin-unsaturated compound
Of a phosphorus-containing polyol resin-unsaturated compound
Method for producing neutralized lukari. 2. The phosphorus-containing polyol resin according to claim 1.
Obtained by the method for producing an alkali neutralized product of an unsaturated compound
Phosphorus-containing polyol resin-alkali neutralization of unsaturated compounds
Product (C), urea-formaldehyde condensate and / or
Melamine-formaldehyde condensate (D) and water
A water-soluble coating resin composition comprising: