JPS6081262A - Resin composition for low temperature drying electrodeposition paint - Google Patents

Abstract

PURPOSE:The titled composition, obtained by dispersing or dissolving a specific anionic or cationic resin prepared from an epoxy resin, unsaturated fatty acid and ethylenically unsaturated monomer in water, and capable of giving films having improved cold curability and corrosion resistance, and suitable for electrodeposition. CONSTITUTION:A resin composition obtained by (A) neutralizing a product prepared by grafting (ii) 60-20wt% ethylenically unsaturated monomer containing 3wt% or more acrylic acid or methacrylic acid onto 40-80wt% epoxy resin ester intermediate obtained by adding or condensing (i) 30-60wt% epoxy resin with 30-60wt% unsaturated fatty acid with (iii) an amine or alkali, and dispersing or dissolving the neutralized product in water or (B) neutralizing a product obtained by grafting (iv) 60-20wt% ethylenically unsaturated monomer containing 5wt% dimethylaminoethyl acrylate, etc. onto 40-80wt% component (i) with (v) an acid, and dispersing or dissolving the neutralized product in water.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-dispersible or water-soluble coating resin composition that provides a coating film with excellent low-temperature curability and excellent corrosion resistance. More particularly, the present invention relates to a coating resin composition particularly suitable for electrodeposition comprising an anionic or cationic resin prepared from an epoxy resin, an unsaturated fatty acid and an ethylenically unsaturated monomer.

Conventionally, electrodeposition paints have been used for various purposes as primers. However, such a paint requires a high temperature of 160 to 180°C to be sufficiently cured, which is not preferable from the viewpoint of energy saving. Although efforts have been made to develop low-humidity curing electrodeposition paints in order to improve these drawbacks, it seems that nothing useful has yet been found.

As a result of intensive research aimed at developing a low-temperature curing resin for coatings, the present inventors discovered that a resin obtained from a graft polymer containing an epoxy resin, an unsaturated fatty acid, and an ethylenically unsaturated monomer as essential components was discovered. The present inventors have discovered that it provides a coating film with excellent low-temperature effectiveness and good corrosion resistance, and is suitable as an electrodeposition coating material, leading to the completion of the present invention.

The present invention uses 30 to 60% by weight of an epoxy resin, 30 to 60% of unsaturated fat M, and if necessary, a monovalent to trivalent organic acid and a monovalent to 411Illi alcohol in a total amount of 70%. The number average molecular weight obtained by addition or condensation within the range of weight or less is 500 to 5000, the weight average molecular weight is 1000 to 20000, and the acid value is O
~50% by weight of an epoxy resin ester intermediate having a hydroxyl value of O~100 and at least 3% by weight of acrylic acid and /' or methacrylic acid. The number average molecular weight obtained by graft polymerizing 20% by weight is 1000 to 600.
0, the weight average molecule (4) is 5000 to 2oooooo, and the acid value is 25 to 100? 1 (A-1') is neutralized with amine@(B) or alkaline <C) and dissolved in water. 81], or 30 to 60% by weight of epoxy resin and 30 to 60% by weight of unsaturated fatty acid
and, if necessary, a monovalent to trivalent organic acid and a monovalent to tetravalent alcohol within a range where the total amount is 70% by weight or less, resulting in a number average molecule □ □□ or 500 to 5000, and the weight average molecular weight is io.

40 to 20,000, an epoxy resin ester intermediate having an acid value of O to 20 and a hydroxyl value of O to 100
80% by weight of at least one member of the group f)
The number average molecule m obtained by graft polymerizing 60 to 20% by weight of ethylenically unsaturated 1m body containing % polymerization direction is 100
0 to 6000, tan average molecule ffl ffi 50
00 to 20,000 o and an amine value of 30 to 100, the resin composition for low temperature drying paint [Embodiment 2] is prepared by neutralizing the product (A-2) with an acid <DJ and dispersing or dissolving it in water. provide.

Regarding conventional electrodepositing resin compositions, there are numerous patents and several review articles, such as [Petroleum and Petrochemistry J 18
(3), 101-105 (1974) or [Paint Technology J1973 (1), 155-164, etc.]. However, all of these have various drawbacks; for example, in the case of the composition with a weight of bC51-32655, it takes 30 minutes at 170 DEG C. to dry the coating film.

Also, J, Oil Qol, Cbem, ASSOC
,,53°353-362 (1970) Reference f'
R00111T e-mperature Curin
G E Electrodeposited Coati
n-gsJ describes an electrodeposition paint that cures at room temperature, but this is a two-component system, and one electrodeposition paint cannot be used for a long period of time. In contrast, the electrodeposition coating composition according to the present invention has a -wave type, is stable for a long period of time, and has a
It differs from conventional electrodeposition coating compositions in that it provides sufficient hardness, corrosion resistance, and other general coating properties when dried at a low temperature of 0 to 100°C.

As the epoxy resin used in the present invention, a dicrycidyl ether type epoxy resin of hisphenol A is suitable, and a dicrycidyl ether type epoxy resin of 500 or more is required for molecular use. If it is less than 500, sufficient quick drying properties and hardness cannot be obtained. Other epoxy resins that can be used include polyglycidyl ethers such as bisphenol F1 phenol novolak and cresol novolak, which have a melting point of 40°C or higher. The resin composition must contain 30 to 6 o*m% of at least one or more of the above-mentioned epoxy resins in the intermediate raw material.

As the fatty acids used in the present invention, drying oil fatty acids having an iodine value of 130 or more are suitable. Examples of such dry fatty acids include linseed oil fatty acids, eno oil fatty acids, linseed oil fatty acids, soybean oil, and the like. In addition to drying oil fatty acids, semi-drying oils with an iodine value of 100 to 130, such as cottonseed oil, rapeseed oil, rice bran oil, etc., or non-drying oils with an iodine value of 100 or less, such as palm oil, coconut oil, etc., may also be used. good.

These fatty acids may be used alone or in combination of two or more. However, in order to have sufficient normal temperature drying properties, the resin composition of the present invention must contain 30 to 60% fatty acid having at least one unsaturated carbon-carbon bond in the epoxy resin ester intermediate raw material. Must be.

The epoxy resin ester intermediate used in the present invention includes:
In addition to the epoxy resin and the unsaturated fatty acid, mono- to tri-functional moromi and mono- to tetra-functional alcohol, which are used as raw materials for ordinary alkyds, may be included as raw materials. Finally, the epoxy resin ester intermediate has a number average molecular weight of 500 to 50.
00. Weight average molecular weight 1000-20000. Acid value O~
The epoxy resin ester intermediate resin can be synthesized using one or more of the necessary mono- to trifunctional acids and mono- to tetrafunctional alcohols so as to have a Examples of the above mono- to trifunctional a include various aliphatic carboxylic acids, such as acetic acid, butyric acid,
Oleic acid, aromatic carboxylic acids such as benzoic acid, tert-butylbenzoic acid, phthalic acid, isophthalic acid, various other dimer acids, various fatty acids and maleic acids, or Examples include mellitic acid. Examples of the above-mentioned mono- to tetrafunctional alcohols include various aliphatic alcohols such as t-butyl alcohol, amyl alcohol, 2-ethylhexyl alcohol, various aromatic alcohols such as hensyl alcohol, and other ethylene alcohols. Examples include glycol, propylene glycol, neopentyl glycol, chrycerol, trimethylolethane, and pentaerythritol.

The ring-opening reaction between an epoxy resin and a carboxylic acid is promoted by an amine catalyst, so a high boiling point amine such as dimethylhensylamine is
It is effective to add 00.

The esterification reaction between a hydroxyl group and a carboxyl group starts from 150 to
It is appropriate to carry out the reaction at 250°C.

Since oxygen in the reaction system reacts with carbon-carbon double bonds, it is necessary to proceed with the reaction in an atmosphere of inert gas (nitrogen-carbon dioxide, etc.).

The reaction is carried out at a predetermined molecular weight (number average 500 to 5000) or a viscosity value corresponding to it (in Embodiment 1, O to 5000).
50, and in embodiment 2 O to 20), the process is stopped by lowering the temperature or mixing a water-soluble organic solvent or the like. The water-soluble organic solvents used are preferably alkanols, such as methanol, ethanol, propyl alcohol, etc., alcohols such as monoalkyl diethylene glycols, monoalkyl diethylene glycols, etc., or other water-soluble solvents, such as acetone, THF, dioxane, etc. can also be used.

The aqueous solvent solution of the epoxy resin ester intermediate is then used for graft polymerization with an ethylenically unsaturated monobase. In the polymerization reaction according to aspect 1, the epoxy resin ester intermediate solid portion is 40 to 80ffiff
i% ethylenically unsaturated monomer 60~20@Q
% graft polymerization, number average molecular fa1000-600
0. Weight average molecular weight 5000-200000. Acid value 25
Synthesize ~100 craft stand resins. The ethylenically unsaturated monomer used in this kraft polymerization must contain at least 3% by weight of acrylic acid, methacrylic acid, or both. Furthermore, other monomers include styrene, acrylic esters, methacrylic esters, itaconic esters, fumaric esters, acrylonitrile, methacrylate trile, ol'
Examples include e-vinyl, vinyl lactam, and vinyl chloride.

The resulting graft polymerization 1fil aqueous solvent solution is neutralized with a neutralizing agent such as triethylamine, jetanolamine, etc. (diamines, ammonia, sodium hydroxide, etc.), and further deionized water is added.
Stable aqueous solutions or dispersions can be obtained.

The dispersion referred to herein generally consists of a resin having a particle size of 10 μm or less and a continuous aqueous phase.

This dispersion may be optically transparent or opaque.

When performing electrodeposition coating using the aqueous solution or dispersion according to embodiment 1, it is first filled into a container so as to immerse the conductive cathode and the conductive anode to be coated, and then a voltage is applied between the two electrodes. is applied to electrodeposit an adhesive film of the coating composition onto the anode. Voltage conditions are 1-1000v, typically 5
It is 0 to 300v. The current density is usually reduced from a maximum of 0.1 A/Cr112 to zero A,/am2 during the electrodeposition process.The pH is usually set at 7-11.

In the polymerization reaction according to Embodiment 2, 60 to 20% by weight of an ethylenically unsaturated monomer is kraft-polymerized to 40 to 80% by weight of the solid portion of the epoxy resin ester intermediate, and the number average molecular weight is 11,000 to 6,000, and the weight average Molecular weight 5000
~200,000 and a graft polymer resin having an amine value of 30 to 100 is synthesized. The ethylenically unsaturated monomers used in this craft polymerization are dimethylaminoethyl acrylate,
It must contain at least 5% by weight of one or more of dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, and diethylaminoethyl methacrylate. Further, other monomers include styrene, acrylic esters, methacrylic esters, itaconic esters, fumaric esters, acrylonitrile, methacryloni-1-lyl, vinyl acetate, vinyl lactam, vinyl chloride, etc. I can do it.

The obtained graft polymer resin aqueous solvent solution is neutralized with a neutralizing agent, for example, organic acids such as phosphoric acid, acetic acid, and lactic acid, or inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and further deionized water is added. A stable aqueous solution or dispersion similar to that in embodiment 1 can be obtained.

When performing electrodeposition coating using the aqueous solution or dispersion according to Embodiment 2, it is first filled in a container so as to immerse the conductive anode and the conductive cathode to be coated, and then filled between the two electrodes. A voltage is applied to electrodeposit an adhesive film of the coating composition onto the cathode. Voltage conditions are 1-1000v1 typically 50-300v. The current density usually decreases from a maximum of 01 A/cm2 to zero A/cm2 during the electrodeposition process.

l) H is usually set to 5-9.

Electrodeposition coating using the composition of the present invention can be applied to iron, aluminum,
Suitable for conductive substrates such as copper.

Curing and drying of the adhesive film is usually carried out at 120 to 200°C, but when the composition of the present invention is used, the temperature is 60 to 120°C.
It is also possible to obtain sufficient hardness, corrosion resistance d5, and other physical properties.

The paint according to the present invention can be applied to various objects other than metals.
Coating can be done using any coating method such as brush coating, spray coating, roller coating, or dip coating, but it is most suitable for electrodeposition coating on conductive metal products such as those mentioned above.

Next, the present invention will be specifically explained using Examples and Comparative Examples. Percentages and parts are by weight.

Example 1 In a reaction vessel purged with Nl, 470 parts of linseed oil fatty acid and 50 parts of dehydrated castor oil fatty acid are heated to 140 parts C. Epoxy resin (Dainippon Ink K.

After adding 450 parts of Ebicuron 1050), the system was further heated, and at the point when the system became homogeneous and transparent, 0.5 part of dimethylpencylamine was added, and the temperature was further raised to 180°C, and the mixture was heated at 180° C. for 1 hour. Keep at ℃.

After lowering the temperature to 120'C, 10 parts of maleic anhydride and 120 parts of phthalic anhydride H were added, and the mixture was gradually heated and raised to 230°C over 3 hours. Proceed with the condensation reaction while maintaining the temperature at 230°C, and when the acid value reaches 15 and the cartoner viscosity of the 60% butyl cellosolve solution of the resin reaches N, immediately
The temperature is lowered to .degree. C., and 20 parts of butyl cellosolve and about 500 parts of ethyl cellosolve are added to prepare an epoxy ester intermediate resin solution having a resin non-volatile content of 50%.

11,200 parts of this epoxy ester intermediate resin solution was added with N
Heat to 130° C. in a 2-substituted reaction vessel. To this resin solution, 225 parts of styrene, 53 parts of lauryl methacrylate, 40 parts of methyl methacrylate, and 41 parts of acrylic acid were added.
A mixture of 1 part and 25 parts of a peroxide polymerization initiator (NOF, Ni, ', Barbdel Z) was added dropwise over 3 hours. The graft polymerization was further maintained at 130° C. for 6 FR to complete the graft polymerization.

This graft polymerization resin solution has a resin nonvolatile part of 62.5.
%, Gardner viscosity is 71, and the acid value of the non-volatile part of the resin is 41.

160 parts of this graft polymerization resin solution, 100 parts of titanium dioxide (JR600E, manufactured by Teikoku Kako), 20 parts of butyl cellosolve, and 20 parts of ethyl cellosolve are kneaded in a sand mill to prepare a mill base having an NV of 67% and a PWC of 50%.

120 parts of the above Kraft polymer resin solution, this Mill Base 7
5 parts of triethylamine and 6.5 parts of triethylamine, 798.5 parts of ion-exchanged water was gradually added to the mixture with stirring to prepare 1000 parts of an aqueous N-wearing paint dispersion.

The aqueous dispersion had a breakdown voltage of 300 V and a pH of 9.5, and was deposited on an iron phosphate-treated mild steel plate anode at 200 V for 2 minutes and dried at 80°C for 15 minutes, resulting in a film thickness of 2.
A smooth hard flexible coating of 0 μm was obtained. This coating has a wearable pencil hardness of IffH and a salt spray resistance test of 20
The cellophane tape peeling width at 0 hours was within 3+++n1 on one side.

Example 2 1200 parts of the epoxy ester intermediate resin solution of Example 1 is heated to 130° C. in a reaction vessel purged with N2. To this resin solution, 261 parts of styrene, 20 parts of lauryl methacrylate, 30 parts of butyl methacrylate, 40 parts of methyl methacrylate, 49 parts of methacrylic acid, and 25 parts of a peroxide polymerization initiator (Nippon Oil Co., Ltd., Perbutyl Z) were added.
part of the mixture was added dropwise over a period of 3 hours. The graft polymerization was further maintained at 130° C. for 6 hours to complete the graft polymerization. This graft polymerization resin solution has a nonvolatile resin content of 62.5%, a Gardner viscosity of 71, and an acid value of 41 for the nonvolatile resin content.

160 parts of this graft polymerization resin solution, 100 parts of titanium dioxide (JR600E, manufactured by Teikoku Kako), 20 parts of butyl cellosolve, and 20 parts of ethyl cellosolve are kneaded in a sand mill to prepare a mill base having an NV of 67% and a PWC of 50%.

120 parts of the above Kraft polymer resin solution, this Mill Base 7
5 parts of triethylamine and 6.5 parts of triethylamine, 798.5 parts of ion-exchanged water was gradually added to the mixture with stirring to prepare 10'00 parts of an aqueous electrodeposition coating dispersion.

The breakdown voltage of the aqueous dispersion was 300 V, and I)H was 9°5. By molding it on an iron phosphate-treated mild steel plate anode at 200 V for 2 minutes and drying it at 100° C. for 15 minutes,
A smooth, hard and flexible coating film with a film thickness of 20 μm was obtained. This coating film had a pencil hardness of 2 days, and the cellophane tape peeling width was within 3nln1 on one side in a 200-hour salt water spray test.

Comparison Example 1 In a reaction vessel containing N2Et, linseed oil fatty acid 363
parts, 371 parts of phthalic anhydride, 8 parts of trimethylolpropane
Prepare 0 parts and 186 parts of pentaerythritol, 3
Gradually heat to 190°C over time. The condensation reaction was continued while maintaining the temperature at 190°C, and when the acid value reached 55 and the cartoner viscosity of the 60% butyl cellosolve solution of the resin reached R, the temperature was quickly lowered to 80°C, about 400 parts of isopropyl alcohol was added, and the resin A resin solution with a solid content of 70% is prepared.

1143 parts of the resin bath, titanium dioxide (to Teikoku Kako, to
, JR600E) and 57 parts of isopropyl alcohol were kneaded in Santo Mill to obtain NV67%, PW0
50% mill base II.

While stirring a mixture of 1,107 parts of the resin bath, 75 parts of the millbase, and 6.5 parts of triethylamine, 811.5 parts of ion-exchanged water was gradually added to form an aqueous electrodeposition coating dispersion 1.
Prepare 000 parts.

The coating film obtained in the same manner as in Example 1 had a tear pencil hardness of 4B or less, and a peeling width of cellophane tape on one side of 8 mm or more after 100 hours of salt water spray resistance test.

Comparative Example 2 In a N,substituted reaction vessel, 366 parts of linseed oil fatty acids are heated to 180°C. Epoxy resin (Ebikuron 40
50) Add 95 parts and 0.1 part of catalyst dimethylhensylamine, raise the humidity to 180'C again, and keep at 180'C for 1 hour. After the temperature was lowered to 150°C, 321 parts of phthalic anhydride and 218 parts of pentaerythrol were added, and the mixture was gradually heated to 321 parts.
The temperature is raised to 190°C over time. The condensation reaction was carried out while maintaining the temperature at 190°C, and when the acid value reached 70 and the Cardner viscosity of the 6096 butyl cellosolve resin solution reached W,
The temperature is quickly lowered to 80°C, and about 400 parts of isopropyl alcohol is added to prepare a resin solution containing 70% resin solids.

An aqueous electrodeposition paint dispersion was prepared in the same manner as in Comparative Example 1, and rough electrodeposition coating was performed. The resulting coating film had a frayed spearhead hardness of F-H, and after a salt water rfQ fog test test of 100, the tape peeling width was about 501 m on one side.

EXAMPLE 3 In an N8-substituted reaction vessel, 422 parts of linseed oil fatty acid and 43 parts of dehydrated castor oil fatty acid are heated to 140°C. Epoxy resin (Dainippon Ink K.

After adding 513 parts of Epicron 1050), the system was further heated, and when the system was homogenized and the temperature became 3 nm, 0.5 part of dimethyl silamine was added, and the temperature was further heated at 180'C.
and keep at 180"C for 1 hour.

After the temperature was lowered to 120°C, 5 parts of anhydrous maleic alcohol was added, and the mixture was gradually heated to 230°C over 3 hours.

The condensation reaction was carried out while maintaining the temperature at 230°C, and when the acid value reached 6 and the Gardner viscosity of the 60% butyl cellosolve solution of the resin reached V, the temperature was quickly lowered to 80'C and about 500 parts of butyl cellosolve and about 500 parts of ethyl cellosolve were added. Add 500 parts to prepare an epoxy ester intermediate resin solution having a resin non-volatile content of 50%.

1200 parts of this epoxy ester intermediate resin solution was mixed with N
Heat to 80° C. in a 2-substituted reaction vessel. To this resin solution, 160 parts of styrene, 40 parts of lauryl methacrylate, 24 parts of methyl methacrylate, 8 parts of butyl acrylate, 168 parts of dimethylaminoethyl methacrylate, and a peroxide polymerization initiator (NOF, Ni, Perbutyl 0) 40 parts of the mixture are added dropwise over a period of 3 hours. The mixture was further maintained at 80° C. for 6 hours to complete the graft polymerization.

This kraft polymer resin solution has a resin non-volatile part of 62.5.
%, Gardner viscosity is X, resin non-volatile part amine value is 60
It is.

160 parts of this graft polymer resin bath A, 100 parts of titanium dioxide (Teikoku Kako, Ni, JR600E), 20 parts of butylceronlube, and 20 parts of ethyl cellosolve are kneaded in a sand mill to prepare a mill base with NV of 67% and PWC of 50%.

120 parts of the above graft polymerization resin solution, this mill base 7
801 parts of ion-exchanged water were gradually added to a mixture consisting of 5 parts and 4 parts of acetic acid while stirring to prepare 1000 parts of an aqueous electrodeposition coating dispersion.

The aqueous dispersion had a breakdown voltage of 300 V and a pH of 6°0, and was heated at 200 V for 2 minutes on a mild steel plate cathode treated with iron phosphate.
A smooth, hard and flexible coating film with a thickness of 20 μm was obtained by electrodepositing the entire sample and drying at 80° C. for 15 minutes. This coating film had a wearable pencil hardness of H, and the cellophane peeling width after 200 hours of salt water frost resistance test was within 3 mm on one side.

Example 4 Linseed oil fatty acid 470
50 parts of castor oil fatty acid are heated to 140'C. Epoxy resin (Dainippon Ink K.

After adding 450 parts of Ebicuron 1050), the system was further heated, and when the system became homogeneous and transparent, 0.5 part of dimethylpencylamine was added, and the temperature was further raised to 180'C and heated for 1 hour. Keep at ℃.

After lowering the temperature to 120°C, 10 parts of maleic anhydride and 20 parts of phthalic anhydride were added, and gradually heated to 23°C over 3 hours.
Raise the temperature to 0°C. The condensation reaction was carried out while maintaining the temperature at 230°C, and when the acid value reached 15 and the Cardner viscosity of the 60% butyl cellosolve solution of the resin reached N, the temperature was quickly lowered to 80°C, and about 500 parts of butyl cellosolve and about 500 parts of ethyl cellosolve were added. Add 500 parts to prepare an epoxy ester intermediate resin solution having a resin non-volatile content of 50%.

Add 1200 parts of this epoxy ester intermediate resin solution,
Heat to 80° C. in a reaction vessel purged with N2. To this resin solution, 136 parts of styrene, 46 parts of methyl methacrylate, 168 parts of dimethylaminoethyl methacrylate
A mixture of 1 part and 25 parts of a peroxide polymerization initiator (NOF, Perbutyl O) was added dropwise over a period of 3 hours.

The mixture was further maintained at 80° C. for 6 hours to complete the graft polymerization.

This graft polymerization resin solution has a resin nonvolatile part of 62°5.
%, Gardner viscosity x 1 resin non-volatile part amine value 60
It is.

160 parts of this graft polymerization resin solution, 100 parts of di-sunvalent titanium (JR600E, manufactured by Teikoku Kako), 20 parts of butyl cellosolve and 20 parts of ethyl cellosolve are kneaded in a sand mill to prepare a millhose containing 67% N and 50% PwC.

120 parts of the above craft chassis resin solution, this mill base 7
5 parts of acetic acid and 4 parts of acetic acid, gradually added 801 parts of ion-exchanged water to prepare 1000 parts of an aqueous electric field paint dispersion.

The breakdown voltage of the aqueous dispersion is 300 V, l) H is 6°O
By electrodepositing on a phosphate-treated mild steel plate cathode at 200 V for 2 minutes and drying at 80° C. for 15 minutes, a smooth hard flexible coating film with a thickness of 20 μm was obtained. This coating has a hardness of H and a salt spray resistance test of 15.
The cellophane tape peeling width after 0 hours was within 3111n1 on one side.

Comparison Example 3 In a reaction vessel substituted with N2, 363 parts of linseed oil fatty acid, 371 parts of phthalic anhydride, and 80 parts of trimethylolpropane were added.
Prepare 186 parts of Pentaerythri and 1 Hele, 3
Gradually heat to 190°C over time. The condensation reaction was continued while maintaining the temperature at 190°C, and when the acid value reached 55 and the cardner viscosity of the 60% butyl cellosolve solution of the resin reached R, the temperature was quickly lowered to 80°C and about 400 parts of isopropyl alcohol was added. , a resin solution containing 70% resin solids is prepared.

143 parts of the resin bath A, titanium dioxide (to Teikoku Kako, to
, JR600E) and 57 parts of isopropyl alcohol were kneaded in a sand mill to give NV67% and PWC5.
Prepare 0% Milhose.

While stirring a mixture of 107 parts of the resin solution, 75 parts of the millbase, and 6.5 parts of triethylamine, 811.5 parts of ion-exchanged water was gradually added to the mixture, and N coating aqueous dispersion 1 was prepared.
Prepare 000 parts.

The coating film obtained in the same manner as in Example 3 had a tear pencil hardness of 4B or less and a salt water spray test [~100
The peeling width of the cellophane tape after a period of time was greater than or equal to Bn+m on one side.

Comparative Example 4 In a reaction vessel purged with N2, 366 parts of linseed oil fatty acids are heated to 180°C. Epoxy resin Ebikuron 4
050) 95 parts and 0.1 part of catalyst dimethylbenzylamine were added and the temperature was raised to 180°C again.jffi L/, 180°C
Keep for 1 hour. After cooling down to 150℃, phthalic anhydride 321
Part J5 218 parts of 1-1 pentaerythritol was added and gradually heated to 190° C. over 3 hours. 190
Proceed with the condensation reaction while keeping the temperature at °C until the acid value reaches 70. Resin 6
When the Cardner viscosity of the 0% phtyl cellosolve solution reaches W, the temperature is immediately lowered to 80'C, and about 400 parts of isopropyl alcohol is added to prepare a resin solution with a resin solid content of 70%.

An aqueous electrodeposition paint dispersion was prepared in the same manner as in Comparative Example 3, and rough electrodeposition coating was performed. The obtained coating film had a pencil hardness of F-H with wear and tear, and the cellophane peeling width after 100 salt water spray tests was unilaterally 5n+n+.

Claims (1)

[Claims] 30-60% by weight of epoxy resin and 130-60% of unsaturated fat
60% by weight, and if necessary, a monovalent to trivalent organic acid and a monovalent to tetravalent alcohol are added or condensed within a range where the total amount is 70% by weight or less. The molecular weight is 500 to 5000, and the weight average molecular weight is 1
000 to 20,000, an acid value of O to 50, and a hydroxyl value of O to 100.
The number average molecular Q obtained by graph l-polymerizing 60 to 20% by weight of an ethylenically unsaturated monomer containing at least 3FFFF1% of acrylic acid and/or methacrylic acid to 80% of the total weight is 1000 to 600°. A product (A-1) having an average molecular weight Mlfi of 5,000 to 200,000 and an acid value of 25 to 100 is mixed with amines <B
) or neutralized with alkali (C) and dispersed or dissolved in water, or epoxy resin 30~
60% by weight and 30 to 60% by weight of unsaturated fatty acids, and if necessary, monovalent to trivalent W4 acids and monovalent to trivalent W4 acids.
The number average molecular weight obtained by adding or condensing tetrahydric alcohol within the range of 70% by weight or less in total is 50%.
0-5000, weight average molecular weight 1000-2000
0, an acid value of 0 to 20, and a hydroxyl value of 40 to 80% by weight of an epoxy resin ester intermediate of 0 to 100,
An ethylenically unsaturated monomer containing 5% by weight of at least one selected from the group consisting of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate-1, diethylaminoethyl acrylate-1 and diethylaminoethyl methacrylate. A product (A-2) having a number average molecular weight of 1,000 to 6,000, a weight average molecular weight of 5,000 to 200,000, and an amine value of 30 to 100 obtained by polymerizing 20% by weight of Graph 1 to acids <
A resin composition for low-temperature drying paints, which is neutralized by D) and dispersed or dissolved in water.