Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines

Definitions

• the present invention relates to a water-dispersible self-curable resin composition, and more particularly, to a method of using a water-dispersible self-curable resin composition as a cathode having an object to be coated as a cathode.
• Background technology relating to low-temperature-curable self-curing resin compositions suitable for electrodeposition coating
• Background TechnologyCathion electrodeposition coating is compared to conventional anion electrodeposition coating. Due to the insufficient protection of the substrates, their use has been increasing in recent years, especially in the field of automotive painting, and the resin compositions used in such electrodeposition coatings are also being used.
• various types have been proposed, those actually used are, for example, proposed in Japanese Patent Application Laid-Open Nos.
• Such a pro-clip-shape polysonet is a hardening type
• WIPO Cationic electrodeposition paints have essential problems such as a higher baking temperature and a larger amount of generation than conventional anion electrodeposition paints.
• DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have obtained polyamine resin having an amino group and / or an imino group. By introducing an amine group into the pendant, the following equation can be obtained.
• the amine group is thermally decomposed and rearranged at a low temperature (120 or more, preferably 140 to 160) to demineralize the third amine and form an isocyanate group.
• the resulting isocyanate groups react with hydroxyl groups and / or amino or imino groups in the resin to form a three-dimensional structure, which is infusible.
• the stable ionizable resin can be obtained.
• the aqueous dispersion was found to be usable for cation electrodeposition coating, and the present invention was completed.
• the present invention provides a polyamine resin (solid content) having an amino group and / or an imino group of 65 to 95% by weight.
• the present invention relates to a curable resin composition.
• Examples of the polyamine resin having an amino group and / or an imino group (hereinafter, simply referred to as a polyamine resin) used in the present invention include, for example, polyamine resin.
• Polyepoxides are compounds having one or more 1,2 epoxy functional groups.
• polyphenols of polyolefins are used. It is possible to remove the air solely in the presence of the altitude by means of epichlorohydrin or dichlorohydrin. This can be obtained by making into a tellurium).
• the poebol for example, bisphenol A [2,2-bis (4-hydroxyphenol)] ,. ), 1, 1—vis (4—hydroxy) ethane, 2—methyl—1, 1, 1—vis (4—hydroxy) ) Prono. , 1,2-vis (4—Hydroxy — 3—t—Butinolef) And bis (2-hydroxynaphthyl) methane and 1,5-dihydroxynaphthalen.
• oxyalkylated adducts for example, polyphenol adducts with ethylene oxide, propylene oxide adducts, etc.
• Novolac type vinyl resin for example, polyphenol adducts with ethylene oxide, propylene oxide adducts, etc.
• WIPO Polyphenol resins similar to these are used.
• Other polyepoxides include, for example, epoxy resin and polycarbonate resin, glycidyl.
• Polyepoxides may be further reacted to extend the chain and increase their molecular weight.
• a chain extender an active hydrogen-containing compound reactive with an epoxy functional group, for example, a hydroxyl group, an amino group, an imino group, a thiol group, or a carboxyl group
• an epoxy functional group for example, a hydroxyl group, an amino group, an imino group, a thiol group, or a carboxyl group
• an active hydrogen-containing compound reactive with an epoxy functional group for example, a hydroxyl group, an amino group, an imino group, a thiol group, or a carboxyl group
• a sil group eg, glycol, diamin, polyether polyol, dimer acid, hydantoin, bi Phenol A, polyaminoamide, amino acid, etc.
• Polypoxide reacts with amines (polyamine containing primary amine, ketimin-blocky amide amino group) to produce a polyamine resin.
• the first amine may be a monoamine (for example, propylamine, butyramine, amilamine, 2—ethylhexylamine). , Monoethanol amine, etc.).
• a monoamine for example, propylamine, butyramine, amilamine, 2—ethylhexylamine. , Monoethanol amine, etc.
• the first amine reacts with the epoxy group to form a second amine, which is useful for the subsequent reaction in the form of a michael.
• polyamine containing ketimin-blocked amino group are polyamines (for example, diethylene rim, dipropylene rim, dibutyl rim, triethylamine Amino groups in amino acids) react with ketones (eg, acetate, methylethylketone, methylisobutylketone, etc.). Some of them have been converted to ketimine.
• polyamines for example, diethylene rim, dipropylene rim, dibutyl rim, triethylamine Amino groups in amino acids
• ketones eg, acetate, methylethylketone, methylisobutylketone, etc.
• the ketimin-blocked amino-containing polyamine reacts with the epoxy group, and after addition of water, the ketimine group is decomposed, followed by a subsequent reaction. An amino group useful for the quenching reaction is formed.
• Polyamine resin is produced by a usual method, and the basic process example is as follows.
• a part or all of the polyepoxide is charged into a reaction vessel and mixed under an inert gas stream to obtain a uniform liquid. If necessary at this stage, heating, addition of a suitable organic solvent, preliminary reaction of polyepoxide with other components (for example, bisphenol A). It can be performed. Then, while stirring the above-mentioned homogeneous liquid substance at an appropriate temperature under an inert gas stream, polyamines are added. The addition of polyamines is carried out by a method such as charging the whole amount, charging in parts, charging in drops, etc., and changing the type of the polyamines according to the timing of the process. You can do it.
• an ethylenically unsaturated compound having an amiimide group is represented by the following general formula: ⁇
• ⁇ is 1 or 2; R, is a monovalent or divalent ethylenic unsaturated force; a residue of ruponic acid; R 2 , R 3 , and 4 are carbon atoms, respectively) (Representing an alkyl group or a hydroxyl group represented by the formulas 1 to 6), specifically, for example, 1,1,1-trimethyzo.
• a polyamine resin solution is charged into a reaction vessel, and stirred at an appropriate temperature, preferably 70 to 120: under an inert gas stream while stirring.
• An ethylenically unsaturated compound having a chloride group is added.
• the addition of the ethylenically unsaturated compound having an amine group can be carried out by a method such as charging the whole amount, charging the mixture, and charging dropwise. At this stage, heating, cooling, reflux of volatile components, addition of organic solvent, etc. can be performed.
• the reaction is continued at an appropriate temperature and for an appropriate time, if necessary, and then, if necessary, dilution and filtration with an organic solvent.
• a resinous solution which is a Michael-type addition reaction product
• the mixing ratio of the polyamine resin and the ethylenically unsaturated compound having an amide imido group Is preferably 65 to 95% by weight of a polyamine resin (solid content) and 35 to 5% by weight of an ethylenically unsaturated compound having an amiimide group. No. If the amount of the ethylenically unsaturated compound having an amide group is less than 5% by weight, the composition will not be curable at low temperatures, and the physical properties of the resulting coating film will be insufficient. %, Problems may occur in the electrodeposition properties of the resulting aqueous dispersion and the physical properties of the resulting coating film.
• the product of the addition reaction in the form of a microphone is neutralized with an acid by neutralizing the amide group in the reaction product with an acid.
• the acid is an organic acid or an inorganic acid, for example, formic acid, acetic acid, lactic acid, phosphoric acid and the like.
• the proportion of the fourth ammonium salt group, the structure and molecular weight of the various components in the product of the addition reaction in the form of the monomer, and the dispersion stability when the addition reaction product is mixed with water, the electrodeposition must be mutually adjusted in consideration of properties, cross-linking curability, coating film performance, etc. .
• An anode and a cathode are immersed in an aqueous dispersion (ie, cation electrodeposition coating) of a microcellular addition reaction product, and a voltage is applied between both electrodes.
• the electrodepositable resin is deposited on the surface of the cathode as a coating film. .
• Such cation electrodeposition techniques are well known in the art, but the deposited coatings are washed with water after being lifted from the cation electrodeposition paint bath. Must be insensitive to moisture so as not to drop.
• the self-curing resin composition of the present invention basically comprises a product of the addition reaction of a monomer type and an acid which is a neutralizing agent.
• Plasticizers, surfactants, and pigments used in electrodeposition paints for example, titanium dioxide, carbon black, talc, polyol, silica
• Lead silicate for example, titanium dioxide, carbon black, talc, polyol, silica
• Coloring pigments extender pigments, anti-pigment pigments, etc., organic solvents (for example, isopropyl alcohol, butyral) Afreco, Ifre, Etfreso Roso Flep, Buti Zorese Loso Lev,
• OMPI WIPO It is a mixture of hydrophilic and semi-hydrophilic substances such as diacetone alcohol) and water, etc., as appropriate, and it is generally used in the production of paints.
• Mixers and dispersers such as mixers, sand-grind minoles, attritors, roll mills, etc., uniformly mix and disperse the resin content.
• a cathodic electrodeposition coating bath is obtained which is an aqueous dispersion having a solid content of about 10 to 25% by weight.
• electrodeposition coating is performed in the same manner as ordinary cation electrodeposition coating, using the conductive object as the negative electrode, and after washing with water, 130 to 160 A cured film can be obtained by baking for 20 to 40 minutes.
• the baking condition is 150 to 180, which is the conventional baking condition of the blocked polyisocyanate type, which is about 20 times lower than that of 20 to 40 minutes.
• the cured coating film obtained as described above has pencil hardness, adhesiveness, impact resistance, flexibility, corrosion resistance, water resistance, acetate rubbing resistance, acid resistance, etc. It is very good.
• aqueous dispersion was transferred to a vinyl chloride electrodeposition tank, the temperature was adjusted to 30 and the object to be coated (zinc phosphate treated glow plate) was connected to the cathode.
• a stainless steel plate was used as the anode, and a DC current of 180 volts was applied for 2 minutes under stirring to perform cation electrodeposition coating.
• cation electrodeposition coating was performed in the same manner as in Example 1 (however, the voltage was 120 volts). After washing with water, it was baked at 140 ° C. for 25 minutes to obtain a cured coating film having a dry film thickness of 20 ⁇ m.
• Table 1 shows the test results of the obtained cured coating films.
• Example 2 Using the resulting aqueous dispersion, -electrodeposition coating was carried out in the same manner as in Example 1 (except that the voltage was 140 volts). After rinsing with water, bake at 150 for 25 minutes to obtain a cured coating film with a dry film thickness of 20 ⁇ m.
• Table 1 shows the test results of the obtained cured coating films.
• aqueous dispersion having a solid content of 15%.
• cation electrodeposition was performed in the same manner as in Example 1 (however, the voltage was 140 volts). After washing with water, it was baked at 140 ° C. for 25 minutes to obtain a cured coating film having a dry film thickness of 20 ⁇ m.
• Table 1 shows the test results of the obtained cured coating films.
• 2,4-trench solution in a reaction vessel under nitrogen gas flow Charge 652 parts of hexane and 50 parts of methyl isobutyl ketone, stir at 40 with stirring, and drop 536 parts of 2-ethylhexanol over about 5 hours.
• a xanofure half-blocked product was obtained from the 2-, 2- and 4-trylene sociate.
• cation electrodeposition coating was performed in the same manner as in Example 1 (however, the voltage was 160 volts). After washing with water, it was baked at 150 at 25 minutes to obtain a cured coating film having a dry film thickness of 20 ⁇ m.
• Table 1 shows the test results of the obtained cured coating films.
• the coating film after electrodeposition coating was subjected to a test for the amount of generation, and the results are shown in Table 1.
• the amount of generation was calculated by the following equation, where w is the weight loss and w 2 is the weight increase of the rickshaw. '
• Examples 1 to 4 of the present invention are superior to Comparative Example 1 in pencil hardness, impact resistance, flexibility, and acetate rubbing resistance. It can be seen that the generation amount was small.
• Example 3 144 parts of the above-mentioned pigment paste was added to 1000 parts of the aqueous dispersion having a solid content of 15% obtained in Example 3 to obtain a coating composition having a solid content of 18.1%.
• Example 2 Using the obtained coating composition, cation electrodeposition coating was performed in the same manner as in Example 1 (however, the voltage was 240 volts, and the current was applied for 3 minutes). After washing with water, the film was baked at 150 ° C for 25 minutes to obtain a cured film having a dry film thickness of 20 microns.
• Table 2 shows the test results of the obtained cured coating films.
• Example 2 Using the obtained coating composition, cation electrodeposition coating was performed in the same manner as in Example 1 (however, the voltage was 220 volts, and the current was applied for 3 minutes). After washing with water, it was baked at 150 t: for 25 minutes to obtain a cured coating film having a dry film thickness of 20 ⁇ m.
• Table 2 shows the test results of the obtained cured coating films.
• Example 4 of the present invention was excellent in pencil hardness, impact resistance, flexibility, and corrosion resistance, as compared with Comparative Example 2.
• the present invention is suitable for cation electrodeposition coating using a coating object as a cathode, and has a low-temperature curing property.
• a self-curable resin composition having a cured coating film having excellent pencil hardness, impact resistance, flexibility, and corrosion resistance can be obtained.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Paints Or Removers (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Epoxy Resins (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

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• 1983
  • 1983-09-30 JP JP58180777A patent/JPS6072924A/ja active Granted
• 1984
  • 1984-09-28 US US06/740,837 patent/US4596844A/en not_active Expired - Fee Related
  • 1984-09-28 WO PCT/JP1984/000463 patent/WO1985001506A1/ja not_active Ceased
  • 1984-09-28 EP EP84903658A patent/EP0159363B1/en not_active Expired
  • 1984-09-28 DE DE8484903658T patent/DE3483689D1/de not_active Expired - Lifetime

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