JPH0892427A - Water-based resin composition - Google Patents

Abstract

PURPOSE: To obtain a water-based polyolefin resin composition excellent in, e.g. adhesion to organic substrates, metals, inorganic material, etc., by adding a specified amount of a polyhydrazide compound to a mixture in making a (modified) polyolefin water-based. CONSTITUTION: In making a polylefin (e.g. polyethylene) or a modified polyolefin (e.g. chlorinated polyolefin) water-based by using a surfactant, a basic substance, etc., 0.1-30 pts.wt. polyhydrazide compound is added to 100 pts.wt. (in terms of solid content) polyolefin resin to produce a water-based polyolefin resin composition. Examples of the polyhydrazide compounds used include carbohydrazide, malonic dihydrazide and terephthalic dihydrazide. A coating material, an adhesive or other product containing this composition as the film- forming material can form a coating film which is tack-free after being dried and is excellent in gasohol resistance, water resistance, etc., and is excellent in safety because it is substantially free from any organic solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous resin composition, which can be mainly used as a paint, a primer, an ink, an adhesive, a sealing agent, a binder and a surface treatment agent. The resin composition of the present invention is a water-based acrylic, other water-based resin such as polyester, depending on the application,
Since it can be used in combination with a water-soluble resin, it can also be used as a modifier of a film-forming material or an adhesiveness-imparting agent for a non-polar substrate.

Particularly, it is possible to form a coating film or an adhesive layer having excellent adhesion, flexibility, water resistance, gasoline resistance and gas all resistance to a polyolefin substrate having a non-polar surface and having a well-balanced performance. . Therefore, it is useful as a water-based resin for paints, primers, inks, sealing agents, adhesives for plastic parts materials for automobiles, polyolefin films, polyolefin-based moldings and the like. Further, it is also applied as a surface treatment agent or binder for fibrous or particulate base materials.

[0003]

2. Description of the Related Art Conventionally, an aqueous resin (US Pat. No. 340845) obtained by adding a polyol, a surfactant, and a basic substance to a chlorinated polyolefin to make it aqueous, and acid-modified with an unsaturated carboxylic acid or an acid anhydride. A water-based resin (Japanese Patent Application No. 01-323506) obtained by making a chlorinated polyolefin aqueous by using a surfactant and a basic substance has been filed.

Further, as an attempt to produce an aqueous dispersion of chlorinated polyolefin, for example, Japanese Patent Laid-Open No. 15377/1989 was used.
No. 8, JP-A-1-256556, and JP-A-2-
It is disclosed in Japanese Patent No. 284973. Attempts have also been made to produce an aqueous dispersion of a modified polyolefin, for example, JP-A-59-47244 and JP-A-2.
-286724, Japanese Patent Application No. 05-280127,
Japanese Patent Application No. 04-258935, Japanese Patent Application No. 04-25893
No. 6, Japanese Patent Application No. 04-258937, Japanese Patent Application No. 05-64
No. 874 and the like.

On the other hand, examples of application of the hydrazine derivative to an aqueous resin composition include coating compositions for plastic films (JP-A-2-11674) and room temperature cross-linkable cationic emulsion compositions (JP-A-2-155956). , A resin composition for waterborne dry-drying cross-linking paint (JP-A-4-37267)
No. 4, etc.), but no one has found industrial utility by combining with a polyolefin resin. Further, there is no description about the effect of adding the hydrazine derivative to the aqueous polyolefin resin composition.

[0006]

In the conventional aqueous polyolefin resin composition, since a polyolefin or a modified polyolefin is used as a raw material, a large amount of a surfactant, a polyol or the like hydrophilic component which is liquid at room temperature in the process of hydration. Or a polyolefin resin having a relatively low molecular weight was used as a raw material in order to blend the composition or to reduce the melt viscosity during phase inversion emulsification. For this reason, it is often seen that a tack is left on the surface of the base material after coating the base material with the aqueous resin composition and drying, which causes adhesion of dust to the base material after drying, difficulty in handling, and topcoating. It has been a cause of various problems such as pigment aggregation. In recent years, particularly in automobile coatings, gas resistance has become a problem in place of gasoline resistance of the coating film.

As described above, other problems such as tack and gas-all resistance which remain on the surface of the substrate after drying, which have been problems when the conventional polyolefin-based aqueous resin composition is coated or applied on the surface of the substrate, The purpose is to improve while balancing the film performance (weather resistance, water resistance, etc.). Another object is to make it possible to use the aqueous polyolefin resin composition in fields such as normally dry paints and inks that do not require a baking step.

[0008]

[Means for Solving the Problems] In order to achieve the above object, the present inventors have investigated the application of a polyhydrazide compound to an aqueous polyolefin resin composition. In the use of the aqueous polyolefin resin composition, in the drying step performed under the conditions of room temperature to 100 ° C. or higher,
It has been found that the addition effect of the polyhydrazide compound can not only improve the tack remaining on the film on the substrate after the drying step but also improve the film forming property. Furthermore, they have found that the coating film formed by coating and baking the top coat after the drying treatment can improve gasoline resistance and gas all resistance without impairing various properties such as water resistance and adhesion.

That is, the gist of the present invention is: (1) In preparing an aqueous resin composition containing a polyolefin or a modified polyolefin, the polyhydrazide compound is added in an amount of 0.1 to 100 parts by weight of the polyolefin resin solid content.
It is an aqueous polyolefin resin composition characterized by being mixed in an amount of 30 parts by weight.

Further, (2) in preparing an aqueous resin composition containing a polyolefin or a modified polyolefin,
The aqueous resin composition of the above (1) using an aliphatic dicarboxylic acid dihydrazide as the polyhydrazide compound is useful.

Further, (3) the modified polyolefin has an average molecular weight of 1,000 to 500,000 and is characterized by chlorinating a polyolefin resin, and has a chlorine content of 5 to 70.
The above, where it is a chlorinated modified polyolefin of weight%
The aqueous resin compositions (1) and (2) have particularly excellent adhesion to non-polar substrates, and also have excellent corrosion resistance to metal substrates.

(4) An average molecular weight of 100, characterized in that the polyolefin resin is modified with a carboxylic acid having a radical-polymerizable double bond or an anhydride thereof.
The aqueous resin composition according to the above (1) or (2), wherein an acid-modified polyolefin having an acid modification degree of 0 to 500000 and an acid modification degree of 1 to 20% by weight is used as the modified polyolefin, has excellent adhesion to a top coat and also has weather resistance. Excel.

Further, (5) the polyolefin resin is modified by radical polymerization with a (meth) acrylic monomer or a (meth) acrylic oligomer, and has an average molecular weight of 1,000 to 500,000 and a modification degree of 5
The water-based resin composition described in (1) and (2) above, which uses up to 800% by weight of an acrylic-modified polyolefin as a modified polyolefin, has not only excellent compatibility with other acrylic resins but also excellent pigment dispersibility. The coating film thus formed has good weather resistance and surface characteristics.

(6) In the modified polyolefin containing one or more hydroxyl or carboxyl groups in the molecule, a compound having two or more isocyanate groups has a molar ratio of isocyanate groups to hydroxyl or carboxyl groups of 1: 1.2.
It is urethane-modified by reacting a polyhydroxy compound at a molar ratio of residual isocyanate groups to hydroxyl groups of 1 to 1.1 to 4 with respect to the reaction product reacted at a ratio of to 3.5. Characterized by an average molecular weight of 1
The water-based resin composition according to the above (1) or (2), which uses a urethane-modified polyolefin having a modification degree of 5 to 200% by weight of 000 to 500000 as a modified polyolefin, has weather resistance,
Excellent water resistance.

Further, (7) in preparing an aqueous resin composition containing a polyolefin or a modified polyolefin, a polycarbonyl compound having two or more ketone groups in the molecule is added to the hydrazino group in the polyhydrazide compound to form a carbonyl group. The aqueous resin composition according to the above (1) to (5), characterized in that it is used in a ratio of 1: 0.1 to 20, is a room temperature dry type composition having adhesion to a non-polar substrate such as polyolefin. Used as.

(8) In preparing an aqueous resin composition containing a polyolefin or a modified polyolefin, a crosslinkable component having two or more functional groups that react with active hydrogen in the molecule, relative to 100 parts by weight of the polyolefin resin solid content. 1 to
The above (1) to (7) characterized by adding 800 parts by weight
The water-based resin composition described above is excellent in adhesion to a substrate and water resistance.

(9) The aqueous resin composition according to the above (8), which is characterized in that a blocked isocyanate compound is used as a crosslinkable component, not only forms a film excellent in adhesion and water resistance, but also the aqueous resin itself. It has excellent storage stability.

(10) The above characterized in that an aliphatic or aromatic polyglycidyl compound is used as the crosslinkable component.
(8) The water-based resin composition described is not only excellent in water resistance and chemical resistance, but also excellent in cross-linking reactivity, and it is possible to carry out a cross-linking reaction in a wide temperature range by adding a reaction catalyst or the like. It is possible to prepare a product that meets the use conditions such as a paint and an adhesive produced by using the product.

(11) The aqueous resin composition according to the above (8), which is characterized in that an amino resin is used as a crosslinkable component, is excellent in interlayer adhesion to a melamine-based top coating composition and is also excellent in water resistance.

(12) The water-based resin composition according to the above (1) to (11), which comprises 5 to 200 parts by weight of an aqueous urethane resin based on 100 parts by weight of a polyolefin resin. And excellent film forming property.

(13) A coating composition, a primer, an ink film-forming product such as an ink, a sealing agent, an adhesive, a binder and a surface treatment agent containing the resin composition described in (1) to (12) are industrially available. It is valid.

The present invention will be described in detail below. The polyhydrazide compound used in the present invention is carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutamic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, undecanoic acid dihydrazide, and dihydrazide dihydrate. Di (tri) carboxylic acid di (tri) hydroxides such as acid dihydrazide, phthalic acid dihydrazide, itaconic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, glycolic acid dihydrazide, pentane-1,3,5-tricarboxylic acid (tri) hydrazide. ) Hydrazides, ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine, hexylene-1,6-dihydrazine, etc. Aliphatic di-hydrazines and the like. Polyhydrazides other than the above polyhydrazides may be those which are themselves water-soluble, have self-emulsifying properties, or are dispersed in water by some method. The polyhydrazide compound is added in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the solid content of the polyolefin resin. If it is less than 0.1 part, no improvement in tackiness is observed, and if it exceeds 30 parts, the adhesion when the top coat is applied decreases.

As the polyolefin and modified polyolefin used as the hydration raw material in the present invention, those known as the raw material resin of the polyolefin hydration resin composition can be used. For example, the polyolefin used in the present invention may be a homopolymer of ethylene or propylene, or ethylene or propylene and other comonomers such as butene-1, pentene-1, hexene-1, heptene-1, octene-1. A random copolymer or block copolymer with an α-olefin comonomer having 2 or more carbon atoms, preferably 2 to 6, or two or more kinds of these comonomers is used. Preferably, the average molecular weight of the polyolefin is usually from 1000 to 5
It is 00000. The product obtained by a known method may be used, but a product once synthesized to have a high molecular weight and degraded by radicals, oxygen, or heat is also used.

The modified polyolefin means chlorinated polyolefin, acid-modified polyolefin, acrylic-modified polyolefin, urethane-modified polyolefin or chlorinated modification,
Illustrative are modified polyolefins that have been modified with at least two of acid modification, acrylic modification, and urethane modification.

The chlorinated polyolefin is a polyolefin obtained by chlorinating the above polyolefin by a known method.
The chlorine content is preferably 5 to 70%. More preferably, it is 20 to 68%. If it is less than 5%, the effect of chlorine introduction does not appear. If you use more than 70%,
The proportion of the polyolefin component decreases and the adhesiveness decreases.

The acid-modified polyolefin is a polyolefin characterized by being modified with a carboxylic acid having a radical-polymerizable double bond or an anhydride thereof. For example, a polyolefin obtained by modifying a polyolefin with an α, β-unsaturated carboxylic acid or an acid anhydride thereof by a graft reaction is exemplified. In addition, a polyolefin resin that is water-modified by reacting a polyolefin-based resin such as an acid-modified polyolefin with a reactive surfactant with a radical reaction initiator is also used as a water-imparting raw material. Examples of the carboxylic acid having a radical-polymerizable double bond or the anhydride thereof include α, β-unsaturated carboxylic acid and the acid anhydride thereof.

Α, β used for modification of polyolefin
-As the unsaturated carboxylic acid or its acid anhydride, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid,
Examples thereof include allyl succinic acid, mesaconic acid, aconitic acid, and their acid anhydrides. The amount of the α, β-unsaturated carboxylic acid or its acid anhydride graft-copolymerized is preferably 1 to 20% by weight, and if it is 1% by weight or less, the adhesion to the top coating composition is lowered and the dispersibility in water is deteriorated. . If it is 20% by weight or more, the grafting efficiency is poor and it is uneconomical. It is particularly preferably 2 to 15% by weight.

The acid modification degree as used herein means the weight% of the acid component contained in the modified polyolefin. That is,
The graft amount of the acid component is always a value below the acid modification degree.
The acid-modified resin has an average molecular weight of 1,000 to 50.
0000 is used. Preferably 3000-3
It is 00000. If it is less than 1000, the cohesive force will be insufficient and the adhesion to the polyolefin resin will be poor.
When it is 000 or more, the operability when dispersed in water is deteriorated, which is not preferable. In order to adjust the molecular weight to this range, it is possible to select the molecular weight of the raw material or the conditions for carrying out the graft reaction, or it is also possible to carry out the graft reaction after once lowering the molecular weight of the raw material. is there. Further, radical generators and polyolefins degraded by heat are also used.

The method of graft-copolymerizing α, β-unsaturated dicarboxylic acid or its acid anhydride with polyolefin may be carried out by a known method. In particular, the polyolefin is heated and melted at a temperature higher than the melting point thereof in the presence of a radical generator. The graft copolymerization is preferably carried out by the method described in 1.

The acrylic modified polyolefin is obtained by copolymerizing an acrylic or methacrylic (hereinafter referred to as (meth) acrylic) monomer or a (meth) acrylic oligomer with a polyolefin-based raw material resin by some method. It is a modified resin. Here, the degree of acrylic modification means the weight% of the acrylic component contained in the modified polyolefin.

The acrylic monomers include (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polycaprolactone-modified (meth) Acrylate, glycidyl (meth) acrylate,
Examples include allyl glycidyl ether, acrylamide, N-methylol acrylamide, acrylonitrile and the like.

Although these monomers can be graft-copolymerized with the acid-modified polyolefin by a radical reaction, 2-hydroxyethyl acrylate,
In the case of a reactive monomer having both a radical-reactive double bond and a hydroxyl group such as 2-hydroxymethacrylate, the hydroxyl group is used to add to the acid-modified polyolefin solution in advance before the radical reaction to perform graft copolymerization by an esterification reaction. You can leave it. In this case, the reactive surfactant or another reactive monomer can be graft-copolymerized by utilizing the radical-reactive double bond that did not participate in the esterification reaction.

Known radical reaction graft initiators may be used, and organic peroxides are particularly preferred. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 and di-t-butylperoxide. Oxides, t-butyl peroxyisopropyl carbonate, t-butyl hydroperoxide, t-butyl peroxybenzoate, cumene hydroperoxide and the like can be mentioned, which are selected and used according to the reaction temperature. Azo-based initiators such as azobisisobutyronitrile and redox-based initiators can also be used. Also, they may be used in combination.

The amount of (meth) acrylic monomers or (meth) acrylic oligomer added is 5 to 800 parts based on 100 parts of the polyolefin resin raw material. If the amount is less than 5 parts, problems such as a decrease in water-conversion efficiency of the resin and poor compatibility with the pigment occur. On the other hand, if it exceeds 800 parts, a problem arises in the adhesiveness to the base material such as polyolefin.

The urethane-modified polyolefin is a polyolefin having a hydroxyl group or a carboxyl group introduced by some method, and a compound having two or more isocyanate groups has a molar ratio of the isocyanate group to the hydroxyl group or the carboxyl group of 1: 1.2 to 3 A polyolefin obtained by further reacting the reaction product reacted at a ratio of 0.5 with a polyhydroxy compound at a molar ratio of residual isocyanate groups and hydroxyl groups of 1: 1.1 to 4. The polyolefin having a hydroxyl group or a carboxyl group used therein may be one prepared by a known method.

The hydroxyl group can be introduced by grafting a (meth) acrylic monomer or oligomer having a hydroxyl group by radical reaction, or by oxidizing the double bond portion of a polyolefin obtained by copolymerizing a diene component such as polybutadiene with an oxirane. Form a ring and then reduce,
A method of introducing a hydroxyl group is exemplified. Examples of the method for introducing a carboxyl group include the above-mentioned method by acid modification and the method for introducing a carboxyl group by oxidative decomposition of polyolefin.

The isocyanate used for the urethane modification may be a compound having two or more isocyanate groups in one molecule, and examples thereof include aliphatic polyisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and dodecamethylene diisocyanate. Isophorone diisocyanate and its trimer, dicyclohexylmethane diisocyanate and its trimer, cyclohexylene diisocyanate, methylhexylene diisocyanate, and other alicyclic polyisocyanates, xylylene diisocyanate, tetramethyl xylylene diisocyanate, and other aromatic aliphatic poly Isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate Aromatic polyisocyanate and carbodiimide groups based on these polyisocyanates, such as naphthylene diisocyanate, uretdione groups,
A modified product having a uretoimine group, a buret group, or an isocyanurate group is used.

Isocyanate groups are used in a proportion of 1.2 to 3.5 mols per 1 mol of hydroxyl or carboxyl groups. When it is less than 1.2, the number of reaction points with the polyol in the next step decreases, and the reactivity with the polyol deteriorates. When the amount is more than 3.5, a large amount of isocyanate that has not reacted with the polyolefin remains, and a gel substance is generated or phase separation occurs when the polyol is added.

The polyol used next is 2 in the molecule.
Although it is a compound having at least one hydroxyl group, low molecular weight polyols include ethylene glycol, propylene glycol, 1,3 or 1,4-butanediol, 3-methylpentanediol, 1,6-hexanediol, neopentyl glycol, Difunctional glycols such as diethylene glycol, cyclohexylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and sucrose, and aromatic compounds containing two or more hydroxyl groups such as bisphenol A, bisphenol F, bisphenol S, hydroquinone and resorcinol. A compound is illustrated.

Examples of the high molecular weight polyol include polyether polyols (for example, the above low molecular weight polyols, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, aliphatic polyamines such as ethylenediamine, hexamethylenediamine, isophoronediamine and diethylenetriamine, and tolylenediamine. Amine,
For amines such as aromatic diamines such as diphenylmethanediamine, ethylene oxide, propylene oxide,
Butylene oxide, etc. to which one kind of monomer or oligomer of alkylene oxide having 2 to 6 carbon atoms is added, or two or more kinds of random / or block copolymers added), polyester polyol (adipic acid, succinic acid, Uses aliphatic carboxylic acids such as sebacic acid, azelaic acid, fumaric acid, maleic acid, and dimerized linoleic acid, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, and the above low molecular weight polyols or polyether polyols. Polyester polyol having two or more hydroxyl groups in the molecule, polycaprolactone diol, polycarbonate diol, etc.), polybutadiene polyol,
Examples include hydrogenated polybutadiene diol and acrylic polyol. The polyol is used in a ratio of 1.1 to 4 mol of hydroxyl group to 1 mol of the remaining isocyanate group. If it is less than 1.1 mol, the viscosity may increase and gelation may occur. When the amount is 4 mol or more, the amount of unreacted polyol component is large and the water resistance of the coating film is lowered.

The urethane modification degree means the total weight% of the isocyanate component and the polyol component with respect to the polyolefin in the modified urethane.

As a method for making the polyolefin-based raw material resin water-based, a known method can be used. To give an example, a method of adding water to a polyolefin-based raw material resin dissolved in an organic solvent such as toluene or xylene by adding a surfactant, a basic substance, and alcohols if necessary, and replacing the solvent with water while stirring Examples include a method of adding a surfactant, a basic substance, alcohols and the like to the melted raw material resin and gradually adding water to make the raw material resin aqueous by a phase inversion method.

As the basic substance, sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine,
Octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-
2-methyl-1-propanol, morpholine, etc. can be illustrated. Since the degree of hydrophilicity of the resin varies depending on the type of base used, it is necessary to select it appropriately depending on the conditions. The amount of the basic substance used is 0.3 to 1.5 equivalent to the carboxyl group of the acid-modified polyolefin.
The double range is suitable, and preferably 0.5 to 1.2 times.

The reason for adding the monoalcohol or polyol, which is an alcohol, is to increase the affinity of the raw material resin for the water layer, and this effect can reduce the amount of the surfactant used. Furthermore, it is possible to increase the evaporation rate of water at the time of forming a coating film. However,
If alcohol remains in the resin during film formation, it will reduce the water resistance of the coating film, so it is necessary to add an appropriate amount.
It is preferable to add 4 to 60 parts to 100 parts of the raw material resin. If it is less than 4 parts, the effect of addition will not appear, and if it exceeds 60 parts, the water resistance will be significantly lowered. When a large amount of alcohol is contained in the prepared water-based resin composition, the amount of volatile substances contained in the paint or ink produced using the same is large, which is not suitable for the purpose of the present invention.

Examples of the monoalcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, ethylene glycol monoalkyl ether, ethylene glycol monoacetate, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether. Examples thereof include acetate, and examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, glycerin and polyethylene glycol. Among them, a highly hydrophilic polyol is desirable.

Surfactants used in the present invention include reactive surfactants and non-reactive surfactants. The reactive surfactant may be one generally used as a reactive surfactant or a reactive emulsifier, but one having an alkylphenyl group as a hydrophobic group and a polyoxyethylene group as a nonionic hydrophilic group is preferable. For example, JP-A-4-
The alkylpropenylphenol polyethylene oxide adducts, alkyldipropenylphenol polyethylene oxide adducts, and their sulfuric ester salts shown in JP-A-53802 and JP-A-4-50204 are used. Among them, alkyl propenylphenol ethylene oxide 20 mol adduct, the same 30 mol adduct,
The 50 mol adduct, a sulfuric acid ammonium salt of an alkyl propenylphenol polyethylene oxide 10 mol adduct, and a sulfuric acid ammonium salt of a 20 mol adduct are preferable. Further, the 1-alkylphenoxy-3- (2-propenyl) oxypropan-2-ol ethylene oxide adduct or its sulfuric acid ester has excellent resin dispersibility and is polymerized by having an α, β-unsaturated double bond. It is highly preferred and is preferable. These reactive surfactants can be immobilized on the resin by reacting with the water-based resin raw material by a radical reaction initiator by a known method.

The amount of the reactive surfactant used is 0.1 part to 100 parts, preferably 0.1 part to 30 parts, relative to 100 parts of the modified polyolefin which is the water-based raw material resin.
It is a department. The amount to be used can be changed appropriately depending on the amounts of other hydrophilic components such as non-reactive surfactant and alcohol.

When the reactive surfactant is used, the same reaction initiator as that used in the acrylic modification is used. This reactive surfactant may be reacted with the hydration raw material in advance, or may be added during the hydration step.
Further, it may be added at the same time as another acrylic monomer when the acrylic is modified. Known reaction initiators can be used.

The non-reactive surfactant is an anionic type,
Cationic, nonionic, and amphoteric surfactants are used. In addition to nonionic surfactants having a polyalkylene oxide structure, nonionic surfactants include propylene glycol ester, sucrose ester, sorbitan alkyl ester, sorbitan fatty acid ester, polyglycerin ester, fatty acid alkanolamide, fatty acid monoglyceride, alkylamine oxide. Are exemplified. In addition, anionic surfactants such as alkyl sulfate ester salts, alkylphenol sulfonate salts, sulfosuccinic acid ester salts, various carboxylate salts, and phosphoric acid ester salts, higher alkylamines such as laurylamine, stearylamine, and rosinamine Salt, higher alkylamine ethylene oxide adduct, solomine A type cationic surfactant, salpamine A type cationic surfactant, Aybel A type cationic surfactant, imidazoline type cationic surfactant, lauryl dimethyl benzyl ammonium chloride, lauryl trimethyl Quaternary ammonium salt type cationic surfactants such as ammonium chloride, amino acid type amphoteric surfactants such as sodium laurylaminopropionate, lauryl dimethyl betaine, lauryl dihydroxy ester Such amphoteric surfactants such as betaine type, such as Rubetain and can use a mixture of these two or more kinds.

The addition amount of the surface-active component including the non-reactive surface-active agent and the reactive surface-active agent is the modified polyolefin 1.
It is 1 part to 50 parts, preferably 5 parts to 30 parts, relative to 00 parts. Further, the required amount varies depending on the combination and the amount ratio of the surface active components, the addition amount of the alcohol component, and the type and amount of the reactive monomer. The above surface active component can be melt-mixed with the raw material resin, but a part or the whole of the addition amount may be mixed with water and added.

Among the above nonionic surfactants, those having a polyalkylene oxide structure and having a solubility parameter (SP value) of 7 or more and 12 or less are more preferable. For example, polyoxyethylene diol, polyoxypropylene diol, polyoxytetraethylene glycol, copolymer of ethylene oxide and propylene oxide, aliphatic alcohol polyalkylene oxide adduct (polyoxyethylene aliphatic alkyl ether, etc.), secondary alcohol Polyalkylene oxide adduct (polyoxyethylene secondary alcohol ether etc.), alkylamine polyalkylene oxide adduct, alkylamide polyalkylene oxide adduct, polyoxyalkylene alkylphenyl ether (polyoxyethylene nonylphenyl ether, polyoxyethylene dodecyl Phenyl ether, etc.), polyoxyalkylene sterol ether, polyoxyalkylene lanolin derivative, alkylphenol Alkylene oxide derivative of phosphorus condensate, polyoxyalkylene glycerin fatty acid ester (polyoxyethylene glycerin fatty acid ester, etc.), polyoxyalkylene sorbitol fatty acid ester (polyoxyethylene sorbitol fatty acid ester, etc.), polyoxyalkylene glycol fatty acid ester (polyoxyethylene Fatty acid ester, etc.), polyoxyalkylene fatty acid amide (polyoxyethylene fatty acid amide, etc.), polyoxyalkylene alkylamine (polyoxyethylene alkylamine, alkylalkanolamine ethylene oxide propylene oxide polymer adduct, etc.) and the like are used. A substance having a polyalkylene oxide structure is a chemical structure composed of an oligomer or polymer produced by homopolymerization or copolymerization of alkylene oxide such as ethylene oxide and propylene oxide (block copolymerization, random copolymerization, graft copolymerization, etc.). It is a substance that has. Average molecular weight is 200
It is used in the range of 5,000 to 5,000, preferably 300 to 3,000. When the molecular weight is 200 or less, the dispersibility is low and no remarkable effect appears. Also, if the molecular weight is 5000 or more, the resin dispersibility decreases. Moreover, you may use these in combination of 2 or more types. The surface active component is used in an amount of 0.1 to 50 parts, preferably 3 to 30 parts, based on 100 parts of the water-based raw material resin.

The crosslinkable component in the present invention is an active hydrogen such as a hydroxyl group, a carboxyl group or an amine group present in a polyolefin-based raw material resin, a surfactant, a basic substance or the like used in the preparation of an aqueous resin composition. It means a compound that reacts with the functional group it has to form a crosslinked structure, or a compound that reacts with the substrate or topcoat component to be coated. The crosslinkable component may be water-soluble itself or may be dispersed in water by some method.

The crosslinking component is used in a ratio of 1 to 800 parts with respect to 100 parts of the modified polyolefin. When the amount is less than 1 part, the effect of the crosslinking component is not exhibited, and when the amount is more than 800 parts by weight, the adhesiveness is remarkably lowered.

The blocked isocyanate compound in the present invention means an isocyanate compound having two or more isocyanate groups in one molecule, such as ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-
Tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,
4 ', 4 "-triphenylmethane triisocyanate,
4,4'-diphenylmethane diisocyanate, 3,
Isocyanates such as 3'-dimethyl-4,4'-diphenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate and lysine isocyanate, and an excess of the above-mentioned isocyanate compound, for example, ethylene glycol, propylene glycol, Low molecular weight polyols such as 1,3-butylene glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, glycerin and pentaerythritol. A polyisocyanate having two or more functional groups, a polyisocyanate having a burette structure and an allophanate bond, which are obtained by an addition reaction or an addition polymerization reaction with Polyisocyanates, an isocyanate compound blocked with a blocking agent an isocyanate or the like having a isocyanurate structure. Examples of the blocking agent include phenols such as phenol and cresol, alcohols such as methanol, benzyl alcohol and ethylene glycol monomethyl ether, active methylenes such as methyl acetoacetate and dimethyl malonate, acetanilide,
Acid amides such as acetic acid amide, other imides, amines, imidazoles, ureas, carbamates, imines, acetoximes, oximes such as methylethylketoxime, malonic acid esters such as diethyl malonate, mercaptans, There are lactams such as sulfites and epsilon caprolactam.

That is, the blocked isocyanate compound in the present invention generally includes a compound called a blocked isocyanate, a masked isocyanate, a reactive urethane or the like. The blocked isocyanate compound is 5 to 100 parts by weight of the modified polyolefin.
It is used in the range of 300 parts by weight. If it is less than 5 parts, the effect of addition will not be exhibited, and if it is more than 300 parts, the adhesiveness will be significantly reduced.

The content of the isocyanate group contained in the blocked isocyanate compound and the amount of active hydrogen which reacts with the isocyanate group such as hydroxyl group and carboxyl group contained in the components remaining in the coating film after the drying treatment such as the modified polyolefin and the surface active component, The optimum ratio can be determined by the reaction rate of the blocked isocyanate compound under each deblocking condition (temperature, time, etc.) of the blocked isocyanate compound, but it is used in excess when the bond produced by the crosslinking reaction has more active hydrogen. be able to.

When a blocked isocyanate compound is used, it is effective that the blocking agent dissociates after the water content has evaporated in the drying step. Therefore, the dissociation temperature of the blocking agent is preferably equal to or higher than the set temperature in the drying step. When the baking temperature is the same or higher, it is dealt with by adding an excess of the blocked isocyanate compound.

The blocked isocyanate compound may be water-dispersible or water-soluble when preliminarily blended with the reactive monomer, or may not be water-solubilized, but is water-dispersible when blended later in the hydration product. Alternatively, it is preferable to use a water-soluble one.

The aqueous blocked isocyanate compound in the present invention has an isocyanate group in its molecular structure, and the isocyanate group is blocked with a suitable blocking agent and is itself water-soluble or water-dispersible, or itself. Is water-soluble by any method such as addition of a surfactant or formation of a hydrophilic protective colloid even if it has no water solubility or water dispersibility.

In the step of adding and blending the blocked isocyanate compound to the modified polyolefin resin in the present invention, the modified polyolefin resin is dissolved in a solvent and the blocked isocyanate compound is added to the solution, and then the solvent is replaced with water to make it aqueous. Alternatively, an aqueous modified polyolefin resin and an aqueous blocked isocyanate compound may be blended and used.

In the aqueous resin composition of the present invention, if necessary, a catalyst that accelerates the deblocking reaction and the reaction between the activated isocyanate group and other active hydrogen can be used. Dibutyltin laurate as a catalyst,
Dibutyltin fatty acid salt, dibutyltin diacetate, tetra-n-butyl-1,3-diacetoxy-distannoxane, tetra-n-butyl-1,3-dilauryloxy-
Distanoxane, di-n-butyltin oxide, mono-
Examples are n-butyltin oxide and stannous octylate.

In the case of an aqueous resin composition using a blocked isocyanate compound, it is applied to a substrate by some method and then dried at a temperature lower than the deblocking temperature and then treated at a higher deblocking temperature. It is preferable that the isocyanate can be activated to promote the reaction. When a film is formed using an aqueous resin composition containing a blocked isocyanate compound, water is dried and then deblocked to promote the reaction between isocyanate and other active hydrogen at 60 to 200 ° C. for 1 minute to 2 minutes. Perform heat treatment for an hour. Regarding this treatment condition, an optimum value can be set depending on the deblocking condition of the blocked isocyanate compound to be used, the type and addition amount of the deblocking catalyst.

The polyglycidyl compound used in the present invention is a compound which has one or more oxirane structures in its molecular structure and is liquid at room temperature, or becomes solid by adding an organic solvent even if it is solid at room temperature. If you can use it. Typical examples include glycidyl ether, glycidyl ester, glycidyl amine, glycidyl group derivatives such as glycidyl imine, polyolefin epoxide, cycloalkene epoxide, and epoxy doacetal. Specifically, bisphenol A diglycidyl ether represented by bisphenol A epoxy resin, novolac epoxy resin, polyphenol epoxy resin, polyhydroxybenzene epoxy resin, phenyl glycidyl ether, cresol monoglycidyl ether Epoxidized derivative, copolymer of glycidyl methacrylate and other acrylic monomer,
Examples thereof include cyclohexene oxide-based epoxy resins, epoxy resins composed of aniline derivatives, triglycidyl isocyanurate, and the like.

When the polyglycidyl compound is blended, a curing agent or a curing catalyst may be blended depending on the conditions of use of the aqueous product to prepare a formulation suitable for the film forming conditions.
Examples of the curing agent and the curing catalyst are as follows. Specifically, aliphatic polyamines typified by diethylenetriamine, aromatic polyamines typified by metaphenylenediamine, piperidine, secondary amines typified by pyrrolidine, triethanolamine, hexamethylenetetramine, typified by trisdiaminomethylphenol. Acid anhydrides represented by tertiary amines, phthalic anhydride, citraconic anhydride, pyromellitic anhydride, etc., boron acid fluoride amine complex, phenol novolac resin, urea resin initial condensate, melamine resin initial condensate , Dicyandiamide and the like.

In the present invention, the polyglycidyl compound is used in an amount of 2 to 500 parts by weight based on 100 parts by weight of the polyolefin resin. If the amount used is less than 2 parts, the effect of addition is not exhibited, and if it is less than 500 parts, the adhesion to the non-polar substrate decreases.

Known urethane resins can be used for the present invention. Furthermore, when preparing the aqueous resin composition of the present invention, when the urethane resin is blended in the form of an aqueous solution, the urethane resin previously hydrated by some method is used. Examples of the active hydrogen-containing compound used for polyurethane include high-molecular polyols, low-molecular polyols and polyamines.

As the low molecular weight polyol, ethylene glycol, propylene glycol, 1,3 or 1,4-
Butanediol, 3-methylpentanediol, 1,6
-Difunctional or higher-functional polyols such as hexanediol, neopentyl glycol, diethylene glycol, cyclohexylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, bisphenol A, bisphenol F,
Examples thereof include aromatic compounds containing two or more hydroxyl groups such as bisphenol S, hydroquinone, and resorcinol.

Examples of the high molecular weight polyol include polyether polyols (for example, the above low molecular weight polyols, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, aliphatic polyamines such as ethylenediamine, hexamethylenediamine, isophoronediamine and diethylenetriamine, and tolylenediene. Amine,
Addition of one kind of monomer or oligomer of alkylene oxide having 2 to 6 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, etc. to amines such as aromatic diamine such as diphenylmethane diamine, or random or block of two or more kinds Copolymers added), polyester polyols (adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid, and aliphatic carboxylic acids such as dimerized linoleic acid, phthalic acid, isophthalic acid, terephthalic acid) Polyester polyol having two or more hydroxyl groups in the molecule using aromatic polycarboxylic acid such as the above and the above low molecular weight polyol or polyether polyol, polycaprolactone diol, polycarbonate diol, etc.), polybutadiene polyol,
Examples include hydrogenated polybutadiene diol and acrylic polyol.

Further, as the polyol component, hydroxycarboxylic acids such as lactic acid, tartaric acid, citric acid, salicylic acid and dimethylolpropionic acid, and methanol, ethanol, propanol, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). A monoalcohol such as acrylate may be used in combination.

Examples of the polyamine include aliphatic diamines such as ethylenediamine, hexamethylenediamine, isophoronediamine and diethylenetriamine, tolylenediamine, diethyltolylenediamine, phenylenediamine,
Aromatic polyamines such as benzidine, diphenylmethanediamine and dichlorodiphenylmethanediamine, 4,4 '
Alicyclic polyamines such as diaminodicyclohexylmethane, 4,4'-diaminodimethylcyclohexylmethane, 1,4-diaminocyclohexane and isophoronediamine, alkanolamines such as diethanolamine, monoethanolamine and propanolamine, and polyalkylene oxide polyamines Examples are polyamines.
Further, one kind or two or more kinds of these polyamines can be used in combination, but hexamethylenediamine, isophoronediamine, and 4,4′-diaminodicyclohexylmethane are preferably used.

Examples of the polyisocyanate used for urethane include aliphatic polyisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, isophorone diisocyanate and its trimer, dicyclohexylmethane diisocyanate and its trimer, cyclohexyl. Cylylene diisocyanate, alicyclic polyisocyanate such as methylhexylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, araliphatic polyisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, naphthylene diisocyanate Aromatic polyisocyanates such as Carbodiimide groups based on these polyisocyanates, uretdione, uretonimine groups, is modified product having a biuret group, or an isocyanurate group is used.

A known method can be used in the production of the urethane resin. The aqueous urethane is used in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polyolefin. 5
If the amount is less than 200 parts, the effect of addition will not be exhibited and 200
If the amount is more than the amount, the adhesion to the polyolefin substrate will be significantly reduced.

The amino resin used in the present invention is urea,
It means a thermosetting resin obtained by reacting an amino compound such as melamine, benzoguanamine and acetoguanamine with formaldehyde. As the amino resin used in the present invention, known amino resins can be used, but those which are liquid at around room temperature or which become liquid by addition of some solvent are preferable. Further, even a solid substance may be used as long as it is soluble in the reactive monomer or the modified polyolefin. Furthermore, when the amino resin is blended in the form of a hydrate when preparing the aqueous resin composition of the present invention, the amino resin hydrated in advance by any method can be blended.

The amount of the amino resin used is 5 to 500 parts with respect to 100 parts of the polyolefin resin. If the amount is less than 5 parts, the addition effect does not appear, and if the amount is 500 parts or more, the adhesion to the polyolefin substrate is insufficient.

The polycarbonyl compound used in the present invention is a compound having two or more carbonyl groups in the molecule, and it is water-soluble per se or stable in water by some method even if it is not water-soluble. It may be dispersed. Known compounds can be used as long as they are water-soluble or water-dispersible. For example, an aqueous dispersion of a carbonyl group-containing copolymer of an olefinically unsaturated monomer can be produced by emulsion polymerization of a monoolefinic unsaturated monomer having a carbonyl group and another olefinically unsaturated monomer by a conventional method. it can. In addition, JP-A-4-2495
No. 87, a diacetone acrylamide copolymer, a compound containing an acetoacetyl group represented by acetoacetylpolyvinyl alcohol as disclosed in JP-A-4-255784, JP-B-61-
The acrylic polycarbonyl compounds and the like found in Japanese Patent No. 6861 are exemplified.

In the present invention, when an aqueous resin composition is prepared by blending a polycarbonyl compound, it is divided into a polyhydrazide-containing part and a polycarbonyl compound-containing part depending on the reactivity of the polycarbonyl compound and the polyhydrazide. Also, it is used as a two-pack type that is mixed and used immediately before use, or as a one-pack type film-forming material that is mixed at the time of preparing an aqueous resin composition. The polycarbonyl compound is used such that the ratio of the ketone group to the hydrazino group in the polyhydrazide compound is 1: 0.1-20. When it is less than 0.1, the effect of addition does not appear. When 20 or more is added, the effect of improving film forming ability by polyhydrazine does not appear.

In the present invention, if necessary, other water-based resins such as water-based acrylic resins, water-based phenol resins, water-based polybutadiene resins, water-based alkyd resins, water-based chlorinated rubbers and water-based silicone resins may be blended. Is also used.

Further, the aqueous resin composition of the present invention contains, if necessary, a film forming aid, a wettability improver for improving wettability with respect to a substrate, pigments such as rust preventive pigments, color pigments and extender pigments, dyes, Thixotropic agents, viscosity modifiers, flow aids, surface modifiers, primary rust preventives, defoamers, preservatives, fungicides, plasticizers, various stabilizers for improving heat resistance and weather resistance, organometallic compounds It is used by adding necessary amounts of various additives such as coordination compounds and mixing.

Examples of pigments include inorganic pigments such as carbon black, titanium oxide, chromium oxide, zinc oxide, iron oxide mica, and navy blue, and coupling azo-based, condensed azo-based, anthraquinone-based, perylene-based, quinacridone-based, thioindigo-based pigments. Examples of organic pigments include dioxazine-based and phthalocyanine-based organic pigments.

Examples of the inorganic filler include calcium carbonate, silica, talc, glass fiber, clay and the like.

Examples of the organic filler include fluorine resin powder, silicone resin powder, polyamide resin powder, urethane resin powder, polystyrene powder, various latexes and the like.

Examples of the organic metal coordination compound include organic zirconium coordination compounds such as zirconium tetraacetylacetonate and diisopropoxyzirconium bisacetonate, and organic titanium coordination compounds such as titanium tetrakisacetylacetonate and diisopropoxytitanium bisacetylacetonate. Examples thereof include compounds, aluminum trisacetylacetonate, and organic aluminum coordination compounds such as aluminum chilisisoporopoxide.

These additives may be added simultaneously or separately before, during, or after the production of the composition of the present invention.

[0084]

EXAMPLES The present invention will now be described in more detail with reference to Examples. In the following, "parts" or "%" means "parts by weight" or "% by weight". The present invention is not limited to these examples.

(Prototype Example 1) A propylene-α-olefin copolymer (propylene component 7) was placed in a four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel.
5 mol%, ethylene component 20 mol%, 1-butene component 5
Mol%, number average molecular weight 25,000) 300 parts was dissolved in 700 parts of toluene by heating, and then the temperature of the system was kept at 115 ° C. with stirring to 13 parts of maleic anhydride and di-t-butyl as a radical generator. 12 parts of peroxide was added dropwise over 2 hours, and then reacted for 3 hours. After the reaction, the reaction product was cooled to room temperature and then poured into 5000 parts of acetone for purification to obtain a maleic anhydride graft copolymer having a graft amount of 2.1% by weight (number average molecular weight 1850).
0) was obtained. Tosoh HP
The column TSK-GEL was attached to LC-8020, the sample was melt | dissolved in THF (tetrahydrofuran), it measured at 40 degreeC, and calculated | required the molecular weight from the calibration curve created with the polystyrene standard sample.

(Prototype Example 2) In a four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel, a propylene-butene-ethylene copolymer (68 mol% of propylene component, 24 mol% of butene component, After ethylene component 8 mol% and number average molecular weight 68000) 300 parts were heated and melted, maleic anhydride 40 parts and dicumyl peroxide 5 parts as a radical generator were respectively stirred while maintaining the system temperature at 180 ° C. It was made to dripped over 3 hours, and reaction was performed after that for 3 hours. After the reaction, the reaction product was cooled to room temperature and then poured into 5000 parts of acetone for purification to obtain a maleic anhydride graft copolymer having a graft amount of 6.2% by weight. The number average molecular weight measured by GPC is 2600.
It was 0.

(Trial Production Example 3) The maleic acid-modified polyolefin 300 obtained in Prototype Example 2 was placed in a four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel.
Parts were dissolved in 1000 parts of xylene with stirring at 80 ° C. After adding 0.3 part of p-toluenesulfonic acid, 20 parts of hydroxyethyl acrylate was added dropwise over 30 minutes. After reacting for 1 hour, the temperature of the system was raised to 110 ° C., and 5 parts of di-t-butyl peroxide, 30 parts of cyclohexyl methacrylate and 10 parts of methacrylic acid were simultaneously added over 1 hour. After completion of the addition, post-reaction was carried out for 2 hours, and then xylene was distilled off under reduced pressure. The reaction product was cooled to room temperature to obtain an acrylic modified polyolefin.

(Prototype Example 4) In a four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel, the chlorine content was 23%, the number average molecular weight was 5300, and the carboxyl group content was 1.7% by weight. 300 parts of chlorinated oxidatively degraded polyolefin was dissolved in 1000 parts of toluene by stirring at 85 ° C. Hexamethylene diisocyanate (19 parts) was dissolved in toluene (100 parts) and added to the reactor over 1 hour. Further, polyester diol (average molecular weight 500) 5
6 parts were added all at once and reacted for 2 hours. Then, xylene was distilled off under reduced pressure. The reaction product was cooled to room temperature to obtain a urethane-modified polyolefin.

Example 1 100 parts of the modified polyolefin resin obtained in Prototype Example 1 was charged into a reactor equipped with a stirrer, a thermometer, a cooling pipe, and a pressure metering pump, and heated and melted at 120 ° C. While stirring, 6 parts of morpholine was added as a basic substance, and 10 parts of polypropylene oxide (average molecular weight 400) as a surface-active component, polyoxyethylene nonylphenyl ether (manufactured by NOF Corporation,
10 parts of Nonion NS-208.5) were added. After stirring until uniform, 400 parts of warm water of about 90 ° C. was added under pressure of 1.6 kg / cm ² to obtain an aqueous product by a phase inversion method. To the obtained aqueous product, adipic acid dihydrazide dissolved in a small amount of water was added with stirring at a solid content of 0.5 part. Resin solid content in hydrate is 2
It was 3%.

(Example 2) 100 parts of the modified polyolefin resin obtained in Prototype Example 2 was charged into a reactor equipped with a stirrer, a thermometer, a cooling tube, and a pressure metering pump, and heated and melted at 120 ° C, While stirring, 6 parts of morpholine was added as a basic substance, and further 10 parts of coconut oil amine ethylene oxide propylene oxide block polymer adduct as a surface-active component, polyoxyethylene nonyl phenyl ether (Nonion NS-208.
5) 10 parts were added. After stirring until uniform, 1.6 kg / cm ² of hot water at about 90 ° C under pressure 400
Parts were added one by one to obtain an aqueous product by a phase inversion method. To the obtained aqueous product, an aqueous solution of adipic dihydrazide was added with stirring at a solid content of 2 parts. The resin solid content in the hydrated product was 25%.

(Example 3) In a four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 100 parts of the modified polyolefin obtained in Prototype Example 2 was dissolved in 200 parts of toluene by heating at 110 ° C to obtain t-butyl. After adding 10 parts of peroxyisopropyl carbonate and 9.6 parts of morpholine, 10 parts of an alkyl propenylphenol ethylene oxide 20 mol adduct (Daiichi Kogyo Seiyaku Co., Aqualon RN-20), 10 parts of 2-hydroxyethyl acrylate toluene (120
(Part) After the solution was added dropwise over 3 hours, a post-reaction was carried out for 4 hours to carry out a graft copolymerization reaction. After the toluene containing the reaction solution was distilled off under reduced pressure, triethylamine 4 was added.
Parts and 10 parts of polyethylene oxide nonylphenyl ether (Nonion NS-208.5, manufactured by NOF CORPORATION) were added, and water was added with stirring to obtain an aqueous reaction solution (solid content 25%). An aqueous solution of adipic dihydrazide was added to this aqueous solution while stirring at a solid content of 2 parts to obtain an aqueous resin composition.

Example 4 100 parts of the modified polyolefin resin obtained in Prototype Example 3 was charged into a reactor equipped with a stirrer, a thermometer, a cooling tube, and a pressure metering pump, and heated and melted at 120 ° C. While stirring, 6 parts of morpholine was added as a basic substance, and further 10 parts of coconut oil amine ethylene oxide propylene oxide block polymer adduct as a surface-active component, polyoxyethylene nonyl phenyl ether (Nonion NS-208.
5) 10 parts were added. After stirring until uniform, 1.6 kg / cm ² of hot water at about 90 ° C under pressure 400
Parts were added one by one to obtain an aqueous product by a phase inversion method. To the obtained aqueous product, an ethanol solution of sebacic acid dihydrazide was added while stirring 2 parts by solid content. The resin solid content in the hydrated product was 24%.

Example 5 100 parts of the modified polyolefin resin obtained in Prototype Example 4 and 200 parts of toluene were charged into a reactor equipped with a stirrer, a thermometer, a cooling pipe, and a pressure metering pump, and heated and dissolved at 80 ° C. After stirring, 6 parts of morpholine was added as a basic substance while stirring, and further 10 parts of coconut oil amine ethylene oxide propylene oxide block polymer adduct as a surface-active component, polyoxyethylene nonylphenyl ether (Nonion N, manufactured by NOF CORPORATION).
S-215) 15 parts was added. After stirring until uniform, the vacuum distillation was repeated until toluene was added to warm water 400
Part was replaced. After adding 2 parts of adipic acid dihydrazide aqueous solution to the obtained aqueous product while stirring with solid content, emulsification treatment was performed using an ultrahigh pressure homogenizer (Nanomizer, manufactured by Tokushu Kikaiki Co., Ltd.) to obtain the desired aqueous product. Obtained. The resin solid content in the hydrated product was 25%.

(Examples 6 to 16) A crosslinking component, a polycarbonyl compound and an aqueous urethane were blended with the aqueous products obtained in Examples 1 to 5 according to the formulation shown in Table 1 to obtain compositions. However, in Examples 13 and 14, the component 2 and magnesium sulfate 1.5 were added immediately before coating with respect to the liquid containing the hydrate and the component 1 obtained in Examples 1 and 4.
Parts were mixed and used.

[0095]

[Table 1]

(Comparative Examples 1 to 8) Each of the above Examples 1, 2 and
Comparative Examples 1 to 4 were prepared by preparing an aqueous resin composition without using a polyhydrazide compound at 4, 5, 6, 11, 12, and 15.
It was set to 8.

[Coating film test] <Method for preparing sample A> The aqueous resin compositions prepared in Examples 1 to 16 and Comparative Examples 1 to 8 were spray-coated on a polypropylene plate and dried at 80 ° C. in a blow dryer at 15 ° C. Dried for ~ 20 minutes. The film thickness was adjusted to 10 to 15 μm.

<Preparation Method of Specimen B> The aqueous resin compositions prepared in Examples 1 to 16 and Comparative Examples 1 to 8 were spray-coated on a polypropylene plate and dried at 80 ° C. for 15 to 2 in a blow dryer.
It was dried for 0 minutes. The film thickness was adjusted to 10 to 15 μm.
Next, after applying a two-component urethane-based top coating composition and allowing it to stand at room temperature for 10 minutes, it is heated at 100 ° C. for 40 minutes using a hot air dryer.
It was baked in minutes. The obtained coated plate was stored at room temperature for 1 week, and then the coating film was tested. However, in Example 10, a melamine-based top coat was used as the top coat, and 13
Baking was performed at 0 ° C. for 40 minutes.

<Coating Film Test Method> [Tackiness Test] The tackiness of the surface of the base material of Specimen A was evaluated by touch. ◎: Very good, ○: Good, △: Slightly bad, ×: Bad,
XX: Very bad

Specimen B was used in the following tests. [Adhesion test] Make 100 cuts at 1 mm intervals by making cuts reaching the substrate with a cutter on the coating film surface, adhere cellophane adhesive tape on it and peel off 5 times in 180 ° direction, and leave I counted the number of eyes. The evaluation is expressed as follows. ◎: Very good, ○: Good, △: Slightly bad, ×: Bad,
XX: Very bad

[Gasoline resistance test] A cut that reaches the substrate with a cutter is made on the surface of the coating film and it is dipped in gasoline (Nisseki, unleaded high octane gasoline), and abnormalities such as blister generation and peeling from the coating edge are observed. The time until generation was visually measured. The evaluation is expressed as follows. ⊚: Good for 240 minutes or more, ◯: 240 to 120 minutes, △:
20 minutes to 60 minutes, XX: 60 minutes to 30 minutes, XX: 30 minutes or less

[Gas-all resistance test] A cut that reaches the base material is made on the surface of the coating film with a cutter, and it is dipped in a mixed solution of gasoline (Nisseki, lead-free regular) / ethanol = 90/10 to make a cut on the coated surface. The time from the occurrence of peeling of 5 mm was visually measured. The evaluation is expressed as follows. ◎: Good for 60 minutes or more, ○: 60 to 30 minutes, △: 30 minutes to
20 minutes, ×: 20 minutes or less

[Moisture resistance test] A lower one-fifth of a coated plate in which a cut was made on the surface of the coating film with a cutter in a closed container was immersed in water and treated at 50 ° C for 5 days, and then blistered. , And the degree of peeling from the break was compared. The evaluation is expressed as follows. ◎: Very good, ○: Good, △: Slightly bad, ×: Bad,
XX: Very bad

[Hot Water Resistance Test] Immersion of coated plate in hot water at 40 ° C. for 240 hours. After checking the state of the coating film such as the occurrence of blister, a cellophane adhesive tape was adhered on it to make 1
It was peeled off 5 times in the direction of 80 ° and the amount of the remaining coating film was compared. The evaluation is expressed as follows. ◎: Very good, ○: Good, △: Slightly bad, ×: Bad,
XX: Very bad

[Weather resistance test] A QUV accelerated weather resistance tester (Q-PAN) was used to form a film having a thickness of 30 μm on a glass plate.
The weather resistance was compared using EL) (treatment conditions; light source, UVB313, 40 watts, temperature 36 ° C., treatment time 400 hours). The glass plate after the treatment was evaluated for yellowing degree of the coating film using a Hunter tester. ◎: Very good, ○: Good, △: Slightly bad, ×: Bad,
XX: Very bad

Table 2 shows the results of tack test, adhesion test, gasoline resistance test, gas all resistance test, moisture resistance test, hot water resistance test, and weather resistance test, which were carried out using each sample. Indicated.

[0107]

[Table 2]

[0108]

EFFECTS OF THE INVENTION The aqueous resin composition of the present invention not only exhibits excellent adhesion to non-polar substrates such as polyolefins, but also to other organic substrates, metals and inorganic materials. . Further, it is possible not only to eliminate troubles due to tack on the surface of the substrate after drying, but also to improve gas-all resistance of a coating film formed using the same. Furthermore, since it contains almost no organic solvent, it is excellent in terms of health and safety and environmental pollution.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09J 123/00 JBW // C08G 18/62 NEN C09K 3/10 Z

Claims (13)

[Claims] 1. In preparing an aqueous resin composition containing a polyolefin or a modified polyolefin, 0.1 to 30 parts by weight of a polyhydrazide compound is blended with 100 parts by weight of a polyolefin resin solid content. Polyolefin resin composition. 2. The aqueous resin composition according to claim 1, wherein an aliphatic dicarboxylic acid dihydrazide is used as the polyhydrazide compound in preparing the aqueous resin composition containing a polyolefin or a modified polyolefin. 3. The aqueous resin composition according to claim 1, wherein a chlorinated modified polyolefin having an average molecular weight of 1,000 to 500,000 and a chlorine content of 5 to 70% by weight is used as the modified polyolefin. 4. An average molecular weight of from 1000 to 50, wherein the polyolefin resin is modified with a carboxylic acid having a radical-polymerizable double bond or an anhydride thereof.
An acid-modified polyolefin having a degree of acid modification of 1 to 20% by weight is used as the modified polyolefin.
The aqueous resin composition described. 5. A polyolefin resin is modified by radical polymerization with a (meth) acrylic monomer or a (meth) acrylic oligomer, and has an average molecular weight of 1,000 to 500,000 and a modification degree of 5 to 800% by weight. The aqueous resin composition according to claim 1 or 2, wherein an acrylic modified polyolefin is used as the modified polyolefin. 6. A hydroxyl group or a carboxyl group in the molecule is 1
Or a modified polyolefin containing more than that, a compound having two or more isocyanate groups has a molar ratio of isocyanate groups to hydroxyl groups or carboxyl groups of 1: 1.2 to.
Urethane-modified by reacting a polyhydroxy compound at a molar ratio of residual isocyanate groups to hydroxyl groups of 1: 1.1 to 4 with respect to a reaction product reacted at a ratio of 3.5. And an average molecular weight of 10
The aqueous resin composition according to claim 1 or 2, wherein a urethane-modified polyolefin having a modification degree of 5 to 200% by weight of 0 to 500,000 is used as the modified polyolefin. 7. When preparing an aqueous resin composition containing a polyolefin or a modified polyolefin, the ratio of the carbonyl group to the hydrazino group in the polyhydrazide compound is 1 for the polycarbonyl compound having two or more ketone groups in the molecule. The aqueous resin composition according to any one of claims 1 to 6, wherein the aqueous resin composition is used in an amount of 0.1 to 20. 8. When preparing an aqueous resin composition containing a polyolefin or a modified polyolefin, a crosslinkable component having two or more functional groups that react with active hydrogen in a molecule is added to 100 parts by weight of a polyolefin resin solid content. 1-8
The aqueous resin composition according to any one of claims 1 to 7, which is added in an amount of 00 parts by weight. 9. When preparing an aqueous resin composition containing a polyolefin or a modified polyolefin, 5 to 300 parts by weight of a blocked isocyanate compound is used as a crosslinkable component with respect to 100 parts by weight of a polyolefin resin solid content. The aqueous resin composition according to claim 8. 10. When preparing an aqueous resin composition containing a polyolefin or a modified polyolefin, 2 to 5 of an aliphatic or aromatic polyglycidyl compound as a crosslinkable component is added to 100 parts by weight of a polyolefin resin solid content.
The aqueous resin composition according to claim 8, which is used in an amount of 00 parts by weight. 11. When preparing an aqueous resin composition containing a polyolefin or a modified polyolefin, 5 to 500 parts by weight of an amino resin is used as a crosslinkable component with respect to 100 parts by weight of a polyolefin resin solid content. Item 9. The aqueous resin composition according to item 8. 12. The aqueous resin composition according to claim 1, wherein 5 to 200 parts by weight of the aqueous urethane resin is mixed with 100 parts by weight of the polyolefin resin. 13. A paint, a primer, a film-formed product such as an ink, a sealing agent, an adhesive, a binder and a surface treatment agent, which comprises the resin composition according to any one of claims 1 to 12.