JP2845755B2 - Aqueous resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous resin composition which can be mainly used as a paint, a primer, an ink, an adhesive, a sealing agent and a surface treating agent. In addition, the resin composition of the present invention can be used in combination with other water-based resins such as water-based acrylics and polyesters and water-soluble resins, depending on the intended use. be able to. Above all, it is not only possible to form a coating and an adhesive layer having excellent adhesion, flexibility and water resistance to a polyolefin substrate having a non-polar surface, etc., unlike the chlorinated polyolefin conventionally used in this field. Since it does not contain chlorine, the weather resistance can be greatly improved. From this, it is useful as an aqueous resin for paints, primers, inks, sealing agents, and adhesives for plastic parts materials such as automobiles, polyolefin films, polyolefin-based molded products, and the like. It is also applied as a surface treatment agent for fibrous or particulate base materials, and as a binder.

[0002]

2. Description of the Related Art Conventionally, polypropylene, polyethylene,
Or propylene, a modified polyolefin composition obtained by modifying a polyolefin such as a copolymer of ethylene and an α-olefin with an unsaturated carboxylic acid or an acid anhydride, or an acid-modified chlorinated polyolefin obtained by chlorinating them is a coating material, a primer, an ink. And so on. However, since these resins are soluble only in aromatic organic solvents such as toluene and xylene, a large amount of aromatic solvents must be used, and there is a problem in terms of safety and health and environmental pollution.

[0003] In recent years, an aqueous resin obtained by adding a polyol, a surfactant and a basic substance to a chlorinated polyolefin to form an aqueous solution (US Pat. No. 3,840,845), and a chlorination modified by an acid with an unsaturated carboxylic acid or an acid anhydride. An aqueous resin in which a polyolefin is made aqueous using a surfactant and a basic substance (Japanese Patent Application No. 1-323506) has been filed.

[0004] As an attempt to produce an aqueous dispersion of a chlorinated polyolefin, Japanese Patent Application Laid-Open No.
No. 8, JP-A-1-256556, JP-A-2-256
No. 2,849,973. Attempts have also been made to produce aqueous dispersions of modified polyolefins, for example, as disclosed in JP-A-59-47244,
No. 286724, Japanese Patent Application No. 5-280127, Japanese Patent Application No. 4-258935, Japanese Patent Application No. 4-258936,
It is disclosed in Japanese Patent Application No. 4-258937.

[0005] However, when a substrate having a hydrophobic surface such as a polyolefin resin or a substrate having a surface having poor smoothness is used as an object to be coated in coating, bonding, or the like, the base of an aqueous composition is get wet are against wood has been a problem. Various surfactants have been used as a conventional get wet been improving agent thereto. For example, as disclosed in Japanese Patent Publication No. 3-17873, an application for blending a fluorinated surfactant with a chlorinated polyolefin to make it aqueous is already known. However, there is no knowledge about using a fluorine-containing surfactant containing a fluoroalkyl group in a polyolefin-based aqueous resin composition containing no chlorine.

Further, adhesion in conventional usage, without lowering the water resistance, it has been characterized to improve get wet Re sex to the substrate. By improving get wet Re sex against the substrate as in the present invention, as compared with the fluorine-based surfactant unused, adhesion, finding that water resistance can be further improved has not been obtained.

[0007]

The present invention 0005] had become a problem when painted or coated with conventional polyolefin aqueous resin composition on the surface of the hydrophobic substrate as described above, get wet it is resistant to the substrate It is an object of the present invention to obtain an aqueous resin composition which is not only improved, but also balanced with other film properties (weather resistance, water resistance, adhesion, etc.). Further, in the past, in the case of incineration disposal of products manufactured using a resin composition containing chlorinated products, and recycling by heat treatment, corrosion of equipment becomes a problem, but an aqueous resin composition which generates less corrosive substances at this time. The purpose is to get.

[0008]

Means for Solving the Problems] To achieve the above object, the present inventors have not only improves get wet Re sex to the substrate of the aqueous polyolefin resin composition, coating or to form therewith An aqueous resin composition containing no chlorine, which can improve the adhesion of the adhesive layer to the base material, and balances weather resistance, water resistance, and recoatability with the top coat, etc., was studied.

As a result, in preparing the aqueous polyolefin resin composition, a modified polyolefin resin containing no chlorine is used as a raw material, and a fluorine-containing surfactant containing a fluoroalkyl group is blended and used. The wettability of the product to the hydrophobic substrate is greatly improved, it penetrates well into non-smooth substrates, and the adhesion interface with the substrate increases, so that the adhesion during coating formation, water resistance, weather resistance, etc. It has been found that a good aqueous polyolefin resin composition is obtained.

[0010]

That is, in an aqueous resin composition obtained by using a non-chlorine-modified polyolefin as a raw material resin and making it aqueous, with respect to 100 parts by weight of the solid content of the raw material resin,
A mixture of one or more surfactants having a polyoxyalkylene structure as part of the hydrophilic component.
An aqueous polyolefin resin composition comprising 0 part by weight and 0.001 to 5.0 parts by weight of a fluoroalkyl group-containing fluorosurfactant. The use of agents is small and economical.

Further, in the above aqueous resin composition wherein the fluorine-based surfactant is perfluoroalkylamine oxide or polyalkylene oxide perfluoroalkyl ether or perfluoroalkyl betaine,
The use amount of the fluorosurfactant can be further reduced, and not only the wettability to the base material but also the coating property of the coating film and the gasoline resistance are good.

Further, coatings, primers, inks, and other film-forming products containing the resin composition of the present invention, sealing agents, adhesives, binders, and surface treatment agents are applied to the substrate.
Get wet is resistant also well useful.

Hereinafter, the present invention will be described in detail. Examples of the fluorosurfactant containing a fluoroalkyl group used in the present invention include perfluoroalkyl carboxylate,
Perfluoroalkyl phosphate, perfluoroalkyltrimethylammonium salt, perfluoroalkylbetaine, perfluoroalkylamine oxide,
Perfluoroalkyl ethylene oxide adducts are exemplified.

As a method of using the fluorine-based surfactant,
It may be added to the main raw material polyolefin or modified polyolefin before waterification, or may be used alone or during the waterification step or other watering auxiliary materials (other surfactants, alcohols, etc.)
And may be introduced into the composition by any method. Further, after the polyolefin or the modified polyolefin is made aqueous, it may be blended.

In preparing an aqueous resin composition containing a polyolefin or a modified polyolefin, a fluorine-based surfactant containing a fluoroalkyl group as a component of a hydrophilic component per 100 parts by weight of a resin solid content is used. The activator is added in an amount of 0.001 to 5.0 parts by weight. Is not get wet are improving effects on the substrate is less than the above range is obtained amount using the resin solids. Further, when the amount is larger than the above range, a phenomenon of repelling an overcoat occurs when a two-component urethane overcoat is further applied on a film formed using the aqueous resin composition of the present invention, or a decrease in solvent resistance. In addition to this, pigment agglomeration in the topcoat may occur.

As the polyolefin and the non-chlorine-modified polyolefin used as the aqueous-forming raw material used in the present invention, those known as raw materials for the chlorine-free polyolefin-based aqueous-forming 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. A random copolymer or block copolymer with an α-olefin comonomer having 2 or more carbon atoms, preferably 2 to 6, such as -1 or a copolymer of two or more of these comonomers is used. More preferably, the average molecular weight of the polyolefin is usually 2000 to 500,000.
It is. Although what was obtained by a well-known method may be used, what was once decomposed | disassembled by radical, oxygen, and heat to the high molecular weight is used.

Examples of the non-chlorine-modified polyolefin include an acid-modified polyolefin, an acryl-modified polyolefin, and polyolefins obtained by modifying these polyolefins.

The acid-modified polyolefin is a polyolefin obtained by modifying the above-mentioned polyolefin with an α, β-unsaturated carboxylic acid or an acid anhydride thereof by a graft reaction.
In addition, a polyolefin resin such as an acid-modified polyolefin or the like and a water-modified polyolefin resin obtained by reacting a reactive surfactant with a radical reaction initiator is also used as a water-based raw material.

Α, β used for modification of polyolefin
-As unsaturated carboxylic acids or anhydrides thereof, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid,
Allyl succinic acid, mesaconic acid, aconitic acid, and acid anhydrides thereof, and the like. The amount of graft copolymerizing the α, β-unsaturated carboxylic acid or anhydride thereof is 1 to
20% by weight is preferable, and when it is 1% by weight or less, stability when dispersed in water is deteriorated, and when it is 20% by weight or more, graft efficiency is deteriorated, which is uneconomical. Particularly preferably, 2 to
15% by weight. Further, the number average molecular weight of the resin obtained by graft copolymerization of an α, β-unsaturated carboxylic acid or an acid anhydride thereof is preferably 3,000 to 100,000, and if it is 3,000 or less, the cohesive strength is insufficient and the adhesion to the polyolefin resin becomes poor, If it is more than 100000, the operability at the time of dispersing in water deteriorates, which is not preferable. In order to keep the molecular weight within this range, it is possible to select the molecular weight of the raw material and the conditions for performing the graft reaction, and it is also possible to perform the graft reaction after once lowering the molecular weight of the raw material.

The method of graft-copolymerizing an α, β-unsaturated carboxylic acid or its anhydride with a polyolefin may be carried out by a known method. Is preferably carried out by a method of graft copolymerization.

The acrylic-modified polyolefin is a resin modified by graft-polymerizing a (meth) acrylic monomer or a monomer having a radically polymerizable unsaturated group to a polyolefin-based raw material resin by any method.

The monomers used herein 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, norbornyl (meth) acrylate, isobornyl (meth) acrylate, allyl glycidyl ether, acrylamide, N- Methylol acrylamide, acrylonitrile, butadiene, isoprene, chloroprene,
Examples thereof include aromatic monomers such as styrene and divinylbenzene, vinyl ester monomers such as vinyl acetate, methyl maleate, and maleic anhydride.

These monomers can themselves be graft-copolymerized to an acid-modified polyolefin by a radical reaction.
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 an acid-modified polyolefin solution before the radical reaction and graft copolymerize by an esterification reaction. You can let it happen. In this case, a reactive surfactant can be graft-copolymerized by utilizing a radical reactive double bond which has not been formed by the esterification reaction.

As the graft reaction initiator by the radical reaction, any known one may be used, and an organic peroxide is particularly preferable. 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-butyl. Peroxide, t-butyl peroxyisopropyl carbonate, t-butyl hydroperoxide, t-butyl peroxybenzoate, cumene hydroperoxide and the like can be mentioned, and they are selected and used depending on the reaction temperature. Azo-based and redox-based initiators such as azobisisobutyronitrile can also be used. They may be used in combination.

The amount of the (meth) acrylic monomer or the monomer having a radically polymerizable unsaturated group is 5 to 500 parts by weight based on 100 parts by weight of the polyolefin resin material. If the amount is less than 5 parts, problems such as a decrease in the aqueous conversion efficiency of the resin and a decrease in the gloss of the coating film occur. On the other hand, if it exceeds 500 parts, there is a problem in adhesion to a substrate such as polyolefin.

A known method can be used for the aqueous method. For example, a method of adding a surfactant, a basic substance, and, if necessary, an alcohol to a polyolefin-based raw material resin dissolved in an organic solvent such as toluene or xylene, and replacing the solvent with water while stirring to make the resin aqueous. And a method in which a surfactant, a basic substance, an alcohol or the like, if necessary, are added to the molten raw material resin, water is gradually added, and the mixture is made aqueous by a phase inversion method.

Examples of the basic substance include 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-
Examples thereof include 2-methyl-1-propanol and morpholine. The degree of hydrophilicity of the resin also varies depending on the type of base used, so it is necessary to select it appropriately depending on the conditions.

The amount of the basic substance used is suitably in the range of 0.3 to 1.5 times the equivalent of the carboxyl group of the acid-modified polyolefin, and preferably 0.5 to 1.2 times.

The reason for adding monoalcohols or polyols, which are alcohols, is to increase the affinity of the raw material resin for water, and this effect can reduce the amount of surfactant used. Further, it becomes 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 reduces the water resistance of the coating film, so it is necessary to add an appropriate amount, and it is preferable to add 4 to 100 parts by weight based on 100 parts by weight of the raw material resin. . If the amount is less than 4 parts by weight, dispersibility in water is poor, and if it exceeds 100 parts by weight, the water resistance is significantly reduced.

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, and propylene glycol monoalkyl. Acetate and the like are exemplified, and examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, glycerin, polyethylene glycol and the like. Among them, a polyol having strong hydrophilicity is desirable.

The surfactant used in the present invention includes a reactive surfactant and a non-reactive surfactant. As the reactive surfactant, those generally used as a reactive surfactant or a reactive emulsifier may be used, but those having an alkylphenyl group as a hydrophobic group and a polyoxyethylene group as a nonionic hydrophilic group are preferable. For example, JP-A-4-5
For example, alkylpropenylphenol-polyethylene oxide adducts, alkyldipropenylphenol-polyethylene oxide adducts, and salts of sulfates thereof described in JP-A-3802 and JP-A-4-50204 are used. Among them, alkylpropenylphenol ethylene oxide 20 mol adduct, 30 mol adduct, 50 mol adduct, and alkylpropenylphenol polyethylenoxide 10 mol adduct sulfate ammonium salt, 20 mol adduct ammonium sulfate salt Is preferred. Further, 1-alkylphenoxy-3- (2-propenyl) oxypropan-2-ol ethylene oxide adduct or its sulfate is excellent in resin dispersibility,
Furthermore, the presence of an α, β-unsaturated double bond is preferred because the polymerization is high. These reactive surfactants can be reacted with an aqueous resin material by a radical reaction initiator by a known method and immobilized on the resin.

The amount of the reactive surfactant to be used is based on 100 parts by weight of the modified polyolefin which is a water-based raw material resin.
It is 0.1 to 100 parts by weight, preferably 0.1 to 30 parts by weight. The amount used can be appropriately changed depending on the amount of addition of a non-reactive surfactant, which is another hydrophilic component. When a reactive surfactant is used, a reaction initiator is used. This reactive surfactant may be reacted in advance with the aqueous material, or may be added during the aqueous process. Known reaction initiators can be used.

Examples of the non-reactive surfactant include a surfactant having a polyalkylene oxide structure as a nonionic surfactant, propylene glycol ester, sucrose ester, sorbitan alkyl ester, sorbitan fatty acid ester, polyglycerin ester, and fatty acid. Examples thereof include alkanolamides, fatty acid monoglycerides, and alkylamine oxides. In addition, anionic surfactants such as alkyl sulfates, alkylphenol sulfonates, sulfosuccinates, various carboxylates, phosphates and the like, amphoteric surfactants such as alkyl betaines and alkyl imidazolines And mixtures of two or more of these.

The amount of the surfactant component, which is a combination of the non-reactive surfactant and the reactive surfactant, is determined by the amount of the modified polyolefin 1
The amount is 1 part by weight to 100 parts by weight with respect to 00 parts by weight, and the necessary amount varies depending on the combination and the amount ratio of the surfactant component, the added amount of the alcohol component and the type and amount of the reactive monomer. The above-mentioned surface active component can be melt-mixed with the raw material resin, but a part or all of the added amount may be mixed with the added water in the aqueous process and added.

Among the nonionic surfactants, surfactants having a polyalkylene oxide structure are more preferred. 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 adducts (eg, polyoxyethylene secondary alcohol ether), alkylamine polyalkylene oxide adducts, polyoxyalkylene alkyl phenyl ethers (eg, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether), polyoxyalkylene sterol ether , Polyoxyalkylene lanolin derivatives, alkyl phenol formalin condensate alkylene oxide derivatives, polyoxyalkylene Glycerin fatty acid ester (such as polyoxyethylene glycerin fatty acid ester), polyoxyalkylene sorbitol fatty acid ester (such as polyoxyethylene sorbitol fatty acid ester), polyoxyalkylene glycol fatty acid ester (such as polyoxyethylene fatty acid ester), and polyoxyalkylene fatty acid amide ( Examples thereof include polyoxyethylene fatty acid amides and the like, and polyoxyalkylene alkylamines (polyoxyethylene alkylamine, ethylene oxide propylene oxide polymer adducts of alkyl alkanolamines and the like) and the like. A substance having a polyalkylene oxide structure refers to an oligomer or a chemical structure composed of a polymer formed by homopolymerization or copolymerization (block copolymerization, random copolymerization, graft copolymerization, etc.) of an alkylene oxide such as ethylene oxide or propylene oxide. Substance. The average molecular weight is from 200 to 5,000, preferably from 300 to 3,000. If the molecular weight is less than 200, the dispersing performance is low and no remarkable effect is exhibited. Further, even if the molecular weight exceeds 5,000, the resin dispersing ability decreases. Further, two or more of these may be used in combination. The surfactant component is used in an amount of 0.1 to 50 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the aqueous resin material.

The aqueous resin composition of the present invention may be used, if necessary, with another aqueous resin such as an aqueous urethane resin, an aqueous epoxy resin, an aqueous acrylic resin, an aqueous phenol resin, an aqueous amino resin, an aqueous blocked isocyanate, an aqueous polybutadiene resin. Water-based resins such as water-based alkyd resins, water-based chlorinated rubbers, and water-based silicone resins can also be used.

The aqueous resin composition of the present invention may further contain, if necessary, other pigments such as rust preventive pigments, color pigments, extender pigments, thixotropic agents, viscosity modifiers, flow aids, surface conditioners, primary rust preventives. Various additives such as antifoaming agents, preservatives, and fungicides are added in necessary amounts and mixed.

[0040]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Trial Production Example-1) In a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, a propylene-α-olefin copolymer (propylene component 75 mol%, ethylene component 20 mol%, 5 mol% of 1-butene component,
300 g of toluene was heated and dissolved in 700 g of toluene, and then 13 g of maleic anhydride and 12 g of di-t-butyl peroxide as a radical generator were added to the system for 2 hours while stirring while maintaining the system temperature at 115 ° C. Then, the mixture was aged for 3 hours. After the reaction, the reaction product was cooled to room temperature, and then poured into 20 L of acetone for purification.
A 2.1% by weight maleic anhydride graft copolymer (average molecular weight 18500) was obtained.

In the measurement of the average molecular weight, Tosoh HP
A column TSK-GEL was attached to LC-8020, the sample was dissolved in THF (tetrahydrofuran), measured at 40 ° C., and the molecular weight was determined from a calibration curve prepared using a polystyrene standard sample.

(Trial Production Example-2) In a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, a propylene-butene-ethylene copolymer (propylene component 68 mol%, butene component 24 mol%, Ethylene component 8 mol%, number average molecular weight 68000) After heating and dissolving 300 g, 40 g of maleic anhydride and 5 g of dicumyl peroxide as a radical generator were each stirred for 3 hours while maintaining the temperature of the system at 180 ° C. and stirring. Then, the reaction was performed for 3 hours. After the reaction, the resultant was cooled to room temperature. The graft amount of the purified reaction product was 6.2% by weight. The number average molecular weight measured by GPC was 26,000.

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) and 10 parts of polyoxyethylene nonylphenyl ether were added as surface active components. After stirring until uniform, 400 parts of warm water at about 90 ° C. was added successively under a pressure of 1.6 kg / cm ² to obtain an aqueous product by a phase inversion method. To the obtained aqueous product, a perfluoroalkylethylene oxide adduct was added with stirring at 0.1 part by solid content. The resin solid content in the hydrate was 23%.

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 pressurized 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) and 10 parts of polyoxyethylene nonylphenyl ether were added as surface active components. After stirring until uniform, 400 parts of warm water at about 90 ° C. was added successively under a pressure of 1.6 kg / cm ² to obtain an aqueous product by a phase inversion method. An aqueous blocked isocyanate (Coronate 2)
507W, made of Nippon Polyurethane, solid content 30%) 100 parts,
Perfluoroalkyl betaine was added with stirring at 0.1 part solids. The resin solids in the hydrate was 25%.

Example 3 In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 100 parts of the maleic anhydride graft copolymer obtained in Prototype Example 2 was heated and dissolved at 110 ° C. in 200 parts of toluene. After adding 10 parts of t-butyl peroxyisopropyl carbonate and 9.6 parts of morpholine, alkylpropenylphenol ethylene oxide 20 mol adduct 10
Parts, 2-hydroxyethyl acrylate 10 parts toluene
(120 parts) After the solution was added dropwise over 3 hours, a post-reaction was performed for 4 hours to carry out a graft copolymerization reaction. After the toluene contained in the reaction solution was distilled off under reduced pressure, 4 g of triethylamine, 10 parts of polyethylene oxide nonylphenyl ether and 0.2 part of a perfluoroalkylethylene oxide adduct were added, and water was added with stirring to obtain an aqueous solution (solid content: 25%). %).

(Comparative Examples 1 to 4) In each of the above Examples, aqueous products were prepared by changing the addition amount of the fluorine-based surfactant according to the formulation shown in Table 1.

[0048]

[Table 1]

Comparative Example 5 Chlorinated polypropylene resin
500 g of Supercron 803 MW (manufactured by Nippon Paper Industries Co., Ltd., chlorine content 29.5%, solid content wt% 20% toluene solution)
After heating at 110 ° C. and adding 9.6 g of morpholine, 25 g of polyethylene oxide nonylphenyl ether and 0.2 part of a perfluoroalkylethylene oxide adduct were added. After the toluene was distilled off under reduced pressure, water was gradually added while stirring at 100 ° C., and an aqueous resin composition (solid content: 40%) was obtained by a phase inversion emulsification method.

[0050] [Test Method] <get wet been testing method for specimen> Examples 1-3, the aqueous resin composition prepared in Comparative Example 1-5 was adjusted to 20% solids by dilution with water, dried film 10 μm thick
Was spray-coated on a polypropylene plate.
The get wet Re sex of the substrate immediately after the spray coating was evaluated on the following criteria. ◎: very good, △: good, △: slightly poor, ×: bad,
Xx: very bad

<Testing method for recoatability> The aqueous resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were spray-coated on a polypropylene plate.
Drying was performed for 20 minutes. The film thickness was adjusted to 10 to 15 μm. Next, a two-component urethane top coat was spray-coated on the coated film surface after drying so as to have a film thickness of 30 to 35 μm. Get wet is against undercoating immediately after coating, the pigment aggregation state in top coating, was evaluated by the following five steps as a comprehensive evaluation and coats of the presence or absence of inversion in the topcoat. ◎: very good, ○: good, Δ: slightly poor, ×: bad,
Xx: very bad

<Method for Preparing Specimen> The aqueous resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were spray-coated on a polypropylene plate and dried at 80 ° C. for 15 to 20 minutes. The film thickness is
It was adjusted to 10 to 15 μm. Next, a two-component urethane top coat was applied, left at room temperature for 10 minutes, and baked at 100 ° C. for 40 minutes using a hot air drier. After the obtained coated plate was stored at room temperature for one week, the coating film was tested.

<Coating film test method> [Adhesion test] A cut is made on the coating film surface to reach the substrate with a cutter, and 100 gobangs are made at 1 mm intervals. 5 degrees
It was peeled off and the number of remaining goban eyes was counted. In addition, the evaluation result was expressed as follows. ◎: very good, ○: good, Δ: slightly poor, ×: bad,
Xx: very bad

[Gasoline resistance test] A cut was made on the surface of the coating film to reach the substrate with a cutter, and the film was immersed in gasoline (Nisseki, unleaded high-octane gasoline), and abnormalities such as blistering and peeling off from the end of the coating film were observed. The time until the occurrence was measured visually. In addition, the evaluation result was expressed as follows. ◎: good for 240 minutes or more, ○: 120 to 240 minutes, △: 60 to 120
Minutes, ×: 30 minutes to 60 minutes, XX: 30 minutes or less

[Moisture resistance test] In a closed container, the lower fifth of the coated plate was immersed in water and treated at 50 ° C for 5 days.
The state of the coating film, such as the occurrence of blisters, was examined. afterwards,
Make a cut on the coating surface to reach the substrate with a cutter.
The film was peeled off and the amount of the remaining coating film was compared. In addition, the evaluation result was expressed as follows. ◎: very good, ○: good, Δ: slightly poor, ×: bad,
Xx: very bad

[Warm water resistance test] Painted board 240 in warm water of 40 ° C
After examining the state of the coating film such as the state of occurrence of time immersion blister, make a cut to reach the base with a cutter on the painted surface,
A cellophane adhesive tape was adhered thereon and peeled off five times in the direction of 180 degrees, and the amount of the remaining coating film was compared. In addition,
The evaluation results were expressed as follows. ◎: very good, ○: good, Δ: slightly poor, ×: bad,
Xx: very bad

[Bending Resistance Test] The coated plate was bent 180 ° with a 1φ inch mandrel, and the state of the coating film was examined. In addition,
The evaluation results were expressed as follows. ◎: Passed at −20 ° C., ○: Passed at room temperature, Δ:
Slightly cracked at room temperature, ×: Cracked at room temperature, XX: Broken at room temperature

[Storage stability test] A prepared aqueous resin composition sample (solid content: 20%) was placed in a glass container having a capacity of 250 ml, and at room temperature, the degree of separation of the aqueous phase from the emulsion phase and the degree of formation of resin aggregates Were compared with time. The evaluation results were expressed as follows. ：: stable for 3 months or more at room temperature, ：: stable for 1 to 3 months at room temperature, Δ: stable for 2 weeks to 1 month at room temperature, ×: 1-2 at room temperature
Weekly stable, XX: 1 week or less at room temperature

[Weather Resistance Test] In the above method for preparing a test piece, a 30 μm-thick film was formed on a glass plate by drying and baking under the same conditions as above except that the two-component urethane overcoat was not applied. -V Accelerated Weathering Tester (Q-PAN
(Manufactured by EL Co., Ltd.) to compare the weather resistance (processing conditions; light source, UVB313, 40 watts, temperature 36 ° C., processing time 400)
time). The glass plate after the treatment was evaluated for the yellowing degree of the coating using a Hunter tester. In addition, the evaluation result was expressed as follows. ◎: very good, ○: good, Δ: slightly poor, ×: bad,
Xx: very bad

[0060] Table 2 get wet it is test, recoating test, shows the results of storage stability test and the weathering test. Table 3
The results of an adhesion test, a gasoline resistance test, a moisture resistance test, a hot water resistance test, and a flex resistance test performed using each specimen are shown in FIG.

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

The aqueous resin composition of the present invention exhibits not only exhibits excellent adhesion to polyolefin exhibits excellent get wet Re sex. Further, the coating film formed thereby is excellent in moisture resistance, water resistance, flexibility and the like, and is stable to heat and light because it does not contain chlorine, and shows excellent weather resistance.
Furthermore, in the case of incineration disposal of products that have been coated, bonded, printed, surface treated, sealed, etc. using those containing them, and recycling by heat treatment, corrosive substances such as hydrochloric acid are not generated, and the equipment is corroded. There are few things.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 3/10 C09K 3/10 Z (72) Inventor Taro Abe 2-8-1 Iidacho, Iwakuni-shi, Yamaguchi Japan Nihon Paper Stock (56) References JP-A-62-215090 (JP, A) JP-A-1-158091 (JP, A) JP-A-6-80845 (JP, A) JP-A-6-80738 (JP, A) JP 40-1653 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 23/00-23/36 C09D 123/00-123/36 C09J 123 / 00-123/36 C09K 3/10

Claims (7)

(57) [Claims] 1. An aqueous resin composition obtained by using a non-chlorine-modified polyolefin resin as a raw material resin and converting the same into an aqueous resin, wherein the solid content of the non-chlorine-modified polyolefin resin is 1%.
A fluorine-containing surfactant containing a fluoroalkyl group and 0.1 to 40 parts by weight of a mixture of one or more surfactants having a polyoxyalkylene structure as a part of the hydrophilic component with respect to 00 parts by weight A non-chlorine-based aqueous polyolefin resin composition characterized by using 0.001 to 5.0 parts by weight in combination. 2. The non-chlorine-based aqueous polyolefin resin composition according to claim 1, wherein the fluorine-based surfactant is perfluoroalkylamine oxide, polyalkylene oxide perfluoroalkyl ether or perfluoroalkylbetaine. 3. A film-forming product comprising the non-chlorine-based aqueous polyolefin resin composition according to claim 1. 4. A sealing agent comprising the chlorine-free aqueous polyolefin resin composition according to claim 1. 5. An adhesive comprising the chlorine-free aqueous polyolefin resin composition according to claim 1. 6. A binder comprising the non-chlorine-based aqueous polyolefin resin composition according to claim 1. 7. A surface treating agent comprising the non-chlorine-based aqueous polyolefin resin composition according to claim 1.