JP2769958B2 - Aqueous polyolefin 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 capable of forming a coating film having excellent adhesion, flexibility, storage stability and water resistance to polyolefins, and paints, primers and inks containing them. It relates to an adhesive and a sealing agent.

[0002]

2. Description of the Related Art Conventionally, polypropylene, polyethylene,
And 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 the same is used as a coating material, a primer or an ink. And so on. However, at present, since these resins are dissolved 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. 340845), and a chlorinated acid modified with an unsaturated carboxylic acid or an acid anhydride. An aqueous resin obtained by converting a polyolefin into an aqueous solution using a surfactant and a basic substance (Japanese Patent Application No. 1-323506) has been filed. However, when a film is formed using these water-soluble polyolefin resins, there is a disadvantage that hydrophilic components such as polyols and surfactants remain in the film and are eluted by moisture, resulting in poor water resistance of the film. Was.

[0004] On the other hand, the applicant of the present invention has proposed an aqueous resin obtained by making a polyolefin resin, a chlorinated polyolefin resin, or an acid-modified polyolefin resin aqueous using a reactive surfactant (Japanese Patent Application Nos. 4-258935 and 4-258936). issue,
An application was filed for an aqueous resin (Japanese Patent Application No. 4-326118) characterized by using a combination of a modified polyolefin resin and a blocked isocyanate. An object of these inventions is to improve the water resistance of a coating by fixing a hydrophilic substance present in the coating to the coating.

However, in order to obtain a stable aqueous product having a low resin dispersing ability as compared with a non-reactive surfactant having a similar structure, a reactive surfactant must be added in a large amount or used in other polyols. , A non-reactive surfactant and the like had to be used together.

In addition, even when a crosslinked structure is introduced by combination with a blocked isocyanate to further fix a hydrophilic component, the amount of the blocked isocyanate to be used is limited in order to maintain the adhesion of the formed film to the substrate. In particular, it has been necessary to reduce as much as possible a hydrophilic substance having active hydrogen which reacts with isocyanate in order to improve the water resistance of the coating and maintain the adhesion to the substrate.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to improve water resistance and moisture resistance, which are problems when a coating or an adhesive layer is formed using an aqueous composition of a polyolefin or a modified polyolefin. .

[0008]

Means for Solving the Problems In order to achieve the above object, the present inventors diligently studied a polyolefin-based aqueous resin composition which is free from problems such as toxicity and pollution, and is excellent in safety and water resistance. As a result, in preparing the aqueous resin composition, a solubility parameter (sp value) 7 cal ^{1/2 was used.}
cm ^-3/2 or ^{12 cal} 1/2 ^{cm -3/2} polyalkylene oxide derivatives and bases in which at less
It has been found that a stable aqueous hydrate can be effectively obtained with a smaller amount by using an active substance than in the case of using alcohols, low molecular weight glycols, and other surfactants. It has also been found that when the surfactant component of the present invention is used in combination, the affinity of the aqueous solvent for the resin is improved and the amount of the surfactant used can be further reduced. Such effects also appeared when used in combination with other hydrophilic third components such as other surfactants, alcohols and glycols.

As a result, the amount of the hydrophilic component and the amount of the hydrophilic functional group in the coating formed by the prepared aqueous resin can be reduced, and the water resistance of the coating can be remarkably improved. This effect also appears when block isocyanates are used in combination, and the water resistance of the coating film is higher than when using a blocked polyisocyanate in combination with an aqueous polyolefin resin that has been made aqueous using conventional alcohols, low molecular weight glycols, and surfactants. It has been found that the properties can be further improved.

That is, the present invention relates to (A) polyolefin and / or modified polyolefin 1
00 parts by weight, (B) having a polyalkylene oxide structure solubility parameter (SP ^{value) 7cal 1/2 cm -3/2} or more 1
2cal ^1/2 cm ^-3/2 or less of surfactant ingredient 0.0
An aqueous polyolefin resin composition comprising: 0.01 to 50 parts by weight; (C) 0.01 to 25 parts by weight of a basic substance; and (D) water as a dispersion medium.

In the present invention, the aqueous polyolefin resin composition further has a polyalkylene oxide structure as a constituent and a solubility parameter (s
^{p-value) 7cal 1/2 cm -3/2} or more 12cal
^1/2 cm ^−3/2 or less and an average molecular weight of 200 to
5,000 substances in a ratio of 0.001% by weight to 50% by weight and containing polyolefin and / or modified polyolefin.
An aqueous polyolefin resin composition containing 0.01 to 25 parts of a basic substance per 100 parts of fins .

[0012]

In preparing the aqueous resin composition, a polyoxyalkylene diol represented by the following general formula (1) is used as a substance having a polyalkylene oxide structure, or in preparing the aqueous resin composition: When an aliphatic alcohol ethylene oxide propylene oxide adduct represented by the following general formula (2) is used as a substance having a polyalkylene oxide structure, or when an aqueous resin composition is prepared, a polyalkylene oxide structure is used. It is effective to use an aliphatic amine ethylene oxide propylene oxide adduct represented by the following general formula (3) as a substance.

General formula (1)

General formula (2)

General formula (3)

The modified polyolefin of the component (A) may be a chlorinated polyolefin, a polyolefin modified with an unsaturated carboxylic acid or an acid anhydride, a polyolefin modified by copolymerizing a radical polymerizable monomer, or a chlorinated polyolefin. It is more effective to use a modified polyolefin modified by a combination of two or more of any one of modification, graft and block copolymerization.

The component (B) has the general formula (1), (2),
At least one kind of the surface active component represented by (3) or the surface active component having a polyoxyethylene alkylphenyl ether structure represented by the general formula (4) is mixed with a substance having another polyoxyalkylene structure at a ratio of 1: 200 to 200:
There is an effect when used together at a ratio of 1.

General formula (4)

In preparing the aqueous resin composition, a blocked isocyanate may be incorporated as a part of the constituent during or after the aqueous conversion step.

Still another aspect of the present invention is a film-forming product such as a coating agent, a primer, or an ink, a sealing agent, and an adhesive containing any one of the above resin compositions.

Hereinafter, the present invention will be described in detail. As the polyolefin used in the present invention, a homopolymer of ethylene or propylene, or ethylene or propylene and other comonomers such as butene-1, pentene-1,
Random copolymers or block copolymers with α-olefin comonomers having 2 or more carbon atoms, preferably 2 to 6, such as hexene-1, heptene-1, octene-1, or copolymers of two or more of these comonomers Is used. The average molecular weight of the polyolefin is usually from 2000 to 100,000.
A material obtained by a known method may be used, but a material once synthesized to a high molecular weight and degraded by radicals, oxygen or heat is also used.

The chlorinated polyolefin is obtained by chlorinating the above polyolefin by a known method. The acid-modified polyolefin is a polyolefin obtained by modifying the above polyolefin with an α, β-unsaturated carboxylic acid or an acid anhydride thereof by a graft reaction. Further, a modified polyolefin modified by a combination of chlorination and acid modification is also used. Further, an aqueous modified polyolefin resin obtained by reacting a reactive surfactant with a polyolefin resin such as an acid-modified polyolefin or a chlorinated polyolefin with a radical reaction initiator is also used as an aqueous-forming raw material.

When a film is formed on a polypropylene substrate, the proportion of the propylene component is preferably at least 55 mol%, and if it is less than 55 mol%, the adhesion to polypropylene is inferior, which is not preferred.

Α, β used for modification of polyolefin
-Examples of unsaturated carboxylic acids or acid anhydrides thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, mesaconic acid, aconitic acid, and acid anhydrides thereof. The amount of graft copolymerizing the α, β-unsaturated carboxylic acid or anhydride thereof is 1 to 20.
% By weight is preferred, and if it is less than 1% by weight, the stability when dispersed in water is deteriorated, and if it exceeds 20% by weight, the grafting efficiency is deteriorated, which is uneconomical. Particularly preferably, 2 to 15
% By weight.

The number average molecular weight of the resin obtained by graft copolymerizing an α, β-unsaturated carboxylic acid or its acid anhydride is 30.
It is preferably from 00 to 40,000, and if it is less than 3000, the cohesive force is insufficient and the adhesion to the polyolefin resin is deteriorated.
If it exceeds 0000, the operability when dispersing in water is deteriorated, which is not preferable. In order to make the molecular weight fall 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 the molecular weight of the raw material is reduced. In addition,
The number average molecular weight can be measured by GPC (gel permeation chromatography).

The polyalkylene oxide structure used in the present invention has a solubility parameter (sp value) of 7
cal ^1/2 cm ^-3/2 or more ^12cal 1/2 cm
Examples of the surfactant component having a content of ^−3/2 or less include polyoxyethylene diol, polyoxypropylene diol, polyoxytetraethylene glycol, ethylene oxide and propylene, including the compounds described in the above general formulas (1), (2) and (3). Oxide copolymer, polyoxyethylene polyoxypropylene block polymer, aliphatic alcohol polyalkylene oxide adduct (polyoxyethylene aliphatic alkyl ether, etc.), secondary alcohol polyalkylene oxide adduct (polyoxyethylene secondary alcohol ether) Etc.), alkylamine polyalkylene oxide adducts, alkylamide polyalkylene oxide adducts, polyoxyalkylene alkyl phenyl ethers (polyoxyethylene nonyl phenyl ether, polyoxyethylene N-decylphenyl ether), polyoxyalkylene sterol ether, polyoxyalkylene lanolin derivative, alkylene oxide derivative of alkylphenol formalin 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), polyoxyalkylene alkylamine (polyoxyethylene alkylamine, Ethylene oxide propylene oxide polymer adduct of alkyl alkanolamine, etc.) Used. 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. Also the molecular weight
Even if it 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, preferably 3 to 30 parts, per 100 parts of the aqueous resin material.

Each solubility parameter was calculated from the chemical composition of the substance by the method of Fedors.

Surfactants which can be used in combination with the above-mentioned surfactant include a reactive surfactant and a non-reactive surfactant.

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 preferred. For example, alkyl propenyl phenol polyethylene oxide adducts, alkyl dipropenyl phenol polyethylene oxide adducts, and salts of sulfates thereof as disclosed in JP-A-4-53802 and JP-A-4-50204 are used. Among them, alkylpropenylphenol ethylene oxide 20 mol adduct, 30 mol adduct thereof, 50 mol adduct thereof, and alkylpropenylphenol polyethylene oxide 10 mol adduct sulfate ammonium salt, 20 mol adduct sulfate ammonium salt thereof Is preferred.

Further, 1-alkylphenoxy-3- (2
The -propenyl) oxypropan-2-ol ethylene oxide adduct or a sulfate thereof is excellent in resin dispersibility, and further has high polymerizability by having an α, β-unsaturated double bond, and thus is preferable. 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 reactive surfactant is used in an amount of 0.1 to 100 parts of the modified polyolefin, which is a water-based raw material resin.
Parts to 100 parts, preferably 0.1 to 30 parts.
The amount used can be changed as appropriate according to the added amount of other hydrophilic components such as non-reactive surfactants. When a reactive surfactant is used, a reaction initiator is added.
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.

Non-reactive surfactants include nonionic surfactants such as propylene glycol ester, sucrose ester, sorbitan alkyl ester, sorbitan fatty acid ester, polyglycerin ester, fatty acid alkanolamide, fatty acid monoglyceride, and alkylamine oxide; In addition to ester salts, alkylphenol sulfonates, sulfosuccinate salts and the like, carboxylate salts, phosphate ester salts and the like can also be exemplified. Anionic surfactants, amphoteric surfactants such as alkyl betaines and alkyl imidazolines, and the like. A mixture of two or more types can be used.

The amount of the non-reactive surfactant to be used is 0.1 to 100 parts, preferably 0.1 to 90 parts, per 100 parts of the modified polyolefin which is the aqueous resin material. When a surfactant having no polyoxyalkylene structure is used in combination, the total amount thereof is desirably 0.1 to 100 parts, preferably 0.1 to 30 parts, based on 100 parts of the aqueous starting resin.

[Aqueous Conversion Method] As a method for adding a surfactant having an alkylene oxide structure to a water-based raw material resin, a method in which a surface active component is added thereto while melting and stirring the raw material resin and a method in which both components are dissolved are used. There is a method of obtaining a mixture by dissolving each in an organic solvent and removing the organic solvent by distillation under reduced pressure or the like. In preparing the mixture, other surfactant components can be added. Water is added while the mixture is melt-stirred to disperse the resin in the water. In the addition of water, a part or all of the surface active component may be added to water to be added in advance to make the surface water-soluble.

In addition, in a water-forming step of an acid-modified polyolefin or the like, the dispersibility of the resin in water can be controlled by adding a basic substance to neutralize the resin and ionizing the hydrophilic group. Further, the pH of the aqueous compound can be controlled by adding a basic substance. These basic substances can be added during the melting and stirring of the resin, or can be added to the aqueous solution.

Examples of the basic substance include sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate, potassium carbonate, 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 amount of the basic substance to be used varies depending on the aqueous base resin, but is 0.01 to 25 parts.

The blocked isocyanate used in the present invention has an isocyanate group in its molecular structure, and the isocyanate group is blocked by a suitable blocking agent, and the blocking agent is deblocked under some conditions to regenerate the isocyanate group. Refers to a compound. In addition, the aqueous blocked isocyanate is a blocked isocyanate compound itself having water solubility or water dispersibility among the blocked isocyanates, or itself having water solubility and water dispersibility without adding a surfactant or a hydrophilic protective colloid. It is one that has been made aqueous by any method such as formation.

The blocked isocyanate is defined as 2 per molecule.
Isocyanate compounds having at least two isocyanate groups, for example, 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, 3,3'-dimethyl-4,
4'-diphenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate,
An excess of isocyanate such as isophorone diisocyanate and lysine isocyanate and the above-mentioned isocyanate compound, for example, ethylene glycol, propylene glycol, 1,3-butylene glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, Bifunctional or higher functional polyisocyanate, polyisocyanate having buret structure, allophanate obtained by addition reaction or addition polymerization reaction with low molecular polyol such as hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, etc. An isocyanate compound obtained by blocking a polyisocyanate having a bond, an isocyanate having a nullate structure, or the like with a blocking agent.

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, acetanilides and amides such as acetoamide. Acid amides, other imides, amines, imidazoles, ureas, carbamates, imines, oximes, mercaptans, sulfites, lactams, and the like.

That is, the blocked isocyanate referred to in the present invention includes a compound generally called a blocked isocyanate, a masked isocyanate, a reactive urethane or the like.

The ratio of the blocked isocyanate compound to the modified polyolefin can be used in the range of 1: 200 to 100: 1, preferably 1:20 to 2: 1.

The content of the isocyanate group contained in the blocked isocyanate compound and the amount of the functional group which reacts with the isocyanate group such as a hydroxyl group and a carboxyl group contained in the components remaining in the coating film after the drying treatment, such as the modified polyolefin and the surfactant component, The optimum ratio can be determined by the deblocking rate and the like under each deblocking condition (temperature, time, etc.) of the blocked isocyanate.

When a blocked isocyanate is used, it is effective to dissociate the blocking agent after the water has evaporated in the drying step, so that the dissociation temperature of the blocking agent is preferably higher than the temperature set in the drying step.

The blocked isocyanate is not necessarily water-dispersible or water-soluble, but may be any water-miscible organic solvent, surfactant, hydrophilic protective colloid or the like.

Further, in the aqueous resin composition of the present invention, a dissociation catalyst for accelerating the deblocking reaction can be used if necessary.

In the present invention, in the step of adding and blending the blocked isocyanate to the modified polyolefin resin, the modified polyolefin resin is dissolved in a solvent and the blocked isocyanate compound is added to the solution. Or an aqueous modified polyolefin resin and an aqueous blocked isocyanate compound.

In the case of an aqueous resin composition using a blocked isocyanate, after being applied to a substrate by any method, water is once dried at a temperature lower than the deblocking temperature, and then treated at a higher deblocking temperature. The reaction is advanced by activating the isocyanate. Claim 4 of the present invention
When a film is formed using the aqueous resin composition described above, the water is dried, then deblocked and reacted at 60 to 200 ° C. for 1 minute to advance the reaction between the isocyanate and other active hydrogen.
Heat treatment is performed for 2 hours. With respect to the treatment conditions, an optimum value can be set depending on the conditions for deblocking the blocked isocyanate to be used, the type and the amount of the deblocking catalyst used.

The resin composition of the present invention dispersed in water in this way has excellent adhesion to polyolefins, and is excellent not only as a primer for painting and bonding, but also as a vehicle resin for aqueous coatings, aqueous adhesives. And a binder resin for aqueous inks. Further, the aqueous resin composition of the present invention is used by adding 0.01 to 15 parts of a drying accelerating component such as alcohol, if necessary, in order to improve the evaporation rate of water during drying. In addition, various additives such as pigments such as rust preventive pigments, coloring pigments, extender pigments, thixotropic agents, viscosity adjusters, flow aids, surface conditioners, primary rust preventives, defoamers, preservatives, fungicides, etc. The required amount of the agent is added and mixed for use.

Further, other aqueous resins such as aqueous urethane resins, aqueous epoxy resins, aqueous acrylic resins, aqueous phenolic resins, aqueous amino resins, aqueous polybutadiene resins, aqueous alkyd resins, aqueous chlorinated rubbers, aqueous silicone resins, etc. Can also be used.

[0052]

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 (a propylene component of 75 mol%, an ethylene component of 20 mol%, 6 mol% of 1-butene component,
300 g of toluene was dissolved in 700 g of toluene by heating. 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 maintaining the temperature of the system at 115 ° C. with stirring. 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 melting 300 g, 40 g of maleic anhydride and 5 g of dicumyl peroxide as a radical generator were each added for 3 hours while stirring while maintaining the temperature of the system at 180 ° C. Then, the reaction was performed for 3 hours.
After cooling to room temperature after the reaction, the reaction product was poured into 20 L of acetone and purified to obtain a maleic anhydride graft copolymer having a graft amount of 6.2% by weight. The number average molecular weight measured by GPC was 26,000.

(Trial Production Example 3) 200 parts of the acid-modified polyolefin resin obtained in Trial Production Example 2 and 1,000 parts of carbon tetrachloride were charged into a reactor equipped with a reflux tube, uniformly dissolved at 65 to 70 ° C., and purged with nitrogen gas. Chlorine was blown into the reaction solution at a rate of 20 parts per hour to carry out a chlorination reaction until the chlorination degree reached 25%. After the reaction, carbon tetrachloride was replaced with toluene under normal pressure, and residual chlorine was removed to obtain a toluene solution of acid-modified chlorinated polyolefin. The toluene was distilled off from the toluene solution under reduced pressure to obtain an acid-modified chlorinated polyolefin.

(Trial Production Example 4) In a reaction vessel similar to that used in Trial Production Example 1, 100 parts of the unmodified amorphous polyolefin used in Trial Production Example 2 was dissolved in toluene, and stirred at 80 ° C. as a radical generator. 15 g of -t-butyl peroxide was added dropwise, and then toluene was distilled off under reduced pressure to give a molecular weight of 2
4000 degraded amorphous polyolefins were made.

Example 1 As shown in Tables 1 and 2, 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 dropping funnel. Then, 6 parts of morpholine was added as a basic substance while stirring, and 40 parts of polyethylene oxide was added as a surfactant. After stirring until uniform, 600 parts of water was added little by little to obtain an aqueous product by a phase inversion method. The pH of the aqueous solution was adjusted to 6 to 8, and then an aggregate having a particle size of 100 μm or more was removed by filtration to obtain an aqueous resin composition (solid content: 16%). Aggregates at 130 ° C, 24
After drying for an hour, the weight was measured. The amount of aggregates is
4.7%.

Examples 2 to 20 Example 1 was repeated except that the surfactant and the basic substance were replaced by the formulations shown in Tables 1 and 2.
Aqueous treatment was carried out in the same manner as in the above to obtain an aqueous resin composition, and the amount of generated aggregates was measured.

(Example 21) As shown in Table 3, the aqueous polyolefin resin obtained in Example 6 was stirred for 100 equivalents of the solid content of the aqueous polyolefin resin, and the aqueous isocyanate was blocked (Duranate X-1118, manufactured by Asahi Kasei Corporation). Is added as an equivalent to 100 parts as a solid content, and the water content is further adjusted to make the solid content 20%
Was obtained.

(Examples 22 to 26) In the same manner as in Example 21, various blocked isocyanates were blended at the blending ratios shown in Table 3 to obtain aqueous resin compositions.

(Comparative Examples 1 to 7) An aqueous resin composition was obtained in the same manner as in Example 1 by substituting the surfactants according to the formulations shown in Tables 1 and 2 to obtain an aqueous resin composition, and the amount of generated aggregates was measured. did.

(Comparative Examples 8 to 12) The aqueous resin obtained in Comparative Examples 1, 3, 5, 6, and 7 was mixed with the blocked isocyanate at the compounding ratio shown in Table 3 in the same manner as in Example 21 to obtain an aqueous resin composition. I got something.

[0064]

[Table 1]

[0065]

[Table 2]

The symbols in Tables 1 and 2 above represent the following. A: Polyethylene oxide B: Polypropylene oxide C ₁ : Dodecylphenol ethylene oxide 10 mol adduct C ₂ : Nonylphenol ethylene oxide 8.5 mol adduct D: Palm oil amine ethylene oxide propylene oxide 16 mol adduct (block copolymer type) E: lauryl alcohol ethylene oxide propylene oxide adduct (block copolymer type) F: laurylamine ethylene oxide propylene oxide adduct (block copolymer type) G: myristylamine ethylene oxide propylene oxide adduct (random copolymer type) H: Ethylene glycol I: Diethylene glycol J: Trimethylolpropane K: 1,6-Hexamethylenediol L: Nonylbenzenesulfur Phosphate M: Ethanol 1) chlorinated polypropylene chlorination degree of 67% (trade name SUPERCHLON 406, Sanyo Kokusaku Pulp) * The unit of sp value in the table ^cal 1/2 cm
^−3/2 .

[0067]

[Table 3]

In Table 3, A: Duranate X-1118 (manufactured by Asahi Kasei) B: Coronate 2507W (manufactured by Nippon Polyurethane) C: Elastron BN-44 (manufactured by Daiichi Kogyo Seiyaku)

The results of stability test, moisture resistance test and adhesion test of the aqueous dispersions of Examples 1 to 20 and Comparative Examples 1 to 7 after standing for one month are shown in Table 4 below.

Table 5 below shows the results of the moisture resistance test, the adhesion test result, the gasoline resistance test result, the hot water resistance test result and the flex resistance test result of Examples 21 to 26 and Comparative Examples 8 to 12. . The test method is as follows.

The aqueous resin compositions prepared in Examples 1 to 26 and Comparative Examples 1 to 12 were spray-coated on a polypropylene plate.
Drying was carried out at ℃ for 15-20 minutes. The film thickness was adjusted to 10 to 15 μm. Then, apply a two-component urethane top coat,
After leaving it at room temperature for 120 minutes,
After the heat treatment at 2 ° C. for 2 to 15 minutes, forced drying was performed at 80 ° C. for 30 minutes. After the obtained coated plate was allowed to stand at room temperature for one day, the following coating films were tested.

Adhesion test A cut was made on the surface of the coating film to reach the substrate with a cutter, and 100 goban eyes were made at 1 mm intervals, and a cellophane adhesive tape was adhered thereon, and peeled off 180 times in a direction of 180 degrees. The number of remaining goban eyes was counted.

Gasoline Resistance Test A cut was made on the surface of the coating film to reach the substrate with a cutter, immersed in gasoline (Nisseki, unleaded high-octane gasoline) for 4 hours, and the state of the coating film was visually observed.

Moisture resistance test The lower one-fifth part of the coated plate was immersed in water in a closed container.
Treated at 0 ° C. for 5 days. After examining the state of the coating such as the occurrence of prister, make a cut on the surface of the coating with a cutter to reach the substrate, adhere a cellophane adhesive tape on it and peel it off 180 times in the direction of 180 ° to remove the remaining coating Were compared.

Warm water resistance test The coated plate was immersed in warm water of 40 ° C. for 240 hours, and the state of the coating film such as blister generation was examined. The adhesive tape was adhered and peeled off five times in the 180 ° direction, and the amount of the remaining coating film was compared.

Bending resistance test A coated plate was bent 180 ° with a 1φ inch mandrel, and the state of the coating film was examined.

Storage stability test A prepared aqueous resin composition sample (solid content: 25%) 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 time of the formation of resin aggregates were measured. The changes were compared.

[0078]

[Table 4]

[0079]

[Table 5]

[0080]

The aqueous resin composition of the present invention has excellent adhesion to polyolefin, good storage stability, and good film flexibility. In addition, a water-resistant film can be formed as compared with a conventional polyolefin-based aqueous resin composition using a polyol or a surfactant. The same water resistance improving effect can be obtained in a film forming system having a crosslinked structure. Further, since it can be made water-soluble without using any organic solvent, it is excellent in terms of safety and health and environmental pollution.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 11/10 C09D 11/10 123/00 123/00 C09J 5/02 C09J 5/02 123/00 123/00 C09K 3/10 C09K 3/10 Z // C08L 23:00 (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 23/00-23/36 C08J 3/00-3/05 C09K 3/10 C09D 5 / 00 C09D 123/00-123/36 C09J 5/02 C09J 123/00-123/36 C09D 11/00-11/20

Claims (13)

(57) [Claims] 1. A (A) a polyolefin and / or 100 parts by weight of modified polyolefin, (B) a solubility parameter has a polyalkylene oxide structure (SP ^value) 7cal 1/2 ^{cm -3/2} or ^{12 cal} 1/2 cm
An aqueous polyolefin resin comprising: 0.001 to 50 parts by weight of a surface active component of ^-3/2 or less, (C) 0.01 to 25 parts by weight of a basic substance, and (D) water as a dispersion medium. Composition. 2. Component (B) has an average molecular weight of 200 to 500.
The aqueous polyolefin resin composition according to claim 1, wherein the value is 0. 3. The aqueous polyolefin resin composition according to claim 1, wherein the component (B) is a polyoxyalkylene diol represented by the general formula (1). General formula (1) n, m: an integer of 0 or more and 100 or less, 4 ≦ n + m ≦ 100 / indicates a structure obtained by random copolymerization or block copolymerization, and when either n or m is 0, it indicates a homopolymer. . 4. The aqueous polyolefin resin composition according to claim 1, wherein the component (B) is an aliphatic alcohol ethylene oxide propylene oxide adduct represented by the general formula (2). General formula (2) RO-[(PO) _m / (EO) _n ] -HR; a group consisting of a hydrocarbon having 1 to 50 carbon atoms n, m: an integer of 0 or more and 50 or less, 2 ≦ n + m ≦ 100 / indicates a structure obtained by random copolymerization or block copolymerization, and when either n or m is 0, it indicates a homopolymer. . 5. The aqueous polyolefin resin composition according to claim 1, wherein the component (B) is an aliphatic amine ethylene oxide propylene oxide adduct represented by the general formula (3). General formula (3) R: a group consisting of a hydrocarbon having 1 to 50 carbon atoms n, m; an integer of 0 or more and 50 or less, 2 ≦ n + m ≦ 100 l, k; an integer of 0 or more and 50 or less, 2 ≦ l + k ≦ 100 / represents a random copolymer or a block copolymer,
When either m or n is 0, or when either l or k is 0
In the case of, a homopolymer is shown. 6. The modified polyolefin of component (A) is a chlorinated polyolefin, a polyolefin modified with an unsaturated carboxylic acid or an acid anhydride, a polyolefin modified by copolymerizing a radical polymerizable monomer, or a chlorinated modified polyolefin. The aqueous polyolefin resin composition according to any one of claims 1 to 5, wherein the modified polyolefin is a modified polyolefin modified by combining two or more of any one of acid modification, grafting, and block copolymerization. 7. The component (B) is a compound represented by the general formula (1), (2),
The surfactant component represented by (3) or the surfactant component represented by the general formula (4)
Polyoxyethylene alkyl phenyl ether structure
At least one of the surfactant components having
A substance having a xyalkylene structure and 1: 200 to 200:
The composition according to any one of claims 1 to 6, which is used in combination at a ratio of 1.
Aqueous polyolefin resin composition. General formula (4)R: lower alkyl groupX: a hydrogen atom, a lower alkyl group, or a nonion or
Anionic hydrophilic group n; integer from 0 to 50 Y; hydrogen atom, or —CH₂-O-CH₂-CH = CH
₂  Z: hydrogen atom, or -CH = CH-CH₃  However, Y and Z do not have a double bond at the same time. 8. A modified polyolefin as the component (A), wherein the blocked isocyanate compound is used in an amount of 200: 1 to 1:
The aqueous polyolefin resin composition according to any one of claims 1 to 7, which is blended at a ratio of 100. 9. A coating agent comprising the resin composition according to any one of claims 1 to 8. 10. A primer comprising the resin composition according to any one of claims 1 to 8. An ink comprising the resin composition according to any one of claims 1 to 8. A sealing agent comprising the resin composition according to any one of claims 1 to 8. 13. An adhesive comprising the resin composition according to claim 1. Description: