JPH06256592A - Aqueous polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition providing a coating film composition having excellent adhesivity to polyolefin, flexibility, storage stability and water resistance by using a specific substance as a capillary active component in making a polyolefin and a modified polyolefin aqueous. CONSTITUTION:This resin composition comprises a polyolefin and/or a modified polyolefin as a raw material resin and contains 0.001-50wt.% of a substance having a polyalkylene structure and 7-12Cal<1/2>cm<-3/2> solubility parameter (SP value) as a surface active component. A polyoxyalkylene diol of the formula (EO is ethylene oxide; PO is propylene oxide; (n) and (m) are 0-100 and 4<=n+m<=100) is preferably used as the substance. A chlorinated polyolefin or a polyolefin modified with an unsaturated dicarboxylic acid is preferable as the modified polyolefin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous resin composition capable of forming a coating film excellent in adhesion to polyolefin, flexibility, storage stability and water resistance, and coatings, primers, inks containing them. The present invention relates to adhesives and sealing agents.

[0002]

2. Description of the Related Art Conventionally, polypropylene, polyethylene,
And modified polyolefin compositions obtained by modifying polyolefins such as propylene, copolymers of ethylene and α-olefins with unsaturated carboxylic acids or acid anhydrides, and acid-modified chlorinated polyolefins obtained by chlorinating them are coating materials, primers and inks. It is used for etc. However, at present, 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 are problems in terms of safety and hygiene and environmental pollution.

Therefore, in recent years, a water-based resin (US Pat. No. 340845) obtained by adding a polyol, a surfactant, and a basic substance to a chlorinated polyolefin to make it water-soluble, chlorinated by acid modification with an unsaturated carboxylic acid or an acid anhydride. An application has been filed for an aqueous resin (Japanese Patent Application No. 1-323506) in which a polyolefin is made aqueous by using a surfactant and a basic substance. However, when a film is formed using these water-based polyolefin resins, there is a drawback that the water resistance of the film is poor because hydrophilic components such as polyols and surfactants remain in the film and are eluted by water. It was

On the other hand, the applicant of the present invention has made a water-based resin obtained by making a polyolefin resin, a chlorinated polyolefin resin, and an acid-modified polyolefin resin water-soluble using a reactive surfactant (Japanese Patent Application Nos. 4-569935 and 4-256936). Issue, Japanese Patent Application No. 4-256937
(Japanese Patent Application No. 4-326118), which is characterized in that a modified polyolefin resin and a blocked isocyanate are used in combination. The purpose of these inventions is to improve the water resistance of the coating by immobilizing a hydrophilic substance present in the coating on the coating.

However, in order to obtain a stable aqueous product, the reactive surfactant has a lower resin dispersibility as compared with a non-reactive surfactant having a structure similar to that of the reactive surfactant. , A non-reactive surfactant and the like had to be used in combination.

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

[0007]

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

[0008]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventors diligently studied a polyolefin-based water-based resin composition which is free from problems such as toxicity and pollution and is excellent in safety and water resistance. As a result, alcohols, low molecular weight glycols, by using a polyalkylene oxide derivative having a solubility parameter (SP value) of 7 or more and 12 or less in preparing an aqueous resin composition,
It has been found that a stable hydrate can be obtained effectively in a smaller amount as compared with the case of using other surface active ingredients.
It was also found that when the surfactant of the present invention is used in combination, the affinity of the aqueous solvent for the resin is improved and the amount of surfactant used can be further reduced. Such an effect was also exhibited when used in combination with other surfactants, hydrophilic third components such as alcohols and glycols.

As a result, it was possible to reduce the amount of hydrophilic components and the amount of hydrophilic functional groups in the coating film formed from the prepared aqueous resin, and to significantly improve the water resistance of the coating film. This effect also appears when combined with blocked isocyanates, compared to conventional alcohols, low-molecular-weight glycols, and water-based polyolefin resins that have been hydrated with a surfactant, and even when combined with blocked isocyanates. It was found that the sex can be further improved.

That is, in the present invention, when a polyolefin or a modified polyolefin is made water-based, 0.001% by weight or more of a substance having a polyalkylene oxide structure as a constituent and having a solubility parameter (SP value) of 7 or more and 12 or less is used.
An aqueous polyolefin resin composition containing 50% by weight or less.

When preparing the above aqueous polyolefin resin composition, it has a polyalkylene oxide structure as a constituent and has a solubility parameter (SP value) of 7 or more.
0.001 for substances with an average molecular weight of 200 to 5000
The water-based polyolefin resin composition is contained in an amount of 50% by weight or more and 50% by weight or less.

Further, in preparing the above aqueous resin composition, it is effective to further add a basic substance in the aqueous step.

Further, in preparing the above aqueous resin composition, 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. , 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 has a polyalkylene oxide structure in preparing an aqueous resin composition. It is effective to use the aliphatic amine ethylene oxide propylene oxide adduct represented by the following general formula (3) as the substance.

General formula (1)

General formula (2)

General formula (3)

Further, as a modified polyolefin used in preparing the above aqueous resin composition, a chlorinated polyolefin, a polyolefin modified with an unsaturated carboxylic acid or an acid anhydride, a polyolefin modified by copolymerizing a radical polymerizable monomer, Alternatively, it is more effective to use a modified polyolefin such as a modified polyolefin obtained by combining two or more kinds of modification such as chlorination modification, acid modification, grafting or block copolymerization.

Further, in preparing the above aqueous resin composition, a surfactant component having a polyoxyethylene alkylphenyl ether structure represented by the following general formula (4), the above general formula (1), (2), or (3) It is effective to use at least one of the substances represented by the formula (1) in combination with another substance having a polyoxyalkylene structure in a ratio of 1: 200 to 200: 1.

General formula (4)

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

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

The present invention will be described in detail below. 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, and octene-1, or copolymers of two or more of these comonomers. Is used. The average molecular weight of the polyolefin is usually 2000 to 100000.
The product obtained by a known method may be used, but a product obtained by once synthesizing it to a high molecular weight and degrading it by radicals, oxygen or heat is also used.

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

When a film is formed on a polypropylene substrate, the proportion of the propylene component is preferably 55 mol% or more, and if it is less than 55 mol%, the adhesion to polypropylene is poor, which is not preferable.

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

The number average molecular weight of the resin obtained by graft-copolymerizing the α, β-unsaturated carboxylic acid or its acid anhydride is 30.
00 to 40,000 is preferable, and if it is less than 3000, the cohesive force is insufficient and the adhesion to the polyolefin resin is deteriorated.
When it exceeds 0000, the operability when dispersed in water is deteriorated, which is not preferable. In order to control the molecular weight within this range, it is possible to select the molecular weight of the raw material and the conditions for carrying out the graft reaction, or a method of once lowering the molecular weight of the raw material and then carrying out the graft reaction. 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
As the surface active component of 12 or more and 12 or less, the general formula (1),
Polyoxyethylene diols, polyoxypropylene diols, polyoxytetraethylene glycols, copolymers of ethylene oxide and propylene oxide, polyoxyethylene polyoxypropylene block polymers, aliphatic alcohols, including the compounds described in (2) and (3) 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 alkyl phenyl ether (polyoxyethylene nonyl fanyl ether,
Polyoxyethylene dodecyl phenyl ether, etc.), 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 alkyl) Ethylene oxide propylene oxide polymerization of amines and alkylalkanolamines Adduct) and the like. A substance having a polyalkylene oxide structure is an oligomer formed by homopolymerization or copolymerization (block copolymerization, random copolymerization, graft copolymerization, etc.) of alkylene oxide such as ethylene oxide and propylene oxide,
Alternatively, it is a substance having a chemical structure composed of a polymer.

The average molecular weight is 200 or more and 5000 or less, preferably 300 or more and 3000 or less. When the molecular weight is less than 200, the dispersibility is low and no remarkable effect is exhibited. In addition, the molecular weight
If it exceeds 5,000, the resin dispersibility will decrease. 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.

Solubility parameters were calculated from the chemical composition of each substance by the method of Fedors.

Surfactants that can be used in combination with the above-mentioned surface-active ingredients 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 preferred. For example, the alkylpropenylphenol polyethylene oxide adducts, the alkyldipropenylphenol polyethylene oxide adducts, and their sulfuric acid ester salts disclosed in JP-A-4-53802 and JP-A-4-50204 are used. Among them, alkyl propenylphenol ethylene oxide 20 mol adduct, the same 30 mol adduct, the same 50 mol adduct, and alkyl propenylphenol polyethylene oxide 10 mol adduct sulfuric acid ester ammonium salt, the same 20 mol adduct sulfuric acid ester ammonium salt Is preferred.

Further, 1-alkylphenoxy-3- (2
The -propenyl) oxypropan-2-ol ethylene oxide adduct or its sulfuric acid ester is preferable because it has excellent resin dispersibility and further has an α, β-unsaturated double bond and thus has high polymerizability. 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 with respect to 100 parts of the modified polyolefin as the water-based raw material resin.
Parts to 100 parts, preferably 0.1 to 30 parts.
The amount to be used can be changed appropriately depending on the amount of the other hydrophilic component such as a non-reactive surfactant added. When using a reactive surfactant, a reaction initiator is added.
This reactive surfactant may be reacted with the hydration raw material in advance, or may be added during the hydration step. Known reaction initiators can be used.

Non-reactive surfactants include propylene glycol esters, sucrose esters, sorbitan alkyl esters, sorbitan fatty acid esters, polyglycerin esters, fatty acid alkanolamides, fatty acid monoglycerides, nonionic surfactants such as alkylamine oxides, and alkyl sulfates. In addition to ester salts, alkylphenol sulfonates, sulfosuccinic acid ester salts, etc., carboxylate salts, phosphoric acid ester salts, etc. can be exemplified as anionic surfactants, amphoteric surfactants such as alkyl betaines, alkyl imidazolines, and the like. A mixture of two or more types can be used.

The amount of the non-reactive surfactant used is 0.1 part to 100 parts, preferably 0.1 part to 90 parts, relative to 100 parts of the modified polyolefin which is the water-based raw material resin. When a surfactant having no polyoxyalkylene structure is used in combination, it is desirable that the total addition amount thereof be 0.1 part to 100 parts, preferably 0.1 part to 30 parts, relative to 100 parts of the water-based raw material resin.

[Aqueousizing method] As a method of adding a surface-active component having an alkylene oxide structure to a water-based raw material resin, the surface-active component is added to the raw material resin while being melted and stirred, or both components are dissolved. There is a method of obtaining a mixture by dissolving each in an organic solvent and then removing the organic solvent by distillation under reduced pressure or the like. Other surface active ingredients may be added in preparing the mixture. The resin is dispersed in water by adding water while melt stirring the mixture. When water is added, it is also possible to add a part or all of the surface-active component to water to be added in advance to make it water-soluble.

In addition, by adding a basic substance to neutralize the resin and ionize the hydrophilic group in the step of water-solubilizing the acid-modified polyolefin or the like, the dispersibility of the resin in water can be controlled. Further, the pH of the hydrated product can be controlled by adding a basic substance. These basic substances can be added during the resin melt stirring, or can be added to the aqueous product.

As the basic substance, 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-
2-methyl-1-propanol, morpholine, etc. can be illustrated. The addition amount of the basic substance used is 0.01 to 25 parts, although it varies depending on the water-based raw material resin.

The blocked isocyanate used in the present invention has an isocyanate group in its molecular structure, and the isocyanate group is blocked with an appropriate blocking agent, and the blocking agent is deblocked by some conditions to regenerate the isocyanate group. Refers to a compound. Further, the aqueous blocked isocyanate is a blocked isocyanate compound itself is water-soluble or water-dispersible among blocked isocyanates, or even if it itself is water-soluble, even if it does not have water dispersibility It is made water-based by some method such as formation.

A blocked isocyanate is 2 in one molecule.
Isocyanate compounds having more than one isocyanate group, 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, 3,3'-dimethyl-4,
4'-diphenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate,
An excess of an isocyanate such as isophorone diisocyanate or 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, Hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, glycerin, bifunctional or higher functional polyisocyanate obtained by an addition polymerization reaction with a low molecular weight polyol such as pentaerythritol, a polyisocyanate having a buret structure, and allophanate It is an isocyanate compound obtained by blocking a polyisocyanate having a bond, an isocyanate having a nurate structure and 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, acetanilide and acetic amide. Acid amide type, other imide type, amine type, imidazole type, urea type, carbamate type, imine type, oxime type, mercaptan type, sulfite type, lactam type and the like.

That is, the blocked isocyanate as referred to 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 and the modified polyolefin can be used in a ratio 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 capable of reacting with the isocyanate group such as the hydroxyl group and the carboxyl group contained in the component 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 deblocking rate of the blocked isocyanate under each deblocking condition (temperature, time, etc.).

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

The blocked isocyanate may be any one that is not water-dispersible or water-soluble per se, but is made water-soluble by a water-miscible organic solvent, a surfactant, a hydrophilic protective colloid, or the like.

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

In the present invention, in the step of adding and blending a 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, 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 case of an aqueous resin composition using a blocked isocyanate, it can be obtained by applying the method to a substrate by some method, drying the water once at a temperature lower than the deblocking temperature, and then treating it at a higher deblocking temperature. The isocyanate can be activated and the reaction can proceed. Claim 4 of the present invention
In the case of forming a film using the water-based resin composition described, after drying the water, it is deblocked and the reaction between isocyanate and other active hydrogen is promoted at 60 to 200 ° C. for 1 minute to
Heat treatment is performed for 2 hours. Regarding this treatment condition, an optimum value can be set depending on the deblocking condition of the blocked isocyanate used, the type of deblocking catalyst and the addition amount.

The resin composition of the present invention thus dispersed in water is excellent in adhesion to polyolefin and is not only excellent as a primer for coating and adhesion, but also as a vehicle resin for water-based paints and water-based adhesion. It can also be applied as an agent and a binder resin for water-based inks. Further, the aqueous resin composition of the present invention is used by adding 0.01 to 15 parts of a drying promoting component such as alcohol in order to improve the evaporation rate of water during drying, if necessary. In addition, various additives such as rust preventive pigments, coloring pigments, extender pigments, thixotropic agents, viscosity modifiers, flow aids, surface modifiers, primary rust preventives, defoamers, preservatives, fungicides, etc. The required amount of the agent is added and mixed before use.

Further, other aqueous resins such as aqueous urethane resin, aqueous epoxy resin, aqueous acrylic resin, aqueous phenol resin, aqueous amino resin, aqueous polybutadiene resin, aqueous alkyd resin, aqueous chlorinated rubber, and aqueous silicone resin. It is also used by blending.

[0052]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

(Prototype Example 1) In a four-necked flask equipped with a stirrer, a cooling pipe, a thermometer and a dropping funnel, a propylene-α-olefin copolymer (propylene component 75 mol%, ethylene component 20 mol%, 1-butene component 6 mol%,
After 300 g of number average molecular weight 25,000) was dissolved in 700 g of toluene by heating, 13 g of maleic anhydride and 12 g of di-t-butyl peroxide as a radical generator were stirred for 2 hours while maintaining the temperature of the system at 115 ° C. And allowed to drip, and then aged for 3 hours. After the reaction, the reaction product was cooled to room temperature, and the reaction product was poured into 20 L of acetone for purification and the graft amount.
A 2.1% by weight maleic anhydride graft copolymer (average molecular weight 18500) was obtained.

To measure the average molecular weight, HP manufactured by Tosoh Corporation
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 (propylene component 68 mol%, butene component 24 mol%, Ethylene component 8 mol%, number average molecular weight 68000) 300 g was melted by heating, then maleic anhydride 40 g and dicumyl peroxide 5 g as a radical generator were taken for 3 hours while stirring while maintaining the system temperature at 180 ° C. And allowed to drop, and then reacted for 3 hours.
After the reaction, the reaction product was cooled to room temperature and then poured into 20 L 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 was 26000.

(Prototype Example 3) 200 parts of the acid-modified polyolefin resin obtained in Prototype Example 2 and 1000 parts of carbon tetrachloride were charged into a reactor equipped with a reflux tube and uniformly dissolved at 65 to 70 ° C., followed by purging with nitrogen gas. Chlorine was blown into the reaction solution at a rate of 20 parts per hour to carry out the chlorination reaction until the degree of chlorination 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. Toluene was distilled off from the toluene solution under reduced pressure to obtain an acid-modified chlorinated polyolefin.

(Trial Production Example 4) 100 parts of the unmodified amorphous polyolefin used in Trial Production Example 2 was dissolved in toluene in a reaction vessel similar to that used in Trial Production Example 1 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 obtain a molecular weight of 2
4000 degraded amorphous polyolefins were created.

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 tube and a dropping funnel, and 120 ° C. After heating and melting with, 6 parts of morpholine as a basic substance was added with stirring and 40 parts of polyethylene oxide as a surface-active component was added. 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 hydrated product was adjusted to 6 to 8 and further filtered to remove aggregates having a particle size of 100 μm or more to obtain an aqueous resin composition (solid content 16%). Aggregate is 130 ℃, 24
It was dried for an hour and weighed. The amount of aggregate is
It was 4.7%.

(Examples 2 to 20) Example 1 was carried out by substituting the surface active ingredient and the basic substance according to the formulations shown in Tables 1 and 2.
Aqueous treatment was carried out in the same manner as in 1. to obtain an aqueous resin composition, and the amount of aggregates generated was measured.

(Example 21) As shown in Table 3, the water-based blocked isocyanate (Duranate X-1118, manufactured by Asahi Kasei) was stirred to 100 parts of the aqueous polyolefin resin solid content obtained in Example 6 with stirring. Is added as a solid content in an amount of 100 parts, and the water content is further adjusted to obtain a solid content of 20%.
A water-based resin composition of

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

(Comparative Examples 1 to 7) The surface active components were replaced according to the formulations shown in Tables 1 and 2 to carry out water solubilization in the same manner as in Example 1 to obtain an aqueous resin composition and to measure the amount of aggregates generated. did.

(Comparative Examples 8 to 12) In the same manner as in Example 21, the aqueous resin compositions obtained by blending the hydrates obtained in Comparative Examples 1, 3, 5, 6, and 7 and the blocked isocyanate at the blending ratios shown in Table 3. I got a thing.

[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: coconut 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: nonylbenzenesulfonic acid M: ethanol 1) Chlorinated polypropylene 67% chlorination (Product name: Super Clone 406, Sanyo Kokusaku Pulp)

[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 Co., Ltd.)

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

Further, the moisture resistance test results, adhesion test results, gasoline resistance test results, hot water resistance test results and flex resistance test results of Examples 21 to 26 and Comparative Examples 8 to 12 are shown in Table 5 below. . 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,
It was dried at ℃ for 15 to 20 minutes. The film thickness was adjusted to 10 to 15 μm. Then, apply a two-component urethane topcoat paint,
After allowing to stand at room temperature for 1 minute, use a hot air dryer for 120 to 130
After heat treatment at 2 ° C for 15 minutes at 80 ° C, forced drying was performed at 80 ° C for 30 minutes. After leaving the obtained coated plate at room temperature for 1 day, the following coating film test was conducted.

Adhesion test A cut that reaches the substrate is made on the surface of the coating film with a cutter to make 100 crevices at 1 mm intervals, and a cellophane adhesive tape is adhered on it and peeled off five times in the 180 degree direction, I counted the number of remaining Gobang eyes.

Gasoline resistance test A slit that reaches the substrate was made on the surface of the coating film with a cutter, and after dipping in gasoline (Nisseki, unleaded high octane gasoline) for 4 hours, the state of the coating film was visually observed.

[0074]Moisture resistance test  Cut the coating surface to the substrate with a cutter in a closed container.
Dip the lower fifth of the coated plate in water into water at 50 ° C.
After processing for 5 days, the amount of blister, peeling from the break
The degree of was compared.

Hot water resistance test A coated plate was immersed in 40 ° C. hot water for 240 hours to examine the state of the coating film such as the blister generation state. Then, a cellophane adhesive tape was adhered onto the coated plate and drawn 5 times in the 180 ° C. direction. After peeling, the amount of the remaining coating film was compared.

Bending Resistance Test The coated plate was bent 180 degrees 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 the degree of separation of an aqueous phase from an emulsion phase and the degree of formation of resin aggregates were measured at room temperature. 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 flexibility of the coating. In addition, it is possible to form a water-resistant coating as compared with a conventional polyolefin-based water-based resin composition using a polyol or a surfactant. The same effect of improving the water resistance is brought about even in a film forming system having a crosslinked structure. Furthermore, since it can be made aqueous without using any organic solvent, it is excellent in terms of safety and hygiene and environmental pollution.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 24, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

The polyalkylene oxide structure used in the present invention has a solubility parameter (SP value) of 7
As the surface active component having 12 or more and 12 or less, polyoxyethylene diol, polyoxypropylene diol, polyoxytetraethylene glycol, ethylene oxide and propylene oxide including the compounds represented by the general formulas (1), (2) and (3) are included. 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 adduct, alkylamide polyalkylene oxide adduct, polyoxyalkylene alkyl phenyl ether (polyoxyethylene nonylphenyl E vinyl ether, polyoxyethylene ), 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 alkylalkanolamine, etc.) 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.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0074

[Correction method] Change

[Correction content]

Moisture resistance test 5% of the lower part of the coated plate was immersed in water in a closed container to form 5
It was treated at 0 ° C. for 5 days. After investigating the state of the coating film such as the occurrence of plisters, make a cut on the surface of the coating film with a cutter to reach the base material, adhere the cellophane adhesive tape on it and peel it off 180 times in the direction of 180 °, the remaining coating film Were compared in quantity.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction content]

Hot water resistance test A coated plate was immersed in hot water at 40 ° C. for 240 hours to examine the state of the coating film such as the occurrence of blister, and then a slit was made on the surface of the coating film with a cutter to reach the substrate, and cellophane was placed on it. The adhesive tape was adhered and peeled off in the 180 ° direction 5 times, and the amount of the remaining coating film was compared.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction content]

[0079]

[Table 5] ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 17, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

[0008]

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

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

That is, the present invention provides Upon to aqueous the polyolefin or modified polyolefin, a solubility parameter (sp ^value) has a polyalkylene oxide structure as a constituent 7cal ^{1/2 cm -3/2} or 12c
It is an aqueous polyolefin resin composition containing a substance having an al ^1/2 cm ^−3/2 or less in a proportion of 0.001% by weight or more and 50% by weight or less.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

When the above-mentioned aqueous polyolefin resin composition is prepared, it has a polyalkylene oxide structure as a constituent and has a solubility parameter (sp value) of 7 ca.
l ^1/2 cm ^-3/2 or more ^12cal 1/2 cm
^-3/2 in which an aqueous polyolefin resin composition comprising a and and a substance with an average molecular weight from 200 to 5,000 in an amount of 50 wt% or less 0.001% by weight or more or less.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

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
^-3/2 or less surface-active components include polyoxyethylene diol, polyoxypropylene diol, polyoxytetraethylene glycol, ethylene oxide and propylene, including the compounds described in the above general formulas (1), (2) and (3). Copolymer of oxide, 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 alkylphenyl ethers (polyoxyethylene nonylphenyl ether, polyoxyethyl 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 alkylalkanolamine, etc.) 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.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction content]

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: Coconut 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: Nonylbenzenesulfone Acid M: Ethanol 1) Chlorinated polypropylene 67% chlorination (Product name: Super Clone 406, manufactured by Sanyo Kokusaku Pulp) * In addition, the unit of sp value in the table is cal ^1/2 cm
^-3/2 .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09D 123/00 PEP 7107-4J C09J 5/02 JGP 7415-4J 123/00 JBW 7107-4J C09K 3 / 10 Z

Claims (10)

[Claims] 1. A water-soluble polyolefin and / or modified polyolefin, which has a polyalkylene oxide structure as a constituent and has a solubility parameter (SP).
Value) An aqueous polyolefin resin composition containing a substance of 7 or more and 12 or less in a proportion of 0.001% by weight or more and 50% by weight or less. 2. A substance having a polyalkylene oxide structure as a constituent and having a solubility parameter (SP value) of 7 or more and 12 or less and an average molecular weight of 200 to 5000 and 0.001% by weight or more and 50% by weight of the aqueous polyolefin resin composition. The water-based polyolefin resin composition according to claim 1, wherein the water-based polyolefin resin composition is contained in a proportion of not more than%. 3. The method according to claim 1 or 2, wherein a basic substance is further added in the step of making the aqueous solution to prepare the aqueous resin composition.
The aqueous resin composition described. 4. The aqueous resin according to claim 1, 2 or 3, wherein the polyoxyalkylene diol represented by the general formula (1) is used as a substance having a polyalkylene oxide structure in preparing the aqueous resin composition. Composition.
General formula (1) 5. An aliphatic alcohol ethylene oxide propylene oxide adduct represented by the general formula (2) is used as a substance having a polyalkylene oxide structure in the preparation of an aqueous resin composition. 3. The aqueous resin composition according to 3. General formula (2) 6. An aliphatic amine ethylene oxide propylene oxide adduct represented by the general formula (3) is used as a substance having a polyalkylene oxide structure in preparing an aqueous resin composition.
Or the aqueous resin composition according to item 3. General formula (3) 7. A modified polyolefin used for preparing an aqueous resin composition 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, Alternatively, it is a modified polyolefin such as a modified polyolefin obtained by combining two or more kinds of modification such as chlorination modification, acid modification, grafting or block copolymerization, and the like. The aqueous resin composition described. 8. A surface active component having a polyoxyethylene alkylphenyl ether structure represented by the general formula (4), a general formula (1), in preparing an aqueous resin composition,
At least one of the substances represented by (2) or (3) is in a ratio of 1:20 with another substance having a polyoxyalkylene structure.
The aqueous resin composition according to claim 1, 2, 3, 4, 5, 6, or 7, which is used in a ratio of 0 to 200: 1. General formula (4) 9. The method of preparing a water-based resin composition, wherein a blocked isocyanate is compounded as a part of the constituents during or after the water-hydration step.
The aqueous resin composition according to 4, 5, 6, 7 or 8. 10. The method according to claim 1, 2, 3, 4, 5, 6, 7,
A coating agent, a film-forming product such as a primer or an ink, a sealing agent and an adhesive, each of which contains the resin composition according to 8 or 9.