DE4338599B4 - Aqueous polyolefin resin composition - Google Patents

Abstract

An aqueous polyolefin resin composition characterized by having a substance having a poly (alkylene oxide) structure and a solubility parameter (SP value) of not less than 7 cal ^1/2 · cm ^-3/2 to not more than 12 cal ^1/2 · ^{Cm -3/2} in a proportion of not less than 0.001 wt% to not more than 50 wt% as a constituent component in the aqueous conversion of modified polyolefin, wherein the modified polyolefin is selected from one or more of the following types is:
a) a polyolefin modified by graft copolymerization with an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride,
b) a chlorinated polyolefin,
c) a polyolefin modified by graft copolymerization of a reactive monomer having radical polymerizability.

Description

The The present invention relates to an aqueous resin composition which mainly as a paint, primer, ink, adhesive and sealing material can be used. In addition, the resin composition of the present invention in the formulation of other aqueous resins and water-soluble Resins, such as water-soluble Urethane, acrylic, polyester and epoxy resin are used, the is called, it can also be used as a modifier of film-forming materials become.

There they form a film and an adhesive layer with excellent Adhesiveness Flexibility and Water resistance, especially on a non-polar surface polyolefin substrate especially as a resin for Automotive parts, etc., paint for polyolefin films, polyolefin forms, etc., primer, ink, sealant and adhesive.

traditionally, be for Paint materials, primers or inks modified polyolefin compositions used, that is modified polyolefins such as polypropylene, polyethylene and copolymers of propylene, ethylene and α-olefin with unsaturated carboxylic acid or acid anhydride and acid-modified chlorinated polyolefins. However, these resins dissolve only in aromatic organic solvents, such as toluene and xylene, so that a large amount of organic solvents must be used in terms of safety and health as well as environmental pollution Causes problems.

For this reason, in recent years, for example, an aqueous resin in which the aqueous conversion has been carried out by adding polyol, surfactant and a basic substance to chlorinated polyolefin ( US-A-340845 ), or an aqueous resin of a chlorinated polyolefin aqueous-modified using surfactant and a basic substance, which has been modified with an unsaturated carboxylic acid or anhydride ( JP-A-01-323506 ) used.

Furthermore, attempts have been made to produce aqueous dispersions of chlorinated polyolefin, such as in JP-A-1 153 778 , 1-256 556 and 2-284 973, but aromatic organic solvents are used in the preparation so that their complete elimination was difficult. Furthermore, attempts have been made to prepare aqueous dispersions of modified polyolefin, such as in US Pat JP-A-59-47244 and 2-286 724. However, when used as a paint or adhesive, they have the disadvantages of poor adhesiveness and water resistance as well as poor paintability when the articles to be coated and articles to be bonded are polyolefin resins, so that such aqueous compositions have not yet come into practical use. Furthermore, according to the JP-A-3 182 534 Attempts to improve the usefulness of a coating film by carrying out the aqueous conversion of modified chlorinated polyolefin using a surfactant and further admixing an aqueous polyurethane resin.

by virtue of of non-reactivity of the water-soluble Urethane resin and surfactants, dissolves However, the active ingredient from the coating film through Water, which due to the defect of the coating film, which appears to occur thereby, the phenomenon of reduced water resistance occurs.

Farther are used in film formation using an aqueous-converted chlorinated Polyolefin resin, wherein the aqueous conversion using of polyol and a surfactant which has been made hydrophilic Ingredients such as polyol and surfactant left in the film, which dissolve by moisture and the disadvantage of a low water resistance of the film.

There Furthermore, the chlorinated resin component is contained in large quantities arise a number of problems with disposal and recycling the final product formed in the form of, for example, a film or an adhesive layer.

The present inventors have filed a patent application relating to an aqueous resin comprising an aqueous-reacted polyolefin resin, a chlorinated polyolefin resin or an acid-modified polyolefin resin using a reactive surfactant ( JP-A-04-256 935 , 04-256 936 and 04-256 937). These inventions are aimed at improving the water resistance of the film by fixing the hydrophilic substances present in the film in the film.

The reactive surfactant is currently in the emulsion polymerization been used. It has a surface efficiency to during the Emulsion polymerization to suspend the monomer in water, and since it reacts with other monomers, it is incorporated into the structure of the Polymer added, as a result, an improvement in water resistance of the reaction product is effected.

Compared similar to a non-reactive surfactant However, structure shows the reactive surfactant less dispersibility of the resin, so that the Added amount or another polyol, non-reactive surfactant, etc. had to be used in combination to form a stable aqueous conversion product to obtain.

Aqueous block isocyanates are commonly used in fiber processing, as crosslinking agents and modifiers of resins such as latex, acrylic and urethane resin, in the surface treatment and plastic films and the like are used, but there are none Publications about new ones Uses and features in which these are treated with an aqueous polyolefin resin be combined.

Furthermore was at launch the crosslinking structure by combination with a block isocyanate and further fixation of the hydrophilic constituents also the Application rate of the block isocyanate limited to the adhesion of the formed film opposite to maintain a substrate, in particular it was necessary the hydrophilic substance with active hydrogen, which with isocyanate reacts as little as possible reduce the water resistance of the film and to maintain the adhesion to the substrate.

on the other hand becomes the aqueous conversion a polyolefin resin is generally carried out by a method at after the dissolution the resin starting material in a solvent hydrophilic ingredients, such as a surfactant and a basic substance are added and then the solvent through Water is replaced.

According to one Further methods are the resin starting material, surfactant and basic Substance mixed and at a temperature above the melting point The resin was melted and then gradually added to water to to effect the phase inversion, whereby the aqueous conversion is carried out. However, this method is conventionally under ambient pressure carried out, so that, for example in the case of high viscosity resin starting material below 100 ° C the Water addition the temperature of the resin while increasing the viscosity of the molten liquid lowered, resulting in a reduced stirring efficiency and ability a homogeneous phase reversal in many cases.

As described above, have been conventional modified polyolefin compositions as solutions in organic solvents used, causing problems with the toxicity of the solvent, the pollution, etc. occurred. Furthermore, in the case aqueous resin compositions using surfactants which should solve the above problems the inadequate water resistance still not solved satisfactorily.

The The object of the invention is to provide an aqueous resin composition, which at the same time all the above problems in terms of toxicity, pollution and low water resistance of a coating film dissolves.

Farther it is an object of the invention to solve the problem of the residual solvent, which in the conventional Process of aqueous conversion of polyolefin resins as well as the problem of residual undispersed Solids, which is caused by the heterogeneous phase reversal, to solve.

Furthermore Another object of the invention is to improve water resistance without impairment of adhesiveness and the adhesion one with the aqueous resin composition made of polyolefin or modified polyolefin film over a Substrate in the application of the aqueous resin composition.

When Result of serious research on an aqueous resin composition which have no problems, such as toxicity and pollution, and thus from the point of view of safety and also in terms of water resistance without impairment of adhesiveness and the adhesion is excellent, the inventors have made the following invention.

By Use of the block isocyanate whose isocyanate groups are blocked and do not react with water, this does not react with water at the stages of aqueous conversion adding water to the modified resin and the coating the aqueous resin composition on a substrate as well as drying, however, is deblocked underneath Formation of activated isocyanate groups when it undergoes further heat treatment at higher Temperature is subjected to drying or if it is the heat treatment by burning at a higher Temperature is exposed as the drying temperature after a further film-forming component has been coated. The activated isocyanate group reacts with remaining in the film Surfactant, the modified polyolefin or other hydrophilic groups, such as such as hydroxyl, carboxyl and amino groups, which, for example, in the overcoated Painting available. It has been shown that when used in Combined with a modified polyolefin resin an improvement effect in terms of water resistance of the film occurs by fixing the hydrophilic component or transferring the hydrophilic functional group into a more hydrophobic functional group without impairment the properties of the polyolefin.

Further, in the preparation of the aqueous resin composition, it has been found that by using polyalkylene oxide derivatives having a solubility parameter (SP value) of not less than 7 cal ^1/2 cm ^-3/2 to not more than 12 cal ^1/2 · ^{Cm -3/2} , as compared with the use of alcohols, low molecular weight glycols or other surface-active ingredients, in a smaller amount can be effectively obtained a stable aqueous conversion product. Further, when the above-described surfactants are used in combination, it has been found that the affinity of the aqueous solvent for the resin is improved, so that the application amount of the surfactant can be further reduced. Such effects also occurred in the case of the combined use of hydrophilic third components, such as other surfactants, alcohols and glycols.

consequently could the amounts of hydrophilic components and hydrophilic functional groups in the with the produced aqueous resin formed film, thereby reducing the water resistance the film considerably was improved. This effect also occurred in the case of combined Application of a block isocyanate, wherein it has been shown that the water resistance the film can be even further improved over the Using a conventional aqueous-converted polyolefin resin, when the aqueous conversion using alcohols, low molecular weight glycols and surfactants in combination with a block isocyanate.

The invention comprises an aqueous polyolefin resin composition which is characterized by having a substance having a poly (alkylene oxide) structure and a solubility parameter (SP value) of not less than 7 cal ^1/2 · cm ^-3/2 to not more as 12 cal ^1/2 · cm ^-3/2 in a proportion of not less than 0.001 wt .-% to not more than 50 wt .-% as a constituent component in the aqueous conversion of polyolefin or modified polyolefin.

The Modified polyolefin resin is a modified polyolefin which one or more types of (A) modified polyolefin, which by graft copolymerization with an unsaturated carboxylic acid and / or anhydride has been modified, (B) modified polyolefin which by Chlorination has been modified and (C) modified polyolefin, which by graft copolymerization of a reactive monomer with radical polymerizability has been modified.

Preferably is a polyolefin and / or a modified polyolefin having a melt viscosity within a viscosity range from 0.100 to 30,000 Pa · s (100 to 30,000 cps) at a temperature range of 60 to 300 ° C at the aqueous conversion used by polyolefin or modified polyolefin.

The Substance having a poly (alkylene oxide) structure preferably has an average molecular weight of 200 to 5,000.

n, m: eine ganze Zahl von nicht weniger als 0 bis nicht mehr als 100; 4 ≤ n + m ≤ 100/: eine Randomcopolymerisations- oder Blockcopolymerisationsstruktur, wenn jedoch n oder m 0 ist, bedeutet es eine Homopolymerstruktur;
ein Ethylenoxid-Propylenoxid-Addukt eines aliphatischen Alkohols der allgemeinen Formel (2):
Formel (2) RO-[(PO)_m/(EO)_n]-H worin bedeuten:
R: eine eine Kohlenwasserstoffgruppe umfassende Gruppe mit 1 bis 50 Kohlenstoffatomen;
E: -CH₂CH₂-

m, n: eine ganze Zahl von nicht weniger als 0 bis nicht mehr als 50, 2 ≤ m + n ≤ 100/: eine Randomcopolymerisations- oder Blockcopolymerisationsstruktur, wenn jedoch n oder m 0 ist, bedeutet es eine Homopolymerstruktur;
ein Ethylenoxid-Propylenoxid-Addukt eines aliphatischen Amins der allgemeinen Formel (3): Formel 3

worin bedeuten:
R: eine eine Kohlenwasserstoffgruppe umfassende Gruppe mit 1 bis 50 Kohlenstoffatomen;
E: -CH₂CH₂-

m, n: eine ganze Zahl von nicht weniger als 0 bis nicht mehr als 50, 2 ≤ m + n ≤ 100;l, k: eine ganze Zahl von nicht weniger als 0 bis nicht mehr als 50, 2 ≤ l + k ≤ 100;/: eine Randomcopolymer- oder Blockcopolymerstruktur, wenn jedoch n oder m 0 ist, oder wenn l oder k 0 ist, bedeutet es eine Homopolymerstruktur;
ein Tensid-Bestandteil mit einer Polyoxyethylenalkylphenylether-Struktur der allgemeinen Formel (4) in Kombination mit mindestens einer Art von durch die allgemeinen Formeln (1), (2) und (3) angegebenen Substanzen als Substanz mit anderer Polyoxyalkylenstruktur in einem Anteil von 1 zu 200 bis 200 zu 1: Formel (4)

worin bedeuten:
R: eine Niederalkylgruppe;

X: Wasserstoffatom, Niederalkylgruppe oder nichtionische oder anionische hydrophile Gruppe;
Y: Wasserstoffatom oder -CH₂-O-CH₂-CH=CH₂;
Z: Wasserstoffatom oder -CH=CH-CH₃,
wobei jedoch Y und Z nicht gleichzeitig eine Doppelbindung aufweisen.The substances indicated below are preferably used as the substance having a poly (alkylene oxide) structure:
a polyoxyalkylene diol of the general formula (1):
Formula 1) HO - [(PO) _n / (EO) _m ] -H in which mean:
E: -CH ₂ CH ₂ -

n, m: an integer of not less than 0 to not more than 100; 4 ≤ n + m ≤ 100 /: a random copolymerization or block copolymerization structure, but when n or m is 0, it means a homopolymer structure;
an ethylene oxide-propylene oxide adduct of an aliphatic alcohol of the general formula (2):
Formula (2) RO - [(PO) _m / (EO) _n ] -H in which mean:
R: a group comprising a hydrocarbon group having 1 to 50 carbon atoms;
E: -CH ₂ CH ₂ -

m, n: an integer of not less than 0 to not more than 50, 2 ≤ m + n ≤ 100 /: a random copolymerization or block copolymerization structure, but when n or m is 0, it means a homopolymer structure;
an ethylene oxide-propylene oxide adduct of an aliphatic amine of the general formula (3): Formula 3

in which mean:
R: a group comprising a hydrocarbon group having 1 to 50 carbon atoms;
E: -CH ₂ CH ₂ -

m, n: an integer of not less than 0 to not more than 50, 2 ≤ m + n ≤ 100; l, k: an integer of not less than 0 to not more than 50, 2 ≤ l + k ≤ 100; /: a random copolymer or block copolymer structure, but when n or m is 0, or when l or k is 0, it means a homopolymer structure;
a surfactant component having a polyoxyethylene alkylphenyl ether structure of the general formula (4) in combination with at least one kind of substances represented by the general formulas (1), (2) and (3) as a substance having another polyoxyalkylene structure in a proportion of 1 to 200 to 200 to 1: Formula (4)

in which mean:
R: a lower alkyl group;

X: hydrogen atom, lower alkyl group or nonionic or anionic hydrophilic group;
Y: hydrogen atom or -CH ₂ -O-CH ₂ -CH = CH ₂ ;
Z: hydrogen atom or -CH = CH-CH ₃ ,
however, Y and Z do not simultaneously have a double bond.

An embodiment of the invention is further an aqueous polyolefin resin composition obtainable by a method comprising the steps of, after the starting resin material is melted at an applied pressure of 0.1 to 100 bar (0.1 to 100 kg / cm ² ) and the surfactant or Alcohols and a basic substance are added, water is gradually added with stirring to effect a phase inversion, whereby the aqueous conversion with coexistence of the resin component, the water and other ingredients within a range of not less than 100 ° C to not higher is performed as 300 ° C in the aqueous conversion of polyolefin and / or modified polyolefin.

A preferred embodiment is an aqueous polyolefin resin composition of one-component type, available by the admixture or formulation of an aqueous block isocyanate to a aqueous polyolefin resin composition of the invention, in which the aqueous conversion already done in a weight proportion of 0.1: 1 to 20: 1.

A further preferred embodiment is an aqueous polyolefin resin composition of the two-component type, available by the admixture or formulation of a block isocyanate an aqueous polyolefin resin composition of the invention, in which the aqueous conversion was carried out is, in a coating process or during painting,

Preferably, a block isocyanate in which a hexamethylene diisocyanate-based polyisocyanate has been used as a starting material is used as the block isocyanate:
The invention also includes the use of the aqueous polyolefin resin composition to make a film former such as a paint, primer, ink, coating material, sealant or adhesive.

following the invention will be closer explained.

When Polyolefins to be used in the invention become homopolymers of ethylene or propylene, random copolymers or block copolymers of ethylene or propylene with other comonomers of 2 or more Carbon atoms, for example, butene-1, pentene-1, hexene-1, heptene-1, octene-1, preferably α-olefin comonomers with 2 to 6 carbon atoms or copolymers of 2 or more Types of these comonomers used. The average molecular weight of the polyolefin usually 2000 to 100000. It can obtainable by known methods Polyolefins can be used as well as one made of a polyolefin high molecular weight degraded by radicals, oxygen or heat or degraded polyolefin can be used.

The chlorinated polyolefin is a polyolefin chlorinated by known methods. The acid-modified polyolefin is a polyolefin modified with an α, β-unsaturated carboxylic acid or anhydride thereof by grafting reaction. Furthermore, a polyolefin modified by combination of chlorination and acid modification can also be used. In addition, such a polyolefin resin is also used as the starting material for the aqueous conversion, in which a reactive surfactant having a polyolefin resin such as an acid-modified polyolefin or chlorinated polyolefin, using a Ra dikalreaktionsinitiators has been implemented to carry out an aqueous modification.

at the formation of a film on a polypropylene-containing substrate is the proportion of propylene component is preferably not less than 55 mole%. If it is below 55 mol%, the adhesiveness to polypropylene becomes bad, which is not desirable is.

When for the modification of polyolefin to be used α, β-unsaturated carboxylic acids or their anhydrides can for example, maleic acid, fumaric acid, itaconic, citraconic, Allyl succinic acid, mesaconic acid, aconitic acid or whose anhydrides are called. The amount of α, β-unsaturated carboxylic acid or their anhydride for the graft copolymerization is preferably 1 to 20 wt .-%. If it is less than 1 wt .-% is the stability when dispersed in water bad, and when they are more than 20 wt .-% is, the grafting efficiency is low, which is uneconomical. Especially 2 to 15% by weight are preferred. Furthermore, the number average molecular weight of α, β-unsaturated carboxylic acid or their anhydride graft copolymerized resin is preferable 3000 to 40000. Below 3000, the cohesive force is insufficient, causing a low adhesion across from results in a polyolefin resin. Above 40000, the influence is low when dispersed in water, which is not preferred. The Adjustment of the molecular weight within this range is possible by selecting the molecular weight of the starting material or conditions the graft reaction, it is also possible to apply a method wherein the molecular weight of the starting material once decreased and then the grafting reaction is carried out. The number average Molecular weight can be determined by GPC (gel permeation chromatography) be determined.

The Method of graft copolymerization of an α, β-unsaturated carboxylic acid or their anhydride on polyolefin can be carried out according to the known methods, however, it is particularly preferable to use a method in the polyolefin by heating over the Melting point is melted and the graft copolymerization in Presence of a radical generator is performed.

According to the invention can in the preparation of an aqueous polyolefin resin composition Formulation with polyolefin, modified polyolefin or block isocyanate, basic substances, alcohols, surfactants, reactive surfactants and radical reaction initiators be added as well.

The Addition of a basic ingredient is for the purpose of better Dispersion in water by ionization of hydrophilic groups, such as such as carboxyl groups and sulfonic acid groups, however, its application is not required in some cases the reactive surfactant and non-reactive surfactant used already neutralized with a base and the like.

When Bases can Exemplary sodium hydroxide, potassium hydroxide, ammonia, methylamine, Ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, Propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, Diethylamine, triethylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine, etc. may be mentioned. Of the Degree of hydrophobicity of the resin can depend on the base used vary so that depending on the conditions a appropriate selection is required.

The The amount of the basic substance to be used is suitably within of the range of 0.3 to 1.5 times the equivalent weight in terms of Carboxyl group of the acid-modified Polyolefins, preferably in the range of 0.5 to 1.2 times. Farther it is necessary in some cases when adding a basic substance the pH of the aqueous resin composition to be prepared to regulate that way in the neutrality range lies, depending stability of the admixed block isocyanate.

In the invention, the addition of alcohols, such as a monoalcohol or polyol, occurs due to an increased affinity of the starting resin material for water, which effect allows a reduced amount of application of the surfactant. Furthermore, it also becomes possible to increase the evaporation rate of water in the film formation. However, if alcohol remains in the resin during film formation, it reduces the water resistance of the coating film, so that an appropriate amount is required, with the addition of 4 to 200 parts per 100 parts of starting resin material being preferred. When less than 4 parts, the dispersibility in water becomes poor, and when more than 200 parts, the decrease in water resistance becomes remarkable. As monoalcohols, for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, ethylene glycol monoalkyl ether, ethylene glycol monoacetate, propylene glycol monoalkyl ether, propylene glycol monoacetate, etc. may be mentioned, and as polyols, for example, ethylene glycol, diethylene glycol, triethylene glycol , Propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, Glycerol, polyethylene glycol, etc. may be mentioned. Among these, highly hydrophilic polyols are preferred.

When in the invention to be used with surface active ingredients a polyalkylene oxide structure and a solubility parameter (SP value) of not less as 7 to not more than 12, for example, polyoxyethylene diol, Polyoxypropylene diol, polyoxytetraethylene glycol, copolymer of ethylene oxide with propylene oxide, poly (alkylene oxide) adduct of an aliphatic alcohol (Polyoxyethylene aliphatic alkyl ether, etc.), poly (alkylene oxide) adduct a sec-alcohol (polyoxyethylene-sec-alcohol ether, etc.), poly (alkylene oxide) adduct an alkylamine, poly (alkylene oxide) adduct of an alkylamide, polyoxyalkylene alkylphenyl ethers (Polyoxyethylene nonylphenyl ether, polyoxyethylene dodecylphenyl ether, etc.) Polyoxyalkylensterolether, Polyoxyalkylenlanolinderivat, oxidized Alkylene derivative of an alkylphenol formalin condensate, Polyooxyalkylenglycerinfettsäureester (polyoxyethylene etc.), polyoxyalkylene sorbitol fatty acid ester (polyoxyethylene sorbitol fatty acid ester etc.), polyoxyalkylene glycol fatty acid esters (Palyoxyethylenglykolfettsäureester etc.), polyoxyalkylene fatty acid amide (Polyoxyethylenfettsäureamid etc.), polyoxyalkylene alkylamine (polyoxyethylene alkylamine, ethylene oxide-propy lenoxidpolymer adduct of an alkylalkanolamine, etc.), including the above compounds of the formulas (1) to (4) used. The Substance with a polyalkylene oxide structure is a substance with a chemical structure comprising an oligomer of one by homopolymerization or copolymerization (block copolymerization, random copolymerization, Graft copolymerization, etc.) of alkylene oxides such as ethylene oxide and propylene oxide, polymers produced. The average molecular weight is not less than 200 to not more than 5000 and preferably not less than 300 to not more than 3000. If the molecular weight Below 200, the dispersibility is low and it turns out no remarkable effect. On the other hand, if the molecular weight exceeds 5,000 is, then decreases the dispersibility of the resin. Farther can These are used in combination of two or more species. The aforementioned surface-active Component is added in amounts of 0.1 to 50 parts per 100 parts of starting resin material for the aqueous conversion and preferably from 3 to 30 parts.

Of the solubility is determined by the chemical composition of the corresponding substance the Fedor's Method calculated.

The Surfactants which combine the combined with the surface active Allow components, include reactive surfactants and non-reactive surfactants.

The reactive surfactant may be one which is generally used as a reactive surfactant or a reactive emulsifier, but one having an alkylphenyl group as a hydrophobic group and a polyoxyethylene group as a nonionic hydrophilic group is preferable. For example, a polyethylene oxide adduct of an alkylpropenylphenol, a polyethylene oxide adduct of an alkyldipropenylphenol, and salts in the form of sulfates, such as those described in U.S. Pat JP-A-4-53802 and 4-50204. Among them, preferred are a 20 mole, 30 mole or 50 mole ethylene oxide adduct of alkyl propenyl phenol and an ammonium sulfate salt of a 10 mole or 20 mole ethylene oxide adduct of alkyl propenyl phenol. Further, an ethylene oxide adduct of 1-alkylphenoxy-3- (2-propenyl) oxypropan-2-ol or its sulfate is excellent in dispersibility of the resin, furthermore, the polymerizability is also high because of its unsaturated double bond, which is preferable. These reactive surfactants can be reacted with the starting resin material for aqueous conversion by known methods using a radical reaction initiator to be fixed in the resin.

The Application amount of the reactive surfactant is 0.1 to 100 parts per 100 Parts of modified polyolefin as starting resin material for aqueous conversion, preferably 0.1 to 30 parts.

The Application quantity may vary depending on the amount of a non-reactive surfactant, etc. as another hydrophilic component changed become. When using a reactive surfactant, the reaction initiator becomes used. The reactive surfactant may be pre-mixed with the starting material for the aqueous conversion be implemented or it may be during the aqueous conversion process be added. As reaction initiators, the well-known be used.

When non-reactive surfactants can nonionic surfactants, such as propylene glycol esters, sucrose esters, sorbitan alkyl esters, sorbitan Polyglycerol esters, fatty acid alkanolamide, Fatty acid monoglyceride and Al kylaminoxid, anionic surfactants such as alkyl sulfate, alkylphenolsulfonate, Sulfosuccinate, as well as carboxylate, phosphate, etc., ampholytic surfactants, such as alkylbetaine and alkylimidazoline and the like, as well as mixtures of two or more kinds thereof may be used.

The addition amount of the surface-active ingredient as a combination of the non-reactive surfactant with reactive surfactant is 1 to 100 parts per 100 parts of modified polyolefin, the necessary content may vary depending on the combination and the proportion of the surface active ingredients, the amount of addition of the alcohol component and the kind and amount of the reactive monomer.

Of the surfactants Component can be melted and mixed with the base resin material, however, he can after mixing with a part or the whole Addition amount of water can be added.

When Reactive monomers to be used in the invention may include acrylic monomers, such as acrylic acid, Methacrylic acid, Methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, Acrylonitrile, acrylamide and hydroxyethyl acrylate, conjugated diene monomers, such as butadiene, isoprene and chloroprene, halogenated olefin monomers, such as vinyl chloride and vinylidene chloride, aromatic monomers, such as styrene and divinylbenzene, vinyl ester monomers, such as Vinyl acetate, methyl maleate, maleic anhydride, etc., called become.

reaction initiators for initiating the reaction of the reactive monomer and reactive Surfactants can be well known, with both water-soluble initiators and oil-soluble initiators, such as azobisisobutyronitrile, hydrogen peroxide and potassium persulfate, can be used. Likewise Redox initiators are used. Furthermore, these can be used in combination become.

When organic peroxides can for example, benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, cumene hydroperoxide, etc. be mentioned, these depending on the reaction temperature and reaction time selected become.

The used aqueous block isocyanate compound denotes such a compound, which in its molecular structure has an isocyanate group, wherein the isocyanate group with a suitable blocking agent is blocked, and which itself is water soluble or water dispersible or, if not themselves water soluble or water dispersible is that they by any method, such as adding a surfactant or forming a hydrophilic protective colloid, water convertible is.

The Block isocyanate is an isocyanate-blocked polyisocyanate compound with two or more functions, available by addition reaction or addition polymerization reaction between isocyanate; connection with two or more isocyanate groups in one molecule, for example Isocyanate, 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, isophorone diisocyanate or lysine isocyanate and excess of these Isocyanate compound and low molecular weight polyol, for example Ethylene glycol, propylene glycol, 1,3-butylene glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, Hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, Glycerine, pentaerythritol or the like, polyisocyanate with biuret structure, Polyisocyanate with allophanate bond, isocyanate with isocyanurate structure or the like with a blocking agent. Such blocking agents include phenolic types such as phenol and cresol, alcohol types, such as methanol, benzyl alcohol and ethylene glycol monomethyl ether, those of the active methylene type, such as methyl acetoacetate and dimethyl malonate, acid amide types, such as acetanilide and acetomide and also of the imide type, amine type, Imidazole type, urea type, carbamate type, imine type, oxime type, mercapto type, Sulfite type, lactam type and the like. In other words, include the block isocyanates referred to as such compounds which generally as blocked isocyanate or block isocyanate, masked Isocyanate and reactive urethane can be referred to or similar Links. The relationship from block isocyanate compound to modified polyolefin is within of the range from 1:20 to 10: 1.

Regarding the content of the isocyanate groups contained in the block isocyanate compound and the number of functional groups, which with the isocyanate groups react, such as hydroxyl groups and carboxyl groups, which contained in the components which in the coating film remain after the drying treatment, as modified Polyolefin and surfactant Ingredients, the optimum proportion may be due to the reaction rate of the block isocyanate under appropriate deblocking conditions (Temperature, time, etc.) of the block isocyanate.

When using the block isocyanate it comes to the dissociation of the blocking agent after the Evaporation of moisture in the drying process, so that the dissociation temperature of the blocking agent is preferably higher than the temperature set in the drying process.

The Block isocyanate may be water dispersible or water soluble or it can not be converted to water.

Farther in the aqueous resin composition, if necessary, use a catalyst to initiate the deblocking reaction and the reaction of the activated isocyanate group with another to promote active hydrogen.

When Catalysts can for example dibutyltin laurate, dibutyltin fatty acid salt, Dibutyltin diacetate, tetra-n-butyl-1,3-diacetoxydistannoxane, tetra-n-butyl-1,3-dilauryloyldistannolane, Di-n-butyltin oxide, mono-n-butyltin oxide, tin (II) octylate, etc. to be named.

At the Method of adding and formulating the block isocyanate to the modified polyolefin resin may be the aqueous conversion in the manner carried out be that modified polyolefin resin is dissolved in a solvent and that after Add the block isocyanate compound to this solution, replacing the solvent with water will, or that modified polyolefin resin after the aqueous conversion to the aqueous block isocyanate compound is mixed or prepared for use.

in the Case of an aqueous resin composition using block isocyanate, this becomes a substrate coated by any method and after a single drying at a temperature below the deblocking temperature Removal of moisture, this will continue at the higher deblocking temperature treated, whereby the isocyanate is activated to the reaction to let progress. When using the block isocyanate-containing aqueous polyolefin resin composition to form the film is the heat treatment while 1 to 2 hours at 60 to 200 ° C performed to effect deblocking and the reaction between isocyanate and further active hydrogen after Drying to remove moisture. With regard to these treatment conditions, the optimal values in dependence the deblocking conditions of the used block isocyanate and set the type and the addition amount of Deblockierungskatalysators become.

The An aqueous resin composition of the present invention can also by means of well-known aqueous conversion process for polyolefin resins be prepared, such as an aqueous conversion method by Solvent exchange and an emulsification process by phase inversion at ambient pressure.

When Method for adding the surface-active Component of the starting resinous material for the aqueous conversion are suitable a method in which the surface-active ingredient under stir to the molten starting resin material and a method to obtain a mixture by dissolving both components in an organic solvent, which to their resolution is capable and then remove the organic solvent by distillation under reduced pressure, etc. The mixture becomes melted and water gradually with stirring added to effect the phase inversion and thus the resin in to disperse the water. When adding water, it is also possible to have a part or the entire amount of the surface active ingredient beforehand in the water to be used to solve the aqueous conversion perform.

Farther it is the aqueous conversion process of, for example, acid-modified Polyolefin possible, the dispersibility of the resin in the water by adding the basic To regulate substance to neutralize the resin and hydrophilic Ionize groups. Furthermore, it is also possible to adjust the pH of the aqueous conversion product by adding the basic substance to regulate. This basic Substance can during stirring of the molten resin or may be added to the aqueous conversion product become.

According to the invention was still with regard to the aqueous conversion process developed a new method, which has the disadvantages of the known Process improved.

This consists in an aqueous conversion process which is characterized in that in the aqueous conversion of polyolefin and / or modified polyolefin a starting material mixture which is a mixture of starting resin material with other starting materials for aqueous conversion (other hydrophilic components, such as surfactant and basic substance), is mixed above the softening temperature of the raw material mixture and below its decomposition temperature, and water is gradually added to the molten raw material mixture with further stirring, thereby effecting the high temperature phase transformation.

in this connection it is necessary to add the added water at a higher temperature as the softening temperature of the raw material mixture liquid to keep increasing the internal pressure of the reaction device. The is called, by applying pressure to the water at a temperature which for the aqueous conversion As a condition has been set to keep liquid, can liquid water and the starting material mixture at the set temperature coexist, allowing homogeneous phase inversion.

The temperature to be used herein for the aqueous conversion is above the softening temperature of the raw material mixture and below its thermal decomposition temperature, but not less than 100 ° C to not higher than 300 ° C, and preferably not lower than 110 ° C to not higher than 250 ° C. The pressure to be applied is 0.1 to 100 bar (0.1 to 100 kg / cm ² ), preferably 0.5 to 50 bar (0.5 to 50 kg / cm ² ).

at the preparation of the starting material mixture can be heated, melted and at ambient pressure, or may be mixed under these conditions melted and mixed. Water can be added to the water high temperature and under high pressure, as reaction conditions for the aqueous conversion set, gradually may be added to the system or it may be heated at ambient pressure gradually fed to the system become.

When Reaction device for the aqueous conversion only has to one with a stirrer equipped pressure reaction device according to the conditions for the aqueous conversion be used, but under the conditions of a higher temperature and a higher one Pressure as well as a pressurized high temperature extruder etc. can be used.

The water-dispersed resin composition of the present invention in this manner is not only excellent in adhesiveness to polyolefin and excellent as a primer or primer for a paint or varnish as well as the adhesion, but also applicable as a carrier resin an aqueous color, as an aqueous adhesive, Binder resin of an aqueous ink and as an aqueous coating material. Furthermore you can in the aqueous resin composition of the present invention, if necessary, 0.01 to 15 parts of a drying support Constituents are added, such as an alcohol, to the moisture evaporation rate to improve when drying. In addition, various additives in necessary quantities for the end use is added and mixed in, such as pigments, including Antirust pigments, coloring pigments and extender pigments, thixotropic agents, viscosity modifiers, liquefying aids, surface modifier, primary Anti-rust agent, defoamer, antiseptic agents and mold release agents.

As well can other aqueous resins for the Be mixed in application, for example, 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.

in the Case of an aqueous resin composition with used block isocyanate, this is by any method coated on a substrate and after the single drying at a temperature below the deblocking temperature Removal of moisture continues at the higher deblocking temperature which activates Isocy anate to progress the reaction allow. When using the aqueous resin composition to form a film, the heat treatment during 1 Minute to 2 hours at 60 to 200 ° C performed to effect deblocking and the reaction between isocyanate and other active hydrogen after drying to remove moisture to proceed to let. With regard to these process conditions, the optimal values depending on the Deblocking conditions of the block isocyanate used and the Type and amount of addition of Debloekierungskatalysators set become.

following the invention will be explained in more detail by way of examples.

Production Example 1

In one with stirrer, Cooling tube, Thermometer and dropping funnel equipped four-necked flask were 300 g of propylene-α-olefin copolymer (Propylene component 75 mole%, ethylene component 20 mole% and 1-butene component 5 mole%; number average molecular weight 25,000) in 700 g of toluene under heating solved, then while maintaining the temperature of the system at 115 ° C with stirring, 13 g of maleic anhydride and 12 g of di-t-butyl peroxide added as a radical generator dropwise for 2 hours and afterwards during 3 hours of aging. After the reaction, the reaction product was cooled to room temperature and then in 20 l of acetone for purification, wherein a maleic anhydride graft copolymer with a grafting rate of 2.1% by weight (average molecular weight 18500).

to Determination of the average molecular weight was a TSK-GEL column on an HPLC-8020 (manufactured by Tosoh Corp.), the sample was in THF (Tetrahydrofuran) dissolved and the measurement at 40 ° C carried out. The molecular weight was determined by using a polystyrene standard sample determined calibration curve determined.

Production Example 2

In one with stirrer, Cooling tube, Thermometer and dropping funnel equipped four-necked flask were 300 g of propylene-butene-ethylene copolymer (propylene component 68 mol%, Butene component 24 mol% and ethylene component 8 mol%, number average Molecular weight 68,000) with heating, then under Keep the temperature of the system at 180 ° C with stirring 40 g of maleic anhydride and 5 g of dicumyl peroxide as a radical generator dropwise during 3 Hours were added and then the reaction was carried out for 3 hours. To In the reaction, the reaction product was cooled to room temperature and then in 20 l of acetone for purification, wherein a maleic anhydride graft copolymer with a grafting rate of 6.2% by weight. The means GPC number average molecular weight was 26,000.

Production Example 3

In a reactor equipped with a reflux condenser 200 parts of the acid-modified product obtained in Preparation Example 2 were obtained Polyolefin resin and 1000 parts of carbon tetrachloride. After homogeneous dissolution at 65 to 70 ° C The inside air was purged with nitrogen gas, after which it became the chlorination reaction Chlorine gas in the reaction liquid in a relationship blown in from 20 parts per 1 hour until the degree of chlorination 25% achieved. After the reaction, carbon tetrachloride became replaced by toluene and at the same time remaining chlorine at ambient pressure removed to a toluene solution an acid modified to obtain chlorinated polyolefin. Toluene was absorbed by the toluene solution distilled off under reduced pressure to form an acid-modified chlorinated To obtain polyolefin.

Production Example 4

in the same reactor as used in Preparation Example 1 were 100 Parts of unmodified used in Preparation Example 2 amorphous polyolefin dissolved in toluene and 15 g of di-t-butyl peroxide added as a radical generator dropwise at 80 ° C with stirring. After that was Toluene distilled off under reduced pressure to a degraded or degraded amorphous polyolefin having a molecular weight to get from 24,000.

example 1

In one with stirrer, Thermometer, cooling tube and dropping funnel equipped Reactor were 100 parts of that obtained in Preparation Example 1, given modified polyolefin. After melting at 120 ° C with warming were 6 parts of morpholine as a basic substance with stirring and further 40 parts of polyethylene oxide as a surface-active Ingredient added. After stirring until obtaining a homogeneous 600 parts of water were added in small portions, wherein obtained by the phase inversion method, an aqueous conversion product has been. After adjusting the pH of the aqueous conversion product on 6 to 8 were the aggregates with a particle diameter of more than 100 μm removed by filtration to an aqueous resin composition (solids content 16%). The aggregates were dried for 24 hours at 130 ° C, to determine their weight. The amount of aggregates was 4.7%, based on the starting resin material.

Examples 2 to 20

Under Replacing the surfactant Ingredient and the basic substance according to those shown in Tables 1 and 2 Formulations, by the same method as in Example 1 the aqueous conversion carried out, to aqueous resin compositions while also measuring the amount of aggregates produced has been.

Example 21

To a 100 parts solids equivalent amount of the example 1 of the obtained aqueous polyolefin resin For example, an amount corresponding to 100 parts of solids was aqueous-converted Block isocyanate (Duranate X-1118, manufactured by Asahi Chemical Industry Co.) with stirring, Further, the water content was adjusted to be an aqueous resin composition to obtain with a solids content of 20%.

Examples 22 to 26

Similar example 21, various block isocyanates were shown in Table 3 preparation conditions blended to aqueous resin compositions to obtain.

Example 27

In one with stirrer, Thermometer, cooling tube and dropping funnel equipped pressure reactor were 100 parts of the modified polyolefin obtained in Production Example 1 given. After melting at 120 ° C with heating, 6 parts of morpholine as a basic substance with stirring and further 40 parts of polyethylene oxide as a surface active agent Added ingredient. After stirring until obtaining a homogeneous Mixture, the reaction system was sealed and with nitrogen gas to an overpressure of 2 atm adjusted. Then, 600 parts of warm water of 90 ° C in portions with stirring added to an aqueous conversion product by the phase inversion method to obtain. When adding the warm water, the temperature became kept within the system at 110 to 120 ° C. The aqueous conversion product was at 40 ° C chilled and the pressure is lifted. After adjusting the pH to 6 to 8, the aggregates with a particle diameter of more than 100 μm through Filtration removed to an aqueous resin composition (Solids content 16%). The aggregates were during 24 Hours at 130 ° C dried to determine their weight. The amount of remaining Aggregate was less than 0.05 wt .-%, based on the starting resin material.

Example 28

In one with stirrer, Thermometer, cooling tube and dropping funnel equipped pressure reactor were 100 parts of the modified polyolefin obtained in Production Example 2 brought in. After melting at 120 ° C with heating, 10 parts of diethylamine as a basic substance with stirring and further 20 parts of an ethylene oxide-propylene oxide adduct of Laurylamine as a surface active Added ingredient. After stirring until obtaining a homogeneous Mixture, the reaction system was sealed and with nitrogen gas to an overpressure set of 15 atm. Then, 600 parts of warm water of 90 ° C in portions with stirring added to an aqueous conversion product by the phase inversion method to obtain. When adding the warm water, the temperature became kept within the system at 180 to 190 ° C. After complete addition of the warm water, the system was kept under stirring for 1 hour. The aqueous conversion product was at 40 ° C chilled and the pressure is lifted. After adjusting the pH to 6 to 8, the aggregates with a particle diameter of more than 100 μm through Filtration removed to an aqueous resin composition (Solids content 16%). The aggregates were during 24 Hours at 130 ° C dried to determine their weight. The amount of remaining Aggregate was 0.05 wt .-%, based on the starting resin material.

Example 29

Into a four-necked flask similar to that used in Preparation Example 1, 100 g of the maleic anhydride graft copolymer obtained in Preparation Example 1 was melted at 120 ° C under heating, after adding 10 g of ethylene glycol and 15 g of morpholine, 10 g of a 10-mole ethylene oxide adduct of 1-alkylphenoxy -3- (2-propenyl) oxypropan-2-ol (Adeka Reasoap NE-10, manufactured by Asahi Denka Kogyo KK), the temperature was lowered to 110 ° C, and water of 90 ° C was gradually added to prepare an aqueous reaction liquid , To this was added 10 g of sodium persulfate as a radical reaction initi Ator added and the reaction carried out for 4 hours at 80 ° C with stirring, so as to carry out the polymerization reaction. After the reaction, 4 g of triethylamine was added to obtain an aqueous converted reaction liquid (solid content of 30%). After treating for 48 hours with an ultrafiltration membrane having a fractional molecular weight of 5,000, the aqueous converted reaction liquid was again concentrated to obtain an aqueous acid-modified polyolefin resin having a solid content of 45%. The aqueous acid-modified polyolefin resin thus obtained and an aqueous block isocyanate (Elastoron BN-69, manufactured by Kai-ichi Kogyo Seiyaku Co.) were mixed at a solid content of 2: 1 to obtain an aqueous resin composition.

Example 30

In similar to a four-necked flask 100 g of that used in Preparation Example 1 was used in Preparation Example 1 2 maleic anhydride graft copolymers obtained in 200 g of toluene at 110 ° C under warming solved and after addition of 10 g of t-butyl peroxyisopropyl carbonate and 9.6 g. Morpholine was a toluene (120 g) solution of 10 g of a 20 mol ethylene oxide adduct of alkylpropenylphenol (Aquaron RN-20, manufactured by Dai-ichi Kogyo Seiyaku Co.) was added dropwise over 3 hours, then there was an after-reaction during 4 hours, so as to carry out the graft copolymerization. After distilling off the in the reaction liquid containing toluene under reduced pressure, 4 g of triethylamine and 20 g of propylene glycol monomethyl ether and water under stir added to an aqueous converted reaction liquid (Solids content 25%). After treatment during 48 Hours with an ultrafiltration membrane with a fractional molecular weight from 5000 the aqueous was transformed Reaction fluid again concentrated to an aqueous, acid-modified To obtain polyolefin resin having a solids content of 40%. To this aqueous acid-modified Polyolefin resin became an aqueous block isocyanate (Elastoron BN-08, manufactured by Dai-ichi Kogyo Seiyaku Co.) in a solids ratio of 2: 1 added to an aqueous resin composition to obtain.

Example 31

In similar to a four-necked flask 100 g of that used in Preparation Example 1 was used in Preparation Example 1 2 maleic anhydride graft copolymers obtained at 110 ° C under heating melted and after addition of 40 g of ethanol, 5 g Polyethylenoxidnonylphenylether (NS-212, manufactured by Nippon Oil and Fats Co.) and 9.6 g morpholine was the temperature at 100 ° C kept and water of 90 ° C with stirring added to an aqueous acid-modified Polyolefin resin composition (solids content 45%) to obtain. To this aqueous modified Polyolefin resin became an aqueous block isocyanate (Colonate 2507W, manufactured by Nippon Polyurethane Industry Co.) in a solids ratio of 4: 3 is added to an aqueous resin composition to obtain.

Example 32

After this 500 g Superclone 803MW (manufactured by Nippon Paper Industries Co., Ltd., chlorine content 29.5%, solid content 20% by weight, toluene solution) at which is a chlorinated polypropylene resin, heated to 110 ° C and 9.6 g of morpholine were added, 5 g of polyethylene oxide nonylphenyl ether (NS-212, manufactured by Nippon Oil and Fats Co.). After distilling off of the toluene under reduced pressure was added 20 g of ethylene glycol and water at 100 ° C with stirring added to an aqueous resin composition (Solids content 40%). The resulting aqueous, chlorinated Polyolefin resin and an aqueous block isocyanate (Elastoron BN-44, manufactured by Dai-ichi Kogyo Seiyaku Co.) were used in a Solid ratio of 2: 1 mixed to form an aqueous resin composition to obtain.

Example 33

In 200 g of toluene were 100 g of an acid-modified polyolefin resin, obtained using a low-viscosity acid-modified Polyolefin resin (molecular weight = 12,000, grafting rate 9.6% by weight), which by replacing the used in Preparation Example 2 Starting polyolefin material degraded by oxidative at 60 ° C. Polyolefin (molecular weight = 30,000) was obtained, dissolved, and after Addition of 50 g of TDI-based block isocyanate (Desmodule BL-1100, manufactured by Sumitomo Bayer Urethane Co.), 5 g of polyethylene oxide nonylphenyl ether (NS-212, Nippon Oil and Fats Co.). After distilling off of toluene under reduced pressure was added 20 g of ethylene glycol and water at 100 ° C with stirring added to an aqueous resin composition (Solids content 40%).

Comparative Examples 1 to 7

By Replacing the surfactant Component according to the in Table 1 showed the aqueous conversion after the same Method as in Example 1, to aqueous resin compositions The quantities of generated aggregates were also measured.

Comparative Examples 8 until 12

In The same manner as in Example 21, that in Comparative Examples 1, 3, 5, 6 and 7 obtained aqueous, converted products with block isocyanate with those given in Table 2 mixing ratios blended or formulated to aqueous resin compositions to obtain.

Comparative Example 13

In similar to a four-necked flask 100 g of that used in Preparation Example 1 was used in Preparation Example 1 2 maleic anhydride graft copolymers obtained at 110 ° C under warming melted, and after addition of 9.6 g morpholine were 15 g Polyethylenoxidnonylphenylether (NS-212, Nippon Oil and Fats Co.). Then water got under stir added to an aqueous resin composition (Solids content 40%).

Comparative Example 14

After this 500 g Superclone 803MW (manufactured by Nippon Paper Industries Co., Ltd., chlorine content 29.5%, solid content 20% by weight, toluene solution) at which is a chlorinated polypropylene resin, heated to 110 ° C and To 9.6 g of morpholine was added 15 g of polyethylene oxide nonylphenyl ether (NS-212, manufactured by Nippon Oil and Fats Co.). To Distilling off the toluene under reduced pressure became water at 100 ° C with stirring added to an aqueous resin composition (solid content 40%).

Comparative Examples 15 and 16

To 100 g solids content of those prepared in Examples 29 and 30 aqueous, acid-modified polyolefin resins was a predetermined amount of Superflex 110 (manufactured by Dai-ichi Kogyo Seiyaku Co.), which is a nonionic aqueous urethane resin ester type, added in place of the aqueous block isocyanate and then water while stirring added to aqueous resin compositions to obtain a solids content of 45%.

The Results of the stability test, moisture resistance test and Adhesion test of the aqueous dispersions Examples 1 to 20 and Comparative Examples 1 to 7, after these are kept for 1 month are shown in Table 4.

The Results of moisture resistance test, adhesion test, gasoline resistance test, hot water resistance test and Bending resistance test of aqueous dispersions Examples 21 to 26 and Comparative Examples 8 to 12 are in Table 5 is shown. The test methods were carried out as follows.

The prepared in Examples 1 to 26 and Comparative Examples 1 to 12 aqueous resin compositions were spray-coated on a polypropylene plate and while 15 dried at 80 ° C for 20 minutes. The film thickness was adjusted to 10 to 15 μm. After that was applied a urethane-based two-component paint and allowed to stand at room temperature for 10 minutes. Then after the heat treatment while 2 to 15 minutes at 120 to 130 ° C in a blower dryer a heat drying while 30 minutes at 80 ° C carried out. The varnished plate thus obtained became one day at room temperature allowed to test the coating film.

Check for adhesion

With a cutting device were reaching to the bottom reaching incisions on the surface of the Coating film executed, to create 100 rectangular sections at intervals of 1 mm. Cellophane tapes were applied firmly and subtracted 5 times in the 180 ° direction, the Number of remaining rectangular sections was counted.

Gasoline resistance test

With a cutting device were reaching to the bottom reaching incisions on the surface of the Coating film prepared and after immersion in gasoline (unleaded High octane gasoline manufactured by Nippon Oil Co.) during 4 Hours, the condition of the coating film was visually evaluated.

Moisture resistance test

To Dipping one fifth The painted plate in warm water at 50 ° C for 240 hours became the Condition of the coating film, such as the generation of bubbles, checked, then cellophane adhesive tapes became firmly applied to it, which then five times in the 180 ° direction were subtracted to the proportion of the remaining coating film to compare.

Warm water resistance test

To Dip the painted plate in warm water at 40 ° C during 240 Hours became the state of the coating film, such as the formation from bubbles, checked, and then cellophane tapes applied on it, which then five times in the 180 ° direction were subtracted to the proportion of the remaining coating film to compare.

Bending resistance test

The lacquered plate was used with 180 ° a 2.54 cm (1 inch) diameter mandrel bent to condition of the coating film.

Storage stability test

A Sample of the prepared aqueous resin composition (Solids content 25%) was placed in a glass jar with a volume of 250 ml given and the changes in terms of the degree of separation of the aqueous phase from the emulsion phase and the degree of formation of resin aggregates were progressing compared to the time at room temperature.

The Results of the stability test, check up Adhesiveness Gasoline resistance, resistance to water and bending resistance the aqueous dispersions Examples 29 to 33 and Comparative Examples 13 to 16 after they have been allowed to stand for 1 month are shown in Table 6. The test methods were the same as above.

Table 1

Table 2

The symbols in Tables 1 and 2 mean the following:
A: polyethylene oxide
B: polypropylene oxide
C ₁ : dodecylphenol ethylene oxide 10 mol adduct
C ₂ : nonylphenol ethylene oxide-8.5 molar adduct
D: coconut oil amine · ethylene oxide · propylene oxide-16 mol adduct (block copolymerization type)
E: lauryl alcohol · ethylene oxide · propylene oxide adduct (block copolymerization type)
F: laurylamine · ethylene oxide · propylene oxide adduct (block copolymerization type)
G: myristylamine · ethylene oxide · propylene oxide adduct (random copolymerization type)
H: ethylene glycol
I: diethylene glycol
J: trimethylolpropane
K: 1,6-hexamethylenediol
L: nonylbenzenesulfonic acid
M: ethanol
1) chlorinated polypropylene; Degree of chlorination 67% (trade name Superclone 406, manufactured by Nippon Paper Industries Co., Ltd.)

Table 3

Table 4

Table 5

Table 6

As described above possess the aqueous resin compositions of the present invention excellent adhesion across from Polyolefin, a good storage stability and also a good flexibility of the coating film. Furthermore, they allow the formation of a more water resistant Coating film compared to conventional aqueous polyolefin resin compositions using polyol or a surfactant. This also results in a film-forming system involving a network structure the same effect. Further, as the aqueous conversion without use any aromatic organic solvent is possible they are from the point of view of safety and health and pollution.

Claims (3)

An aqueous polyolefin resin composition characterized by having a substance having a poly (alkylene oxide) structure and a solubility parameter (SP value) of not less than 7 cal ^1/2 · cm ^-3/2 to not more than 12 cal ^1/2 · ^{Cm -3/2} in a proportion of not less than 0.001 wt% to not more than 50 wt% as a constituent component in the aqueous conversion of modified polyolefin, wherein the modified polyolefin is selected from one or more of the following types a) a polyolefin modified by graft copolymerization with an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, b) a chlorinated polyolefin, c) a polyolefin modified by graft copolymerization of a reactive monomer having radical polymerizability. An aqueous polyolefin resin composition according to claim 1, obtainable by a process comprising the steps of, after the starting resin material is melted at an applied pressure of 0.1 to 100 bar (0.1 to 100 kg / cm ² ) and the surfactant or alcohols and a basic one Substance is mixed, water is gradually added with stirring to effect a phase inversion, whereby the aqueous conversion under the coexistence of the resin component, the water and other ingredients within a range of not less than 100 ° C to not higher than 300 ° C. in the aqueous conversion of polyolefin and / or modified polyolefin is performed. Use of an aqueous polyolefin resin composition according to claim 1 or 2 for the preparation of a film former.