FR2697847A1 - An aqueous polyolefinic resin composition and film-forming products containing it - Google Patents

Abstract

Disclosed is an aqueous polyolefin resin composition. The composition is characterized in that it contains a substance having a poly (alkylene oxide) structure and a solubility parameter of at least 7 cal1 / 2 cm- 3/2 and at most 12 cal1 / 2 cm-3/2 in an amount of at least 0.001% by weight and at most 50% by weight as a constituent ingredient introduced for the conversion into aqueous form of a polyolefin or modified polyolefin. The substance having a poly (alkylene oxide) structure may be, for example, a polyoxyalkylene diol, an adduct of ethylene propylene oxide on an aliphatic alcohol or an adduct of ethylene oxide. ethylene propylene oxide on an aliphatic amine. An isocyanate can also be included for crosslinking by curing. The invention also relates to film-forming products containing the composition. Application to paints, primers, inks, coating products, sealants and adhesives.

Description

The present invention relates to an aqueous resin composition which

  can be used mainly as

  paint, primer, ink, adhesive and sealant.

  In addition, the resin composition of the invention can be used in the preparation of other aqueous resins and water-soluble resins such as polyurethane resins, acrylics, polyesters, according to the uses, and can therefore also be used as a film-forming product modifier. . First of all, because it makes it possible to form a film

  and an adhesive layer having excellent adhesion qualities

  Because of its flexibility, flexibility and water resistance, especially on a polyolefinic substrate, etc. having a non-polar surface, the composition of the invention is useful as a resin for automobile parts, etc., polyolefin film paint, mold polyolefin, etc.,

  primer, ink, sealant and adhesive.

  Modified polyolefin compositions comprising modified polyolefins such as polypropylene, polyethylene and a propylene-ethylene-α-olefin copolymer modified with an unsaturated carboxylic acid or anhydride and acid-modified chlorinated polyolefins have been conventionally used to However, in the current circumstances, these resins only dissolve in organic aromatic solvents such as toluene and xylene, and so large amounts of organic solvents must be used, problems concerning

  safety, health and environmental pollution.

  For this reason, in recent years an aqueous resin has been used, the conversion of which in aqueous form is carried out by adding a polyol, a surfactant and a basic substance to a chlorinated polyolefin (US Pat. No. 340845), an aqueous resin of chlorinated polyolefin modified with an unsaturated carboxylic acid or acid anhydride converted into aqueous form by use of a surfactant and a basic substance (Japanese Patent Application No. Hei 01-323506). ), etc. In addition, there have been attempts to produce aqueous dispersions of chlorinated polyolefin, which are known, for example, from Japanese Unexamined Patent Publication No. Hei 1-153778, No Hei 1-256556, No Hei 2-284973, etc., but these make use of an aromatic organic solvent in production, so

  that the complete elimination of the latter has been difficult.

  In addition, there have also been attempts to produce modified aqueous polyolefin dispersions, which are known from, for example, Japanese Unexamined Patent Publication Nos. Sho 59-47244, No Hei 2-286724, etc. However, in the field of paints, adhesives, etc., these dispersions have the disadvantages of low adhesiveness, poor water resistance, poor paint application, etc., when the articles to be coated and the articles to be glued are polyolefinic resins, so that these compositions

  have not yet come into practical use.

  In addition, in Japanese Unexamined Patent Publication No. Hei 3182534, an improvement in the properties of the applied film is achieved by performing the aqueous conversion of a modified chlorinated polyolefin using a surfactant and incorporating more a resin

  water-soluble polyurethane However, because of

  reactivity of the water-soluble polyurethane resin and the surfactant, the active ingredient is extracted from the applied film by dissolution with water, which causes a phenomenon of lesser resistance to water which appears to be

attributable to the film itself.

  In addition, when forming the film using a chlorinated polyolefinic resin converted into aqueous form using a polyol and a surfactant, the hydrophilic ingredients such as the polyol and the surfactant remain in the film and they are dissolved by moisture, which gives the film the defect

low resistance to water.

  In addition, since the chlorinated resin is an ingredient contained in large quantities, there are many problems in the treatment of destruction and recycling of the final product where a film, a layer of adhesive, etc. is formed. The Applicant has filed a claim for an aqueous resin consisting of polyolefinic resin, chlorinated polyolefinic resin or acid-modified polyolefinic resin in aqueous form using a reactive surfactant (Japanese Patent Applications).

  No Hei 04-256935, No Hei 04-256936 and N O Hei 04-256937).

  These inventions aim to improve the water resistance of the film by fixing the hydrophilic substances present in the film.

the film.

  The reactive surfactant has been used heretofore for emulsion polymerization. It has a surface activity suitable for suspending a monomer in water during emulsion polymerization and, because it reacts with another monomer, it is captured in the polymer structure, so that an effect of improving the water resistance is exerted on the

reaction product.

  However, when compared with a non-reactive surfactant having a similar structure, the reactive surfactant has a lower resin dispersancy and therefore its addition rate must be increased or a combination of polyol, non-reactive surfactant, etc., to obtain a product of

  conversion in aqueous form which is stable.

  Aqueous protected isocyanates are generally used for the treatment of fibers, as crosslinking agents and resin modifiers such as latexes, acrylic resins and urethanes, for the surface treatment of plastic films, etc., but there are no documents indicating that they have found new uses with new characteristics by being associated

  to an aqueous polyolefin resin.

  In addition, when forming the crosslinked structure by combination with a protected isocyanate and the subsequent attachment of the hydrophilic ingredient, the

  addition of the protected isocyanate was limited for

  to maintain the adhesiveness of the film formed on the substrate and, in particular, it was necessary to minimize as much as possible the quantity of hydrophilic substance carrying active hydrogen reactive with isocyanate to

  improve the water resistance of the film and maintain adhesion

sivity to the substrate.

  On the other hand, the aqueous conversion of a polyolefinic resin is generally carried out by a process according to which, after the starting resin has been dissolved in a solvent, hydrophilic ingredients such as a surfactant and a basic substance are

  added, then the solvent is replaced by water.

  In addition, there is a method in which the starting resin, the surfactant and the basic substance are mixed and melted at a temperature above the melting point of the resin, and then water is gradually added to the mixture to provoke the inversion of

  phases, thus achieving the conversion in aqueous form.

  This process is however traditionally conducted at ambient pressure and therefore, in the case of a starting resin having a high viscosity below C, the addition of water lowers the temperature of the resin by increasing the viscosity molten liquor, which reduces the stirring efficiency and homogeneous inversion capability of the phases in many cases. As described above, conventional modified polyolefin compositions have been used as solutions in organic solvents and thus problems have been posed by solvent toxicity, environmental pollution, etc. In addition, with respect to concerns

  aqueous resin compositions using a surfactant

  have been developed to try to solve these problems, the controversial point of water resistance remains unresolved. The object of the invention is to provide an aqueous resin composition which simultaneously solves all these problems of toxicity, environmental pollution

  and poor water resistance of the applied film.

  In addition, the object of the invention is to solve the problem posed by a residual solvent used in the conventional method of converting in aqueous form a polyolefin resin and also the problem posed by the resulting non-dispersed residual solids.

  a heterogeneous inversion of the phases.

  Further, the object of the invention is to improve the water resistance without impairing the adhesiveness and substrate adhesiveness of the film formed with the modified polyolefin or polyolefin aqueous resin composition in

  the use of said aqueous resin composition.

  The Applicant has arrived at the present invention as a result of diligent research on an aqueous resin composition that does not pose problems such as toxicity and pollution, and thus offers excellent safety, and has excellent resistance to water without impairing adhesiveness and adhesion, to achieve

the aforementioned purposes.

  By using the protected isocyanate whose isocyanate group is blocked and does not react with water, this

  isocyanate does not react with water in the conversion stage.

  in aqueous form by adding water to a modified resin and the steps of applying the aqueous resin composition to a substrate and drying, but is released by having an activated isocyanate group when subjected to a treatment Subsequent thermal heat at higher temperature after drying, or when subjected to heat treatment by baking at a temperature higher than the drying temperature after the application of another film-forming overlayer component. The activated isocyanate group reacts with the surfactant remaining in the film ingredients, the modified polyolefin or other hydrophilic groups such as a hydroxyl group, a carboxyl group and an amino group present in the coating paint, etc. In this way, when it is used in combination with a polyolefinic resin

  modified, there is an effect of improving the resistance

  to the water of the film by fixing the hydro-

  phile or transformation of the hydrophilic functional group into a hydrophobic functional group without degradation of

  characteristics of the polyolefin.

  Furthermore, it has been found that by using poly (alkylene oxide) derivatives having a solubility parameter (PS index) of at least 7cai / 2cm 3/2 and at most 12call / 2 cm-3/2 when preparing the aqueous resin composition, a stable conversion product in aqueous form can be effectively obtained by using them in less quantity than in the case where alcohols, low glycols are used

  molecular weight or other surfactant ingredients.

  In addition, when the surfactant ingredients described in the invention are used in combination, it has been found that the affinity of the aqueous solvent for the resin improves, thereby further reducing the rate of agent addition. surfactant These effects are also manifested in the cases of joint use of third hydrophilic ingredients such as other surfactants,

alcohols and glycols.

  As a result, it is possible to reduce the amounts of hydrophilic ingredients and hydrophilic functional groups in the film formed with the prepared aqueous resin, which remarkably improves the water resistance of the film. a protected isocyanate is used together and it has been found that the water resistance of the film can improve even more than in the case where the conventional aqueous polyolefinic resin whose conversion in aqueous form has been carried out using Alcohols, low molecular weight glycols and surfactants are used in combination with a protected isocyanate. The present invention provides: (1) an aqueous polyolefinic resin composition characterized by containing a substance having a polyalkylene oxide structure and a solubility parameter of at least 7 cif / 2 cm 3 / 2 and not more than 12 cc 11/2 cm-3/2 in a proportion of not less than 0.001% by weight and not more than% by weight as a constituent ingredient introduced for

  the conversion in aqueous form of a polyolefin or poly-

  modified olefin, and film-forming products such as paints, primers, inks and coating products, sealants and adhesives which contain it as part of their constituent ingredients; (2) the aforementioned aqueous resin composition characterized in that the modified polyolefin is a modified polyolefin resin comprising one or more species of (A) polyolefin modified by graft copolymerization with an unsaturated carboxylic acid and / or anhydride, ( B) polyolefin modified by chlorination and (C) polyolefin modified by graft copolymerization of a reactive monomer capable of radical polymerization, and film-forming products such as paints, primers, inks and coating products, sealants and adhesives which contain as part of their constituent ingredients; (3) an aqueous polyolefinic resin composition characterized by containing a substance having a polyalkylene oxide structure and a solubility parameter of at least 7 1/2 cm-3/2 and at most 12 cal / 2 cm -3 / 2 in a proportion of at least 0.001% by weight and at most 50% by weight as a constituent ingredient introduced for the conversion in aqueous form of a modified polyolefin obtainable by two or more kinds of modifications selected from an acid modification, a chlorination modification and a reactive monomer modification, as mentioned respectively in (A), (B) and (C) above, and products film-forming materials such as paints, primers, inks and coating products, sealants and adhesives which contain it as part of their constituent ingredients; (4) an aqueous polyolefin resin composition characterized by containing a substance having a polyalkylene oxide structure and a solubility parameter of at least 7 ca 11/2 c M-3/2 and of not more than 12 Cm / 2 Cm 3/2 in a proportion of at least 0.001% by weight and not more than% by weight as a constituent ingredient and in that it is obtained by the use of a polyolefin and / or a modified polyolefin having a melt viscosity of from 100 m Pa S to 30,000 m Pa S in a temperature range of 60 to 300 ° C when converting a polyolefin into aqueous form or modified polyolefin, and film-forming products such as paints, primers, inks and coating products, sealants and adhesives which contain it as part of their constituent ingredients; (5) an aqueous polyolefinic resin composition characterized in that it contains a substance having a polyalkylene oxide structure, a solubility parameter of at least 7 cal 1/2 Ccm 3/2 and not more than 12 cc 11/2 cm 3/2 and an average molecular weight of 200 to 5000 in a proportion of at least 0.001% by weight and not more than 50% by weight as a constituent ingredient introduced for the preparation of a aqueous polyolefinic resin composition which can be

  obtained by the conversion in aqueous form of a poly-

  olefin or modified polyolefin, and f ilmogenic products

  such as paints, primers, inks and coating products

  sealants and adhesives which contain it as part of their constituent ingredients; (6) an aqueous resin composition characterized by the use of a polyoxyalkylene diol represented by the general formula 1) as a substance having a polyalkylene oxide structure for the preparation of an aqueous polyolefin resin which can be obtained by the aqueous conversion of a modified polyolefin or polyolefin, and film-forming products such as paints, primers, inks and coating products, sealants and adhesives which contain it as part of their constituent ingredients ; general formula 1): HO-1 (PO) n / (EO) ml-H

E: -CH 2 CH 2-

P: -CH 2 CH-

  I CH 3 n, m: integers between 0 and inclusive and such that 4 <N + m S 100 /: indicates a structure of random copolymer or block copolymer, but, if either of N or m is 0, this sign indicates a homopolymer structure; (7) an aqueous resin composition characterized by

  the use of an ethylene oxide adduct

  propylene oxide on an aliphatic alcohol, represented by the general formula 2), as a substance having a poly (alkylene oxide) structure for the preparation of an aqueous polyolefinic resin composition obtainable by conversion into form aqueous solution of a modified polyolefin or polyolefin, and film-forming products such as paints, primers, inks and coating products, sealants and adhesives which contain it as part of their constituent ingredients; general formula 2): RO-1 (PO) m / (EO) n -H-R: a hydrocarbon group having 1 to 50 carbon atoms,

E: -CH 2 CH 2-

P: -CH 2 CH-

  CH 3 n, m: integers between 0 and inclusive and such that 2 m + N <100 /: indicates a structure of random copolymer or block copolymer, but, if either of N or m is 0, this sign indicates a homopolymer structure; (8) an aqueous resin composition characterized by

  the use of an ethylene oxide adduct

  propylene oxide on an aliphatic amine, represented by the general formula 3), as a substance having a polyalkylene oxide structure for the preparation of an aqueous polyolefinic resin composition obtainable by conversion into form aqueous solution of a modified polyolefin or polyolefin, and film-forming products such as paints, primers, inks and coating products, sealants and adhesives which

  contain as part of their constituent ingredients

  tutifs; general formula 3): l (PO) m / (EO) nl -H

R-N

  (PO) e / (EO) kI-H R: a hydrocarbon group having 1 to 50 carbon atoms,

E: -CH 2 CH 2-

P: -CH 2 CH-

  CH 3 n, m: integers between O and inclusive and such that 2 <m + N <100 1 1 e, k: integers between O and inclusive and such that 2 e + k <100 /: indicates a structure of random copolymer or block copolymer, but if either of N or m is 0, or if either of e or k is 0, this sign indicates a homopolymer structure ; (9) an aqueous polyolefinic resin composition characterized by the use of a surfactant ingredient

  having a polyoxyalkylphenyl ether structure

  ethylene, represented by the general formula 4), in association

  with at least one species of the substances represented

  by the general formulas 1), 2) and 3) as

  having another polyoxyalkylene structure in one

  ratio of 1: 200 to 200: 1 for the preparation of a composi-

  an aqueous polyolefin resin obtainable by the aqueous conversion of a modified polyolefin or polyolefin, and film-forming products such as paints, primers, inks and coating products, sealants and adhesives which contain it as a part of their constituent ingredients; general formula 4): ## STR2 ## a lower alkyl group

R ': -CH 2 CH 2, -CH 2 CH-

  CH 3 X: a hydrogen atom, lower alkyl group or nonionic or anionic hydrophilic group, Y: a hydrogen atom or -CH 2 -O-CH 2 -CH = CH 2 Z: a hydrogen atom or -CH = CH-CH 3, provided that Y and Z do not simultaneously contain a double bond; (10) an aqueous polyolefinic resin composition produced by a process wherein, after melting the starting resin under an applied pressure of 9.8 k Pa to 9.8 Pa, and mixing the surfactant or of alcohols and a basic substance, water is gradually added with stirring to cause the phase inversion, thus performing the conversion in aqueous form while the resinous ingredient, the water and other ingredients coexist at a constant temperature. a temperature of at least 1000 ° C. and at most 300 ° C. for the conversion in aqueous form of a modified polyolefin and / or polyolefin; (11) an aqueous resin composition characterized by incorporating a protected isocyanate to a polyolefin and / or a modified polyolefin in a weight ratio of 0.1: 1 to 20: 1 during conversion into aqueous form or after the conversion in aqueous form for the preparation of an aqueous polyolefinic resin composition which can be

  be obtained by the conversion into aqueous form of a poly-

  olefin or modified polyolefin, and film-forming

  such as paints, primers, inks and coating products

  sealants and adhesives which contain it as part of their constituent ingredients; (12) A single component type aqueous polyolefin resin composition characterized by incorporating an aqueous protected isocyanate in a weight ratio of 0.1: 1 to 20: 1, the conversion in aqueous form having already been

  performed by any method to form a composi-

  Aqueous polyolefinic resin composition according to any one of the above (1) to (10) or other aqueous polyolefinic resin composition, and film forming products.

  such as paints, primers, inks and coating products

  sealants and adhesives which contain it as part of their constituent ingredients; (13) a two-component type aqueous resin composition characterized by incorporating a protected isocyanate at the time of paint application, the conversion in aqueous form having been performed to form an aqueous polyolefin resin composition according to any of the above (1) to (10) or other aqueous polyolefinic resin composition, and film-forming products such as paints, primers, inks and coating products, sealants and adhesives using said system. two components, one of which contains one component as part of its constituent ingredients and the other contains the other component as a constituent ingredient;

  (14) finally, the aqueous resin composition of

  graph (11), (12) or (13) above in which a protected isocyanate using a hexamethylene diisocyanate-based polyisocyanate as the starting material is used as the protected isocyanate, and film-forming products

  such as paints, primers, inks and coating products

  products, sealants and adhesives containing it

  as part of their constituent ingredients.

  The present invention will be described in detail in this

following.

  As polyolefins used in the invention, it is possible to use a homopolymer of ethylene or of propylene,

  a random copolymer or a block copolymer of ethyl

  ethylene or propylene with another comonomer having at least two carbon atoms such as butene-1, pentene-1, hexene-1, hepten-1, octene-1, etc., preferably a α-olefinic comonomer having 2 to 6 carbon atoms, or a copolymer formed with two or more species of these comonomers The average molecular weight of the polyolefin is usually from 2,000 to 100,000. A polyolefin obtained by publicly known methods can be used.

  but it is also possible to use a polyolefin degraded by radicals, oxygen or heat after its synthesis at a high molecular weight.

  The chlorinated polyolefin is obtained by chlorination of said polyolefin according to publicly known methods.

  The acid-modified polyolefin is a product for modifying said polyolefin with an α, β-unsaturated carboxylic acid or an anhydride thereof by a reaction.

  In addition, it is also possible to use a poly-

  In addition, it is also possible to use as starting material for the conversion in aqueous form a polyolefinic resin produced by reaction of the surfactant reactive with a polyolefinic resin. such as a polyolefin modified with a chlorinated acid or polyolefin using a reaction initiator

  radical to effect the modification in aqueous form.

  When the film is formed on a substrate containing polypropylene, the proportion of propylene ingredient is preferably not less than 55 mol%. If this proportion is less than 55 mol%, the polypropylene adhesiveness

  becomes bad, which is unfavorable.

  As the α, β or unsaturated carboxylic acids thereof to be used for the modification of the polyolefin, there may be mentioned, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, mesaconic acid, aconitic acid, their anhydrides, etc. The amount of unsaturated carboxylic acid at a, P or anhydride thereof to be graft copolymerized is preferably from 1 to 20% by weight. If this amount is less than 1% by weight, the stability becomes poor when dispersed in water and, if it exceeds 20% by weight, the yield

  grafting becomes weak, which is not economical.

  An amount of 2 to 15% by weight is particularly preferable. In addition, the number average molecular weight of the copolymerized resin grafted with an unsaturated carboxylic acid or an anhydride thereof is preferably from 3000 to 40,000. it is less than 3000.35 the cohesion force is insufficient, which results in low adhesiveness to a polyolefin resin and, if it is greater than 40 000, the handling during the

  dispersion in water becomes difficult, which is

  It is possible to bring the molecular weight into this range by choosing the molecular weight of the starting material or the conditions of the grafting reaction, and this is also possible by a method according to which the molecular weight of the departure is

  first lowered, then the grafting reaction is conducted.

  Incidentally, the number average molecular weight can be determined by gel permeation chromatography (GPC).

  The graft copolymerization of the carboxylic acid

  The unsaturated acid, or anhydride thereof, on a polyolefin can be carried out by methods publicly.

  known, but it is particularly preferable to

  kill by a process in which the polyolefin is melted by heating above its melting point and graft copolymerization is conducted in the presence of

of a radical generator.

  In the invention, when preparing an aqueous polyolefinic resin composition comprising a polyolefin, a modified polyolefin or a protected isocyanate, it is also possible to add a basic substance, alcohols, a surfactant, a surfactant or active

  reagent and a radical reaction initiator.

  The addition of the basic ingredient is justified by

  the best dispersion in the water which is due to ionisation

  hydrophilic groups such as the carboxyl group and the sulfonic acid group, but its use is not necessary in some cases, for example when a reactive surfactant and a non-reactive surfactant

  used are already neutralized with a base.

  Examples of bases include hydroxide

  sodium hydroxide, potassium hydroxide, ammonia, methyl-

  amine, ethylamine, lapropylamine, labutylamine, hexyl-

  amine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine,

  diethylamine, triethylamine, N, N-dimethylethanol-

  amine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-

  2-methyl-1-propanol, morpholine, etc. The degree of hydro-

  Resin philie may vary depending on the type of base used and an appropriate choice must therefore be made according to the conditions. The amount of basic substance to be used is suitably in a range of 0.3 to 1.5 times the equivalent weight of the carboxyl group of the acid-modified polyolefin, and preferably 0.5 to 1.2 times. when a basic substance is added, it is necessary in certain cases to adjust the pH of the aqueous resin composition to be prepared in the vicinity of the neutrality, according to the stability of the protected isocyanate included in the

formulation.

  In the invention, the addition of a monoalcohol or polyol which is one of the alcohols is justified by a greater affinity of the starting resin for the water and this

  This effect makes it possible to reduce the rate of addition of surfactant

  In addition, it is also possible to increase the

  evaporation rate of the water during the formation of the film.

  However, if the alcohol remains in the resin during film formation, it then decreases the water resistance of the applied film, so that an appropriate amount is needed and the addition of 4 to 200 parts per 100 parts of the starting resin is preferable If this amount is less than 4 parts, the dispersibility in water becomes bad and if it is greater than 200 parts,

  the decrease in water resistance becomes important.

  As examples of monoalcohols, there may be mentioned methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, a monoalkyl ether of ethylene glycol, ethylene glycol monoacetate, a propylene glycol monoalkyl ether, propylene glycol monoacetate, etc., and as examples of polyols, mention may be made of ethylene glycol, diethylene glycol,

  triethylene glycol, propylene glycol, dipropylene

  glycol, butanediol, pentanediol, hexanediol, glycerol, polyethylene glycol, etc. Of these,

  very hydrophilic polyols are advantageous.

  As surfactant ingredients having a polyalkylene oxide structure and a solubility parameter of at least 7 ca / 2 cm -3/2 and at most 12 call / 2 cm 3/2 for use in the invention uses a polyoxyethylene diol, a polyoxypropylene diol, a polyoxytetraethylene glycol, a copolymer of ethylene oxide with propylene oxide, an adduct of polyalkylene oxide on an alcohol aliphatic (polyoxyethylene aliphatic alkyl ether, etc.), an adduct of poly (alkylene oxide) on a secondary alcohol (secondary alcohol ether and polyoxyethylene, etc.), a poly (oxide) adduct alkylene) on an alkylamine, a polyalkylene oxide adduct on an alkylamide, a polyoxyalkylene alkylphenyl ether (polyoxyethylene nonylphenyl ether, polyoxyethylene dodecylphenyl ether, etc.), a sterol and polyoxyalkylene, a polyoxyalkylated derivative of lanolin , an oxidized alkylene derivative of a

  alkylphenol-formaldehyde condensation product, a polyoxyalkylated glycerol fatty acid ester (polyoxyethylated glycerol fatty acid ester, etc.), a polyoxyalkylated sorbitol fatty acid ester (polyoxyethylated sorbitol fatty acid ester, etc.), a polyoxyalkylene fatty acid ester

  glycol (polyoxyethylene glycol fatty acid ester, etc.), a polyoxyalkylene fatty acid amide (polyoxyethylene fatty acid amide, etc.), a polyoxyalkylated alkyl amine (polyoxyethylated alkyl amine, polyoxyethylene fatty acid addition product) ethylene-propylene oxide on an alkylalkanol

  amine, etc.), as well as others, including the compounds of formulas 1), 2), 3) and 4) given above. The substance having a polyalkylene oxide structure is a substance having a chemical structure comprising an oligomer or polymer produced by homopolymerization or

  copolymerization (block copolymerization, copolymer-

  The average molecular weight is at least 200 and at most 5000, and preferably at least 300 and not more than 3000 If the molecular weight is less than 200,

  the dispersal power is low and no remarkable effect

  In contrast, if the molecular weight is greater than 5000, the dispersion power of the resin decreases. In addition, they can be used in combination of two or more species. The above-mentioned surfactant ingredient is used in amounts of from 0.1 to 50 parts by weight per 100 parts of the starting resin used for conversion to aqueous form, and

preferably 3 to 30 parts.

  The solubility parameter (PS) is calculated from the chemical composition of the respective substances by the

Fedor's method.

  Surfactants that can be used in

  combination with said surfactant ingredients

  a reactive surfactant and a surfactant

non-reactive

  The reactive surfactant may be of a type generally used as a reactive surfactant or

  as a reactive emulsifier, but such an agent

  both an alkylphenyl group as a hydrophobic group and a polyoxyethylene group as a nonionic hydrophilic group is preferable. For example, a product can be used.

  addition of poly (ethylene oxide) to an alkylpropenyl

  phenol, an alkyldipropenylphenol poly (ethylene oxide) adduct and the salts of their sulphates described in Japanese unexamined patent publications NO Hei 4-53802 and No Hei 4-50204 Preferred compounds among them are an adduct of 20 mol, 30 mol or 50 mol of ethylene oxide to an alkylpropenylphenol and the ammonium salt of the sulphate of a 10 mol or 20 mol ethylene to an alkylpropenylphenol In addition, an oxide adduct

  of ethylene on a 1-alkylphenoxy-3- (2-propenyl) oxypropane

  2-ol or its sulfate imparts excellent dispersibility to the resin and, furthermore, its ability to polymerize is high due to its unsaturated double bond, which is preferable. These reactive surfactants can be reacted with the resin. starting material used for conversion to aqueous form by publicly known methods using a radical reaction initiator

to fix them to the resin.

  The rate of addition of reactive surfactant is from 0.1 to 100 parts per 100 parts of modified polyolefin used as starting resin for conversion

  in aqueous form, and preferably from 0.1 to 30 parts.

  The level of addition can be appropriately modified depending on the rate of addition of non-reactive surfactant and other hydrophilic ingredients. When using the reactive surfactant, the reaction initiator is used. The reactive surfactant may be reacted previously with the starting resin used for the conversion in aqueous form, or it may be added during the conversion treatment in aqueous form.

are publicly known.

  As non-reactive surfactants, surfactants of the nonionic type such as a propylene glycol ester, a sucrose ester, an alkyl sorbitan ester, a sorbitan fatty acid ester, may be used. a polyglycerol ester, a fatty acid alkanolamide, a fatty acid monoglyceride and an alkylamine oxide, anionic surfactants such as an alkyl sulphate, an alkylphenolsulfonate, a sulphosuccinate and a carboxylate, phosphate, etc., ampholytic surfactants such as alkylbetaine and alkylimidazoline, etc., as well as

  mixtures of two or more species thereof.

  The rate of addition of the total surfactant ingredient including the non-reactive surfactant and the reactive surfactant is from 1 to 100 parts per 100 parts of modified polyolefin and the rate required may vary depending on association and the quantitative ratio of surfactants, the rate of addition of the alcohol

  and the type and amount of the reactive monomer.

  This surfactant ingredient can be melted and mixed with the starting resin, but it can also be added after being partially or totally mixed with

some water.

  As reactive monomers for use in the invention,

  acrylic monomers such as acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylonitrile, acrylamide and hydroxyethyl acrylate, monomers of the diene type

  conjugates such as butadiene, isoprene and chloro-

  prene, halogenated olefinic monomers such as vinyl chloride and vinylidene chloride,

  aromatic monomers such as styrene and divinyl

  benzene, vinyl ester monomers such as vinyl acetate, methyl maleate, maleic anhydride, and the like. The reaction initiators for initiating the reaction of the reactive monomer and the reactive surfactant may be publicly known initiators and water-soluble initiators may be used as well.

  that oil-soluble initiators, such as azobisiso-

  butyronitrile, hydrogen peroxide and potassium persulfate. In addition, it is also possible to use redox initiators.

use in combination.

  As examples of organic peroxides, it is possible to

  mention benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, 2,5-dimethyl-2,5-di (t-butyl-

  peroxy) hexyne-3, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, cumene hydroperoxide, etc., and they are selected according to the temperature

  reaction time and the reaction time.

  The aqueous protected isocyanate used in the invention is a compound having the isocyanate group in its molecular structure, the isocyanate group being protected by a suitable blocking agent, and is itself soluble in water or dispersible in water or even if it is not itself soluble or dispersible in water, it is convertible in aqueous form by any method such as the addition of a surfactant or the formation

  a hydrophilic protective colloid.

  The protected isocyanate is a protected polyisocyanate having two or more functions which can be obtained by the addition reaction or the addition polymerization reaction between an isocyanate; a compound having two or more isocyanate groups in each molecule, for example an isocyanate such as ethylene diisocyanate,

  propylene diisocyanate, tetrasodium diisocyanate

  methylene, hexamethylene diisocyanate, diisocyanate

  decamethylene, m-phenylene diisocyanate, diiso-

  p-phenylene cyanate, 2,4-tolylene diisocyanate,

  2,6-tolylene diisocyanate, 1,5-diisocyanate

  naphthylene, 4,4 ', 4 "-triisocyanato-triphenylmethane, 4,4'-diisocyanato-diphenylmethane, 3,3'-dimethyl-4,4'-diphenylene diisocyanate, m-xylylene diisocyanate, diisocyanate pxylylene, isophorone diisocyanate or lysine isocyanate, and an excess of said isocyanate and a low molecular weight polyol, for example

  ethylene glycol, propylene glycol, 1,3-butylene

  glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentane-

  diol, hexamethylene glycol, cyclohexanedimethanol,

  trimethylolpropane, hexanetriol, glycerol, penta

  erythritol, etc., a polyisocyanate with a biuret structure, an allophanate-linked polyisocyanate, an isocyanate

  with an isocyanurate structure, or the like, with a blocking agent.

  These blocking agents include those of the phenol type such as phenol and cresol, of the alcohol type such as methanol, benzyl alcohol and ethylene glycol monomethyl ether, of the type having an active methylene group such as methyl acetylacetate and dimethyl malonate, of the acid amide type such as acetanilide and acetamide, and also of the imide, amine, imidazole, urea, carbamate, imine, oxime, mercaptan, sulphite, lactam types, etc. In other words, the protected isocyanates so designated in the invention include the generally known protected isocyanate, masked isocyanate and urethane reactive compounds or compounds thereof. The ratio of protected isocyanate to

  the modified polyolefin is between 1:20 and 10: 1.

  Regarding the amount of isocyanate groups contained in the protected isocyanate and the amount of isocyanate-reactive functional groups, such as hydroxyl and carboxyl groups, which must be contained in the ingredients remaining in the applied film after the treatment such as the modified polyolefin and the surfactant ingredient, the optimum ratio can be determined by the degree of reaction of the protected isocyanate under the respective conditions of deprotection

  (temperature, time, etc.) of the protected isocyanate.

  When protected isocyanate is used, the dissociation

  of said blocking agent is effective after the evaporation of moisture in the drying treatment, and it is therefore preferable that the dissociation temperature of the blocking agent be greater than the temperature employed in the drying process.

drying treatment.

  The protected isocyanate may be water dispersible or water soluble, otherwise it can not be converted

in aqueous form.

  In addition, in the aqueous resin composition of the invention, a catalyst may be used, if necessary, to facilitate the deprotection reaction and the reaction of the

  activated isocyanate group with active hydrogen.

  Examples of catalysts include

  dibutyltin dilaurate, a dibutyl fatty acid salt

  tin, dibutyltin diacetate, tetra-n-butyl-1,3diacetoxydistannoxane, di-n-butyltin oxide, mono-nbutyltin oxide, stannous octylate, etc. In the invention, in the process of addition and

  of incorporation of the protected isocyanate with the polyresin

  modified olefinic acid, the conversion in aqueous form can be carried out in such a way that the modified polyolefinic resin is dissolved in a solvent and, after addition of the protected isocyanate to this solution, the solvent is replaced with water, or the modified polyolefin resin, after conversion in aqueous form, may be added aqueous protected isocyanate for use. In the case where the aqueous resin composition containing the protected isocyanate is used, it is applied to a substrate by any technique and, after a first drying at a temperature below the deprotection temperature to remove the moisture, it is further treated at a higher deprotection temperature, thereby to activate the isocyanate and to advance the reaction. When the aqueous polyolefin resin composition containing the protected isocyanate is used to form the film as described in paragraphs (11) to (14) above, the heat treatment is carried out for 1 minute to 2 hours between 60 and 200 C to achieve the

  deprotection and advance the reaction between isocyanate and active hydrogen, after drying to remove moisture

  With respect to these processing conditions, the optimum values can be determined according to the deprotection conditions of the protected isocyanate used and the type and rate of deprotection catalyst addition.

  The aqueous resin composition of the invention may also be produced by polyolefin resin aqueous resin conversion processes that are publicly known, such as a solvent-converted aqueous conversion process and an emulsification method. -

  by phase inversion at ambient pressure.

  With regard to the methods of adding the surfactant ingredient to the starting resin for conversion in aqueous form, there is a method of adding the surfactant ingredient to the molten starting resin with stirring and a method of forming a mixture by dissolving the two ingredients respectively in an organic solvent capable of dissolving them, then removing the organic solvent by distillation under reduced pressure, etc. The mixture is melted and water is added gradually with stirring to cause the phase inversion, thus dispersing the resin in the water When adding water, it is also possible to dissolve some or all of the surfactant ingredient in the water to be used before

  to perform the conversion in aqueous form.

In addition, in the conversion process in aqueous form of an acid-modified polyolefin, etc., it is possible to adjust the dispersibility of the resin in water by adding the basic substance to neutralize the resin and ionize the groups. In addition, it is also possible to adjust the pH of the conversion product in aqueous form by addition of the basic substance. This basic substance can be added during stirring of the molten resin or can be added to the reaction mixture.

  conversion product in aqueous form.

  In the invention, a new process has been discovered

  in addition to the conversion process in aqueous form

  the disadvantages of conventional methods.

  Thus, it is a conversion process in aqueous form characterized in that, in the conversion in aqueous form of a modified polyolefin and / or polyolefin, a starting mixture which is a mixture of starting resin with d Other starting materials for conversion into aqueous form (other hydrophilic ingredients such as a surfactant and a basic substance) are mixed above the softening temperature of the starting mixture and below its decomposition temperature, and water is added gradually to the molten starting mixture while stirring is continued, to cause

  thus the inversion of the phases at high temperature.

  In this case, to maintain in the liquid state the added water at a high temperature above the temperature

  softening of the starting mixture, it becomes necessary to

  to increase the internal pressure of the reaction device. Thus, by applying the appropriate pressure to

  keep the water in a liquid state at a pre-

  As a condition for the conversion in aqueous form, the liquid water and the starting mixture can coexist at the predetermined temperature by permitting an inversion.

homogeneous phases.

  The temperature to be used here for the conversion in aqueous form is greater than the softening point

  of the starting mixture and below its decomposition

  However, preferably, it is not less than 1000 ° C. and not more than 300 ° C., and more preferably not less than 1100 ° C. and not more than 2500 ° C. The pressure to be applied is 9.8 kPa. at 9.8 M Pa, preferably 49 K Pa

at 4900 kPa.

  For the preparation of the starting mixture, it can be heated, melted and mixed at ambient pressure

  or it may be melted and mixed in the said conditions

  For the addition of water, water brought to a temperature

  ture and high pressure such as under the conditions

  in aqueous form may be added progressively.

  system, or water heated to ambient pressure can be added gradually to the system.

  As a reaction device for the conversion in aqueous form, it suffices to use a pressure reaction device equipped with an agitator corresponding to the conditions employed for the conversion in aqueous form, but under the conditions of higher temperature and more high pressure, one can also use a high temperature extruder under pressure, etc. The resin composition of the invention thus dispersed in water is not only excellent in its

  adhesiveness to a polyolefin and as a primer for

  However, it is also useful as a resinous vehicle for an aqueous paint, an aqueous adhesive, an aqueous resin resin binder, and an aqueous coating product. In addition, in the aqueous resin composition of the invention, there is added , if necessary, 0.01 to parts of an ingredient facilitating drying, such as

  alcohol to improve the rate of evaporation of moisture

  In addition, various additives may be added and mixed in the amount necessary for use, for example pigments such as antirust pigment, coloring pigment and diluent pigment, thixotropic agent, viscosity modifier, and the like. , an adjuvant

  fluidizer, a surface modifier, an anti-

  primary rust, antifoam, an antiseptic and

a mildew agent.

  In addition, other aqueous resins may also

  For example, an aqueous polyurethane resin, an aqueous epoxy resin, an aqueous acrylic resin, an aqueous phenolic resin, an aqueous amino resin, an aqueous polybutadiene resin, an aqueous alkyd resin, an aqueous chlorinated rubber may be mixed for use, for example an aqueous polyurethane resin, an aqueous epoxy resin, an aqueous silicone resin, etc. In the case where the protected isocyanate-containing aqueous resin composition is used, it is applied to a substrate by any technique and, after being dried first at a temperature below the deprotection temperature to eliminate moisture, it is further treated at a higher deprotection temperature, thereby to activate the isocyanate and to advance the reaction. When the aqueous resin composition is used to form the film as described in paragraphs (11) to (14). ) above, the heat treatment is performed for 1 minute to 2 hours between and 200 ° C to effect deprotection and advance the reaction between isocyanate and active hydrogen after drying to remove moisture. these treatment conditions, the optimal values can be

  determined according to the conditions of deprotection of the iso-

  protected cyanate used and type and rate of addition

deprotection catalyst.

  In what follows, the invention is illustrated in more detail by examples, but the invention is not limited.

to these.

  Experimental Production Example 1 In a four-necked flask equipped with a stirrer, a refrigerant tube, a thermometer and a

  300 g of propylene-propylene copolymer are

  α-olefin (75 mol% of propylene, 20 mol% of ethylene and mol% of butene-1, number average molecular weight of 000) in 700 g of toluene under heating, then, while maintaining the temperature of the system at 1150 ° C. with stirring, 13 g of maleic anhydride and 12 g of di-t-butyl peroxide, respectively, are added dropwise in the course of 2 hours, after which aging is carried out for 3 hours after the reaction. the reaction product was cooled to room temperature and then sprayed into 20 liters of acetone to purify it to produce a maleic anhydride graft copolymer having a grafting rate of 2.1% by weight (average molecular weight of 18,500). For determination of the average molecular weight, a TSK-GEL column is attached to an HPLC-8020 chromatograph

  made by Tosoh Corp. and, after dissolution of the sample

  tetrahydrofuran (THF), the measurement is carried out at 40 ° C. The molecular weight is determined from a calibration curve established with a sample of

standard polystyrene.

  Experimental Production Example 2 In a four-necked flask equipped with a stirrer, a refrigerant tube, a thermometer and a separatory funnel, 300 g of propylene-butene-ethylene copolymer ( 68 mol% of propylene, 24 mol% of butene and 8 mol% of ethylene, number average molecular weight of 68,000), then, while maintaining the temperature of the system at 1800 ° C. with stirring, is added

  40 g of anhy-

  maleic anhydride and 5 g of dicumyl peroxide as gen-

  After the reaction, the reaction product is cooled to room temperature and then sprayed into liters of acetone to purify it to produce a maleic anhydride-grafted copolymer having a temperature of about 10 hours. grafting rate of 6.2% by weight The number average molecular weight determined by GPC is 26 000. Experimental Production Example 3 In a reactor equipped with a reflux tube, 200 parts of the modified polyolefin resin are placed

  by an acid obtained in the Experimental Example of Produc-

  2 and 1000 parts of carbon tetrachloride After homogeneous dissolution between 65 and 700 ° C, the internal air is removed by purging with nitrogen and chlorine is blown into the reaction liquor at a rate of 20 parts per hour until The degree of chlorination reaches 25% to effect a chlorination reaction. After the reaction, the carbon tetrachloride is replaced by toluene and, at the same time, the remaining chlorine is removed at ambient pressure to give a toluene solution of modified chlorinated polyolefin. toluene is removed from the

  toluene solution by distillation under reduced pressure to produce an acid-modified chlorinated polyolefin.

  Experimental Production Example 4 In the same reactor as used in Experimental Production Example 1, 100 parts of the unmodified amorphous polyolefin used in Experimental Production Example 2 are dissolved in toluene and drop at 80 C with stirring 15 g of

  di-t-butyl peroxide as a generator of radicals.

  Then, the toluene is distilled off under reduced pressure to produce an amorphous polyolefin

  degraded having a molecular weight of 24,000.

Example 1

  In a reactor equipped with a stirrer, a thermometer, a refrigerant tube and a dropping funnel, 100 parts of the modified polyolefin obtained in Experimental Production Example 1 are obtained. After melting by heating at 120 ° C. 6 parts of morpholine are added with stirring as the basic substance and another 40 parts of poly (ethylene oxide) are added as surface-active agent. After stirring until a homogeneous mixture is obtained, little is added. to 600 parts of water to obtain a conversion product in aqueous form by the phase inversion method After adjusting the pH of the conversion product in aqueous form between 6 and 8, the aggregates having a particle diameter greater than 100 They are removed by filtration to produce an aqueous resin composition (16% dry matter). The aggregates are dried for 24 hours at 130 ° C to determine their weight. The amount of aggregates was 4.7% relative to the starting resin. Examples 2 to 20 Replacing the surfactant ingredient and the basic substance according to the formulations given in FIGS.

  Tables 1 and 2, the conversion in aqueous form is carried out by the same method as in Example 1 to produce aqueous resin compositions and at the same time measure the amount of aggregates generated.

Example 21

  At a quantity corresponding to 100 parts of dry matter of the aqueous polyolefin resin obtained

  In Example 1, a corresponding amount is added with stirring.

  to 100 parts dry matter of protected isocyanate converted to aqueous form (Duranate X-1118, produced by Asahi Chemical Industry Co) and the water content is then adjusted to obtain an aqueous resin composition

  having a dry matter content of 20%.

  Examples 22 to 26 In the same manner as in Example 21, it incorporates

  various protected isocyanates in the proportions of

  shown in Table 3 for compositions

of aqueous resin.

Example 27

  In a pressure reactor equipped with a stirrer, a thermometer, a refrigerant tube and a dropping funnel, 100 parts of the polyolefin are placed

  obtained in the Experimental Experimental Example of Produc-

  After melting by heating at 1200 ° C., 6 parts of morpholine are added with stirring as the basic substance and another 40 parts of polyethylene oxide are added as surface-active ingredient. a homogeneous mixture, the reaction system is sealed and pressurized with nitrogen to a pressure of 0.2 M Pa. Then, 600 parts of hot water are gradually added to 900 C while by stirring to obtain a conversion product in aqueous form by the phase inversion method During the addition of hot water, the internal temperature of the system is maintained between 110 and 1200 C. The conversion product in aqueous form is cooled to 400 C and the pressure is released After adjusting the pH between 6 and 8, the aggregates having a particle diameter greater than 100 μm are removed by filtration to produce an aqueous resin composition (16% dry matter) The aggregates are

  dried for 24 hours at 130 ° C to determine their weight.

  The amount of aggregates is less than 0.05% by weight per

compared to the starting resin.

Example 28

  In a pressure reactor equipped with a stirrer, a thermometer, a refrigerant tube and a dropping funnel, 100 parts of the polyolefin are placed

  obtained in the Experimental Experimental Example of Produc-

  After melting by heating at 120 ° C., 1 part of diethylamine is added with stirring as the basic substance and another 20 parts of an ethylene oxide-propylene oxide adduct are added. laurylamine as surfactant ingredient After stirring until a homogeneous mixture is obtained, the reaction system is sealed and pressurized with nitrogen to a manometric pressure of 1.5 M Pa. 600 parts of hot water are gradually added at 90 ° C. while stirring to obtain a conversion product in aqueous form by the phase inversion method. During the addition of hot water, the internal temperature of the system is maintained between 180 and 1900 C After the end of the addition of hot water, the system is maintained for 1 hour with stirring. The conversion product in aqueous form is

  cooled to 400 C and the pressure is released after adjusting

  Between 6 and 8, the aggregates having a particle diameter greater than 100 μm are removed by filtration to produce an aqueous resin composition (16% dry matter). The aggregates are dried for 24 hours at 1300 C to determine their composition. weight The amount of aggregates is less than 0.05% by weight with respect to the resin

departure.

Example 29

  In a four-necked flask similar to that of Experimental Production Example 1, 100 g of the maleic anhydride-grafted copolymer obtained in Experimental Production Example 1 were melted by heating to 120 ° C. and, after addition of 10 g of ethylene glycol, g of morpholine and 10 g of a 10 mol adduct

  of ethylene oxide to a 1-alkylphenoxy-3- (2-propenyl) oxy-

  propane-2-ol (Adeka Reasoap NE-10, produced by Asahi Denka Kogyo K K), the temperature is lowered to 110 C and water is added gradually to 90 C to prepare a

  aqueous reaction liquor 10 g of

  sodium sulphate as a radical reaction initiator and the reaction is carried out for 4 hours at 80 ° C.

  stirring, to thereby effect the polymerization reaction.

  After the reaction, 4 g of triethylamine were added to obtain a converted aqueous reaction liquor (30% dry matter). After being treated for 48 hours with an ultrafiltration membrane having a threshold molecular weight of 5000, the liquor reacted in aqueous form is concentrated again to give an acid-modified polyolefinic resin

  aqueous form having a solids content of 45%.

  The aqueous-modified polyolefin resin in aqueous form thus obtained and an aqueous protected isocyanate (Elastoron BN-69, produced by Dai-ichi Kogyo Seiyaku Co) are mixed at a solids ratio of 2: 1 to

  produce an aqueous resin composition.

Example 30

  In a four-necked flask similar to that of Experimental Production Example 1, 100 g of the maleic anhydride graft copolymer obtained in Experimental Production Example 2 were dissolved in 200 g of toluene.

  by heating at 110 ° C. and, after addition of 10 g of peroxygen

  O-isopropyl carbonate and OL-butyl and 9.6 g of morpholine is added dropwise over 3 hours a solution in 120 g of toluene of an adduct of 20 mol of ethylene oxide on an alkylpropenylphenol (Aquaron RN-20, produced by Dai-ichi Kogyo Seiyaku Co),

  then a post-reaction is conducted for 4 hours, to thereby perform a graft copolymerization.

  After removal of the toluene contained in the reaction liquor by distillation under reduced pressure, 4 g of triethylamine and 20 g of propylene glycol monomethyl ether are added and water is added with stirring to obtain a reaction liquor converted under aqueous form (25% dry matter) After having been treated for 48 hours with an ultrafiltration membrane having a threshold molecular weight of 5000, the converted aqueous reaction liquor is concentrated again to give an acid-modified polyolefinic resin under

  aqueous form having a solids content of 40%.

  To this aqueous-modified polyolefinic resin in aqueous form, an aqueous protected isocyanate (Elastoron BN-08, produced by Daiichi Kogyo Seiyaku Co) is added at a dry matter ratio of 2: 1 to produce a

aqueous resin composition.

Example 31

  In a four-necked flask similar to that of Experimental Production Example 1, 100 g of the maleic anhydride-grafted copolymer obtained in Experimental Production Example 2 were melted by heating at 1100 C and, after addition of 40 g of ethanol, 5 g of nonylphenyl poly (ethylene oxide) ether (NS-212, produced by Nippon Oil and Fats Co.) and 9.6 g of morpholine, the temperature is maintained at 1000 ° C. and Water is added at 900 ° C with stirring to prepare an aqueous modified polyolefinic resin composition in aqueous form (45% solids). To this aqueous modified polyolefin resin is incorporated an aqueous protected isocyanate (Colonate 2507 W). , produced by Nippon Polyurethane Industry Co.) at a dry matter ratio of 4: 3 to produce a

aqueous resin composition.

Example 32

  After having heated at 1100 C a load of 500 g of Superclone 803 MW (produced by Nippon Paper Industries Co., Ltd, solution in toluene, chlorine content of 29.5%, dry matter content of 20% by weight), which is a chlorinated polypropylene resin, 9.6 g of morpholine and 5 g of nonylphenyl poly (ethylene oxide) ether (NS-212, produced by Nippon Oil and Fats Co.) are added. After removal of toluene by distillation under reduced pressure, 20 g of ethylene glycol are added and water is added at 100 ° C. with stirring to obtain a composition

  of aqueous resin (40% dry matter).

  chlorinated olefinic acid thus obtained and an aqueous protected isocyanate (Elastoron BN-44, produced by Dai-ichi Kogyo Seiyaku Co) are mixed with a ratio of dry matter

  of 2: 1 to produce an aqueous resin composition.

Example 33

  In 200 g of toluene, 100 g of an acid-modified polyolefinic resin obtained by using a polyolefinic resin modified with a low-viscosity acid (PM = 12,000, grafting rate = 9.6% by weight) are dissolved at 60.degree. weight) obtained by replacing the starting polyolefin for use in Experimental Production Example 2 with an oxidatively degraded polyolefin (MW = 30,000) and, after adding 50 g of protected TDI-based isocyanate (Desmodur BL- 1100, produced by Sumitomo Bayer Urethane Co),

  5 g of nonylphenyl poly (ethylene oxide) ether are added

  lene) (NS-212, Nippon Oil and Fats Co) After removal of toluene by distillation under reduced pressure, g of ethylene glycol is added and water is added at 100 ° C. with stirring to obtain a resin composition aqueous

(40% dry matter).

  Comparative Examples 1 to 7 By replacing the surfactant ingredient according to the formulations given in Table 1, the conversion in aqueous form is carried out by a method similar to Example 1

  to produce aqueous resin compositions and deter-

  at the same time undermine the quantities of aggregates generated.

  Comparative Examples 8 to 12 Using the procedure described in Example 21, a protected isocyanate is incorporated in the aqueous converted products respectively obtained in Comparative Examples 1, 3, 5, 6 and 7 in the formulation ratios indicated in US Pat.

  Table 2 for producing aqueous resin compositions

  Comparative Example 13 In a four-necked flask similar to that of Experimental Production Example 1, maleic anhydride grafted copolymer obtained in Experimental Production Example 2 was melted by heating to 'C' and after After adding 9.6 g of morpholine, 15 g of poly (ethylene oxide) nonylphenyl ether (NS-212, Nippon Oil and Fats Co) are added. Water is then added with stirring to obtain a composition. of resin

aqueous (40% dry matter).

  Comparative Example 14 After heating at 110 ° C a load of 500 g Superclone 803 MW (produced by Nippon Paper Industries Co., Ltd., toluene solution, chlorine content 29.5%, dry matter content 20% by weight), which is a chlorinated polypropylene resin, 9.6 g of morpholine and 15 g of poly (ethylene oxide) nonylphenyl ether (NS-212, produced by Nippon Oil and Fats Co) are added. toluene by distillation under reduced pressure, water is added at 100 ° C. with stirring to obtain an aqueous resin composition (40% of material

dried).

  Comparative Examples 15 and 16 To 100 g of dry matter of the acid-modified aqueous polyolefin resins prepared in Examples 29 and 30 was added a predetermined amount of Superflex 110 (produced by Dai-ichi Kogyo Seiyaku Co) which is a urethane resin. aqueous solution of the nonionic ester type in place of the aqueous protected isocyanate, then stirring water is added to obtain aqueous resin compositions having a solids content of 45%. Table 4 gives the results of stability test, the moisture resistance test results and

  the adhesiveness test results obtained with the dispersions

  Examples of Examples 1 to 20 and Comparative Examples

  from 1 to 7 after having rested for 1 month.

  Table 5 gives the test results of resistance

  humidity, adhesion test results, gasoline resistance test results, hot water resistance test results, and results.

  flexural strength test results obtained with the

  Examples 21 to 26 and Comparative Examples

8 to 12.

  The test methods employed are as follows. The aqueous resin compositions prepared in Examples 1 to 26 and Comparative Examples 1 to 12 are spray applied to a polypropylene plate and dried for 15 to 20 minutes at 80 ° C. of film is adjusted between 10 and 15 pm Then, a two-component urethane-based overcoat paint is

  applied and allowed to stand for 10 minutes at

  ambient temperature After heat treatment for 2 to 15 minutes between 120 and 130 ° C in a fan dryer, forced drying is carried out for 30 minutes at 80 C. The painted plate thus obtained is left standing for 1 day at room temperature before testing

applied film.

  Tape Testing Incisions to the substrate are made with a blade on the surface of the applied film to produce grid sections at 1 mm intervals Cellophane adhesive tapes are applied to adhere

  tightly and peeled five times by 180 degree pull. The remaining grid sections are counted.

  Essence of resistance to gasoline Incisions reaching the substrate are made with a blade on the surface of the applied film and, after immersion in gasoline (high-octane unleaded gasoline, produced by Nippon Oil Co) during 4 hours

  the state of the applied film is observed visually.

  Moisture Resistance Test After immersing one fifth of the painted plate in hot water at 500 C for 240 hours, the condition of the

  applied film is examined, for example to detect the

  blistering, then Cellophane adhesive tapes are applied to it so as to adhere closely and peeled off five times by 180 degree pull and the amount of film

remaining applied is evaluated.

  Hot water resistance test After immersing the painted plate in hot water at 400 ° C. for 240 hours, the state of the applied film is examined, for example to detect the appearance of blisters, then adhesive tapes. Cellophane is applied in such a way as to adhere tightly and peeled off five times by 180 degrees and the amount of film applied

remaining is evaluated.

  Flexural strength test The painted plate is bent 180 degrees on a mandrel 2.54 cm in diameter and the state of the applied film

is examined.

  Storage stability test A sample of the prepared aqueous resin composition (25% dry matter) is placed in a glass container having a volume of 250 ml and the variations of the degree of separation between the aqueous phase and the phase of emulsion and the degree of formation of resin aggregates

  are evaluated over time at room temperature.

  Table 6 gives the stability test results.

  adhesiveness test results, gasoline resistance test results, water resistance test results and flexural strength test results obtained with aqueous dispersions Examples 29 to 33 and Comparative Examples 13 to 16 after

  Let them rest for 1 month. The test methods are the same as above.

TABLE 1

TABLE 2

  Surfactant Ingredient Base Aggregates and Residues Exqmpgédet esi-ctf Filtration Baum NO O p Quantity PS Amount Quantity (% vs Type (Parts) cal / 2 n-3/2 PM Type (Parts) to Resin) 1 _ Morpholine 6 4,7 2 il I 3,1 3 _ Monoethanol 3 2,0 amine

4 "" 4.0

_ "" 1,2

6 Morpholine 4 0.1

7 _ "" 1,7

8 _ "" 0.7

9 8 1.0

  "0.0 i 11 i" 12 _ Monoethanol 4 amine

13 "" 0.2

  14 F 5 8.8 1350 Diethanol 10 0.0 14F 5 8.8 1350 min 10 0.0 amine

G 3 "1300" "

  16 _ Diethylamine "2.8 17 Propylamine 15 0.1

18 "" 0.8

19 Morpholine 8 0.2

4 0.0

Example

comparison

ratify N 1 Morpholine 4 75.0

2 53.4

3 - "48.8

  4 Diethylamine 10 61.1 Morpholine 68.3

6 9.6 8.2

7 = "" 10.3

  The symbols in Table 1 and Table 2 below

  have the following meanings: A: Poly (ethylene oxide) B: Poly (propylene oxide) C 1: Addition product of ethylene oxide (10 mol) on dodecylphenol C 2: Addition product of ethylene oxide (8.5 mol) on nonylphenol D: adduct of ethylene oxide-propylene oxide (16 mol) on amine coconut oil (block copolymerization) E: Ethylene oxide-propylene oxide adduct on lauryl alcohol (block copolymerization) F: Ethylene oxide-propylene oxide adduct on laurylamine (block copolymerization) G: Ethylene oxide-propylene oxide adduct on myristylamine (random copolymerization) H: Ethylene glycol I: Diethylene glycol J: Trimethylolpropane K: 1,6-hexamethylene diol L: Acid Nonylbenzenesulfonic M: Ethanol 1) Chlorinated polypropylene, degree of chlorination: 67% (Trademark Superclone 406, Produ it by Nippon Paper Industries Co, Ltd)

TABLE 3

  Aqueous Polyolefin Protected Isocyanate Example NO QuantityT Qua Type (Parts) Type (Parts) 21 Example 6 100 A 100

22 "11 B 100

23 "11 he A 200

24 "12 B 120

"12 C 100

26 "18 to 80

  Example Example 100 to 100 Comparative 8 Comparative 1

"9" 3 B 100

5 B 200

he 6 to 100

"12 7 B 100

  In Table 3: A: Duranate X-1118 (produced by Asahi Chemical Industry Co.) B: Colonate 2507 W (produced by Nippon Polyurethane Industry Co.) C: Elastoron BN-44 (produced by Dai-ichi Kogyo Seiyaku Co.)

TABLE 4

  Stability 6 a u I: Resistance to Example NO Stability to Adhesiveness Resistance to storage moisture

1 85/100 A

2 92/100

3 95/100

4 100/100

100/100

6 100/100

7 98/100

8 100/100

9 100/100

100/100

11 100/100

12 100/100

13 100/100

14 100/100

100/100

16 100/100

17 98/100 A

18 100/100

19 100/100

100/100

Example 51/100 X Comparative 1

"2 to 34/100 X

"3 0/100 XX

"4 0/100 XX

"5 43/100 XX

"6 68/100 A

"7 75/100 A

  : Very good; X: Bad; : Good; A: Poor; XX: Very bad

TABLE 5

  Resistance Resistance Resistance Resistance to Gasket adhesion to moisture bending hot water Example 21 100/100

"22 100/100

"23 100/100

"24 100/100

"25 100/100

"26 100/100

Example

  Comparative 8 60/100 X A XX Comparative 8 "9 13/100 X X xx

53/100 A A XX

he "11100/100 A XX

"12 100/100 A X

TABLE 6

  Flexural strength Stability d Resistance Resistance oau Gasoline adhesion to water Temperature -20 o C ambient

Example 29

"30" 31

"32 A A

* "33

Example

Comparative 15 X A X X

16 XX TO X XX

"17 A A

18 A A

  : Very good; X: Bad; : Good; A: Poor; XX: Very bad As described above, the aqueous resin compositions of the invention offer both excellent adhesiveness to polyolefins, good storage stability and good flexibility of the applied film. However, they allow the formation of a more applied film. water resistant than aqueous polyolefinic resin compositions

  using a polyol or a surfactant.

  The same effect is also produced in a film system

  In addition, since the conversion in aqueous form is possible without using any aromatic organic solvent, these compositions are excellent in the aspects of safety, health and pollution.

of the environment.

Claims (12)

  An aqueous polyolefinic resin composition, characterized in that it contains a substance having a polyalkylene oxide structure and a solubility parameter of at least 7 calV / 2 cm 3/2 and at most 12 call / 2 cm 3/2 in a proportion of not less than 0,001% by weight and not more than% by weight as a constituent ingredient introduced for   the conversion in aqueous form of a polyolefin or poly- modified olefin.   An aqueous resin composition according to claim   cation 1, characterized in that the modified polyolefin is a modified polyolefinic resin comprising one or   several species of (A) polyolefin modified by copoly-   grafting with unsaturated carboxylic acid and / or anhydride, (B) polyolefin modified by chlorination and (C) polyolefin modified by graft copolymerization of a reactive monomer capable of radical polymerization. An aqueous polyolefin resin composition, characterized in that it contains a substance having a polyalkylene oxide structure and a solubility parameter of at least 7 ca / 2 cm 3/2 and at most 12 cal / 2 cm 3/2 in a proportion of not less than 0,001% by weight and not more than% by weight as a constituent ingredient introduced for the conversion in aqueous form of a modified polyolefin   obtainable by two or more kinds of modifications   selected from acid modification, chlorination modification and reactive monomer modification, respectively indicated in (A), (B) and (C) in claim 2.   An aqueous polyolefin resin composition according to claim 1, characterized in that it contains a substance having a poly (alkylene oxide) structure and a solubility parameter of at least 7 call / 2 cm-3/2 and not more than 12 cc 11/2 cm-3/2 in a proportion of not less than 0.001% by weight and not more than 50% by weight as a constituent ingredient and in that it is obtained by the use of a polyolefin and / or a modified polyolefin having a melt viscosity of between 100 m Pa S and 000 m Pa S in a temperature range of 60 to 300 C when converting in aqueous form a polyolefin or modified polyolefin.   An aqueous polyolefinic resin composition according to claim 1, characterized in that it contains a substance having a polyalkylene oxide structure, a solubility parameter of at least 7 1/2 cm -3 / 2 and of not more than 12 call / 2 cm 3/2 and an average molecular weight of at least 5000 in a proportion of at least 0.001% by weight and not more than 50% by weight as a constituent ingredient introduced for the preparation of a resin composition   aqueous polyolefin which can be obtained by converting   in aqueous form of a modified polyolefin or polyolefin.   An aqueous resin composition according to claim   cation 1, characterized by the use of a polyoxy   alkylene diol represented by the general formula 1) as a substance having a poly (alkylene oxide) structure for the preparation of an aqueous polyolefin resin obtainable by the aqueous conversion of a modified polyolefin or polyolefin; general formula 1): HO-1 (PO) n / (EO) ml-H E: -CH 2 CH 2- P: -CH 2 CH-   CH 3 n, m: integers between 0 and inclusive and such that 4 <N + m _ 100 /: indicates a structure of random copolymer or block copolymer, but, if either of N or m is 0, this sign indicates a homopolymer structure.   An aqueous resin composition according to claim   cation 1, characterized by the use of an ethylene oxide-propylene oxide adduct on an aliphatic alcohol, represented by the general formula (2), as a substance having a poly (oxide) structure. alkylene) for the preparation of a resin composition   aqueous polyolefin which can be obtained by converting   in aqueous form of a modified polyolefin or polyolefin; general formula 2): RO-1 (PO) m / (EO) n -H-R: a hydrocarbon group having 1 to 50 carbon atoms, E: -CH 2 CH 2- P: -CH 2 CH-   CH 3 n, m: integers between 0 and inclusive and such that 2 <m + N <100 /: indicates a structure of random copolymer or block copolymer, but, if either of N or m is 0, this sign indicates a homopolymer structure.   An aqueous resin composition according to claim   cation 1, characterized by the use of an ethylene oxide-propylene oxide adduct on an aliphatic amine, represented by the general formula (3), as a substance having a poly (oxide) structure. alkylene) for the preparation of a resin composition   aqueous polyolefin which can be obtained by converting   in aqueous form of a modified polyolefin or polyolefin; general formula 3): l (PO) m / (EO) n H -H R-N l (PO) e / (EO) kI-H R: a hydrocarbon group having 1 to 50 carbon atoms, E: -CH 2 CH 2- P: -CH 2 CH-   CH 3 n, m: integers between O and inclusive and such that 2 S m + N s <100 e, k: integers between O and inclusive and such that 2 S e + k S 100 /: indicates a structure of random copolymer or block copolymer, but if either of N or m is 0, or if either of e or k is 0, this sign indicates a homopolymer structure.   An aqueous polyolefinic resin composition according to claim 1, characterized by the use of a surfactant ingredient having a polyoxyethylene alkylphenyl ether structure, represented by the general formula 4), in combination with at least one species of the substances represented by the general formulas 1), 2) and 3) as a substance having another polyoxyalkylene structure in a ratio of 1: 200 to 200: 1 for the preparation of an aqueous polyolefinic resin composition obtainable by the conversion in aqueous form of a modified polyolefin or polyolefin; general formula 4): -O-ECH 2 CHOH-1R'O ln-X R R: a lower alkyl group R ': -CH 2 CH 2, -CH 2 CH-   CH 3 X: a hydrogen atom, lower alkyl group or nonionic or anionic hydrophilic group, Y: a hydrogen atom or -CH 2 -O-CH 2 -CH = CH 2 Z: a hydrogen atom or -CH = CH-CH 3, provided that Y and Z do not contain simultaneously a double bond.   An aqueous polyolefinic resin composition produced by a process comprising steps o, after melting the starting resin under a pressure   applied from 9.8 k Pa to 9.8 Pa and mixed the surfactant with   or alcohols and a basic substance, water is gradually added with stirring to cause the phase inversion, thereby performing the conversion in aqueous form while the resinous ingredient, water and other ingredients coexist at a temperature of at least 1000 ° C and at most 300 ° C for conversion under   aqueous form of a modified polyolefin and / or polyolefin.   An aqueous resin composition, characterized by incorporating a protected isocyanate to a polyolefin and / or modified polyolefin in a weight ratio of 0.1: 1 to 20: 1 during conversion to aqueous form or after conversion in aqueous form in the preparation of an aqueous polyolefinic resin composition obtainable by the aqueous conversion of a   polyolefin or modified polyolefin.   A single component type aqueous polyolefinic resin composition, characterized by incorporating an aqueous protected isocyanate in a weight ratio of from 0.1: 1 to 20: 1, the conversion in aqueous form having already been carried out by a any method for forming an aqueous polyolefin resin composition according to any one   any of claims 1 to 10 or another composi-   aqueous polyolefin resin.   An aqueous resin composition of the two-component type, characterized by the incorporation of an isocyanate   protected at the time of painting, the conversion   aqueous form having been carried out to form an aqueous polyolefin resin composition according to one of   any of claims 1 to 10 above or another   aqueous polyolefinic resin composition.   An aqueous resin composition according to claim   cation 11, 12 or 13, characterized in that a protected isocyanate using a polyisocyanate based on hexamethylene diisocyanate as starting material is used as the protected isocyanate.   Film-forming products such as paints, primers, inks and coating products, products   sealing agents or adhesives, characterized in that they   hold an aqueous polyolefinic resin composition   defined according to any one of claims 1 to 12 and claim 14.   16 Film-forming products such as paints, primers, inks and coating products, products   sealing agents or adhesives, characterized in that they   contain a two-component type aqueous resin composition defined in claim 13, wherein the two-component system comprises two components, one of which contains one of the components as part of its constituent ingredients and the other contains the other component as constituent ingredient.