JP2603174B2 - Aqueous resin composition and method for making polyolefin aqueous - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous resin composition and a method for converting a polyolefin into an aqueous solution. The aqueous resin composition of the present invention is mainly used as a resin for paints, primers, inks, adhesives and sealing agents. Can be used.
It is also possible to use it in combination with an aqueous resin such as aqueous acrylic or polyester.

[0002]

2. Description of the Related Art Conventionally, polypropylene, polyethylene,
And a modified polyolefin composition obtained by modifying a polyolefin such as a copolymer obtained by combining two or more of propylene, ethylene and another α-olefin with an unsaturated carboxylic acid and / or an acid anhydride, and further chlorinating them. Acid-modified chlorinated polyolefins are used in coating materials, primers, inks, and the like. However, at present, since these resins are dissolved only in aromatic organic solvents such as toluene and xylene, a large amount of aromatic solvents must be used, and there is a problem in terms of safety and health and environmental pollution.

[0003] Attempts have been made to produce aqueous dispersions of chlorinated polyolefins.
153778 JP, JP-A-1-256556, JP-A-2-284973
However, they use an aromatic organic solvent at the time of production, and it has been difficult to completely eliminate the aromatic organic solvent. Attempts have also been made to produce aqueous dispersions of modified polyolefins, which are disclosed, for example, in JP-A-59-47244 and JP-A-2-286724. However, when the object to be coated and the object to be bonded are polyolefin resin in coating, bonding, etc., there are drawbacks such as poor adhesion and poor water resistance or poor paintability, and such an aqueous composition is still in practical use. Has not been reached. In Japanese Patent Application Laid-Open No. H3-182534, the performance of a coating film is improved by converting a modified chlorinated polyolefin into an aqueous solution using a surfactant and further adding an aqueous polyurethane resin. However, since the surfactant is not reactive, the surfactant component is eluted from the coating film by water, which causes a phenomenon that the water resistance of the coating film is reduced due to a defect of the coating film which is considered to be caused thereby. In addition, reactive surfactants have been used in emulsion polymerization so far. In emulsion polymerization, they have a surfactant activity to suspend monomers in water and react with other monomers to form a polymer. , Resulting in the effect of improving the water resistance of the reactant.

On the other hand, it has already been carried out to polymerize radically polymerizable monomers into polyolefins, and in Japanese Patent Application Laid-Open Nos. 62-256812 and 1-146917, styrene, vinyl monomers, acrylic monomers, Attempts have been made to graft unsaturated monomers such as methacrylic monomers to polyolefins. However, the monomer used here may be basically an unsaturated monomer, and there is no description about the functional group to be possessed by the grafting monomer or the surface activity.

The modified polyolefin is also used as a binder for inks, a resin for a sealing material, and a resin for road marking, because of its good adhesion to a substrate and its low solubility in water and its low hydrophobicity. Have been. In these applications, the use of an organic solvent is not preferable, and the dissipation of the solvent into the environment is a problem.

[0006]

As described above, an aqueous resin composition using a surfactant based on a modified polyolefin has heretofore been known to have a film formed by using a film-forming material containing the same. There was a problem that it would drop. The present invention not only eliminates the organic solvent released into the environment by making the polyolefin resin aqueous without using an organic solvent by a novel aqueous method of graft copolymerizing a reactive surfactant, Improves the water resistance, bending resistance, adhesion and other properties of the film-forming material containing the aqueous resin composition having good storage stability produced by this aqueous method, and the film and adhesive layer formed by the adhesive and the like. It is intended to provide an aqueous resin composition that can be used.

[0007]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies on an aqueous resin composition which is free from problems such as toxicity and pollution, and which is excellent in safety and water resistance. Invented the invention.

In the aqueous conversion of a polyolefin resin including both unmodified and modified polyolefins, it is not possible to obtain an aqueous solution such as when an unsaturated monomer is simply graft-polymerized or when an oil-soluble monomer is used. It became clear that it was necessary to select the hydrophilic and lipophilic functional groups of the monomers appropriately, because there are often problems with the storage stability even if they can be made water-based simply by having a functional group. . Therefore, a reactive surfactant, which is a reactive compound that has an ionic or nonionic hydrophilic functional group such as a carboxyl group, a hydroxyl group, a sulfone group, or a polyoxyethylene group and a hydrophobic functional group and has surface active ability, is grafted. As a result of studying copolymerization, the present invention has been achieved.

[0009] That is, the present invention is polyolefin, chlorinated polyolefin, the reactive surfactant in any of the modified polyolefin with an unsaturated carboxylic acid and / or acid anhydride, thereby graft-polymerizing a reactive monomer necessary The basic feature is that a basic substance, a non-reactive surfactant is added to the reactant before or after the reaction, or both, if necessary, and water is further added to the reactant. A water-based resin composition, a water-based method for converting a polyolefin and a coating agent having improved water resistance, storage stability, and film bending resistance by containing the water-based resin composition,
The present invention relates to a film-forming product such as a primer and ink, a sealing agent, and an adhesive.

Hereinafter, the present invention will be described in detail. The polyolefin used in the present invention is a homopolymer of ethylene or propylene, or ethylene or propylene and other comonomers having 2 carbon atoms such as butene-1, pentene-1, hexene-1, heptene-1, octene-1, and the like.
As described above, it is preferably a random copolymer or a block copolymer with 2 to 6 α-olefin comonomers, and a random copolymer is more preferable than a block copolymer. Further, two or more of these comonomers may be copolymerized. The chlorinated polyolefin is obtained by chlorinating the above polyolefin by a known method. The acid-modified polyolefin is a polyolefin obtained by modifying the above-mentioned polyolefin with an α, β-unsaturated carboxylic acid or an acid anhydride thereof by a graft reaction.

The polyolefin-based resin used as the water-based raw material resin can basically be used in the present invention if it is melted at a temperature lower than the thermal decomposition temperature of the reactive surfactant and the reactive monomer used for the grafting reaction or dissolved in a solvent. Can be applied.

The polyolefin used for the acid modification is ethylene or propylene and other comonomers such as butene-1, pentene-1, hexene-1, heptene.
1, octene-1 or the like having 2 or more carbon atoms, preferably 2 to 2 carbon atoms
6 is a random copolymer or a block copolymer with an α-olefin comonomer, and a random copolymer is more preferable than a block copolymer. Further, two or more of these comonomers may be copolymerized, and among them, ethylene or 1-butene is preferred in view of the physical properties of the resin.
When a film is formed on a polypropylene substrate, the proportion of the propylene component is preferably at least 55 mol%, and if it is less than 55 mol%, the adhesion to polypropylene is poor, which is not preferable.

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

The number average molecular weight of a resin obtained by graft copolymerizing an α, β-unsaturated carboxylic acid or an acid anhydride thereof is 30.
It is preferably from 00 to 35,000, and if it is less than 3000, the cohesive force is insufficient and the adhesion to the polyolefin resin is deteriorated.
If it is more than 5000, the operability when dispersing in water becomes poor, which is not preferable. In order to make the molecular weight fall within this range, it is possible to select the molecular weight of the raw material and the conditions for performing the graft reaction, and it is also possible to perform the graft reaction after the molecular weight of the raw material is reduced. The number average molecular weight can be measured by GPC (gel permeation chromatography).

The method of graft-copolymerizing an α, β-unsaturated carboxylic acid or its anhydride with a polyolefin may be carried out by a known method. In particular, the polyolefin is heated and melted to a temperature equal to or higher than its melting point, and is heated in the presence of a radical generator. Is preferably carried out by a method of graft copolymerization. In this method, use a reaction vessel equipped with a powerful stirrer, a Banbury mixer, a kneader, an extruder, etc., and use
An α, β-unsaturated carboxylic acid or its anhydride and a radical generator are added and reacted at a temperature of 00 ° C. or lower, and the product is pelletized by a known method. As another method, it is also possible to carry out the method of heating and dissolving the polyolefin in an organic solvent such as xylene and reacting it in the presence of a radical generator, but it takes time and effort to remove the organic solvent and the organic solvent remains. Is not preferred.

The radical generator used in the acid modification reaction of the polyolefin can be appropriately selected from known ones, and an organic peroxide is particularly preferred. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3, and di-t-butylperoxide. Oxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, cumene hydroperoxide and the like can be mentioned, and they can be selected and used depending on the reaction temperature.

In the present invention, the basic substance is added to ionize hydrophilic groups such as a carboxyl group and a sulfone group to improve dispersion in water. If the reactive surfactant has already been neutralized with a base, it may not be necessary to add it. Basic substances include sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine,
Ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1 −
Examples include propanol and morpholine.

The degree of hydrophilicity of the resin varies depending on the type of the base used, so it is necessary to select it appropriately depending on the conditions. The amount of the basic substance used is suitably in the range of 0.3 to 1.5 times the equivalent of the carboxyl group of the acid-modified polyolefin, and preferably 0.5 to 1.2 times. Also,
In the addition of these basic substances, they may be added before the radical grafting reaction as necessary, or may be added after the grafting reaction.

The reactive surfactant used in the present invention may be any of those generally used as a reactive surfactant or a reactive emulsifier, but is preferably one described in JP-A-4-53.
JP-A-802-100, JP-A-4-50204, alkylpropenylphenol polyethylene oxide adducts, alkyldipropenylphenol polyethylene oxide adducts and salts of sulfates thereof,
Allylalkylphenol polyethylene oxide adducts, allyl dialkylphenol polyethylene oxide adducts, and salts of sulfates thereof described in JP-A-62-221431 and JP-A-62-221431. Among them, alkylpropenylphenol ethylene oxide 20 mol adduct, 30 mol adduct and 50 mol adduct (Aqualon RN
-20, RN-30, RN-50, manufactured by Daiichi Kogyo Seiyaku) and alkylpropenylphenol polyethylene oxide
Ammonium sulfate ammonium salt of 10 mol adduct, ammonium ammonium sulfate of 20 mol adduct (Aqualon HS
-10, HS-20, manufactured by Daiichi Kogyo Seiyaku). Also, a plurality of reactive surfactants can be used in combination.

Non-reactive surfactants that can be used if necessary include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, and polyoxyethylene propylene polyol. (Pluronic type), nonionic surfactants such as alkylolamide, sorbitan alkyl ester, polyglycerin ester, alkyl sulfate ester salt, alkyl phenol sulfonate salt, sulfosuccinate ester salt, and other carboxylate and phosphate ester salts It is also possible to use anionic surfactants which can be exemplified, amphoteric surfactants such as alkyl betaines and alkyl imidazolines, and mixtures of two or more of these. . However, it is not preferable to add a large amount of a non-reactive surfactant because the water resistance decreases.

Reactive monomers that can be used in the present invention include acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylonitrile, acrylamide, hydroxyethyl acrylate, methacrylic acid. Acrylic monomers such as acid hydroxyethyl ester, 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 acetate and the like Examples include ester monomers, methyl maleate, and maleic anhydride. The reactive monomer itself can be graft-copolymerized to an acid-modified polyolefin by a radical reaction, but a reactive monomer having both a radical reactive double bond and a hydroxyl group such as 2-hydroxyethyl acrylate and 2-hydroxy methacrylate. In this case, the hydroxyl group can be used to add the acid-modified polyolefin solution in advance before the radical reaction and graft-copolymerize it by an esterification reaction. In this case, a reactive surfactant can be graft-copolymerized by utilizing a radical reactive double bond which has not been subjected to the esterification reaction.

Known initiators for the graft reaction by radical reaction may be used, and organic peroxides are particularly preferred. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3, and di-t-butylperoxide. Oxide, t-butyl peroxyisopropyl carbonate, t-butyl hydroperoxide, t-butyl peroxybenzoate, cumene hydroperoxide and the like can be mentioned. Azo-based and redox-based initiators such as azobisisobutyronitrile can also be used. They may be used in combination.

Aqueous Conversion Reaction Method The polyolefin, chlorinated polyolefin, and modified polyolefin as the aqueous conversion raw material used in the present invention may be those produced by a known method, and may be other than the melting point of the resin as the aqueous conversion raw material or the solubility in the solvent. Regarding the factor (1), the aqueous method of the present invention is not limited at all by the production method of the raw material and the degree of modification.

[0024] as a graft method of a reaction surfactant in the present invention, by heating and melting an aqueous raw material resin (polyolefin, either chlorinated polyolefin, polyolefin modified with an unsaturated carboxylic acid and / or acid anhydride) Graft copolymerization may be carried out by adding a reaction initiator (radical generator) and a reactive surfactant thereto (melt reaction method), and the aqueous resin is dissolved in an organic solvent such as toluene or xylene. After that, a reaction initiator and a reactive surfactant may be added (solution reaction method).

Melt Reaction Method The method of graft copolymerizing a reactive surfactant with a polyolefin may be carried out by a known method, but a method of heating and melting the polyolefin above its melting point and graft-copolymerizing in the presence of a radical generator. Can also be done. In the case of this method, use a reaction vessel equipped with a strong stirrer, a Banbury mixer, a kneader, an extruder, or the like. 5 parts to 150 parts of a reactive surfactant, 1 part to 20 parts of a radical generator and, if necessary, 5 parts to 100 parts of a reactive monomer are successively added to 100 parts of the raw material and reacted. The reaction temperature is desirably determined in consideration of the melting point of the aqueous resin material, the decomposition rate of the reaction initiator (radical generator), the decomposition temperature of the reactive surfactant, the graft ratio, and the like.
The optimum reaction time is determined from the graft ratio and the residual ratio of unreacted monomer, but is preferably 30 minutes to 10 hours. Reactants
After cooling to 100 ° C., water at 90 ° C. is added with stirring, or the reaction product is put into stirring water to obtain an aqueous resin. The basic substance and the non-reactive surfactant to be added to the reactant as necessary may be added to the molten resin before the graft reaction, or may be added after the graft reaction and before adding water. In addition, a basic substance and a non-reactive surfactant to be added as needed may be added to water in necessary amounts in advance.

As another method of the solution reaction method, a method in which a polyolefin is heated and dissolved in an organic solvent such as xylene and reacted in the presence of a radical generator can also be used. The aqueous resin is dissolved in an organic solvent such as toluene or xylene, and a radical generator is added. At room temperature to 160 ° C., a reactive surfactant and, if necessary, a reactive monomer are gradually added. The reaction time is suitably from 1 hour to 18 hours, but the optimum value is determined from the graft ratio and the residual ratio of unreacted monomer. After completion of the reaction, the solvent is removed under reduced pressure, and then the reaction product is added to stirring water, or water is gradually added to the reaction product, and an aqueous resin composition is obtained by a phase inversion method. The basic substance to be added to the reactant and the non-reactive surfactant to be added as necessary may be added to the resin solution before the graft reaction or may be added after the graft reaction and before adding water. In addition, basic substances,
The necessary amount of the non-reactive surfactant to be added as needed may be added to water.

In both the melt reaction method and the solution reaction method, unreacted reactive surfactant remaining in the reaction product can be removed by ultrafiltration or UF membrane treatment. Unreacted reactive monomers can be removed when the solvent is distilled off under reduced pressure in the solution reaction method, and can be distilled off under reduced pressure after the reaction is completed in the melt reaction method. Furthermore, once the aqueous liquid is formed, it can be removed by distillation under reduced pressure using a flash evaporator or vapor stripping.

The water resistance and adhesion of the coating film can be improved by mixing and using the aqueous polyurethane with the aqueous modified polyolefin resin composition. As the aqueous polyurethane, a commercially available aqueous polyurethane resin can be used. In selecting the aqueous polyurethane resin, a film is formed only with the aqueous urethane resin, and the film is subjected to a hot water resistance test (treatment condition: 80 ° C., 2 hours, pH with acetic acid, After immersion in water prepared at 4.0, dry at 130 ° C for 1 hour), moisture resistance test (70
It is desirable to use a material which has a change in tensile strength and elongation before and after the test of 25% or less and has no visual whitening phenomenon of the coating film after being left in a moist heat oven at 95 ° C. and 95% RH for 200 hours.

The resin composition of the present invention dispersed in water in this manner has excellent adhesion to polyolefins, and is excellent not only as a primer for coating and bonding, but also as a vehicle resin for aqueous coatings and aqueous adhesives. It can also be applied as an agent, a binder resin for an aqueous ink, and a resin for a sealing material. Further, the aqueous resin composition of the present invention may be mixed with a pigment as it is, or may be blended with another aqueous resin.

[0030]

Among the aqueous resin composition of the present invention, those that the polyolefin modified with particular unsaturated carboxylic acid and / or acid anhydride as one of the components, not only has excellent adhesion to polyolefins Further, since the surfactant used for aqueous conversion has reactivity, it has been found that the surfactant component is fixed to the film on which the surfactant component is formed by the reaction, and the water resistance after the film formation is remarkably improved.

[0031]

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

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

(Trial Production Example 2) In a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, a propylene-butene-ethylene copolymer (propylene component 68 mol%, butene component 24 mol%) 300 g of ethylene component, 8 mol% of ethylene component, weight average molecular weight of 68000) was heated and melted. Then, 40 g of maleic anhydride and 5 g of dicumyl peroxide as a radical generator were added for 3 hours while stirring while maintaining the temperature of the system at 180 ° C. Then, the reaction was carried out for 3 hours. After cooling to room temperature after the reaction, the reaction product was poured into 20 L of acetone and purified to obtain a maleic anhydride graft copolymer having a graft amount of 9.2% by weight. The weight average molecular weight measured by GPC was 26,000. In the measurement of the weight average molecular weight, column TS was applied to Tosoh HPLC-8020.
K-GEL was added, the sample was dissolved in THF (tetrahydrofuran), measured at 40 ° C., and the molecular weight was determined from a calibration curve prepared with a polystyrene standard sample.

(Example 1) In a four-necked flask similar to that of Trial Production Example 1, 100 g of the maleic anhydride graft copolymer obtained in Trial Production Example 1 was heated and dissolved in 200 g of toluene at 110 ° C. Butyl peroxyisopropyl carbonate 10
g and morpholine 4.6 g were added, and alkylpropenylphenol ethylene oxide 20 mol adduct 60 g toluene
(120 g) After the solution was added dropwise over 3 hours, a post-reaction was performed for 4 hours to perform a graft copolymerization reaction. After toluene contained in the reaction solution was distilled off under reduced pressure, 4 g of triethylamine was added, and water was added with stirring to obtain an aqueous resin composition (solid content: 40%).

(Example 2) In a four-necked flask similar to that of Trial Production Example 1, 100 g of the maleic anhydride graft copolymer obtained in Trial Production Example 2 was heated and dissolved at 200 ° C. in toluene at 110 ° C. Butyl peroxyisopropyl carbonate 10
g and 9.6 g of morpholine were added, and a solution of 60 g of an alkylpropenylphenol ethylene oxide 20 mol adduct (manufactured by Daiichi Kogyo Seiyaku, Aqualon RN-20) in toluene (120 g) was added dropwise over 3 hours, followed by 4 hours of post-reaction. By doing so, a graft copolymerization reaction was performed. After the toluene contained in the reaction solution was distilled off under reduced pressure, 4 g of triethylamine was added, and water was added with stirring to obtain an aqueous reaction solution (solid content: 25%).
%). The aqueous reaction solution was treated with an ultrafiltration membrane having a molecular weight cut-off of 5,000 for 48 hours and then concentrated again to obtain an aqueous acid-modified polyolefin resin having a solid content of 40%. Graft amount is 45 relative to raw material resin
% By weight.

(Example-3) In the same manner as in Example-2, instead of the alkylpropenylphenol ethylene oxide 20 mol adduct, an alkylpropenylphenol ethylene oxide 30 mol adduct (manufactured by Daiichi Kogyo Seiyaku, Aqualon R
N-30) was added and reacted to obtain an aqueous acid-modified polyolefin resin (solid content 40%, graft amount 43% by weight).

Example 4 In a four-necked flask similar to that of Trial Production Example 1, 100 g of the maleic anhydride graft copolymer obtained in Trial Production Example 2 was heated and dissolved in 200 g of toluene at 110.degree. Butyl peroxyisopropyl carbonate 10
g, alkyl propenyl phenol ethylene oxide 20
Ammonium sulfonate salt of molar adduct 65 g of toluene
(130 g) After the solution was added dropwise over 3 hours, a post-reaction was performed for 4 hours to perform a graft copolymerization reaction. After distilling off the toluene contained in the reaction solution under reduced pressure, morpholine 9.6
g was added and water was added with stirring to obtain an aqueous resin composition (solid content: 40%).

Example 5 100 g of the maleic anhydride graft copolymer obtained in Prototype Example 2 was heated and melted at 110 ° C. in a four-necked flask similar to that of Prototype Example 1 to obtain t-butylperoxy. Ammonium sulfonate salt of 10 g of isopropyl carbonate and 20 mol of alkylpropenylphenol ethylene oxide (Aqualon HS manufactured by Daiichi Kogyo Seiyaku)
-20) After the addition of 65 g over 3 hours, a post-reaction was carried out for 4 hours to carry out a graft copolymerization reaction. After the reaction, 9.6 g of morpholine was added, and water was added with stirring to obtain an aqueous reaction solution (solid content: 20%). This was purified in the same manner as in Example 1 and concentrated to obtain an aqueous acid-modified polyolefin resin having a solid content of 40% and a graft amount of 50% by weight.

(Example-6) In a four-neck flask similar to that of Trial Production Example 1, 100 g of the maleic anhydride graft copolymer obtained in Trial Production Example 2 was heated and dissolved in 200 g of toluene at 110 ° C. 20 g of hydroxyethyl acrylate was added and stirred for 1 hour. After adding 10 g of t-butyl peroxyisopropyl carbonate thereto, a graft reaction was carried out in the same manner as in Example 2 below using 60 g of a 30 mol adduct of alkylpropenylphenol ethylene oxide, and 9.6 g of morpholine was distilled off. Was added. Thereafter, purification was performed in the same manner as in Example 2, to obtain an aqueous acid-modified polyolefin resin (solid content: 40%, graft amount: 56 wt%).

(Example-7) In a four-necked flask similar to that of Trial Production Example 1, 100 g of the maleic anhydride graft copolymer obtained in Trial Production Example 2 was heated and dissolved in 200 g of toluene at 110 ° C. -Butyl peroxyisopropyl carbonate 10
g of ammonium sulfate of sulfuric acid ester of alkylpropenylphenol ethylene oxide 30 mol adduct.
g and the same operation as in Example 1 was carried out.
% Of an aqueous resin composition was obtained.

(Example-8) Nonionic ester-based aqueous urethane resin Superflex E2000 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) based on 100 g of the resin solid content obtained in Example-4
Was added, and water was added with stirring to obtain an aqueous resin composition having a solid content of 40%.

Example 9 An aqueous resin composition (solid content 45%, graft amount 55 wt%) was prepared in the same manner as in Example 6 except that 20 g of 2-hydroxyethyl methacrylate was used instead of 2-hydroxyethyl acrylate. I got To 100 g of the obtained resin solid content, 50 g of a nonionic ester-based aqueous urethane resin Superflex E2000 (manufactured by Daiichi Kogyo Seiyaku) was added, and water was added with stirring to obtain a solid content of 40 g.
% Of an aqueous resin composition was obtained.

Example 10 The same operation as in Example 6 was repeated, except that 60 g of the 30 mol adduct of alkylpropenylphenol ethylene oxide was replaced with the reactive surfactant Ramtail S-.
A graft reaction was performed using 20 g of 180A (manufactured by Kao), toluene was distilled off, morpholine was added, and then hot water at 90 ° C. was added to obtain an aqueous resin composition (solid content: 40%).

Example 11 A chlorinated polypropylene resin, Supercron 803 MW (manufactured by Sanyo Kokusaku Pulp Co., Ltd., chlorine content: 29.5%, solid content: 20% by weight, in a four-necked flask similar to that of prototype example-1) 500 g of toluene solution
After heating at 00 ° C. and adding 10 g of t-butyl peroxyisopropyl carbonate, a toluene (200 g) solution of 35 g of ammonium sulfonate of an alkylpropenylphenol ethylene oxide 30 mol adduct was added over 3 hours. Thereafter, the reaction was carried out for 4 hours, and then toluene was distilled off under reduced pressure. While stirring at 100 ° C., 4 g of triethanolamine was added, and water was gradually added to obtain an aqueous reaction solution. Thereafter, the same operation as in Example 3 was performed to obtain an aqueous chlorinated polyolefin resin composition (solid content: 45%, graft amount: 30 wt%).

Example 12 In the same four-necked flask as in Prototype Example 1, a propylene-butene-ethylene copolymer (propylene component 68 mol%, butene component 24 mol%, ethylene component 8 mol%, (Weight average molecular weight 26000) 100 g of toluene was dissolved in 400 g of toluene by heating at 100 ° C., 10 g of t-butylperoxyisopropyl carbonate was added, and a toluene (200 g) solution of 35 g of a sulfonate ammonium salt of an alkylpropenylphenol ethylene oxide 30 mol adduct was added. Added over time. Thereafter, the reaction was carried out for 4 hours, and then toluene was distilled off under reduced pressure. While stirring at 100 ° C., 4 g of triethanolamine was added, and water was gradually added to obtain an aqueous reaction solution. Thereafter, the same operation as in Example 3 was performed to obtain an aqueous polyolefin resin (solid content: 45%, graft weight: 27 wt%).

(Comparative Example 1) In a four-necked flask similar to that of Trial Production Example 1, 100 g of the maleic anhydride graft copolymer obtained in Trial Production Example 1 was heated and dissolved at 110 ° C. to obtain morpholine 4.6.
After the addition of 10 g, 10 g of polyethylene oxide nonyl phenyl ether (NS-208.5, manufactured by NOF Corporation) was added. Water is added with stirring to the aqueous resin composition (solid content
40%).

(Comparative Example 2) In a four-necked flask similar to that of Trial Production Example 1, 100 g of the maleic anhydride graft copolymer obtained in Trial Production Example 2 was heated and dissolved at 110 ° C. to obtain morpholine 9.6
After adding g, 15 g of polyethylene oxide nonyl phenyl ether (NS-212, manufactured by NOF Corporation) was added.
While stirring, water is added to the aqueous resin composition (solid content 40
%).

(Comparative Example 3) Chlorinated polypropylene resin Supercron 803MW (manufactured by Sanyo Kokusaku Pulp Co., Ltd., chlorine content 29.5%, solid content wt% 20% toluene solution)
After heating 500 g to 110 ° C. and adding 9.6 g of morpholine, 15 g of polyethylene oxide nonylphenyl ether (NS-212, manufactured by NOF Corporation) was added. After the toluene was distilled off under reduced pressure, water was added with stirring at 100 ° C. to obtain an aqueous resin composition (solid content: 40%).

Table 1 shows the storage stability test results, adhesion test results, and gasoline resistance test results of the aqueous dispersions of Examples 1-1 to -12 and Comparative Examples -1 to -3. The test method is as follows.

The aqueous resin compositions prepared in Examples 1-1 to -12 and Comparative Examples -1 to -3 were diluted to a solid content of 10%, spray-coated on a polypropylene plate, and forcibly dried at 80 ° C. for 30 minutes to 2 hours. did. The film thickness was adjusted to 10 to 15 μm. Next, a two-pack type urethane top coat was applied, left at room temperature for 10 minutes, and then forcibly dried at 80 ° C. for 40 minutes using a hot air drier. After the obtained coated plate was allowed to stand at room temperature for one day, the following coating films were tested.

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

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

Water resistance test The coated plate was immersed in warm water of 40 ° C. for 48 hours to examine the state of the coating film.

Bending resistance test The coated plate was bent 180 ° with a 1φ inch mandrel, and the state of the coating film was examined. The test was performed at room temperature and -20 ° C.

Storage stability test A prepared aqueous resin composition sample (solid content: 25%) was placed in a glass container having a capacity of 250 ml, and at room temperature, the degree of separation of the aqueous phase from the emulsion phase to the top, and formation of resin aggregates The changes over time were compared.

[0056]

[Table 1]

[0057]

Aqueous method of polyolefin of the present invention, according to the present invention can be effectively applied to the polyolefin resin (polyolefin, either chlorinated polyolefin, polyolefin modified with an unsaturated carboxylic acid and / or acid anhydride),
Further, the aqueous liquid of the polyolefin resin prepared by the method of the present invention has good storage stability. The aqueous resin composition using a chlorinated polyolefin or an acid-modified polyolefin as an aqueous material in the method of the present invention has excellent adhesion to polyolefin, good storage stability, and excellent flexibility in coating film. ing. Moreover, a water-resistant coating film can be formed as compared with a conventional polyolefin-based aqueous resin composition using a surfactant. Furthermore, since it can be made water-based without using any aromatic organic solvent, it is excellent in terms of safety and health and environmental pollution.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08L 51/06 LLD C08L 51/06 LLD C09D 123/26 PFA C09D 123/26 PFA 151/06 PFA 151 / 06 PFA 187/00 JGJ 187/00 JGJ PMX PMX C09J 123/26 JCL C09J 123/26 JCL 151/06 JDH 151/06 JDH

Claims (23)

(57) [Claims] 1. A reaction initiator, wherein 5-150 parts of a reactive surfactant is added to 100 parts of any one of polyolefin, chlorinated polyolefin, and polyolefin modified with unsaturated carboxylic acid and / or acid anhydride. An aqueous resin composition characterized by further adding water to a reaction product obtained by graft copolymerization in the presence of 1 to 20 parts. 2. A polyolefin, a chlorinated polyolefin, a polyolefin modified with an unsaturated carboxylic acid and / or an acid anhydride, and 100 parts of any of the polyolefin, 5 to 150 parts of a reactive surfactant, and 1 to 1 parts of a reaction initiator. A basic substance is added to the reaction product graft-copolymerized in the presence of 20 parts either before or after the reaction, or 0.3 to 1.5 times the equivalent to the carboxyl group of the modified polyolefin, before or after the reaction. And an aqueous resin composition further comprising water. 3. 100 parts of any of polyolefin, chlorinated polyolefin, polyolefin modified with unsaturated carboxylic acid and / or acid anhydride, and 5 to 150 parts of reactive surfactant and 5 to 100 parts of reactive monomer. Aqueous resin composition, characterized by further adding water to a reaction product obtained by adding the above components and then graft-copolymerizing in the presence of 1 to 20 parts of a reaction initiator. 4. A polyolefin, a chlorinated polyolefin, a polyolefin modified with an unsaturated carboxylic acid and / or an acid anhydride, a polyolefin modified with 100 parts, and a reactive surfactant of 5 to 150 parts and a reactive monomer of 5 to 100 parts. To the reactant graft-copolymerized in the presence of 1 to 20 parts of a reaction initiator, before or after the reaction, at one or both times, an equivalent amount of a basic substance to the carboxyl group of the modified polyolefin. Aqueous resin composition characterized by being added 0.3 to 1.5 times of the above, and further adding water. 5. The aqueous resin composition according to claim 1, wherein the reactive surfactant is a radically polymerizable reactive surfactant. 6. The reactive surfactant according to claim 1, wherein the reactive surfactant has a radical-reactive double bond and a polyoxyethylene chain as a nonionic hydrophilic group. The aqueous resin composition as described in the above. 7. The method according to claim 1, wherein the reactive surfactant is an alkyl propenyl phenol polyethylene oxide adduct and / or an alkyl dipropenyl phenol polyethylene oxide adduct and a salt of a sulfate thereof. Aqueous resin composition. 8. The reactive monomer according to claim 3, wherein the reactive monomer has a radical-reactive double bond and a hydroxyl group.
8. The aqueous resin composition according to any one of items 7 to 7. 9. The aqueous resin composition according to claim 3, wherein the reactive monomer is a reactive monomer having a radical-reactive double bond and a carboxyl group. 10. One or more of the aqueous resin compositions according to any one of claims 1 to 9, and 100 parts or more,
An aqueous resin composition comprising 50 parts of an aqueous polyurethane resin. 11. A reaction initiator, in which 5-150 parts of a reactive surfactant is added to 100 parts of any one of polyolefin, chlorinated polyolefin, polyolefin modified with unsaturated carboxylic acid and / or acid anhydride. A water-based method comprising adding water to a reaction product obtained by graft copolymerization in the presence of 1 to 20 parts. 12. 100 parts of any of polyolefins, chlorinated polyolefins, polyolefins modified with unsaturated carboxylic acids and / or acid anhydrides, and 5-150 parts of a reactive surfactant, A basic substance is added to the reaction product graft-copolymerized in the presence of 20 parts either before or after the reaction, or 0.3 to 1.5 times the equivalent to the carboxyl group of the modified polyolefin, before or after the reaction. And further adding water to the reaction product. 13. A reactive surfactant of 5 to 150 parts and a reactive monomer of 5 to 100 parts with respect to 100 parts of any of polyolefin, chlorinated polyolefin, polyolefin modified with unsaturated carboxylic acid and / or acid anhydride. An aqueous method comprising adding water to a reaction product obtained by graft-copolymerizing a part in the presence of 1 to 20 parts of a reaction initiator. 14. A reactive surfactant of 5 to 150 parts and a reactive monomer of 5 to 100 parts with respect to 100 parts of any one of polyolefin, chlorinated polyolefin, polyolefin modified with unsaturated carboxylic acid and / or acid anhydride. To the reactant graft-copolymerized in the presence of 1 to 20 parts of a reaction initiator, either before or after the reaction or at both times, the basic substance is added in an amount of 0 equivalent to the carboxyl group of the modified polyolefin. 3. A method for making aqueous solution, which comprises adding 3 to 1.5 times, and further adding water to the reaction product. 15. The reactive surfactant according to claim 11, wherein the reactive surfactant is a radically polymerizable reactive surfactant.
Item. 16. The reactive surfactant having a radical-reactive double bond and a polyoxyethylene chain which is a nonionic hydrophilic group.
The method for making aqueous solution according to any one of the above. 17. The reactive surfactant is an alkyl propenyl phenol polyethylene oxide adduct and / or an alkyl dipropenyl phenol polyethylene oxide adduct and a salt of a sulfate thereof.
The method for making aqueous solution according to any one of claims 16 to 16. 18. The reactive monomer according to claim 1, wherein the reactive monomer has a radical-reactive double bond and a hydroxyl group.
The aqueous method according to any one of 3 to 17, wherein 19. The method according to claim 13, wherein the reactive monomer is a reactive monomer having a radical-reactive double bond and a carboxyl group. 20. A coating agent comprising the aqueous resin composition according to any one of claims 1 to 10. 21. A film-forming product comprising the aqueous resin composition according to any one of claims 1 to 10. A sealing agent comprising the aqueous resin composition according to any one of claims 1 to 10. An adhesive comprising the aqueous resin composition according to any one of claims 1 to 10.