JP2000345097A - Polyolefin elastomer-based aqueous coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous coating agent which can form a coating film excellent in resistances to water, oil, and chemicals and in adhesion to many materials by incorporating a polyolefin elastomer and an acid-modified polyolefin and/or a higher fatty acid salt into the same and homogeneously dispersing solid components in an aqueous phase to give an aqueous dispersion. SOLUTION: This aqueous coating agent is prepared by melt mixing and kneading a basic substance and water into a melt mixture comprising a polyolefin elastomer and an acid-modified polyolefin and/or a higher fatty acid salt in such an amount of water that the total water concentration is 3-25 wt.% to thereby neutralize and/or saponify at least part of the acid-modified polyolefin and/or the higher fatty acid salt and to thereby disperse solid components in an aqueous phase. Preferably, this coating agent is an aqueous dispersion containing the acid-modified polyolefin and/or the higher fatty acid salt in an amount of 0.5-30 pts.wt. based on 100 pts.wt. polyolefin elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aqueous coating agent comprising a polyolefin elastomer. More specifically, the present invention relates to a water-based polyolefin elastomer coating agent capable of forming a film having excellent water resistance, oil resistance, chemical resistance and adhesion to various materials.

[0002]

BACKGROUND OF THE INVENTION Aqueous dispersions of various polymers have been known, and are applied to the surface of paper, fiber or plastic molded products, wood, metal, etc., and dried to form a resin film. It is used for imparting water resistance, oil resistance, chemical resistance and the like to materials, and as an adhesive such as a heat sealant. Since such an aqueous dispersion uses water as a dispersion medium, it is more advantageous than a solvent-type dispersion medium using a solvent as a dispersion medium in terms of flammability, work environment, and handling. And is used in a wide range of fields.

Among them, an aqueous dispersion known as a so-called powder emulsion which is apparently solid and is redispersed by adding water to form an aqueous dispersion (hereinafter, may be referred to as an aqueous dispersion in the present specification). Has no water content or low water concentration, so there is no need to worry about freezing even when the temperature drops, it is easy to pack and transport, and the storage space is small. More cement,
It also has the advantage that it can be directly mixed with mortar, gypsum or other powdery materials that do not come into contact with water.

[0004] As a production method of such an aqueous dispersion without adding any additives as much as possible and with a reduced energy consumption, the applicant of the present invention disclosed in Japanese Patent Publication No. 5-39975,
A method described in Japanese Patent Publication No. 7-96647 was disclosed. This is a method in which a specific component is melt-kneaded with an extruder or the like and the solid content is phase-inverted into an aqueous dispersion.The aqueous dispersion is apparently in a solid state, and the solid content is changed by adding water. It has the property of being uniformly dispersed in the aqueous phase.

[0005] By the way, in food packaging materials, building materials, woven fabrics, and the like to which strength, gas barrier properties, and moisture proof properties have been imparted, vinyl chloride resins or resins such as resins are applied to the surface of substrates such as films, cloths and papers. Conventionally, coating a base material by applying a vinylidene chloride-based resin has been performed. However, products coated with this vinyl chloride-based resin or vinylidene chloride-based resin are expected to be replaced with other resins such as polyolefins, for example, because hydrogen chloride is generated during waste incineration and the incinerator is damaged. .

On the other hand, polyolefins are inherently hard-to-adhesive resins. Therefore, in order to use them for coating such as painting and bonding, it was necessary to dissolve and disperse the polyolefins in a solvent. Therefore, there is an increasing demand for the above-mentioned water-dispersible coating agent composed of polyolefin.

[0007]

DISCLOSURE OF THE INVENTION The present invention does not generate harmful gases such as hydrogen chloride gas during waste incineration, and is excellent in water resistance, oil resistance, chemical resistance and adhesion to various materials. It is an object of the present invention to provide a water-dispersed aqueous coating agent capable of forming a coated film.

[0008]

According to the present invention, (A)
A polyolefin comprising a polyolefin-based elastomer, (B) a salt of an acid-modified polyolefin and / or a higher fatty acid, and (C) an aqueous dispersion containing water and having a solid content uniformly dispersed in an aqueous phase. An aqueous based elastomeric coating agent is provided.

In the aqueous polyolefin elastomer coating agent of the present invention, the acid-modified polyolefin and / or higher fatty acid salt (B) is contained in an amount of 0.5 to 3 based on 100 parts by weight of the polyolefin elastomer (A).
It is preferable that the aqueous dispersion is comprised of 0 parts by weight.

The aqueous polyolefin elastomer coating agent of the present invention has a solid content concentration of 10 to 70% by weight containing the polyolefin elastomer (A) and an average particle size of solid particles of 0.1 to 5 μm. It preferably comprises a certain aqueous dispersion.

In the preferred aqueous polyolefin elastomer coating agent of the present invention, the polyolefin elastomer (A) is preferably a copolymer composed of ethylene and α-olefin and / or diene.

In the preferred aqueous polyolefin elastomer coating agent of the present invention, the acid-modified polyolefin is preferably a polyolefin wax modified with an unsaturated dicarboxylic acid.

According to the present invention, a basic substance and a total water concentration of 3 to 25% by weight are added to the melt-kneaded product of the (A) polyolefin-based elastomer and the (B ′) acid-modified polyolefin and / or higher fatty acid. %, And the mixture is melt-kneaded to neutralize at least a part of the acid-modified polyolefin and / or higher fatty acid to disperse the solid content in the aqueous phase. Provided.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Each component constituting the aqueous polyolefin elastomer coating agent of the present invention will be described in detail below.

(A) Polyolefin Elastomer The polyolefin elastomer constituting the aqueous dispersion of the present invention is a low crystalline or amorphous olefin copolymer, and may contain a diene if desired. X
The crystallinity measured by the line diffraction method is preferably 50% or less, particularly preferably 30% or less.

Examples of the olefin constituting the copolymer include α-olefins such as propylene, butene-1, pentene-1, hexene-1, and octene-1 in addition to ethylene. These may be used alone or in combination of two or more.

The diene includes isoprene, butadiene, dicyclopentadiene, pentadiene-1,4,2-methyl-pentadiene-1,4, hexadiene-1,4, divinylbenzene, methylidene norbornene, ethylidene norbornene, and the like. These may be used alone or in combination of two or more.

Among these olefin copolymers, rubbery copolymers of ethylene and α-olefin and / or diene are preferred. The ethylene content in the copolymer is preferably 25 to 95 mol%, particularly preferably 50 to 95 mol%. When containing a diene, the diene content is 0.5 to
10 mol% is preferred.

Specific examples of the polyolefin elastomer include ethylene-propylene copolymer, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, ethylene-propylene-hexadiene-1,4 copolymer, Ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 5-vinyl-2-norbornene copolymer, ethylene / butene-1 / 5-ethylidene Examples thereof include 2-norbornene copolymer, ethylene / butene-1 / dicyclopentadiene copolymer, ethylene / dicyclopentadiene copolymer, and ethylene / butadiene copolymer.

The intrinsic viscosity [η] (intrinsic viscosity in decalin solution at 135 ° C.) of the polyolefin elastomer is as follows:
It is preferably from 0.5 to 2.0 dl / g, more preferably from 0.7 to 1.5 dl / g.

(B) Salt of Acid-Modified Polyolefin and / or Higher Fatty Acid One of the components constituting the aqueous dispersion of the present invention is (B) salt of acid-modified polyolefin (B-1) and / or higher fatty acid. It is a salt (B-2). First, the salt of acid-modified polyolefin
(B-1) will be described.

The acid-modified polyolefin salt (B-1) comprises a carboxylic acid salt group (including a carboxylic acid group in the case of a partially neutralized product or a partially saponified product) bonded to the polymer chain of the polyolefin. It is a polyolefin-based resin containing 0.05 to 5 mmol, preferably 0.1 to 4 mmol as a -COO- group per gram.

The acid-modified polyolefin salt (B-1) is obtained by adding a monomer having a neutralized or unneutralized carboxylic acid group to the above-mentioned polyolefin comprising an α-olefin, and / or Alternatively, it can be obtained by graft copolymerizing a monomer having a saponified or unsaponified carboxylic ester group. In some cases, it can be obtained by subjecting the graft copolymerized product to a neutralization reaction or a saponification reaction with a basic substance. In this case, a partially neutralized product or a partially saponified product in which a carboxylic acid group or a carboxylic acid ester group that is not neutralized or saponified in the resin may coexist.

The acid-modified polyolefin salt (B-1) is
An olefin monomer constituting the polyolefin, a monomer having a neutralized or non-neutralized carboxylic acid group, and / or a monomer having a saponified or unsaponified carboxylic acid ester group. It can be obtained by graft copolymerization, block copolymerization or random copolymerization with a monomer. In some cases, the copolymer can be obtained by performing a neutralization reaction or a saponification reaction using a basic substance. In this case, a partially neutralized product or a partially saponified product in which a carboxylic acid group or a carboxylic acid ester group that is not neutralized or saponified in the resin may coexist.

When the acid-modified polyolefin salt (B-1) is obtained by post-neutralization or post-saponification, the polymer as a raw material is obtained by adding a neutralized or unneutralized carboxylic acid group to the polyolefin. A monomer having, and / or a grafted copolymer of a monomer having a saponified or unsaponified carboxylic acid ester group,
A monomer such as α-olefin constituting a polyolefin, a monomer having a neutralized or unneutralized carboxylic acid group, and / or a saponified or unsaponified carboxylic acid ester group And a monomer having the following formula:

Examples of the monomer having a neutralized or non-neutralized carboxylic acid group and the monomer having a saponified or unsaponified carboxylic acid ester group include, for example, ethylenically unsaturated monomers. Examples thereof include carboxylic acids, anhydrides and esters thereof.

The ethylenically unsaturated carboxylic acids include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid and the like.
^TM (endosis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride and the like, and the unsaturated carboxylic acid ester is methyl of the above ethylenically unsaturated carboxylic acid. And monoesters or diesters such as ethyl and propyl. These monomers can be used alone or in combination.

In order to produce a modified product by graft-copolymerizing a graft monomer selected from the above-mentioned monomers onto a polymer to be grafted, various conventionally known methods can be employed. For example, a method in which the polymer to be grafted is melted and a graft monomer is added to carry out graft copolymerization, or a method in which the polymer is dissolved in a solvent and the graft monomer is added to carry out graft copolymerization. In any case, the reaction is preferably performed in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer.

The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The usage ratio of the radical initiator is usually in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the polymer to be grafted. Examples of the radical initiator include organic peroxides, organic peresters, and other azo compounds. Among these radical initiators, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl
-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 1,4-bis (tert-butylperoxyisopropyl) benzene, etc. Dialkyl peroxides are preferred.

The amount of the ethylenically unsaturated carboxylic acid, anhydride or ester to be introduced is -COO-
As a group, it is in the range of 0.05 to 5 mmol, preferably 0.1 to 0.4 mmol, per gram of resin.

Examples of the basic substance used for neutralization and saponification include substances which act as bases in water, such as alkali metals, alkaline earth metals, ammonia and amines, alkali metal oxides, hydroxides, weak bases, and the like. Examples of such substances include hydrides, alkaline earth metal oxides, hydroxides, weak bases, hydrides, and other substances that act as bases in water, and alkoxides of these metals. Examples of such substances are shown below.

The alkali metals include, for example, sodium and potassium, and the alkaline earth metals include, for example, calcium, strontium, barium and the like. Examples of the amine include inorganic amines such as hydroxylamine and hydrazine, and organic amines such as methylamine, ethylamine, ethanolamine, and cyclohexylamine.

Examples of the oxides, hydroxides and hydrides of alkali metals and alkaline earth metals include, for example, sodium oxide, sodium peroxide, potassium oxide, potassium peroxide, calcium oxide, strontium oxide, barium oxide and sodium hydroxide. , Potassium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydride, potassium hydride, calcium hydride and the like.

Examples of weak bases of alkali metals and alkaline earth metals include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate, sodium acetate, potassium acetate, calcium acetate and the like. Examples of the ammonia and amine compounds include ammonium hydroxide, quaternary ammonium compounds such as tetramethylammonium hydroxide, hydrazine hydrate and the like.

As the carboxylate or carboxylate group neutralized or saponified with a basic substance,
An alkali metal carboxylate such as sodium carboxylate and potassium carboxylate or ammonium carboxylate is preferred, and potassium carboxylate is particularly preferred.

Another component constituting the aqueous dispersion of the present invention is a salt of a higher fatty acid (B-2). Salts of higher fatty acids (B-2)
As a salt of a fatty acid having 25 to 60 carbon atoms is preferable,
More preferably, an alkali metal salt, an alkaline earth metal salt, or an amine salt of a fatty acid having 25 to 40 carbon atoms is used.
Particularly preferred are the alkali metal salts of montanic acid.

As a salt of higher fatty acid (B-2), a compound having 25 to 25 carbon atoms
When a salt of a fatty acid of 60, particularly preferably a salt of a montanic acid wax is used, the solid content of an aqueous dispersion composed of a polyolefin elastomer is uniformly dispersed in water without using an acid-modified polyolefin (B-1) in combination. Can be.

The higher fatty acid salt (B-2) constituting the aqueous dispersion of the present invention may contain a higher fatty acid and / or a higher fatty acid ester in addition to the higher fatty acid salt. The alcohol residue constituting the ester preferably has 2 to 30 carbon atoms, and particularly preferably has 6 to 20 carbon atoms. The residue may be linear or branched. A mixture of different carbon numbers may be used. Specific examples of the alcohol residue include higher alcohol residues such as cetyl alcohol, stearyl alcohol, and oleyl alcohol. Particularly preferred are montanic acid ester wax and montan wax.

The higher fatty acid salt (B-2) can be obtained by neutralizing the above acid and / or saponifying the ester of the fatty acid. In this case, a partially neutralized product or a partially saponified product in which a non-neutralized or saponified fatty acid or fatty acid ester coexists may be used. Basic substances that can be used for neutralization and saponification are the acid-modified polyolefins described above.
Examples similar to those described in (B-1) can be exemplified.

The aqueous dispersion of the present invention further contains water in addition to the above-mentioned composition. The water content is preferably 3 to 25% by weight based on the whole, that is, 3 to 25% by weight in the aqueous dispersion. Further, an additive component such as a surfactant, an organic solvent, and an oil is added to the aqueous dispersion of the present invention as needed. Hereinafter, these additive components will be described.

Examples of the additives include surfactants such as alkyl naphthalene sulfonate, sodium salt of naphthalene sulfonic acid formaldehyde condensate, sodium salt of cresol-shefferic acid formaldehyde condensate, alkyl diphenyl ether disulfonate sodium salt, and lignin sulfone. Acid calcium salt, melanin resin sulfonate sodium salt, special polyacrylate, gluconate, olefin / maleic acid copolymer, carboxymethylcellulose sodium salt, metal soap (Zn, Al, Na, K salt),
Sulfonic or carboxylic acid type anionic surfactants such as potassium oleate, sodium oleate, potassium stearate, sodium stearate, potassium tallowate, sodium tallowate, and triethanolamine stearate Agent;

Also, fatty acid monoglyceride, sorbitan fatty acid ester, sugar fatty acid partial ester, polyglycerin fatty acid partial ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial Ester, polyoxyethylene glycerin fatty acid partial ester, polyoxyethylene aliphatic amine, polyoxyethylene (hardened) castor oil, polyoxyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block polymer, hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl Nonionic (nonionic) surfactants such as pyrrolidone and methylcellulose

These surfactants can be used alone or in combination of two or more. Of these surfactants, in order to obtain a more stable aqueous dispersion, it is preferable to use an anionic surfactant, and among them, higher fatty acids are preferable, and in particular, those having 10 to 20 carbon atoms,
Salts of saturated or unsaturated higher fatty acids, especially alkali metal salts, are preferred. Specifically, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachiic acid, lindonic acid, tuzunic acid, petroselic acid, oleic acid, linoleic acid, linoleic acid, arachidonic acid And alkali metal salts such as tallow acid.

The surfactant added to the aqueous dispersion of the present invention as necessary includes an organic compound of a surfactant precursor which becomes a surfactant by a base treatment, for example, an anionic surfactant by a base treatment. An organic compound serving as an agent may be used.

The organic solvent as an additive component may be any one which can dissolve (or swell) the polyolefin-based elastomer (A) and the salt (B) of the acid-modified polyolefin and / or higher fatty acid.
Toluene, xylene, styrene, α-methylstyrene,
Examples thereof include aromatic hydrocarbons such as divinylbenzene, aliphatic hydrocarbons such as hexane and heptane, and halogenated hydrocarbons such as trichloroethylene.

The organic solvent may be contained in the aqueous dispersion of the final product, or may be removed from the final aqueous dispersion by means such as distillation or azeotropic distillation. Good. For example, when the organic solvent is removed by distillation, the boiling point of the organic solvent is desirably 100 ° C. or lower. This organic solvent swells or partially dissolves the polyolefin-based elastomer (A), and is used in an extremely small amount unlike the conventional solvent method.

The oil (natural oil or synthetic oil) used as an additive component includes mineral lubricating oils such as spindle oil and machine oil; mineral oils such as liquid paraffin, electric insulating oil and process oil; Synthetic oils such as olefin oils, diester oils, and alkyl naphthenate oils; vegetable oils such as castor oil, linseed oil, rapeseed oil, coconut oil, and tall oil are used. It is preferable that these oils have a number average molecular weight of 200 or more in order to be stably maintained in the resin solid content.

Aqueous Dispersion The aqueous dispersion of the present invention has an electric resistance value of usually 10 ⁶ Ω · cm or less, most of which exhibit a low value of 10 ⁵ Ω · cm or less. It is inferred from the fact that the continuous phase is a dispersion in which the continuous phase is water. In addition, here, the measurement of the electric resistance value is performed by attaching 1 cm electrodes to both opposing inner sides of a 1 cm cubic insulator container, pressing the dispersion in, and measuring the resistance value between the electrodes at 60 Hz with an AC resistance meter. Can be measured.

The dispersion state of the aqueous dispersion is determined by throwing the dispersion into cold water, stirring the dispersion with an ordinary stirrer having turbine blades, and then filtering the dispersion through a wire mesh of about 100 mesh. Can be confirmed by observing with a microscope. The dispersion of the present invention is substantially spherical particles when dispersed in water, and has an average particle size in the range of 0.1 to 5 μm. This particle size can be measured using a Microtrack.

In the aqueous dispersion of the present invention, it is desirable that each of the above components is contained in a certain ratio. That is, the salt (B) of the acid-modified polyolefin and / or higher fatty acid (B) is 0.5 to 30 parts by weight, preferably 1 to 100 parts by weight of the polyolefin-based elastomer (A).
Desirably, it is contained in an amount of up to 20 parts by weight.

The surfactant added to the aqueous dispersion of the present invention as desired or the organic compound which becomes a surfactant by base treatment is a polyolefin-based elastomer (A)
0.1 to 40 parts by weight, especially 0.2 to 2 parts by weight per 100 parts by weight
It is advisable to mix it in an amount of 0 parts by weight. Further, the compounding amount of the organic solvent optionally added is 10 to 1000 parts by weight per 100 parts by weight of the polyolefin elastomer (A),
In particular, the range of 20 to 700 parts by weight is desirable. The oil to be optionally added is 10 to 500 parts by weight, especially 20 parts by weight, per 100 parts by weight of the polyolefin elastomer (A).
It may be present in an amount ratio of up to 300 parts by weight.

The water content of the aqueous dispersion of the present invention is 3 to 25% by weight, preferably 3 to 20% by weight, based on the whole aqueous dispersion. If the water content is less than 3% by weight, phase inversion (change of the resin solid content from a continuous phase to a dispersed phase due to water) is unlikely to occur, and a suitable aqueous dispersion cannot be obtained. If it exceeds 25% by weight, the aqueous dispersion will have fluidity. That is, by setting the content in the range of 3 to 25% by weight, an apparently solid aqueous dispersion can be obtained.

Production Method of Aqueous Dispersion The aqueous dispersion as described above is prepared by adding water to a melt-kneaded product of the (A) polyolefin-based elastomer and (B) an acid-modified polyolefin and / or a higher fatty acid salt. However, in the present invention, a method for producing an acid-modified polyolefin and / or a higher fatty acid salt by post-neutralization or post-saponification is preferable.

That is, the aqueous dispersion of the present invention is obtained by adding a basic substance and water to a melt-kneaded product of the (A) polyolefin-based elastomer and (B ′) an acid-modified polyolefin and / or a higher fatty acid. It is obtained by melt-kneading, neutralizing at least a part of the acid-modified polyolefin and / or higher fatty acid, and dispersing a solid content in an aqueous phase. At this time, it is preferable that water is added so that the water concentration of the entire dispersion becomes 3 to 25% by weight.

The (B ′) acid-modified polyolefin and / or higher fatty acid added here can be treated with a base to form a carboxylic acid salt group (partially neutralized product or partially saponified product) bonded to the polyolefin polymer chain. Acid-modified polyolefin which can be produced at a concentration of 0.05 to 5 mmol, preferably 0.1 to 4 mmol, as -COO- groups per gram of resin, and / or 60-15 of fatty acids or their esters
0%, preferably 80-130%, are higher fatty acids that can be neutralized or saponified to form salts of fatty acids.

If necessary, an additive such as a surfactant or an organic compound, an organic solvent, or an oil which becomes a surfactant by base treatment may be added to the (A) polyolefin-based elastomer and (B ′) acid-modified. Polyolefin and / or
Alternatively, it may be added to a higher fatty acid and melt-kneaded.

As the melt-kneading means which can be used in the method for producing the aqueous dispersion of the present invention, known methods such as a kneader, a Banbury mixer and an extruder can be mentioned. Among them, an extruder, particularly a multi-screw extruder, is used. It is preferably manufactured. Hereinafter, an example using an extruder will be described, but the present invention can be appropriately applied to a case where other melt-kneading means is used.

An apparatus preferably used for carrying out the method of the present invention will be described with reference to FIG. In FIG. 1, an extruder 1 includes a barrel 2 and a twin screw 3a provided in the barrel.
3b, one end of which has a polyolefin-based elastomer (A) and an acid-modified polyolefin and / or higher fatty acid (B ') or, if necessary, a surfactant or a precursor thereof, an organic solvent, an oil A hopper 4 for supplying water and the like is provided, and a supply port 5 for supplying water or an aqueous solution of a basic substance is provided in the middle of the extruder 1. Further, the other end of the extruder 1;
That is, the cooling device 6 is provided at the extrusion port. The cooling device 6 may be, for example, a static mixer provided with a jacket for passing a cooling medium.

In the production of the aqueous dispersion, first, a hydrophobic polyolefin-based elastomer (A) and an acid-modified polyolefin and / or higher fatty acid (B '), or, if necessary, a surfactant, an organic solvent, an oil agent, etc., are put into a hopper. 4 and melt-knead these components. The temperature at the time of melt-kneading is not lower than the highest melting point or softening point of the resin used, preferably not lower than the temperature at which the melt viscosity is not higher than 10 ⁶ poise, especially not higher than 10 ⁵ poise. When an organic solvent or oil is used in combination, the temperature does not need to be higher than the melting point or softening point of the polymer, and may be a condition under which the melt viscosity of the composition falls within the above range.

Next, water or an aqueous solution of a basic substance is added from the supply port 5 to the portion of the extruder 1 where the melt is filled in the gap between the barrel 2 and the screws 3a and 3b. Whether or not the gap is filled with the melt can be confirmed by the back pressure at that portion and the power (specific energy) of the extruder per resin extrusion amount. After the addition of water or an aqueous solution of a basic substance, the melt kneading of the added mixture is continued to cause phase inversion to an aqueous dispersion.

The formed aqueous dispersion is cooled in the cooling device 6 to a temperature lower than the boiling point of water, and is taken out in the form of a stable aqueous dispersion. Note that cooling of the aqueous dispersion is necessary only when the aqueous dispersion is taken out of the system.If the aqueous dispersion is not taken out of the system and subsequently used for applications such as post-treatment and chemical reaction, cooling is required. do not have to. Water may be further added to the aqueous dispersion obtained here.

The aqueous dispersion produced by melt-kneading is then cooled naturally or artificially to room temperature or below. At this time, the dispersed particles solidify and become a stable dispersion. When a solvent is used, it may be removed by means such as evaporation if necessary.

In the production of the dispersion or the hydrolyzate thereof, various auxiliary materials which can be usually used for an aqueous dispersion, for example, a dispersant such as an anionic surfactant and a nonionic surfactant, an emulsifier, a stabilizer, a wetting agent, and the like. Agents, thickeners, foaming agents, defoamers, coagulants, gelling agents, anti-aging agents, softeners, plasticizers, fillers, coloring agents, fragrances, anti-adhesives, release agents, etc. May be used in combination.

The aqueous dispersion of the present invention may be subjected to a crosslinking treatment on the aqueous dispersion obtained above to form a crosslinking bond in the molecular chain of the polyolefin elastomer (A). The crosslinking treatment can be performed by blending a polyfunctional monomer in the aqueous dispersion and performing a known method such as ionizing radiation crosslinking or organic peroxide crosslinking.

Here, as the polyfunctional monomer, for example, a monomer having two or more ethylenically unsaturated bonds, particularly a vinyl bond, is preferably used. Specifically, divinylbenzene, tetramethylene diacrylate, ethylene glycol Examples thereof include dimethacrylate, 1,2,4-trivinylcyclohexane, and tetraallyloxyethane. The polyfunctional monomer is a polyolefin-based elastomer 100
It is used in a proportion of usually 0.1 to 20 parts by weight, preferably 0.3 to 5 parts by weight, based on parts by weight.

In the ionizing radiation crosslinking, any of α-rays, β-rays, γ-rays, electron beams, X-rays and the like may be used as the ionizing radiation, and the irradiation dose is usually about 1 to 50 Mrad.

The organic peroxide crosslinking is carried out by uniformly dispersing a peroxide in an aqueous dispersion and then heating the peroxide to a temperature not lower than the decomposition temperature of the peroxide. -Screw
(t-butylperoxy) cyclohexane, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di ( (Benzoylperoxy) hexane, 3,5,5-trimethylhexanoyl peroxide,
Examples thereof include benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide, diisopropyl peroxydicarbonate, and di (2-ethylhexyl) peroxycarbonate.

The amount of peroxide used is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the polyolefin elastomer. Further, the degree of crosslinking is not particularly limited, and is appropriately selected depending on the use.

The aqueous dispersion of the present invention produced as described above is applied as a coating material for forming a film on the surface of various materials. The material and shape of the object to be coated
Materials such as wood, paper, resin, metal, glass, and ceramic,
The present invention can be applied to any shape such as a film, a sheet, a fiber, a nonwoven fabric, and a hollow molded article without particular limitation.

Next, a method of forming a coating film on a metal substrate will be described. The coating (coating layer) is formed by applying the aqueous dispersion composition on a metal substrate, drying and curing. The application of the aqueous dispersion composition can be performed by any method such as spraying, curtain, flow coater, roll coater, brush coating, immersion and the like. Drying after the application of the aqueous dispersion composition may be by natural drying, but is preferably performed by baking. The baking is performed by heating at 80 to 250 ° C. for 20 seconds to 10 minutes to form a film. Since the aqueous dispersion composition hardly contains an organic solvent and the like in the step of forming the coating, there is an advantage that the working environment of the manufacturing process can be favorably maintained.

The thickness of the coating is not particularly limited because it is appropriately selected depending on the use of the laminate, the aqueous dispersion composition to be used, and the like. 0.5 to 2
A thickness of 0 μm, especially 1 to 10 μm is preferred.

The aqueous polyolefin elastomer coating agent of the present invention has an average particle diameter of dispersed particles of 0.1 to 5
μm and high concentration, and the coating obtained when applied to various materials is moisture-proof, water-repellent, paper, metal,
Thermal adhesion to wood / fiber (natural fiber, synthetic fiber, inorganic fiber) / non-woven fabric, binding property of inorganic particles, thermal transferability, strength, abrasion resistance, impact resistance, weather resistance, solvent resistance, water resistance Excellent in flexibility. It can also be used for improving the above performance by adding it to other aqueous coating agents.

The particles of the aqueous polyolefin elastomer coating agent of the present invention are subjected to a crosslinking treatment with the above-mentioned crosslinking agent, for example, a combination of a polyfunctional unsaturated compound and a peroxide to give a crosslinked aqueous dispersion particle. can do. The degree of cross-linking of the cross-linked aqueous dispersion particles can be controlled by the amount of the cross-linking agent. can get.

The aqueous polyolefin elastomer coating agent of the present invention can be used as a paper binder for paper coating or a coating agent for fibers (enhancing the strength of fibers, cloths and nets, improving hygroscopicity, improving water repellency, imparting waterproofness),
Coating agent for bundle of various fibers (polyamide fiber, polyester fiber, glass fiber, carbon fiber, ceramic fiber, etc.), lubricant, sealing agent for paper, nonwoven fabric, sterilized paper and coating agent for thermal bonding, heat sealing of paper and film Coating agent, adhesive material, ink / paint binder, ceramic binder, nickel-hydrogen battery, lithium battery, secondary battery electrode binder, thermal transfer ribbon coating agent, inkjet printer paper and film coating agent, It is used as a coating agent for thermal paper, an agent for improving chipping resistance of automotive paints, an additive for floor polish, an agent for improving anti-blocking properties for films, and a dispersant.

The aqueous polyolefin elastomer coating agent of the present invention may further comprise, if necessary, for example,
Water-soluble melamine resin, aqueous acrylic resin, aqueous polycarbodiimide for improving film performance; polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl ether, polyethylene oxide, polyacrylamide for improving the stability of the dispersion and adjusting the viscosity, Organic thickeners such as polyacrylic acid, carboxymethylcellulose, methylcellulose and hydroxyethylcellulose; inorganic thickeners such as silicon dioxide, activated clay and bentonite; nonionic surfactants for improving the stability of the aqueous dispersion; anions -Based surfactants or water-soluble polyvalent metal salts; other rust inhibitors, fungicides, weather stabilizers, heat stabilizers, flame retardants, foaming agents, defoamers; titanium white, red iron,
Pigments such as phthalocyanine, carbon black, and permanent yellow; fillers such as calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, and calcium silicate; You may add in the range which does not impair the objective.

[0076]

The aqueous dispersion of the present invention is excellent in water resistance, oil resistance and chemical resistance and can form a film having excellent adhesion to various materials.
It is applied and dried on the surface of a substrate such as a metal or plastic molded product to form a resin film, and imparts water resistance, oil resistance, chemical resistance, and corrosion resistance to the substrate, or functions as a heat sealant. In addition, the aqueous dispersion of the present invention does not generate harmful gases such as hydrogen chloride gas at the time of waste incineration, and thus has no problem of environmental pollution. Further, the aqueous dispersion of the present invention can be easily produced only by melt-kneading.

[0077]

EXAMPLES (Production Example) Maleic anhydride-modified polyethylene wax (graft amount: 3) was used as an acid-modified polyolefin with respect to 100 parts by weight of ethylene-propylene terpolymer (X3012 manufactured by Mitsui Chemicals, Inc.) as a polyolefin-based elastomer. % By weight, -COO- group: 0.
10 parts by weight of 67 mmol / g-polymer) and 2 parts by weight of potassium oleate are mixed and supplied at a rate of 3000 g / hour from a hopper of a twin screw extruder (PCM-30 L / D = 20 manufactured by Ikega Tekko). The mixture was melt-kneaded at 190 ° C., and a 18.7% aqueous solution of potassium hydroxide was continuously supplied at a rate of 123 g / hour from a supply port provided at a vent portion of the extruder. Extruded.

The extruded melt-kneaded product was cooled to 90 ° C. by a jacketed static mixer installed at the outlet of the extruder, and further poured into warm water of 80 ° C. to obtain a solid content of 4%.
It was adjusted to 7% by weight to obtain an aqueous dispersion. The average particle size of the obtained aqueous dispersion was 0.5 μm as measured by Microtrack.

Example 1 [Coating Agent for Glass Fiber] Average Fiber Diameter 13
A roving made of a bundle of 2,000 μm E glass filaments was held in an oven at 400 ° C. for 5 minutes and then taken out. This roving was mixed with the aqueous dispersion of the above-mentioned Production Example to which aminoisopropyltriethoxysilane was added. And then dried at 130 ° C. Then, a polypropylene mold layer and a processed glass roving, which are arranged in one direction and arranged alternately in 16 layers, are placed alternately in a square mold so that the glass fiber content is about 70% by weight. After heating the square mold to 250 ° C., a pressure of 20 kg / cm ² was applied from above and below the mold to form a laminate. After the heated mold was gradually cooled at 1 ° C./min, the molded plate was taken out, a bending test piece was cut out from the plate, and the strength was measured (measurement method: according to ASTM D790). As a result, the flexural strength was 60 kg / mm ² and the flexural modulus was 46.
It was 00 kg / mm ² .

(Comparative Example 1) A laminate was formed and the bending strength was measured in the same manner as in Example 1 except that the aqueous dispersion was not applied to the roving used in Example 1. As a result, the flexural strength was 30 kg / mm ² and the flexural modulus was 40.
It was 00 kg / mm ² .

[Brief description of the drawings]

FIG. 1 is a side view of a kneading apparatus used for carrying out a manufacturing method according to the present invention.

[Description of Signs] 1 extruder 2 barrel 3a, 3b screw 4 hopper 5 water supply port 6 cooling device 7 pressure gauge

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 191/06 C09D 191/06

Claims (6)

[Claims] 1. A polyolefin elastomer (A),
(B) an aqueous dispersion of a polyolefin-based elastomer, comprising an aqueous dispersion containing (C) a salt of an acid-modified polyolefin and / or a higher fatty acid, and (C) water, wherein a solid content is uniformly dispersed in an aqueous phase. Agent. 2. The salt (B) of the acid-modified polyolefin and / or higher fatty acid (B) in an amount of 0.5 to 30 parts by weight with respect to 100 parts by weight of the polyolefin elastomer (A)
The aqueous polyolefin-based elastomer coating agent according to claim 1, comprising an aqueous dispersion containing the parts by weight. 3. An aqueous dispersion having a solid content concentration of the polyolefin-based elastomer (A) of 10 to 70% by weight and an average particle size of the solid content particles of 0.1 to 5 μm. The aqueous polyolefin elastomer coating agent according to claim 1 or 2, wherein 4. The polyolefin elastomer according to claim 1, wherein the polyolefin elastomer (A) is a copolymer composed of ethylene and α-olefin and / or diene. Aqueous coating agent. 5. The aqueous polyolefin elastomer coating agent according to claim 1, wherein the acid-modified polyolefin is a polyolefin wax modified with an unsaturated dicarboxylic acid. 6. The melt-kneaded product of (A) the polyolefin-based elastomer and (B ′) the acid-modified polyolefin and / or higher fatty acid, so that the basic substance and the total water concentration become 3 to 25% by weight. And melt kneading by adding water to the mixture, neutralizing and / or saponifying at least a part of the acid-modified polyolefin and / or higher fatty acid, and dispersing a solid content in an aqueous phase. A polyolefin-based elastomer aqueous coating agent as described in