JPH0615620B2 - Aqueous dispersion and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an aqueous dispersion of a resin and a method for producing the same, more specifically, an aqueous dispersion of a hydrophobic resin capable of forming a resin thin film having excellent processability. And its manufacturing method. Also,
The present invention relates to an aqueous dispersion suitable for forming a soft and elastic rubber coating and a method for producing the same.

Conventional Techniques and Technical Problems of the Invention Aqueous dispersions of various polymers have hitherto been known. For example, a fluid aqueous dispersion having a water content of about 30% by weight or more (hereinafter referred to as an aqueous dispersion) is applied to the surface of paper, fiber or plastic molded articles, wood, metal, etc. It is dried to form a resin film, which imparts water resistance, oil resistance, and chemical resistance to a substrate, or is used as a heat sealant. Since such an aqueous dispersion uses water as a dispersion medium, it is very advantageous and has a wide range of fields from the solvent type in terms of flammability, working environment and handling. It is used in.

In addition to the above-mentioned aqueous dispersion, an aqueous dispersion which has no fluidity and is apparently solid (hereinafter referred to as an aqueous dispersion in the present specification) is also known. That is, it is a powdery form known as a powder emulsion, which is redispersed by adding water to form an aqueous dispersion liquid. The composition contains no water or at most 2 Since it is 3 to 3% by weight, there is no fear of freezing even at low temperatures, and there is an advantage that the storage space for packaging and transportation is small and the storage space is small. Furthermore, aqueous dispersions have the characteristic that they can be directly mixed with powders and granules that are difficult to contact with water, such as cement, mortar, and gypsum, which was difficult to do, and it is possible to manufacture highly processed preparations. is doing.

By the way, in the conventionally known method for producing an aqueous dispersion,
The above-mentioned aqueous dispersion and aqueous dispersion could not be produced by the same method. That is, in order to produce an aqueous dispersion, an aqueous dispersion having a large water content is once produced by various known methods, and then the aqueous dispersion is sprayed into hot air in a furnace by a sprayer to evaporate the water. And powdered. However, in this method, when an aqueous dispersion of a low softening temperature polymer is used as a raw material, agglomeration of polymer particles occurs during spraying, or the resulting powder emulsion agglomerates into agglomerates under the action of heat or pressure. Tend. Such a powder emulsion does not disperse well even if it is redispersed by adding water, or even if it is dispersed, the viscosity becomes high and the physical properties of the coating film deteriorate. For this reason, various additives such as anti-caking agents and protective colloids are usually added to the aqueous dispersion before spraying and the powder before drying. There is a problem that the physical properties are deteriorated, and since water having a large content is evaporated, energy loss is large and it is not economical. Therefore, it is desired to develop a technique for producing an aqueous dispersion such as a powder emulsion by a method in which an additive is not added as much as possible and energy loss is small.

Improvements are also desired in the production method of the aqueous dispersion.
That is, conventionally known production methods are roughly classified into a method of emulsion polymerization in an aqueous medium in the presence of an emulsifier and a method of stirring and mixing a molten resin and an aqueous medium in the presence of shearing force. The former method is limited in the kinds of resins that can be polymerized, and has problems such as complexity of control of polymerization reaction and complexity of equipment. On the other hand, the latter method has the advantage that it can be applied to any resin and is relatively simple in terms of equipment and operation technology.

Many proposals have been made for this latter method, and for example, JP-A-51-12835 discloses a method of dispersing a kneaded product of a thermoplastic resin and a water-soluble polymer in water. However, since the coating film obtained by using the aqueous dispersion produced by this method contains a water-soluble polymer, there are problems that the mechanical strength is weak and the water resistance is poor. Japanese Patent Publication No. 57-23703 discloses a method of dispersing a kneaded product of polypropylene and a dispersant selected from a surfactant and a water-soluble or water-swellable polymer in water. However, in this method, the diameter of the dispersed particles is relatively large, and a petroleum resin must be used in combination in order to reduce the particle diameter, which causes a problem that the obtained coating film exhibits tackiness. In addition, JP-A-56-2
No. 149 discloses a method of kneading an olefin resin and a partially silicified polyvinyl alcohol aqueous solution to obtain an aqueous dispersion. However, this method also includes a water-soluble resin, and thus the physical properties of the coating film are deteriorated. Moreover, the aqueous dispersion obtained by this method is an aqueous dispersion having a water content of 30% by weight or more. As another method, Japanese Patent Publication No. 58-42207
That is, the method of melt-kneading the polyolefin and the carboxyl group-containing polyolefin into the basic substance-containing hot water and applying a shearing force to obtain a dispersion liquid is a water-soluble or water-swellable polymer. It is a preferable method because it does not contain coalesce and does not use petroleum resin, but on the other hand, there is a problem that the type of raw material resin is limited in order to produce a product having a small dispersed particle system. High temperature,
Since the dispersion step is performed under high pressure, there is a problem that the container used for dispersion must have pressure resistance. Therefore, even in the method for producing an aqueous dispersion in which various methods have been proposed, a method for obtaining an aqueous dispersion of fine particles that can be applied to any resin without using a water-soluble or water-swellable polymer or a petroleum resin. Development is desired.

Further, development of a method for freely and extremely easily producing an aqueous dispersion and an aqueous dispersion without any special process is desired.

SUMMARY OF THE INVENTION AND OBJECTS OF THE INVENTION The present inventors knead a thermoplastic resin, a thermoplastic polymer having a limited amount of carboxylate, an anionic surfactant, and a natural oil or a synthetic oil, and kneaded the composition. When water is added and melt-kneaded, phase inversion is already caused in the presence of a small amount of water, that is, conversion of water to a dispersion medium phase and solid content to a dispersed particle phase occurs, and swelling of the aforementioned oil agent or It has been found that the conversion effect enables dispersion into fine particles, improves the processability of the resin, and enables thin coating. The present inventors have further found that if a resin that is crosslinkable and vulcanizable, such as an ethylene-propylene-non-conjugated diene / terpolymer, is used as the thermoplastic resin, the oil agent does not bleed out and the oil is extended. It was found that a soft rubber can be obtained.

That is, an object of the present invention is to provide an underwater dispersion which is an oil-in-water (O / W) type dispersion having a fine particle size in a state where a resin solid content is swollen or softened with an oil agent, and a method for producing the same. It is in.

Another object of the present invention is to provide an aqueous dispersion having improved resin processability and capable of thin coating.

Still another object of the present invention is to provide a method capable of producing an aqueous dispersion by a melt-kneading operation.

According to the present invention, according to the present invention, (i) a thermoplastic resin, (ii) a polymer 1 having a carboxylate group bonded to a polymer chain.
Per gram A thermoplastic polymer contained at a concentration of 0.1 to 5 mmol equivalent, (iii) anionic surfactant, (iv) natural or synthetic oil having a number average molecular weight of 200 or more, and (V) water An aqueous dispersion having a water content of 3 to 90% by weight and having a resin solid content as a finely dispersed particle phase is provided.

(a) Thermoplastic resin, (b) Neutralizing and / or saponifying group of carboxylic acid, its anhydride or its ester bonded to the polymer chain per gram of polymer A thermoplastic polymer containing a concentration of 0.1 mmol equivalent or more in terms of conversion, or a carboxylate group bonded to a polymer chain per 1 g of the polymer. A thermoplastic polymer which is contained at a concentration of 0.1 to 5 millimol equivalent, (c) an organic compound which reacts with an anionic surfactant or a basic substance to become an anionic surfactant, and (d) has a number average molecular weight of 200 or more. When (c) is an organic compound, a basic substance is added and converted to an anionic surfactant by melt-kneading with a natural oil or a synthetic oil, and when the thermoplastic polymer is not neutralized, the thermoplastic Simultaneously or successively, a step of forming 0.1 to 5 millimol equivalent of carboxylate group per gram of polymer in the polymer and a step of adding water to the melt-kneaded product to perform melt-kneading to form an aqueous dispersion. A method for producing an aqueous dispersion is provided, which is characterized in that it is carried out.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

Blending component The thermoplastic resin (i), which is one of the components constituting the aqueous dispersion of the present invention, is not only insoluble in water and non-swelling in water, but also has dispersibility in water itself. It is a lacking resin, such as low density polyethylene, high density polyethylene,
Polypropylene, poly 1-butene, poly 4-methyl-1
-Pentene or polyolefin such as random or block copolymer of α-olefins such as ethylene, pyropyrene, 1-butene and 4-methyl-1-pentene, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer , Ethylene / vinyl compound copolymers such as ethylene / vinyl chloride copolymer, polystyrene, acrylonitrile / styrene copolymer, ABS, styrene resin such as α-methylstyrene / styrene copolymer, polyvinyl chloride, polychlorinated Vinylidene, vinyl chloride / vinylidene chloride copolymer, polyvinyl compounds such as polymethyl acrylate and polymethyl methacrylate, polyamides such as nylon 6, nylon 6-6, nylon 6-10, nylon 11 and nylon 12, polyethylene terephthalate, Polybutylene terev It may be a resin of any one of thermoplastic polyesters such as tarates, polycarbonates, polyphenylene oxides and the like, or a mixture thereof.

Among these thermoplastic resins, olefin resins are particularly preferable, that is, polyethylene, polypropylene,
Poly-1-butene, poly-3-methyl-1-butene, poly-4-methyl-1-pentene, poly-3-methyl-1
-Pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene represented by propylene / 1-butene copolymer, propylene, 1-butene, 3
-Methyl-1-butene, 4-methyl-1-pentene, 3
-Methyl-1-pentene, 1-heptene, 1-hexene, 1-decene, 1-dodecene, or other α-olefin homopolymers or copolymers, or ethylene / butadiene copolymers or ethylene / ethylidene norbornene copolymers. Representative copolymers of α-olefin and conjugated or non-conjugated diene, ethylene / propylene / butadiene terpolymer, ethylene / propylene / dicyclopentadiene terpolymer, ethylene / propylene / ethylidene norbornene A copolymer of a conjugated diene or a non-conjugated diene with two or more kinds of α-olefins represented by a terpolymer, an ethylene / propylene / 1,5-hexadiene terpolymer and the like can be mentioned. Among them, particularly preferable are α-olefin homopolymers or copolymers.

In the present invention, any of the above-mentioned thermoplastic resins is suitable as long as it has a melt flowability, but particularly, the melt flowability (ASTM D 1238; MFR) of less than 1 g / 10 min is extremely high. When applied to a bad resin, the effect is further exerted.

According to the method of the present invention, it is possible to disperse such a material having poor fluidity at an extremely low temperature as compared with the conventionally known methods.

The thermoplastic polymer (ii) which is another component constituting the aqueous dispersion of the present invention is a carboxylic acid group which is neutralized or is not neutralized by the above-mentioned thermoplastic resin or the monomer constituting the thermoplastic resin. Or a monomer having a saponified or unsaponified carboxylic acid ester group is introduced by means of a graft copolymer, a block copolymer, a random copolymer, etc. Is a neutralization reaction or a saponification reaction with a basic substance, and the total amount of carboxylic acid salt formed in the polymer is 1 g of the polymer. It is adjusted so as to contain 0.1 to 5 mmol equivalent, particularly 0.2 to 4 mmol equivalent in terms of conversion. In this case, the polymer may be a partially neutralized product or partially saponified product in which carboxylic acid groups or carboxylic acid ester groups which are not neutralized or saponified coexist. Also, the thermoplastic polymer (ii) must not be water-soluble or water-swellable. When the total amount of the neutralized carboxylic acid group and / or the saponified carboxylic acid ester group is out of the above range, it does not function to help disperse the thermoplastic resin (i) and a good dispersion is obtained. And can't. If it is water-soluble or water-swellable, the physical properties of the coating film deteriorate.

The above-mentioned thermoplastic polymer (ii) is post-neutralized or post-saponified.
In this case, the raw material polymer is, for example,
Monomers that are common to the monomers that make up the plastic resin (i),
Α-olefin and ethylenically unsaturated carboxylic acid or
A copolymer of the ester,
(Meth) acrylic acid, maleic acid, fumar as boric acid
Acid, tetrahydrophthalic acid, itaconic acid, citracone
Acid, crotonic acid, isocrotonic acid, nadic acid (En
Docis-bicyclo [2,2,1] hept-5-ene-
2,3-dicarboxylic acid), maleic anhydride, anhydrous citra
As the unsaturated carboxylic acid ester such as conic acid,
Mono-es such as methyl, ethyl and propyl of Japanese carboxylic acid
Examples thereof include ter and diester. Of course, multiple monomers
Instead of copolymerizing the components, a thermoplastic resin (i) such as
Olefin resin, ethylenically unsaturated carboxylic acid,
Graft-polymerize monomers such as anhydrides or their esters
Thermoplastic polymerization for post-neutralization or post-saponification
It will be apparent to those skilled in the art that a body is obtained.

The amount of these ethylenically unsaturated carboxylic acid, its anhydride, or its ester monomers introduced should, of course, not be sufficient to give the concentration of the carboxylate salt specified in the claims. Not As a minimum, it should have a concentration of 0.1 millimole equivalent / 1 g polymer, preferably in the range of 0.1 to 5 millimole equivalent / 1 g polymer.

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

(1) Examples of alkali metals include sodium and potassium, examples of alkaline earth metals include calcium, strontium and barium, and (2) amines such as hydroxylamine and inorganic amines such as hydrazine, methylamine, ethylamine and ethanolamine. , Cyclohexylamine, (3) alkali metal and alkaline earth metal oxides, hydroxides, hydrides such as sodium oxide,
Sodium peroxide, potassium oxide, potassium peroxide, calcium oxide, strontium oxide, barium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide,
Strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydride, (4) as weak acid salts of alkali metals and alkaline earth metals, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, Examples of the compounds of calcium hydrogen carbonate, sodium acetate, potassium acetate, calcium acetate, (5) ammonia and amines include amonium hydroxide, quaternary ammonium compounds such as tetramethylammonium hydroxide and hydrazine hydrate.

As the carboxylate or carboxylate ester group neutralized or saponified with a basic substance, sodium carboxylates, alkali metal carboxylates such as potassium carboxylates, ammonium carboxylates are preferable, and potassium carboxylates are particularly preferable. preferable.

The thermoplastic polymer (ii) is the target thermoplastic resin (i)
It is preferable to select a material having a good compatibility with. That is, when the purpose is an aqueous dispersion of an olefin resin,
Polymers containing olefinic monomers in the backbone should be chosen. For example, when polyethylene, polyolefin, ethylene / vinyl acetate copolymer, etc. are used, these maleic acid kraft products or ethylene / (meth)
It is preferable to use a neutralized product or saponified product such as an acrylic acid copolymer or an ethylene / (meth) acrylic acid methyl copolymer. The solubility parameter (Sp value) is one index for selecting an appropriate thermoplastic polymer.
That is, the difference in solubility parameter between the raw material polymer and the thermoplastic resin (i) before being neutralized or saponified is 2 [cal / cm
^3] within ^1/2, particularly 1 [cal / cm ^{3] 1/2} which are within is preferred.

In the present specification, the solubility parameter (Sp value) is
It has the usual meaning, that is, the value defined as the half power of the cohesive energy density. The solubility parameter is the contribution value Vi of the atomic group to the molar volume and the cohesive energy En of the atomic group En.
To DWVan Klevelen “Properties of Polymers” (Else
vier, 1972), using the formula Calculated from

Examples of the anionic surfactant (iii) include primary higher fatty acid salt, secondary higher fatty acid salt, primary higher alcohol sulfate ester salt, secondary higher alcohol sulfate ester salt, primary higher alkyl sulfonate. , Secondary higher alkyl sulfonate, higher alkyl disulfonate, sulfonated higher fatty acid salt, higher fatty acid sulfate ester salt, higher fatty acid ester sulfonate, higher alcohol ether sulfate ester salt, higher alcohol ether sulfonate salt Any anionic surfactant such as an alkylolated sulfate of a higher fatty acid amide, an alkylbenzene sulfonate, an alkylphenol sulfonate, an alkylnaphthalene sulfonate or an alkylbenzimidazole sulfonate may be used. More specific compound names of these surfactants are disclosed in, for example, "Synthetic surfactants" by Hiroshi Horiguchi (Sho 41 Sankyo Shuppan).

Preferable examples of the anionic surfactant include higher fatty acids, particularly salts of saturated or unsaturated higher fatty acids having 10 to 20 carbon atoms, particularly alkali metal salts,
More specifically, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, saturated fatty acids such as margaric acid, stearic acid, and arachidic acid, lindene acid, tsuzuic acid, petroselinic acid, oleic acid, linoleic acid, linolenic acid. Examples thereof include acids, unsaturated fatty acids such as arachidonic acid, and alkali metal salts of mixtures thereof.

The natural oil or synthetic oil (iv) includes mineral oils such as spindle oil and machine oil, liquid paraffin, electric insulating oil,
Mineral oils such as process oils; synthetic oils such as alkylbenzene oils, diolefin oils, diester oils and alkylnaphthenate oils; vegetable oils such as castor oil, linseed oil, rapeseed oil, coconut oil, tall oil and the like are used. These oil agents should have a number average molecular weight of 200 or more in order to be stably retained in the resin solid content.

In the aqueous dispersion according to the present invention, the above-mentioned components are present in a certain range of quantitative ratio. That is, the thermoplastic resin (i)
1 to 60 parts by weight, particularly 2 to 50 parts by weight, of the thermoplastic polymer (ii) per 100 parts by weight, and the anionic surfactant (ii).
i) is 1 to 40 parts by weight, especially 2 to 30 parts by weight, and the oil agent (iv) is 10 to 500 parts by weight, especially 20 to 30 parts by weight.
It is preferably present in an amount ratio of 0 parts by weight.

When the component (ii) is less than this ratio, the thermoplastic resin is not sufficiently dispersed, and when the component (ii) is more than this ratio, the dispersion is different from the intended inherent properties of the thermoplastic resin. When the component (iii) is less than this ratio, it is difficult to make the dispersed particles ultrafine as intended in the present invention, and when it exceeds this ratio, the physical properties of the coating film and the like tend to be deteriorated. If the component (iv) is less than this ratio, it is difficult to soften and solidify the resin solids intended in the present invention, and if it exceeds this ratio, the resin solids are excessively softened and the physical properties of the final coating are deteriorated. And so on.

The aqueous dispersion of the present invention has the above-mentioned constitution and further contains water, and the water content is 3 to 90% by weight of the aqueous dispersion. If the water content is less than 3% by weight, an aqueous dispersion cannot be obtained. If the water content exceeds 90% by weight, the solid content concentration is too low, and the heat energy cost for drying is reduced.
It is also disadvantageous in terms of storage. When the water content is in the range of 3 to 25% by weight, the aqueous dispersion apparently exhibits the characteristics as a solid or paste, while the content of 35% by weight or more exhibits the characteristics as an aqueous dispersion. The water content is preferably in the range of 5 to 70% by weight.

Structure and Properties of Aqueous Dispersion The present invention comprises the above-mentioned thermoplastic resin (i), a carboxylate-type thermoplastic polymer (ii), an anionic surfactant (iii), and an oil agent (iv). Melt kneading composition is 3 to 2
The phase inversion phenomenon occurs in the presence of an extremely small amount of water of 5% by weight, and the O / W type dispersion form in which water is the dispersion medium phase and the resin solid content is the fine dispersion particle phase is stably fixed. It is based on discovery. Of course, the present invention is a liquid dispersion obtained by adding an additional amount of water directly to the solid or paste-like aqueous dispersion in the manufacturing process and adding an additional amount of water at a place different from the manufacturing process. It should be noted that the phase inversion phenomenon itself is performed in the presence of a small amount of water of 3 to 25% also in these cases.

When observing the particle structure of the solid aqueous dispersion according to the present invention by an electron micrograph, the secondary particles of the solid aqueous dispersion of the present invention have a structure in which finely deformed fine primary particles are considerably densely aggregated. I understood it. However, the fact that the primary particles are in the oil-in-water type dispersion form is proved by various facts described below.

Another property of the solid or paste aqueous dispersion is that its electrical resistance value is 10 ⁶ Ω · cm or less, most of which is 10 ⁵ Ω · cm or less. It is presumed that the low electrical resistance value is such that the continuous phase of the dispersion is water and the discontinuous phase is resin. That is, when the continuous phase is a resin or when the resin powder contains only 25% by weight or less of water, the electric resistance value is the value that the resin originally has (generally 10 ⁷ to 10 ¹⁸ Ω · cm). , Mostly 10 ¹⁰ Ω
cm or more).

As another property, when water is added to the aqueous dispersion, the solid content is uniformly dispersed in the aqueous phase. From this, it is estimated that the continuous phase is a dispersion containing water.

In addition, the measurement of the electric resistance value was performed by using the AC resistance measuring device 60HZ to measure the resistance value between the electrodes after attaching electrodes of 1 cm to both inner sides facing each other in a 1 cm cubic insulator container and press-fitting the dispersion. Depends on the method of measurement. The measurement of the dispersed state with water is
It can be confirmed by throwing the dispersion in cold water, stirring it with an ordinary stirrer having a turbine blade, filtering the dispersion with a wire mesh of about 100 mesh, and observing particles in the dispersion with a microscope or the like.

The dispersed particles of the dispersion of the present invention are substantially spherical particles,
The average particle size is in the range of 10 μ or less, and most of the range is 5 μ or less.

This particle size can be measured using a Coulter counter.

In addition, when the solid aqueous dispersion described above was redispersed in water and then the water was dried to obtain only the solid content, an electron micrograph was observed, and it was found that the solid content particles were substantially spherical fine particles.

The aqueous dispersion of the present invention has a low water content and is apparently solid or paste-like, and since it is easily made into an aqueous dispersion by addition of water, there is no fear of freezing, space saving in a storage place, and easy transportation. Features include ease of packaging. In addition, cement, mortar, gypsum, etc. can be mixed with the diameter of powder or granules that do not come into contact with water, and water-repellent liquid can be used to form a water-resistant, oil-resistant, chemical-resistant coating on various materials, or heat treatment. It can also be used as a sealing material. Further, as another usage mode of the aqueous dispersion of the present invention, it is possible to apply an extremely small shearing force or dry it under an extremely mild temperature condition to reduce the pulverization and the water content. It can also be used for other purposes such as binders for new ceramics and polymer modifiers.

Further, the liquid dispersion in the form of a liquid can be used as it is or after being diluted if desired, for the above-mentioned applications such as coating.

In the aqueous dispersion of the present invention, the resin solid content particles are in a state of being softened by the oil agent, the processability of the resin is improved, and further, the particles themselves are miniaturized. It has the advantage of being possible. Further, there is an advantage that an ethylene-propylene-diene copolymer is used as the thermoplastic resin (i), and by crosslinking this, it becomes a soft and elastic rubber, which is suitable as a rubber component of the AES resin.

Manufacturing method In the present invention, the aforementioned (i), (ii), (iii) and (i
Melt and knead the components of v). At this time, instead of using the thermoplastic resin (ii) having a carboxylate group, a group of a carboxylic acid, an anhydride thereof or an ester thereof, which is capable of being neutralized and / or saponified and bound to a polymer chain, is used. Per gram of polymer A thermoplastic polymer containing a concentration of 0.1 mmol equivalent or more in terms of conversion may be used for subsequent neutralization and / or saponification with a basic substance, and the anionic surfactant (ii
Instead of i), kneading may be performed by using an organic compound which becomes an anionic surfactant by neutralization with a basic substance, and then neutralization may be performed later.

In this production method, the resin is melt-kneaded, and the temperature at the time of melt-kneading is not less than the melting point of the higher one of the resins used, preferably not less than the temperature at which the melt viscosity becomes 10 ⁵ poise or less.

In the second step, water is added to the melt-kneaded product to invert the resin solid content to form dispersed particles. The amount of water added is in the range described above. In the second step, when an unneutralized and / or unsaponified thermoplastic polymer is used and / or an unneutralized organic compound for anionic surfactant is used, these are neutralized. Add the basic material needed to do so. Suitable examples of basic substances are those already mentioned above, which may be added directly, but are preferably added in the form of an aqueous solution.

The above-mentioned first step and second step may be sequentially performed, or may be performed next.

The melt-kneading means that can be used in the production method of the present invention may be any known method, but preferably a kneader, a Banbury mixer, or a multi-screw extruder can be exemplified.

The aqueous dispersion produced by melt-kneading by sequentially adding water,
After that, it is cooled to room temperature naturally or artificially. At this time, the dispersed particles solidify to form a stable dispersion.

In the production of this dispersion, various auxiliary materials that can be usually used in an aqueous dispersion, for example, a dispersant such as a nonionic surfactant, an emulsifier, a stabilizer, a wetting agent, a thickener, a foaming agent, a defoaming agent, Foaming agent, coagulant, gelling agent, anti-aging agent,
It goes without saying that a plasticizer, a filler, a coloring agent, a fragrance, an anti-sticking agent, a release agent and the like may be used in combination.

Effect of the Invention According to the present invention, as described in detail above, the thermoplastic resin (i), the thermoplastic polymer (ii) containing a carboxylate group, the anionic surfactant (iii) and the oil agent (iv) ) Is melt-kneaded, and water is added to the mixture to continue the kneading, whereby an aqueous dispersion in which the resin solid content is phase-inverted into finely dispersed particles can be easily obtained. In addition, the obtained aqueous dispersion has the advantages that the dispersed resin particles are softened, the processability is excellent, thin film coating is possible, and the process into a soft rubber is easy.

Examples Preferred examples of the present invention will be shown below, but the present invention is not limited to these examples unless otherwise specified.

A thermoplastic polymer having a carboxylate group was prepared by the method shown in the following Reference Example.

Reference Example 1 Maleic anhydride-grafted polyethylene (maleic anhydride content 3.3 wt%, Mw = 2700, density = 0.94 g / cm ³ , Sp value =
8.06 (cal / cm ³ ) ^1/2 , 100 parts by weight are put into an atmospheric pressure kneader and melt-kneaded at 140 ° C.

3.76 parts by weight of potassium hydroxide in water 12.5 parts by weight of alkaline water having 1.0 chemical equivalent) was gradually added dropwise thereto, and after the water was evaporated, the mixture was kneaded for another 30 minutes and cooled.

When the produced carboxylate was measured using an infrared spectrophotometer The conversion was 0.65 mmol equivalent / g.

Reference example 2 Maleated polybutadiene (NISSO-PB manufactured by Nippon Soda Co., Ltd.)
-BN-1015 Maleic anhydride content 13wt%, viscosity (45
℃) = 800cps, Density = 0.86g / cm ³ , Sp value = 9.53 (cal / c
m ³ ) ^1/2 , 10.6 parts by weight of sodium hydroxide Was added in the same manner as in Reference Example 1 except that 35.3 parts by weight of alkaline water in which 1.0 m of chemical equivalent) was dissolved.

When the produced carboxylate was measured, it was 2.58 mmol equivalent /
It was g.

Reference Example 3 Ethylene-ethyl acrylate resin (ethyl acrylate content 28 wt%, MFR (190 ° C.) = 200 g / 10
Min, density 0.93g / cm ³ , Sp value = 8.22 (cal / cm ³ ) ^1/2 , 4.5 parts by weight of sodium hydroxide On the other hand, the same procedure as in Reference Example 1 was carried out except that 15 parts by weight of alkaline water in which 0.4 chemical equivalent) was dissolved was added, and a saponification reaction was caused to form a carboxylate.

When the produced carboxylate was measured, it was 1.10 mmol equivalent /
It was g.

Example 1 (a) As a thermoplastic resin, an ethylene-propylene copolymer elastomer (ethylene content 75 mol%, MFR = 0.2 g /
10 minutes, density = 0.88 g / cm ³ , Sp value = 7.97 (cal / c
m ³ ) ^1/2 ) 100 parts by weight (b) Maleic anhydride-grafted polyethylene as a thermoplastic polymer (maleic anhydride content = 3.3 wt%, Mw = 2700,
Density = 0.94 g / cm ³ , Sp value = 8.06 (cal / cm ³ ) ^1/2 , = 0.67 mmol equivalent / g) 10 parts by weight (c) 5 parts by weight of oleic acid as an organic compound which reacts with a basic substance to become an anionic surfactant (d) as a mineral oil Diana Process Oil PW-90 (manufactured by Idemitsu Kosan, 100 parts by weight of an average molecular weight of 539) is put into a kneader and kneaded at 125 ° C. for 30 minutes. Next, 15 parts by weight of alkaline water in which 1.38 parts by weight (1.0 chemical equivalent) of potassium hydroxide necessary for neutralizing all carboxylic acids of the thermoplastic polymer and the organic compound was dissolved was used by a pump connected to a kneader. Press in in minutes. The pressure inside the kneader was 3 kg / cm ³ G.

After continuing kneading for 30 minutes, the kneader was cooled to 60 ° C. and opened, and the content was a white viscous substance.
To this, 215 parts by weight of water was added and stirred to obtain a dispersion liquid having a water content of 52%, a viscosity of 95 cps and a pH of 10.2. When the size of dispersed particles was measured with a Coulter counter, the average particle size was 1.9μ.
Met.

The amount of carboxylate formed in the thermoplastic polymer was quantified using an infrared spectrophotometer. The conversion was 0.5 mmol equivalent / g.

Examples 2-7. The composition ratios shown in Table 1 were the same as in Example 1. The results are shown in Table 1.

Example 8. Ethylene-propylene copolymer elastomer used in Example 1 and maleic anhydride grafted polyethylene used from the hopper of a co-rotating intermeshing twin-screw extruder (PCM-45I / D = 30 manufactured by Ikegai Tekko Co., Ltd.) having two vents. A mixture of 100/10/5 parts by weight of oleic acid and oleic acid was supplied at a rate of 115 parts by weight / hour, and 1 process oil Pw-90 was supplied from a supply port provided in the first vent part of the extruder.
15 parts by weight of a 9.2% aqueous solution of potassium hydroxide at a rate of 00 parts by weight / hour and from a supply port provided in the second solid portion.
It was continuously fed at a rate of time by a pump and continuously extruded at a heating temperature of 80 ° C. The product was a white viscous substance, and its properties are shown in Table 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 23/26 LDA 7107-4J 91/00 LSJ 7415-4J 101/00 LSY 7242-4J C09D 5 / 02 PPT 6904-4J PPU 6904-4J 123/02 PEP 7107-4J

Claims (2)

[Claims] 1. A polymer 1 comprising (i) a thermoplastic resin, and (ii) a carboxylate group bonded to a polymer chain.
Per gram A thermoplastic polymer contained in a concentration of 0.1 to 5 mmol equivalent, (iii) an anionic surfactant, (iv) a natural or synthetic oil having a number average molecular weight of 200 or more, and (V) water. And an aqueous dispersion having a water content of 3 to 90% by weight and a resin solid content present as a finely dispersed particle phase. 2. A polymer having (a) a thermoplastic resin, (b) a carboxylic acid capable of being neutralized and / or saponified and bonded to a polymer chain, an anhydride thereof or an ester thereof per gram of the polymer. A thermoplastic polymer containing a concentration of 0.1 mmol equivalent or more in terms of conversion, or a carboxylate group bonded to a polymer chain per 1 g of the polymer. A thermoplastic polymer which is contained at a concentration of 0.1 to 5 millimol equivalent, (c) an organic compound which reacts with an anionic surfactant or a basic substance to become an anionic surfactant, and (d) has a number average molecular weight of 200 or more. A natural oil or a synthetic oil is melt-kneaded with, and when (c) is an organic compound, a basic substance is added to convert it into an anionic surfactant, and when the thermoplastic polymer is not neutralized, a base is added. 0.1 to 5 per gram of polymer by adding a functional substance to the thermoplastic polymer.
The aqueous dispersion is characterized in that the step of forming 3 equivalents of carboxylate groups and the step of adding water to the melt-kneaded product to carry out melt-kneading to form an aqueous dispersion are carried out simultaneously or successively. Manufacturing method.