JPS6134064A - Aqueous dispersion and production thereof - Google Patents

Abstract

PURPOSE:To produce an aq. dispersion having excellent resistance to water, oils and chemicals and adhesion to hydrophobic materials, by dispersing a thermoplastic resin and a water-insoluble thermoplastic polymer in water in the presence of an anionic surfactant. CONSTITUTION:1-60pts.wt. water-insoluble thermoplastic polymer (A) contg. 0.1-5m equivalents (in terms of the group of the formula) (per g of polymer) of carboxyl (anhydride) or ester groups which are attached to the polymer chain and can be neutralized and/or saponified, and 1-40pts.wt. org. compd. (B) which can be converted into an anionic surfactant by the reaction with a basic substance, are melt-kneaded with 100pts.wt. thermoplastic resin (C) having an MFR of 1g/10min or above. A basic substance and 3-25wt% water are added to the kneaded mixture, and the mixture is melt-kneaded to convert component B into an anionic surfactant, to form 0.1-5mmol (in terms of the group of the formula) (per g of polymer) of carboxyl base in component A and to disperse resin solids in water phase, thus obtaining an aq. dispersion having electrical resistance of 10<6>OMEGA.cm or below.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an aqueous dispersion capable of forming a film having excellent water resistance, oil resistance, chemical resistance, and adhesion to hydrophobic materials, as well as the aqueous dispersion. An object of the present invention is to provide a method for producing an aqueous dispersion that can freely produce an aqueous dispersion with a high water content.

Prior Art and Technical Problems of the Invention Aqueous dispersions of various polymers have been known. For example, a fluid aqueous dispersion (hereinafter referred to as an aqueous dispersion) with a water content of about 3 Dur14r or more can be applied to the surface of paper, fibers, plastic moldings, wood, metal, etc. It is dried to form a resin film, which imparts water resistance, oil resistance, and chemical resistance to base materials, and is used as a heat sealing agent. Since such aqueous dispersions use water as a dispersion medium, they are very advantageous compared to solvent-based ones in terms of flammability, work environment problems, and ease of handling, and are used in a wide range of fields. It is used in

In addition to the above-mentioned aqueous dispersions, aqueous dispersions (hereinafter referred to as aqueous dispersions) that have no fluidity and appear to be solids are also known.

In other words, it is a powder-like product known as a powder emulsion, which is redispersed by adding water to form an aqueous dispersion, and its composition contains no water at all, or even if it does, it contains at most 2 to 30% of water. It has the advantage that it is lightweight, so there is no need to worry about freezing even at low temperatures, making it easy to package and transport, and requires less space for storage.

Furthermore, it is possible to directly mix powders and granules that do not want to come into contact with water, such as cement, mortar, and plaster, which is difficult to do with aqueous dispersions, making it possible to manufacture highly processed formulations. are doing.

By the way, in the conventionally known method for producing an aqueous dispersion,
The production of the aqueous dispersions and aqueous dispersions described above could not be carried out in the same manner. In other words, to produce an aqueous dispersion, an aqueous dispersion with a high water content is first produced by various known methods, and then this aqueous dispersion is sprayed into hot air in a furnace using a sprayer to evaporate the water. It is made into a powder. However, when this method uses an aqueous dispersion of a low softening temperature polymer as a raw material, the polymer particles may clump during spraying, or the resulting powder emulsion may clump and agglomerate under the action of heat or pressure. Tend. Even if such a powder emulsion is redispersed by adding water, it may not be well dispersed, or even if it can be dispersed, the viscosity becomes high or 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 or the powder before drying, but if the amount added is not large, the coating will not have a texture, resulting in a coating film. There is a problem that physical properties deteriorate, and furthermore, since a large amount of water 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 using a method that does not add additives as much as possible and has little energy loss.

Improvements are also desired in the method for producing aqueous dispersions.

That is, conventionally known manufacturing methods can be divided into a method in which emulsion polymerization is carried out in an aqueous medium in the presence of an emulsifier, and a method in which a molten resin and an aqueous medium are stirred and mixed in the presence of shear force. The former method has problems such as limitations in the types of polymerizable resins, complicated IT6 reaction control, and complicated 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 operating technology.

Many proposals have been made regarding the latter method; for example, Japanese Patent Application Laid-open No. 12835/1983 discloses a method in which a kneaded material consisting of a thermoplastic resin and a water-soluble polymer is dispersed in water. However, the film obtained using the aqueous dispersion produced by this method has problems such as low mechanical strength and poor water resistance because it contains a water-soluble polymer. Japanese Patent Publication No. 57-23705 discloses a method of dispersing in water a mixture consisting of polypropylene and a dispersant selected from surfactants and water-soluble or water-swellable polymers. However, this method has the problem that the diameter of the dispersed particles is relatively large and that petroleum resin must be used in combination to reduce the particle diameter, resulting in a sticky film. Also, JP-A-56-21
No. 49 discloses a method of obtaining an aqueous dispersion by kneading an olefin resin and an aqueous solution of partially saponified polyvinyl alcohol, but this method also contains a water-soluble resin, resulting in poor film properties. Furthermore, the aqueous dispersion obtained by this method has a water content of 60% by weight or more. Still another method is the technique disclosed in Japanese Patent Publication No. 58-42207, in which a polyolefin and a carboxyl group-containing polyolefin are melted and mixed, then fed into hot water containing a basic substance, and a shearing force is applied to form a dispersion. Although this method is suitable because it does not contain water-soluble or water-swellable polymers and does not use petroleum resins, on the other hand, the type of raw resin is limited in order to produce particles with small dispersed particle sizes. There is a problem of being exposed. Furthermore, since the dispersion process is carried out at high temperature and high pressure, there is a problem in that the container used during dispersion must have pressure resistance.

Therefore, in the production of aqueous dispersions, for which various methods have been proposed, water-soluble or water-swellable polymers,
It is desired to develop a method for obtaining an aqueous dispersion of fine particles that can be applied to any resin without using petroleum resin or the like.

Furthermore, it is also desirable to develop an aqueous dispersion and a method for freely and extremely easily producing an aqueous dispersion without involving any special steps.

Purpose of the Invention The present inventors continued research in view of the current situation, and as a result, thermoplastic resins, carboxylic acids, thermoplastic polymers containing carboxylic acids, their anhydrides, or their ester groups, and basic substances are limited. When melt-kneaded in the presence of an amount of water, phase inversion,
That is, a conversion occurs in which water becomes a dispersion medium phase and solids become a dispersed particle phase, resulting in an apparently solid aqueous dispersion, and once such a phase inversion occurs, there is no It has now been discovered that aqueous dispersions with a wide range of water contents can be obtained by supplementing with additional amounts of water externally.The present invention is an improvement on such technology, which further provides dispersions with ultrafine particle sizes. This invention relates to a technology that uses an anionic surfactant in combination.

By the way, the present inventors have investigated and found that simply adding an anionic surfactant to the above-mentioned technique does not result in ultra-fine particle formation. In other words, in order to produce a dispersion with an ultrafine particle size using an anionic surfactant, an organic compound that reacts with a basic substance to become an anionic surfactant is kneaded with the raw resin, and then mixed with the basic substance. It turned out that it had to be converted into an anionic surfactant through a reaction.

That is, the object of the present invention is to have a resin solid that has an ultrafine particle size and is an oil-in-water dispersion, even though the water content is extremely low. An object of the present invention is to provide an aqueous dispersion having the property of being uniformly dispersed as ultrafine particles in an aqueous dispersion.

Another object of the present invention is to provide an aqueous dispersion in which the dispersed particle size is controlled to an extremely fine range even though it does not contain any water-soluble or water-swellable components.

Still another object of the present invention is to provide a method for producing an aqueous dispersion of a thermoplastic resin in which phase inversion occurs with a small amount of water.

Still another object of the present invention is to provide a method for producing an aqueous dispersion of a thermoplastic resin without requiring large-scale equipment and with low thermal energy costs.

Structure of the Invention According to the present invention, (1) the thermoplastic resin, (ii) the carboxylate group bonded to the polymer chain is 0.1 to 5 mmol in terms of 10-0-group per gram of the polymer. It contains a thermoplastic polymer in an equivalent concentration, (1 ft) anionic surfactant, and θ■) water, and is an apparent solid with a water content of 3 to 25% by weight, and an electrical resistance value of Provided is an aqueous dispersion characterized in that the solid content is 1060·α or less and that the solid content is uniformly dispersed in the aqueous phase as ultrafine particles by adding water.

According to the invention, also (i) a thermoplastic resin, and (II
) Neutralizable and/or saponifiable carboxylic acid, its anhydride, or its ester groups bonded to the polymer chain in an amount of 0.1 mmole equivalent or more calculated as 10-0-groups per gram of the polymer. A process of melt-kneading a thermoplastic polymer containing a concentration of a thermoplastic polymer and (ii+) an organic compound that reacts with a basic substance to become an anionic surfactant, and adding a basic substance and 6 to 25 weight - of the basic substance to the molten mixture. of water was added and melt-kneaded to convert the organic compound (i+D) into an anionic surfactant, and the thermoplastic polymer (1) contained -C-O- groups per gram of polymer. forming 0.1 to 5 mmol equivalents of carboxylate groups and phase inverting the resin solids into an aqueous dispersion, optionally adding additional amounts of water to the aqueous dispersion. A method of making a characterized aqueous dispersion is provided.

Preferred embodiments of the invention The present invention will be explained in detail below.

Ingredients The thermoplastic resin (1), which is one of the components constituting the aqueous dispersion of the present invention, is not only water-insoluble and water-swellable, but also heat-resistant, which itself lacks dispersibility in water. It is a plastic resin, such as low density polyethylene, high density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, or α-olefin such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc. Polyolefins such as random or block copolymers, ethylene/vinyl compound copolymers such as ethylene/vinyl acetate copolymers, ethylene/vinyl alcohol copolymers, ethylene/vinyl chloride copolymers, polystyrene,
Styrenic resins such as acrylonitrile/styrene copolymer, ABS, α-methylstyrene/styrene copolymer,
Polyvinyl compounds such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride/vinylidene chloride copolymer, polymethyl acrylate, polymethyl methacrylate, nylon 6,
Any resin may be used, including polyamides such as nylon 6-6, nylon 6-10, nylon 11, and nylon 12, thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyphenylene oxide, and mixtures thereof.

Among these thermoplastic resins, olefin resins are particularly preferred, such as polyethylene, polypropylene,
poly-1-butene, poly-6-methyl-1-7"thene,
Bo! Ethylene represented by J-4-methyl-1-pentene, poly-3-methyl-1-pentene, ethylene/propylene copolymer, ethylene/1-butene copolymer, propylene/1-butene copolymer, α of propylene, 1-butene, methyl-1-7”tene, 4-methyl-1-pentene, 6-methyl-1-pentene, 1-heptene, 1-hexene, 1-decene, 1-dodecene, etc. - Single or copolymers of olefins, or copolymers of α-olefins and conjugated or non-conjugated dienes, such as ethylene-butadiene copolymers and ethylene-ethylidene norbornene copolymers, or ethylene-propylene-butadiene 6-component copolymer, ethylene/propylene/dicyclopentadiene 6-component copolymer, ethylene/propylene/
Examples include copolymers of two or more α-olefins and conjugated or non-conjugated dienes, such as ethylidenenorbornene terpolymer and ethylene-propylene-'1,5-hexadiene terpolymer. . Particularly preferred among these are α-olefin homopolymers or copolymers.

Melt flow rate of thermoplastic resin (1) (ASTMD
l 238, MFR) is 1r/101M! That's all, preferably! M/10- or higher is better. MFR is 1 F/
If it is less than 10, the melt viscosity becomes too thick and difficult to melt and knead, making it difficult to obtain a suitable aqueous dispersion.

The thermoplastic polymer (ii), which is another component constituting the aqueous dispersion of the present invention, is the above-mentioned thermoplastic resin or a monomer constituting it, with neutralized or non-neutralized carboxylic acid groups. A monomer having a saponified or non-saponified carboxylic acid ester group is introduced by graft copolymerization, block copolymerization, random copolymerization, etc., and in some cases, a basic substance is introduced. The total amount of carboxylic acid salts produced in the polymer is -C-0- in 1 gram of the polymer.
It is adjusted to contain 0.1 to 5 millimole equivalents, specifically 0.2 to 4 millimole equivalents, in terms of base. In this case, the polymer may be 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 coexists. The thermoplastic polymer (ii) must also not be water-soluble or water-swellable. If the total amount of neutralized carboxylic acid groups and/or saponified carboxylic acid ester groups is outside the above range, the thermoplastic resin (1) will not work to aid in dispersion and will not provide a good dispersion. It is not possible to do so. Moreover, if it is water-soluble or water-swellable, the physical properties of the coating film will deteriorate.

A thermoplastic polymer containing the above carboxylate group (ii
) is obtained by post-neutralization or post-saponification, the raw material polymer is, for example, a monomer common to the monomers constituting the above-mentioned thermoplastic resin (1), especially α-olefin and ethylenic non-monomer. Copolymerized with saturated carboxylic acid salts or their esters, and unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and incroton. acid, nadic acid 0 (endocys-bicyclo(2゜2
．． 1] Hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, etc. Monoesters, diesters, etc. of methyl, ethyl, propyl, etc. of the above unsaturated carboxylic acids as unsaturated carboxylic acid esters can be exemplified. Of course, instead of copolymerizing a plurality of monomer components, a monomer such as an ethylenically unsaturated carboxylic acid, its anhydride, or its ester may be graft-polymerized to the thermoplastic resin (1), for example, an olefinic resin. It will be obvious to those skilled in the art that this provides thermoplastic polymers for post-neutralization or post-saponification.

Of course, the amount of monomers of these ethylenically unsaturated carboxylic acids, their anhydrides, or their esters introduced must be sufficient to provide the concentration of the carboxylic acid salt specified in the claim. The concentration of the polymer must be at least 0.1 mmol/1 as -0-0- groups, preferably in the range of 0.1 to 5 mmol/12 polymer.

In addition, basic substances used for neutralization and Keni 1 include:
Alkali metals, alkaline earth metals, substances that act as bases in water such as ammonia and amines, alkali metal oxides, hydroxides, weak acid salts, hydrides, alkaline earth metal oxides, hydroxides, weak acids Examples include substances that act as bases in water, such as salts and hydrides, and alkoxides of these metals. Examples of such substances are shown below.

(1) Alkali metals include, for example, sodium and potassium; alkaline earth metals include, for example, calcium, strontium, and barium; (2) amines include inorganic amines such as hydroxylamine and hydrazine, methylamine, ethylamine, and ethanolamine. , cyclohexylamine, (3) oxides of alkali metals and alkaline earth metals,
Examples of hydroxides and hydrides include 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 hydride, potassium hydride, calcium hydride, (4) Weak acid salts of alkali metals and alkaline earth metals include:
Sodium carbonate, potassium carbonate, sodium bicarbonate,
Potassium hydrogen carbonate, calcium hydrogen carbonate, sodium acetate, potassium acetate, calcium acetate, (5) Examples of ammonia and amine compounds include ammonium hydroxide, quaternary ammonium compounds such as tetramethylammonium hydroxide, hydrazine hydrate, etc. can be mentioned.

As the non-carboxylic acid group or carboxylic acid ester group that is neutralized or saponified by a basic substance, alkali metal carboxylates such as sodium carboxylate and potassium carboxylate, and ammonium carboxylate are suitable, and potassium carboxylate is especially preferred. preferable.

The thermoplastic polymer (ii) is the target thermoplastic resin (1
) should be selected with good compatibility. That is, when the purpose is an aqueous dispersion of an olefin resin, a polymer containing an olefin monomer in the polymer chain should be selected. For example, polyethylene, polyolefin,
When using ethylene-hinyl acetate copolymer, etc., these maleic acid grafts or ethylene (
It is preferable to use a 1-saponified product without a neutralized product, such as a meth)acrylic acid copolymer or an ethylene/methyl(meth)acrylate copolymer. One guideline for selecting an appropriate thermoplastic polymer is the solubility parameter (Sp value).In other words, the ratio between the raw material polymer (ii) and the thermoplastic resin (before neutralization or saponification) is The difference in solubility parameter from 1) is within 2 (ωe/cr/l)7, especially 1
(ad/crl)! It is preferable that it be within

As used herein, the solubility parameter (Sp value) has the usual meaning, ie, a value defined as the square value of the cohesive energy density. This solubility parameter defines the contribution Vi of the atomic group to the molar volume and the cohesive energy EfL of the atomic group as D, F, VanK.
properties of polymers”
It can be determined by using the value described in Evier, 1972) and calculating from the formula.

Examples of the anionic surfactant (ii+) include first-edge higher fatty acid towers, second-level higher fatty acid salts, first-level higher alcohol sulfate salts, second-level higher alcohol sulfate salts, and first-level higher alkyl sulfonates. , second category higher alkyl sulfonates, higher alkyl disulfonates, sulfonated higher fatty acid salts, higher fatty acid sulfate ester salts, higher fatty acid ester sulfonates, higher alcohol ether sulfate ester salts, higher alcohol ether sulfonates , alkylolated sulfate ester salts of higher fatty acid amides, alkylbenzenesulfonates, alkylphenolsulfonates, alkylnaphthalenesulfonates,
Any surfactant that reacts with a basic substance such as an alkylbenzimidazole sulfonate to become an anionic surfactant may be used.

More specific chemical names of these surfactants are disclosed, for example, in Hiroshi Horiguchi's "Synthetic Surfactants 1" (Sankyo Publishing, 1972).

Composition, structure and properties of the aqueous dispersion In the aqueous dispersion according to the invention, each of the above-mentioned components is present in a certain range of quantitative ratios. That is, thermoplastic resin (i)
1 to 60 parts of thermoplastic polymer (ii) per 100 parts by weight
parts by weight, especially 2 to 50 parts by weight, and the anionic surfactant (ii1) is preferably present in an amount of 1 to 40 parts by weight, especially 2 to 30 parts by weight. When the ratio is lower than this, the thermoplastic resin is not sufficiently dispersed, and when it exceeds this ratio, the dispersion results in a dispersion that differs from the original properties of the desired thermoplastic resin. When the component (i+D) is below this ratio, it becomes difficult to make the dispersed particles ultra-fine as intended in the present invention, and when it exceeds this ratio, the physical properties of the coating film etc. tend to deteriorate.

The aqueous dispersion of the present invention further contains water in addition to the above structure, and the water content is 6 to 25% in the aqueous dispersion.
It weighs one. If the water content is less than 6 parts by weight, an aqueous dispersion cannot be obtained, and if it exceeds 25 parts by weight, a fluid aqueous dispersion will be obtained.

In other words, by having a weight in the range of 6 to 25 -, the appearance becomes a top-sided body, and it also exhibits properties as described below.

An important feature of the present invention is that the above-mentioned thermoplastic resin (1), carboxylate type thermoplastic polymer (ii), and (ii1)
A molten mixture with an anionic surfactant undergoes a phase inversion phenomenon in the presence of an extremely small amount of water of 3 to 25% by weight, with water becoming a dispersion medium phase and the resin solid content becoming a finely dispersed particle phase. /TF' type dispersion form is stably fixed.Of course, an additional amount of water can be added directly to the aqueous dispersion of the present invention during the manufacturing process, or Although additional amounts of water can be added elsewhere to obtain a liquid dispersion, in these cases too, the phase inversion phenomenon itself takes place in the presence of small amounts of water, ranging from 3 to 25%. It is necessary to pay attention to the fact that

FIG. 1 of the accompanying drawings is an electron micrograph (magnification: 6000 times) showing the particle structure of the solid aqueous dispersion in the present invention. From this photograph, it is understood that the secondary particles of the solid aqueous dispersion of the present invention have a structure in which slightly deformed fine primary particles are aggregated quite densely. However, the fact that these secondary particles have an oil-in-water (C)/F) type dispersion form is proven from the following various facts.

Another property of the aqueous dispersion is that its electrical resistance value is 106Ω・
Most of them exhibit 105Ω·m or less.

The reason for such a low electrical resistance value is presumed to be that the continuous phase of the dispersion is water and the discontinuous phase is resin. In other words, in the case where the continuous phase is resin or the resin powder simply contains less than 25% water by weight, the electrical resistance value is the value originally possessed by the resin (generally 107~10%).
10'8Ω・m, often 10IOΩ・m or more).

Another characteristic is that when water is added to an aqueous dispersion, solid components are uniformly dispersed in the aqueous phase. This also suggests that it is a dispersion in which the continuous phase is water.

To measure the electrical resistance, 1crl electrodes were pasted on both opposing sides of a 1Crn cubic insulator container, and after the dispersion was press-fitted, the resistance between the electrodes was measured using an AC resistance measuring device at 60Hz. Depends on the method used and measured.

To measure the state of dispersion by adding water, the dispersion is poured into cold water, stirred with an ordinary stirrer equipped with a turbine blade, and then the dispersion is passed through a wire mesh of approximately 1 [] [1 mesh], and the particles in the dispersion are This can be confirmed by observing with a microscope, etc.

The dispersed particles of the dispersion of the present invention are substantially spherical particles,
The average particle size is in the range of 5μ or less, and most of them are 2μ or less. This particle size can be measured using a Coulter counter.

Figure 2 of the accompanying drawings is an electron micrograph (magnification: 50 DO) of the solid aqueous dispersion shown in Figure 1 that was redispersed in water and then dried to remove the water, leaving only the solid content. It can be seen that they are fine particles with an upper spherical shape.

The aqueous dispersion of the present invention has a low water content, has a tophedral appearance, and easily becomes an aqueous dispersion by adding water.
There is no risk of freezing, it saves storage space, and it is easy to transport and package. Furthermore, it can also be mixed into powder and granular materials that do not want to come into contact with water, such as cement, mortar, and plaster.
It can also be used to form oil- and chemical-resistant films and as a heat-sealing material. Further, as another mode of utilization of the aqueous dispersion of the present invention, it is also possible to apply an extremely small shearing force or dry it under extremely mild temperature conditions to make it a fine powder and reduce its water content. It can also be used as a binder for new ceramics and as a polymer modifier.

The present invention relates to a method for producing an aqueous dispersion, and relates to a suitable method for producing an aqueous dispersion having a high water content in addition to the above-mentioned aqueous dispersion.

The first step of the production method of the present invention involves melt-kneading the thermoplastic resin (α), the thermoplastic polymer (b), and the organic compound (c) that reacts with a basic substance to become an anionic surfactant. Become. The thermoplastic resin (a) used at this time is the same as the thermoplastic resin (1) described above. The thermoplastic polymer (b) contains 0 carboxylic acid salts produced by neutralization and/or saponification in terms of -C-0- groups per gram of the polymer.
．． A polymer containing from 1 to 5 mmol may be used, or a polymer containing less than 0.1 mmol may be used, and at least 0.1 mmol may be used in the basic substance addition step described below.
A polymer having a carboxylic acid ester that can be neutralized or saponified to millimolar equivalents may be used.

The organic compound (c) may be any compound as long as it reacts with a basic substance to become an anionic surfactant, and preferred examples include first-class higher fatty acids, second-class higher fatty acids,
1st treatment higher alcohol sulfuric ester, 2nd handling higher alcohol sulfuric ester, 1st edge higher alkyl sulfonic acid, 2nd handling higher alkyl sulfonic acid, xi alkyl disulfonic acid, sulfonated higher fatty acid, higher fatty acid sulfuric ester,
Higher fatty acid ester sulfonic acid, higher alcohol ether sulfate, higher alcohol ether sulfonic acid,
Examples include alkylolated sulfuric esters of higher fatty acid amides, alkylbenzenesulfonic acids, alkylphenolsulfonic acids, alkylnaphthalenesulfonic acids, and alkylbenzimidazolesulfonic acids. Among these, higher fatty acids, particularly saturated or unsaturated higher fatty acids having 10 to 20 carbon atoms, are particularly preferred, including capric acid, undecanoic acid, lauric acid, myristic acid, and palmitic acid. acids, saturated fatty acids such as margaric acid, stearic acid, and arachidic acid; unsaturated fatty acids such as lindelic acid, tuzic acid, petroselic acid, oleic acid, linoleic acid, linolic acid, and arachidonic acid; and mixtures thereof. .

In order to melt and knead the above-mentioned (α) to (C), (α)
~(c) may be added all at once and melt-kneaded, or (α) or (α) and (b) may be melt-kneaded without separating them, and then the remaining ingredients are successively added L7 and melt-kneaded. It's okay. Further, in some cases, a basic substance necessary for neutralizing or saponifying (h) may be included. (A) can be added in any form, from solids such as powder, pellets, and flakes to aqueous dispersions.

The blending ratios of the thermoplastic resin (α), thermoplastic polymer (b), and organic compound (C) are as described above.

The temperature for melt-kneading is at least higher than the higher melting point of the thermoplastic resin or the thermoplastic polymer.

In addition, if the melting point is not clear, the melt viscosity is at least 1
The temperature is set at 0.05poizt or less.

The second step of the production method of the present invention is a step of adding a basic substance to convert the organic compound into an anionic surfactant, and, if necessary, neutralizing and saponifying a predetermined amount of the thermoplastic polymer. . As the basic substance, those mentioned above are used, but two or more types of these may be used. The basic substance is usually added in the form of an aqueous solution.

In this step, a basic substance reacts with the organic compound or thermoplastic polymer that was evenly mixed in the first step, resulting in a neutralization or saponification reaction. Phase inversion occurs and a dispersion with an ultrafine particle size is obtained.

The amount of the basic substance added in this step is such that at least 1 part by weight of the organic compound present in the system is neutralized or saponified, and the amount of the basic substance added in the thermoplastic polymer (h) is such that at least 1 part by weight of the organic compound present in the system is neutralized or saponified. The carboxylic acid salt produced by oxidation is 0.1 to 10-0-group per gram of polymer.
Add the amount necessary for neutralization or saponification to 5 mmol equivalent. In the 6th step, water is added sequentially to invert the phase of the thermoplastic resin or thermoplastic polymer to form an aqueous dispersion. It is the process of obtaining something.

While the composition obtained in the second step is melted and mixed, water is successively added little by little to continue melting and mixing. The amount of water added should be at least 3 parts by weight of the total amount of aqueous dispersion obtained.

If it is less than 3 parts by weight, no phase inversion will occur and therefore no aqueous dispersion will be obtained. Although the upper limit of the amount of water added is not particularly limited, it is preferably at most 90% by weight in view of the use of the aqueous dispersion. Further, although this step may be carried out independently after the second step, the present invention also includes carrying out the step simultaneously with the second step as a modified method. That is, when the basic substance is added in the form of an aqueous solution in the second step, the water in the aqueous solution exhibits the same effect as in this step.

In this melt-kneading process of the present invention, 6 to 25 weight -
In the presence of limited moisture, the thermoplastic resin (1) and the thermoplastic polymer (ii) are melt-kneaded to effect a phase inversion of the resin solid content into an O7W type dispersion. It is a characteristic. Addition of water to the melt crosstalk system exceeds 25% by weight and 9%
In some cases, the phase inversion itself is carried out with an amount of 6 to 25 wt.
It is done in stages.

Of course, if the final amount of water added is between 6 and 25% by weight, a solid aqueous dispersion will be obtained; if it exceeds 25% by weight, especially 65% or more, a fluid liquid dispersion will be obtained. An aqueous dispersion is obtained.

The aqueous dispersion produced by sequentially adding water and melt-kneading is
It is then cooled naturally or artificially to below room temperature. At this time, the dispersed particles solidify and become a stable dispersion.

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

In this way, the production method of the present invention allows liquid and solid aqueous dispersions to be obtained extremely easily by simply changing the amount of water added, and the average dispersed particle size of the resulting dispersion is also 5.
μ or less, often in the range of 2 μ or less, and in the case of a solid aqueous dispersion, it has the characteristic that by adding water1, it can become a dispersion in which the solid content is dispersed in the aqueous phase. ing.

In the method of manufacturing the aqueous dispersion and aqueous dispersion of the present invention, various auxiliary materials that are normally used in aqueous dispersions, such as dispersants, emulsifiers, stabilizers, wetting agents, thickeners, and foaming agents, are used. , defoamers, coagulants, gelling agents, anti-aging agents,
It goes without saying that softeners, plasticizers, fillers, colorants, flavoring agents, anti-blocking agents, mold release agents, and the like may be used in combination.

Preferred embodiments of the present invention are shown below, but the present invention is not limited to these examples unless otherwise specified.

Example 1 Thermoplastic resin and U7 ethylene-vinyl acetate copolymer resin (vinyl acetate content = 19 wt%, MFR = 150r
/10 minutes, density = 0.97? /r:rtl, Sp value = 8.06 (td/crl)'A) 100 parts and maleic anhydride kraft polyethylene (maleic anhydride content = 3.3 wt) as a thermoplastic polymer (maleic anhydride content = 3.3 wt), -C-O
- group = 0.67 minol equivalent/2, Mw = 2
700, density = 0.94 t lad, Sp value = 8
．． 06 parts mlad)') 10 parts and 5 parts of oleic acid as an organic compound that reacts with a basic substance to become an anionic surfactant are placed in a pressurized Ni-Goo, and melt-kneaded at 140C for 30 minutes.

Next, 20 parts of alkaline water containing 1.68 parts (1.0 chemical equivalents) of potassium hydroxide, which is necessary to neutralize all the carboxylic acids in the thermoplastic polymer and organic compound, was added to the pump connected to the kneader. The kneader was press-fitted for 5 minutes.The pressure inside the kneader became 6.2/cr/lG.

After continuing kneading for 60 minutes, the kneader was cooled to 60C and the contents were taken out. The contents were a white solid.

This white solid was filled into a 1 crn cubic container, and its electrical resistance value was measured and found to be 10,000α. Further, 8 parts of the white solid was poured into 10 parts of water, and after stirring with a turbine blade stirrer, the dispersion was filtered through a 100mezh wire mesh, but no residue was observed. %, viscosity 150cp
The pH was 10.5, and the size of the dispersed particles was determined by Coulter.
When measured with a counter, the average particle size was 0.5μ. In addition, when the carboxylic acid salt produced in the thermoplastic polymer was quantified using an infrared spectrophotometer, it was found to be 0 in terms of -C-0- group.
．． It was 50 myrwL equivalent/2.

Examples 2 to 16° The composition ratios shown in Table 1 were the same as in Example 1.

The results are shown in Table 1.

Example 14゜Co-rotating intermeshing twin screw extruder (manufactured by Ikugai Iron Works,
100/101 of the ethylene-vinyl acetate copolymer resin, maleic anhydride kraft polyethylene, and oleic acid used in Example 1 from the hopper of PCM-50L/D=20).
A mixture with a ratio of 5 parts/hour was supplied at a rate of 115 parts/hour, and a 23% aqueous solution of potassium hydroxide was continuously supplied at a rate of 6 parts/hour from the supply port provided in the vent part of the same extruder, followed by heating. Continuous extrusion was carried out at a temperature of 90C.

The product was a white solid whose properties are shown in Table 1. Example 15 In Example 1, 20 parts of alkaline water in which 1.38 parts of potassium hydroxide was dissolved was pumped in, and then 90 parts of alkaline water was added. A portion of water was continuously injected to perform melt mixing.

Thereafter, the kneader was cooled and the contents were taken out. The contents are a white liquid with resin uniformly dispersed, and the solid content is 49.
urt'16, viscosity 143 CJ Cpsr, pH1
0.8, the average size of the dispersed particles was 0.6μ.

Further, when the produced carboxylic acid salt in the thermoplastic polymer was quantified, it was found to be Q in terms of O group, 5 i -1 equivalent C-0-/1.

S Example 100 parts of the same ethylene-vinyl acetate copolymer resin used in Example 1 and 10 parts of the same maleic anhydride kraft polyethylene were placed in a pressure kneader, and heated at 140C for 30 minutes.
Melt knead for minutes.

Next, 0.68 parts of potassium hydroxide (
Using a pump connected to the kneader, 20 parts of freshly melted alkaline water (1.0 chemical equivalent) was injected into the kneader for 5 minutes. The same operations as in Example 1 were performed below. The product was a white solid with an electrical resistance of 7 x 10' ohms and an average particle size of 5.
．． It was 2μ.

Comparative Example 1゜In Example 1, 5 parts of potassium oleate was used instead of oleic acid, and the amount of potassium hydroxide was 0.3 parts, which is necessary to neutralize all the carboxylic acids in the maleic anhydride kraft polyethylene.
The procedure was the same as in Example 1 except that the amount was 8 parts. When the kneader was opened after cooling after injection of alkaline water, the resin and water were separated and no signs of pulverization were observed. Moreover, the electrical resistance was also 1010Ω·α or more.

Comparative Example 2 Same as Example 1 except that the thermoplastic polymer in Example 1 was not used and potassium hydroxide was used at 1.00 parts, which is necessary to neutralize all the carboxylic acids in oleic acid. It was the same.

When the kneader was opened after cooling after injecting alkaline water, the resin and water were separated, and no signs of pulverization were observed. Further, the electrical resistance was also 1010Ω·α or more.

*1 Vinyl acetate content 19wt, MFR=150r
/10 min, density = 0.97 f /crIi, Sp
Value=8,06 (a/atl)y2 *2 Density=0.915 P/cr/iSMFR=70
f/-10 minutes, sp value=7. s o <a117at
x) Tokyo> Ethylene content 96 tons, MFR=15f
/10 min, density = 0.89 f /crIl, Sp
Value, = 7.84 < cd/d) 3 $4 Maleic anhydride content 3.6 wt%, #171 = 27
00, density = 0.94 g/ctd, SP value = 8.06
(d/d) i, 0 -C-0- group = 0.67 mynal equivalent/2*5
A-C polyethylene 5120 manufactured by Allied Chemical ■, acrylic acid content 15wt, viscosity (140C) = 65
0 cps, density=0.93f/all, Sp value=
8.5 s <*7ati)'x, -C-〇- group=
2. i 4 wrwl equivalent/l*6 Nippon Soda ■Nl
5SO-PB B#-1015, maleic anhydride content i
3 wt%, viscosity (45tZ') = 800 cps
, density = 0.86P/cr/1, sp value = 9.53 (7
/dAshi, O-C-0- group=2.65 Md equivalent/? *7 Ethyl acrylate content 28 wt%, MFR=
200P710 minutes, density = 0.93, SP value = -C-O
- group = 2.80 Md equivalent/f 8 Neutralized or saponified O -C-0- group equivalent value per 1 gram of thermoplastic polymer

[Brief explanation of the drawing]

FIG. 1 is an electron micrograph showing the particle structure of the solid aqueous dispersion according to the present invention, and FIG. 2 shows the particle structure of the solid aqueous dispersion shown in FIG. 1 after being redispersed in water and dried. It is an electron micrograph shown.

Claims (7)

[Claims] (1) (i) Thermoplastic resin; (ii) water containing carboxylate groups bonded to the polymer chain at a concentration of 0.1 to 5 mmol equivalents of -C-O- groups per gram of polymer; It contains an insoluble thermoplastic polymer, (iii) an anionic surfactant, and (iv) water, and is an apparent solid with a water content of 3 to 25% by weight, and an electrical resistance value of 10^6Ω. - An aqueous dispersion characterized by having a particle size of less than cm and having a property that the solid content is uniformly dispersed in the aqueous phase as fine particles by adding water. (2) The aqueous dispersion according to claim 1, wherein the thermoplastic resin (i) is an olefin resin. (3) Thermoplastic polymer (ii) contains monomer components common to the monomers constituting thermoplastic resin (i), and an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid at least partially neutralized or saponified. The aqueous dispersion according to claim 1, which is a copolymer comprising an anhydride or an ester monomer component thereof. (4) Thermoplastic resin (i) and thermoplastic polymer (ii)
The solubility parameter (Sp value) of the polymer (ii) before being neutralized or saponified is 2 [axl
/cm^3]^1^/^2 or less. (5) Claims in which the thermoplastic polymer (ii) is present in an amount of 1 to 60 parts by weight and the anionic surfactant (iii) is present in an amount of 1 to 40 parts by weight based on 100 parts by weight of the thermoplastic resin (i). Aqueous dispersion according to item 1. (6) The aqueous dispersion according to claim 1, wherein the solid content is present in the form of an oil-in-water dispersion with a number average particle size of 5 μm or less. (7) (i) a thermoplastic resin; (ii) a neutralizable and/or saponifiable carboxylic acid, anhydride or ester group bonded to the polymer chain;
per gram of polymer ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
A step of melt-kneading a thermoplastic polymer containing a concentration of 0.1 mmol equivalent or more in terms of base, and (iii) an organic compound that reacts with a basic substance to become an anionic surfactant, and adding a base to the melt-kneaded product. The thermoplastic polymer (i
) in terms of -C-O- group per gram of polymer.
to 5 mmol equivalents of carboxylic acid salt groups and phase inversion of the resin solids to an aqueous dispersion, characterized in that an additional amount of water is added to the aqueous dispersion if necessary. Method for producing an aqueous dispersion.