JPS6211544A - Aqueous dispersed material and its preparation - Google Patents

Abstract

PURPOSE:To disperse a resin solid finely and uniformly by melting and kneading a thermoplastic resin, a specified thermoplastic polymer, an anionic surfactant and natural oil or the like having specified mean molecular weight and thereafter adding water, melting and kneading the mixture. CONSTITUTION:(a) A thermoplastic resin, (b) a thermoplastic polymer contg. 0.1-5 millimol equivalent carboxylic acid bonded to a polymer chain expressed in terms of COOH group per 1g polymer, (c) an anionic surfactant and (d) natural oil or synthetic oil having >=200 numerical mean mol.wt. are melted and kneaded. Water is added to the melted and kneaded material and both the melting and the kneading are performed to form an aq. dispersed material. Still further when the above-mentioned (c) is an organic compd. made to an anionic surfactant by allowing it to react with a basic substance, it is necessary that the organic compd. is converted into the anionic surfactant by adding the basic substance.

Description

Detailed Description of the Invention The present invention relates to an aqueous dispersion of a resin and a method for producing the same, and more specifically to an aqueous dispersion of a hydrophobic resin that can form a thin resin film with excellent processability. Regarding its manufacturing method. Also 1
The present invention relates to an aqueous dispersion suitable for forming a soft and elastic rubber coating and a method for producing the same.

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) having a moisture content of about 30% by weight or more can be used on surfaces such as paper, fibers, plastic molded products, wood, metal, etc. It is applied and dried to form a resin film, giving the base material water resistance, oil resistance, and chemical resistance.
It is also used as a heat sealant. 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, ease of handling, etc., 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 have a cylindrical appearance are also known.

In other words, it is in the form of a body 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 at most 2 to 30% if it does contain water. 3% by weight, so there is no need to worry about freezing even at low temperatures, making it easy to package and transport.・It also has the advantage of requiring 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 cementate, mortar, and gypsum, 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, in order 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 aggregate into clumps 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 may become high or the physical properties of the coating film may 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. There is a problem that the physical properties of the film deteriorate, and since the water containing a lot of waste is evaporated, it is not economical because it causes a lot of energy loss. It is desired to develop techniques for producing aqueous dispersions.

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

That is, conventionally known manufacturing methods can be broadly divided into a method in which emulsion polymerization is carried out in the presence of an emulsifier in an aqueous medium, and a method in which a molten resin and an aqueous medium are stirred and mixed in a shearing force. The former method has problems such as the types of resins that can be used are limited, and the control of the polymerization reaction is complicated and the apparatus H is complicated. - The method of the method can be applied to any resin, and has the advantage that it 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 coating film obtained using the aqueous dispersion produced by this method contains a water-soluble polymer and therefore has problems such as low mechanical strength and poor water resistance. Japanese Patent Publication No. 57-23703 discloses a method of dispersing in water a kneaded material of polypropylene, a surfactant, and a dispersant selected from water-soluble or water-swellable polymers. However, this method has the problem that the diameter of the dispersed particles is relatively large, and petroleum resin must be used in combination to reduce the particle diameter, resulting in the resulting coating being sticky. Also, JP-A-5
No. 6-2149 discloses a method for 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 coating properties. Moreover, the aqueous dispersion obtained by this method has a water content of 30% by weight or more. As yet another method,
The technique disclosed in No. 207, that is, the method of melt-kneading a polyolefin and a carboxyl group-containing polyolefin, supplying it to hot water containing a basic substance, and applying a shearing force to obtain a dispersion liquid, Although this is a suitable method because it does not contain swelling subaggregates and does not use petroleum resin, there is a problem in that the type of raw resin is limited in order to produce particles with small dispersed particle sizes. 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 anti-pressure properties.

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, there is also a desire for the development of a method for freely and extremely easily producing aqueous dispersions and aqueous dispersions without involving any special steps.

Children and Objects of the Invention The inventors have compounded a thermoplastic resin, a thermoplastic polymer having a limited amount of carboxylate groups, an anionic surfactant, and a natural or synthetic oil.

When water is added to this kneaded composition and melt-kneaded, phase inversion occurs even in the presence of a small amount of water.

That is, a conversion occurs in which water becomes a dispersion medium phase and the solid content becomes a dispersed particle phase, and the aforementioned swelling or conversion action of the oil agent enables dispersion into fine particles and improves the processability of the resin. The inventors of the present invention have discovered that it is also possible to apply thin coatings. Furthermore, the inventors have discovered that a resin that can be crosslinked and vulcanized, such as an ethylene-propylene-nonconjugated diene terpolymer, can be used as a thermoplastic material. For example, it has been found that a soft rubber can be obtained by oil extension without bleed-out of the oil agent.

That is, one object of the present invention is to provide an in-water dispersion in which the resin solid content is swollen or softened with an oil agent and becomes an oil-in-water (0/W) type dispersion with fine particle size, and a method for producing the same. It is in.

Another object of the present invention is to provide an aqueous dispersion which has improved resin processability and which allows thin coating.

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

According to the present invention, (1) a thermo-OT plastic resin, (11) a carboxylate group bonded to a polymer chain is 0.
a thermoplastic polymer at a concentration of 1 to 5 millimolar equivalents; (Y) an anionic surfactant; (1v) a natural or synthetic oil having a molecular weight of 1200 or more; and (V) water.

There is provided an aqueous dispersion comprising: a water content of 3 to 90% by weight and in which the resin solids are present as a finely dispersed particle phase.

According to the invention, furthermore, (a) Thermoplastic resin.

(b) Neutralizable and/or saponifiable groups of carboxylic acid, its anhydride or its ester bonded to the polymer chain in an amount of 0.1 mmol (calculated as 10-0-groups) per gram of polymer. Contains a thermoplastic polymer in a concentration of 0.1 to 5 millimole equivalents, or carboxylic acid salt groups bonded to the polymer chain, in a concentration of 0.1 to 5 millimole equivalents per 1 duram of the polymer. a thermoplastic polymer, (c) an anionic surfactant or an organic compound that reacts with a basic substance to become an anionic surfactant, and (d) a natural or synthetic oil with a number average molecular weight of 200 or higher.

When (C) is an organic compound, a basic substance is added to convert it into an anionic surfactant.

Furthermore, if the thermoplastic polymer is not neutralized, a step of forming carboxylic acid salt groups in the thermoplastic polymer in an amount of 0.1 to 5 mmol equivalent per gram of the polymer, and adding water to the melt-kneaded product. Provided is a method for producing an aqueous dispersion characterized in that the steps of melt-kneading and forming an aqueous dispersion are performed simultaneously or sequentially.

Moxibustion and 1υL recitation The invention will be explained in detail below.

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 lacks dispersibility in water itself. Resin, such as low density polyethylene, high density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-
Pentene or ethylene, propylene, l-butene,
Polyolefins such as random or block covalent polymers of α-olefins such as 4-methyl-1-pentene,
Ethylene/vinyl compound copolymers such as ethylene/vinyl acetate copolymer, ethylene/vinyl alcohol copolymer, ethylene Φ vinyl chloride copolymer, polystyrene, acrylonitrile/styrene copolymer, ABS, α-methylstyrene/styrene Styrenic resins such as copolymers, polyvinyl chloride, polyvinylidene chloride, vinyl chloride/vinylizo chloride copolymers, polyvinyl compounds such as polymethyl acrylate, polymethyl methacrylate, nylon 6, nylon 6-6, Polyamides such as nylon 6-10, nylon 11, nylon 12, polyethylene terephthalate,
Any resin such as thermoplastic polyester such as polybutylene terephthalate, polycarbonate, polyphenylene oxide, or a mixture thereof may be used.

Among these thermoplastic resins, olefin resins are particularly preferred, such as polyethylene, polypropylene,
Poly-1-butene, poly-3-methyl-1-butene, poly-4-methyl-1-pentene, poly-3-methyl-1
-Pentene, ethylene/propylene co-IL ethylene/1
-butene coffi, ethylene, propylene, 1-butene, 3 represented by propylene/1-butene copolymer
-Methyl-1-butene, 4-methyl-1-pentene, 3
-Methyl-1-pentene, 1-heptene.

- Single or copolymers of α-olefins such as hexene, needlecene, and 1-dodecene, or α-olefins represented by ethylene-butadiene copolymers, ethylene, ethylidene/lupornene copolymers, and conjugated dienes or non-conjugated dienes. Copolymer with diene, or ethylene/propylene/butashev ternary copolymer, ethylene/propylene dicyclopentadiene ternary copolymer, ethylene/propylene/ethylidenenorbornene ternary copolymer, ethylene/propylene-1 , 5-hexadiene terpolymer, and the like, and a conjugated diene or a non-conjugated diene. Particularly preferred among these are α-olefin homopolymers or copolymers.

In the present invention, any thermoplastic resin with melt flowability is suitable as long as it is the above-mentioned thermoplastic resin, but in particular, a thermoplastic resin with melt flowability such that the melt flow rate (ASTM D 1238. MFR) is less than Ig/login is suitable. The effect is even more pronounced when applied to extremely poor resins.

According to the method of the present invention, such materials with poor fluidity can be dispersed at extremely low temperatures compared to conventionally known methods.

The thermoplastic polymer (11), which is another component constituting the aqueous dispersion of the present invention, is a carboxylic acid group that is neutralized or unneutralized in the above-mentioned thermoplastic resin or a monomer constituting it. A monomer having a saponified or non-saponified carboxylic acid ester group is introduced by means of a graft copolymer, block copolymer, random copolymer, etc. is subjected to a neutralization reaction or saponification reaction with a basic substance, and the total amount of carboxylic acid salts formed in the polymer is 0.1 to 5a + io 1 equivalent per 1 gram of polymer, especially 0.2
It was adjusted to contain ~4 mmo I equivalent. 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, and the hydrothermoplastic polymer (11) The thermoplastic phase m(i ) does not show the function of helping the dispersion and cannot be made into a good dispersion.
Moreover, if it is water-soluble or water-swellable, the physical properties of the coating film will deteriorate.

When the thermoplastic subpolymer (11) is obtained by post-neutralization or post-saponification, the raw material polymer is, for example, a monomer common to the monomer constituting the thermoplastic resin (i) described above. ,
In particular, it is a copolymer of α-olefin and ethylenically unsaturated carboxylic acid or its ester, and the unsaturated carboxylic acids include (meth)acrylic acid, maleic acid, and fumaric acid.

Tetrahydroheptalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocys-bicyclo(2,2,1)hept-5-ene-2,3-
dicarboxylic acid), 1M aqueous luic acid, citraconic anhydride, etc., monoesters of the above unsaturated carboxylic acids such as methyl, ethyl, and propyl as unsaturated carboxylic acid esters,
Examples include diester. 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 copolymerized with the thermoplastic resin (1), for example, an olefinic resin. It will be obvious to those skilled in the art that thermoplastic polymers for post-neutralization or post-saponification can be obtained by doing so.

Naturally, the amount of monomers of these ethylenically unsaturated carboxylic acids, their anhydrides, or esters introduced must be above the concentration of the carboxylic acid salt specified in the claim. must have a minimum concentration of 0.1 mmol equivalents/Ig polymer as -C-O- groups,
The range is preferably from 0.1 to 5 mmol/St/g polymer.

Basic substances used for neutralization and saponification include substances that act as bases in water such as alkali metals, alkaline earth metals, ammonia and amines, oxides, hydroxides, weak acid salts, and hydrides of alkali metals. , substances that act as bases in water such as oxides, hydroxides, weak acid salts, and hydrides of alkaline earth metals, and compounds 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.

(2) Examples of amines include inorganic amines such as hydroxylamine and hydrazine, methylamine, ethylamine, ethanolamine, and cyclohexylamine.

(3) oxides of alkali metals and alkaline earth metals,
Examples of hydroxides and hydrides include sodium oxide, sodium peroxide, potassium sulfate, 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 hydrogen carbonate, potassium hydrogen carbonate, r&calcium hydrogen oxide,
Sodium acetate, potassium acetate, calcium acetate, (5) Ammonia and amine compounds.

For example, ammonium hydroxide, quaternary ammonium compounds such as tetramethylammonium hydroxide, hydrazine permanent product, etc. can be mentioned.

As the carboxylic acid group or carboxylic acid ester group that has been neutralized or saponified with 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 (11) 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 resin in the main chain should be selected. For example, when using polyethylene olefin, ethylene-vinyl acetate copolymer, etc., these maleic acid kraft products, ethylene/(meth)acrylic acid copolymer, ethylene/(meth)methyl acrylate copolymer, etc. It is preferable to use a neutralized or saponified product. One guideline for selecting a suitable thermoplastic polymer is the solubility parameter (Sp value), that is, the raw material composite before being neutralized or saponified. and thermoplastic resin (1). The difference in solubility parameters is 2
[. al/. 3] Within y4, especially l (cal/cm3
)” is preferable.

In this specification, the solubility parameter (Sp value) is a value defined as the square value of the cohesive energy density. This solubility parameter defines the contribution Vi to the molar volume of the atomic group and the cohesive energy En of the atomic group as D, W, VanKlevelen'Prop
ertieSofPoly+mar,s”(Else
vier.

Using the values described in (1972), the formula Calculated from.

Examples of the anionic surfactant (iii) include the first
Higher fatty acid salt treated, second treated higher fatty acid salt, first treated higher alcohol sulfate ester salt, second treated higher alcohol sulfate ester salt, first edge higher alkyl sulfonate, second edge higher alkyl sulfonate, higher alkyl disulfonate,
Sulfonated higher fatty acid salts, higher fatty acid sulfate ester salts,
Higher fatty acid ester sulfonate, Vt acid ester salt of higher alcohol ether, sulfonate of higher alcohol ether, fulkyrolated sulfate ester salt of higher fatty acid amide, alkylbenzene sulfonate, alkylphenol sulfonate, alkylnaphthalene sulfonate, Any anionic surfactant such as alkylbenzimidazole sulfonate may be used. More specific compound names of these surfactants are disclosed, for example, in "Synthetic Surfactants" by Hiroshi Horiguchi (published by Sankyo Publishing in 1972).

Suitable anionic surfactants include higher fatty acids, especially salts of saturated or unsaturated higher fatty acids having 10 to 20 carbon atoms, especially alkali metal salts,
More specifically, saturated fatty acids such as capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, and arachidic acid, linderic acid, tuzic acid, petroselic acid, oleic acid, linoleic acid, and linoleic acid. Examples thereof include acids, unsaturated fatty acids such as arachidonic acid, and alkali metal salts of mixtures thereof.

Natural oils or synthetic oils (1v) include mineral lubricating oils such as spindle oil and machine oil; mineral oils such as liquid paraffin, electrical insulation oil, and process oil; alkylbenzene oils, diolefin oils, diester oils, and alkyl naphthinates. Synthetic oils such as oil: castor oil, linseed oil, rapeseed oil, coconut oil,
Vegetable oils such as tall oil are used. These oils are
It 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 invention, each of the above-mentioned components is present in a certain range of quantitative ratios. That is, thermoplastic resin (+)
1 to 60 parts of thermoplastic polymer (11) per 100 parts by weight
Parts by weight, especially 2 to 50 parts by weight, anionic surfactant (
iii) l to 40 parts by weight, especially 2 to 30 ffl
parts and the oil agent (1v) are preferably present in a quantitative ratio of 10 to 500 parts by weight, especially 20 to 300 parts by weight.

When component (11) is below this ratio, the thermoplastic resin is not sufficiently dispersed, and when it is below this ratio, the dispersion results in a dispersion that differs from the original properties of the desired thermoplastic resin. When component (iii) 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. Ingredients (1v
) below this ratio, it becomes difficult to soften and disperse the resin solid content as intended in the present invention, and when it exceeds this ratio, the resin solid content becomes too soft and the physical properties of the final coating deteriorate. I come to do it.

The aqueous dispersion of the present invention further contains water in addition to the above structure, and the water content is 3 to 90% in the aqueous dispersion.
Weight%. If the water content is less than 3% by weight, an aqueous dispersion cannot be obtained, and if it exceeds 90% by weight, the solid content concentration is too low, which is disadvantageous in terms of drying energy costs, transportation, storage, etc. Become. Moisture content is 3 to 25
In the range of % by weight, the aqueous dispersion exhibits properties as an apparent solid or paste, while above 35% by weight it exhibits properties as an aqueous dispersion. Moisture content is between 5 and 70
It is desirable that the amount is within the range of % by weight.

The structure of the aqueous powder and the present invention are characterized by the above-mentioned thermoplastic resin (1), carboxylate type thermoplastic polymer (11), anionic surfactant (iii), and oil agent (1v). The molten cross wire composition is 3
A phase inversion phenomenon occurs in the presence of an extremely small amount of water of 25% by weight, and an o/W type dispersion form in which water becomes a dispersion medium phase and resin solids become a finely dispersed particle phase is stably fixed. This is based on the discovery that Of course, in the present invention, an additional amount of water is added directly during the manufacturing process to a solid or pasty aqueous dispersion, and an additional amount of water is added at a location other than the manufacturing process to form a liquid dispersion. However, even in these cases, it is necessary to pay attention to the fact that the phase inversion phenomenon itself is carried out in the presence of a small amount of water of 3 to 25%.

Observation of the particle structure of the solid aqueous dispersion according to the present invention using an electron microscope shows that the secondary particles of the solid aqueous dispersion according to the present invention have a structure in which slightly deformed fine primary particles aggregate quite densely. I understand. However, the fact that these secondary particles have an oil-in-water type dispersion form is proven from the following various facts.

Another property of the solid to paste aqueous dispersion is:

The electrical resistance value is 106Ω・cm or less, and most of them are 105
Ω11cffl 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 same as that of the resin (generally 107 to 1018 Ω-C).
11, most exhibit 1010 ΩmCM or more).

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

The electrical resistance value is measured here by pasting 1 cm electrodes on the inner sides of opposing circles in a 1 cm cubic insulator container and press-fitting the dispersion, and then measuring the resistance value between the electrodes using a 60H2 AC resistance meter.
Depends on the method of measurement. To measure the state of dispersion by adding water, the dispersion is poured into cold water, stirred with an ordinary stirrer equipped with turbine blades, and then filtered through a wire mesh of about 100 ies, and the particles in the dispersion are filtered using jII# & mirror. This can be confirmed by observing with etc.

The dispersed particles of the dispersion of the present invention are substantially spherical particles,
The average particle size is in the range of less than 10 l, often less than 5 l.

This particle size can be measured using a Coulter counter.

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

The aqueous dispersion of the present invention has a low water content and appears to be solid or paste-like, and can be easily turned into an aqueous dispersion by adding water, so there is no risk of freezing, saving space in storage areas, and facilitating transportation. It has characteristics such as ease of packaging. Furthermore, the diameter can be mixed into powders and granules that do not want to come into contact with water, such as cement, mortar, and plaster, and can be used to form water-resistant, oil-resistant, and chemical crystal-resistant films on various materials by re-water dispersion.
It can also be used 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.

Furthermore, the aqueous dispersion in liquid form can be used as is or diluted as desired for applications such as the coating described above.

In the aqueous dispersion of the present invention, the resin solid particles are in a state IE softened by the oil agent, and the processability of the resin is improved, and the particles themselves are made finer. It has the advantage of being coatable. Furthermore, there is also the advantage that a combination of ethylene-glopyrene-diene is used as the thermoplastic resin (1), and by crosslinking it, it becomes a soft and elastic rubber, which is suitable as the rubber component of AES resin.

In the present invention, the above (t), (ii),
Components (iii) and (1v) are melt-kneaded. In this case, a thermoplastic resin (ii) having a carboxylate group
Instead of using a thermoplastic polymer which is neutralizable and/or saponifiable and contains a carboxylic acid, its anhydride or its anhydride in a concentration of 0.1 millimolar equivalent or more in terms of groups, bound to one polymer chain. , neutralization and/or saponification may be performed later with a basic substance, or the anionic surfactant (mountain)
Instead, crosstalk may be performed using an organic compound that becomes an anionic surfactant by neutralization with a basic substance, and neutralization may be performed afterwards.

In this manufacturing method, the resins are melt-kneaded, and the temperature during melt-kneading is higher than the melting point of the higher resin used, preferably higher than the temperature at which the melt viscosity is 105 poise or lower.

In the second step, water is added to the melt-kneaded material to phase invert the resin solid content into dispersed particles. The amount of water added is within the range described above. In this second step, if 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 necessary basic substance. 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 first step and the second step described above may be performed sequentially or simultaneously.

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

The aqueous dispersion produced by sequentially adding ice 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.

In producing this dispersion, 1. Various auxiliary materials that can be used in the aqueous dispersion, such as dispersants such as nonionic surfactants, emulsifiers, stabilizers, wetting agents, thickeners, foaming agents, and It goes without saying that foaming agents, coagulants, gelling agents, anti-aging agents, plasticizers, fillers, coloring agents, flavoring agents, anti-blocking agents, etc. may be used in combination.

Fish village! According to the present invention, as described in detail, thermoplastic resin (1
), thermoplastic polymers containing carboxylate groups (ii
), anionic surfactant (iii) and oil agent (1v)
An aqueous dispersion in which the resin solid content is phase-inverted into finely dispersed particles can be easily obtained by a simple operation of melt-kneading, adding water, and continuing cross-mixing. In addition, the obtained aqueous dispersion has the advantage that monodispersed resin particles are softened, and it has excellent processability, can be coated with a thin film, and can be easily processed into soft rubber.

X-Rin-1 Preferred examples of the present invention are 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 vt%, M = 2700, density = ., 94
g/c yo318. Value=8. . 6(.al/c+s3)%
.

100 parts by weight of 10-0-group = 0.67 mmol equivalent/g) was put into a normal pressure type Nigu, and melt-kneaded at 140°C.

Next, 3.76 parts by weight of potassium hydroxide, 1.0 chemical equivalent of -crystalline-8- group) and 12.5 parts by weight of dissolved alkaline water were gradually added dropwise, and after the water evaporated,
Cross-wire for another 30 minutes and cool.

When the produced carboxylic acid salt was measured using an infrared spectrophotometer, it was found to be 0.65 aueol equivalent/g in terms of Lo-group.

Reference Example 2 Maleated polybutadiene (Nl5 manufactured by Nippon Soa Co., Ltd.)
SO-Pa BN-1015 anhydrous maleic contact 1113
wt%, viscosity (45°C) = 800 cpg, density = 0.8
8g/arm3, Sp value = 9.53 (cal/
cm3) LA, -A-〇- group = 2.85 mmal weight/1 g), alkaline water 35 in which 100 B parts of sodium hydroxide (1.0 m chemical equivalent to -C-0- group) was dissolved. The procedure was the same as in Reference Example 1 except that .3 parts by weight was added dropwise.

When the produced carboxylic acid salt was measured, it was 2.58 mmo
I equivalent/g.

Reference example 3゜Ethylene-ethyl acrylate resin (contains ethyl acrylate, 128 wt%, MFR (190°C) = 200 g7
10 minutes, density 0.93g/cm3, Sp value = 8.
22 (cal/cm3)%.

Akane-〇-group = 2.80...1 equivalent/g) was used.
The procedure was the same as in Reference Example 1, except that 15 parts by weight of alkaline water in which 4.5 parts by weight of sodium hydroxide (0.4 chemical equivalents to the -C-O- group) was dissolved, and a saponification reaction was caused. to form a carboxylate salt.

When the produced carboxylic acid salt was measured, it was 1.10m
1′! Example 1゜(a) Ethylene-propylene copolymer elastomer (ethylene content 75 mo1%, MFR = 0) as thermoplastic resin
．． 2 g710 min, density = 0.88 g/ca3
, Sp value = 7.97 (cal/c+w3)! /L)
100 parts by weight (b) Maleic anhydride glutinated polyethylene (maleic anhydride content = 3.3 wt%, M
w=2700. Density = 0.94g/cm3.

'A11 Sp value = 8.08 (cal/cm3),
-C-0- group = 0. fi7mmol per Jit/g) 1
0 parts by weight (C) 5 parts by weight of oleic acid as an organic compound that reacts with basic substances to become an anionic surfactant (d) Diana Process Oil PW-90 (as a mineral oil)
(manufactured by Idemitsu Kosan, average molecular weight: 539) Pour 100 stacked parts into a Ni-Goo and knead at 125°C for 30 minutes. Potassium hydroxide necessary to neutralize all the carboxylic acids of the zero-order thermoplastic polymer and the organic compound. 1.38 fi parts (1,0
15 parts by weight of Flukaline water in which a chemical equivalent (chemical equivalent) was dissolved was injected for 5 minutes using a pump connected to a Ni-Goo. The pressure inside the Nigu became 3 Kg/cm'G.

After continuing to mix the mixture for 30 minutes, the Nigu was cooled to 60°C and opened, and the contents were white and viscous.

To this, 215 parts by weight of water was added and stirred to obtain a dispersion with a water content of 52%, a viscosity of 95 cps, and a pH of 10.2.The size of the zero-dispersion particles was measured using a Coulter counter, and the average particle size was 1.9 l. Ta.

Further, when the produced carboxylic acid salt in the thermoplastic polymer was quantified using an infrared spectrophotometer, it was found to be 0.5 mmol equivalent/g in terms of 〇1&〇- groups.

Examples 2 to 7° The composition ratios shown in Table 1 were the same as in Example 1.

The results are shown in Table 1.

Example 8 Co-rotating intermeshing twin screw extruder with two vents (PCM-45, 1/D=30, manufactured by Ikegai Iron Works)
A mixture of the ethylene-propylene copolymer elastomer, maleic anhydride grafted polyethylene, and oleic acid used in Example 1 in a ratio of 100/1015 parts by weight was fed from the hopper of the same extruder at a rate of 115 parts by weight/hour. Process oil Pw-9 is supplied from the supply port provided in one vent part.
0 at a rate of 100 parts by weight/hour, and a 9.2% aqueous solution of potassium hydroxide was added at a rate of 100 parts by weight/hour through the supply port provided in the second vent part.
It was continuously supplied by a pump at a rate of 5 parts by weight/hour and extruded continuously at a heating temperature of 80°C. The product was a white viscous substance, and its properties are shown in Table 1.

Claims (2)

[Claims] (1) (i) Thermoplastic resin, (ii) Carboxylate group bonded to the polymer chain per 1 gram of polymer ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ 0.1 to 5 mmol equivalent in terms of group (iii) an anionic surfactant; (iv) a natural or synthetic oil having a number average molecular weight of 200 or more; and (v) water, with a water content of 3. An aqueous dispersion in which the resin solids are present as a finely dispersed particle phase in an amount of from 90% by weight. (2) (a) a thermoplastic resin; (b) a neutralizable and/or saponifiable carboxylic acid, its anhydride or its ester group bonded to the polymer chain per gram of the polymer; There are chemical formulas, tables, etc. ▼ Thermoplastic polymer containing a concentration of 0.1 mmol equivalent or more in terms of groups, or carboxylic acid salt groups bonded to the polymer chain per gram of polymer ▲ Numerical formulas, chemical formulas, tables, etc. ▼A thermoplastic polymer containing a concentration of 0.1 to 5 millimolar equivalents in terms of groups, (c) an anionic surfactant or an organic compound that reacts with a basic substance to become an anionic surfactant, and (d) A natural oil or a synthetic oil with a number average molecular weight of 200 or more is melt-kneaded, and if (c) is an organic compound, a basic substance is added to convert it into an anionic surfactant, and the thermoplastic polymer is further added to the anionic surfactant. In the case of sum, a basic substance is added to the thermoplastic polymer to form 0.1 to 5 mmol equivalents of carboxylate groups per gram of polymer in three steps,
and a step of adding water to the melt-kneaded product and melt-kneading it to form an aqueous dispersion, either simultaneously or sequentially.