JPH01306451A - Modified ethylenic polymer fine particle dispersion and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title dispersion suitable as a blending agent for printing ink by neutralizing an unsaturated carboxylic acid-modified ethylenic polymer with a basic substance to afford an aqueous dispersion, neutralizing the dispersion with an acid to give an aggregate and re-dispersing the resultant aggregate into an organic solvent. CONSTITUTION:(A) (A part of) carboxyl in a modified ethylenic polymer modified with an unsaturated carboxylic acid (derivative) and having 0.3-75mg KOH/g acid value is neutralized with (B) a basic substance to disperse fine particles having 0.3-20mu average dispersing particle size into an aqueous dispersing medium. (C) An acid of an amount required for neutralizing a basic substance consumed in at least neutralization is added to the resultant aqueous dispersion to aggregate the above-mentioned fine particle and separate the aggregate from water and the resultant aggregate is re-dispersed into (E) a hydrocarbon based organic solvent to provide the aimed dispersion.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a modified ethylene polymer fine particle dispersion and a method for producing the same. The present invention relates to a dispersion of ethylene polymer fine particles in a hydrocarbon organic solvent and a method for producing the same.

Traditionally, in order to improve the tackiness and abrasion resistance of oil-based printing inks, especially lithographic or offset printing inks, polyethylene wax and the like have been added to printing inks. In such cases, the waxes must be mixed uniformly into the printing ink.

As described above, known methods for uniformly blending waxes into printing ink include a method using pulverized wax, a method of kneading solid wax, and a method using wax crystallized in oil.

However, among the above-mentioned methods of blending wax into printing ink, the method of using pulverized wax or the method of kneading solid wax has a wide particle size distribution. There is a problem in that a clear printed image cannot be obtained with such printing ink, and there is also a problem in such a method that the desired effect cannot be obtained unless a large amount of wax is blended into the printing ink. Furthermore, the method using the crystallized wax described above has the problem that the viscosity of the crystallized wax is high, and therefore only a low concentration of the crystallized wax can be obtained, and a large amount needs to be blended into the printing ink.

On the other hand, as a method for producing a polymer dispersion for lithographic ink, JP-A-60-6730 discloses a method of coagulating a polymer-containing aqueous emulsion and adding a non-aqueous vehicle to the resulting coagulated emulsion. Then, a method (flushing method) for producing the dispersion by stirring a mixture of an emulsion coagulate and a non-aqueous vehicle until the aqueous phase is separated, and removing the thus separated aqueous phase is described. has been done.

However, since the above mixture has a fairly high viscosity, there are operational difficulties in that a powerful kneader is required to stir the mixture, and furthermore, the state of dispersion of the polymer particles is not necessarily good. .

By the way, JP-A No. 61-66723 discloses a method in which epoxy-based spherical particles obtained by curing an epoxy-based compound emulsion into particles with an amine-based compound are dispersed from a slurry into an organic solvent by a dispersion medium replacement method. A method for dispersing epoxy-based spherical particles in an organic solvent is disclosed.

Specifically, in this method, water and epoxy resin particles are separated by treating epoxy resin particles dispersed with a surfactant. In such a method in which particles in a dispersed state are directly passed through, the filtration efficiency becomes extremely low. Therefore, such a method has the problem that it is difficult to use in a method for manufacturing ink industrially.

Moreover, the epoxy resin obtained by this method does not have the effect of improving the abrasion resistance of the ink, and therefore cannot be used as an ink compounding agent.

The present invention is intended to solve the problems of the prior art as described above, and has the following objects.

That is, the first object of the present invention is to provide a dispersion in which fine particles of a modified ethylene polymer are uniformly dispersed in a hydrocarbon organic solvent, the fine particles of a modified ethylene polymer having a very low water content. An object of the present invention is to provide an organic solvent dispersion.

A second object of the present invention is to use modified ethylene polymer fine particles that can improve properties such as tackiness, abrasion resistance, anti-transfer performance, and slip resistance of the ink by adding a small amount to the ink. An object of the present invention is to provide an organic solvent dispersion.

A third object of the present invention is to provide a method for efficiently producing the modified ethylene polymer fine particle dispersion without using complicated operations or special equipment.

The modified ethylene polymer fine particle dispersion according to the present invention is a fine particle dispersion consisting of a hydrocarbon-based organic solvent and a fine particle resin dispersed in the solvent, in which the resin is non-containing. It consists of a modified ethylene polymer modified with a saturated carboxylic acid or one of its derivatives, the average dispersed particle size of the resin is 0.3 to 20 μm, and the acid value of the modified ethylene polymer is 0.3 to 20 μm. 75 - OH/g, the concentration of the modified ethylene polymer in the fine particle dispersion is 15 to 60% by weight, and the water content in the fine particle dispersion is 3% or less 1% or less. It is characterized by being

The method for producing a modified ethylene polymer fine particle dispersion according to the present invention comprises a modified ethylene polymer having an acid value of 0.3 to 75 -KOH/l that has been modified with an unsaturated carboxylic acid or a derivative thereof. , by neutralizing at least a part of the carboxyl groups constituting the polymer with a basic substance,
Adding an amount of acid necessary to neutralize at least the basic substance consumed in neutralization to an aqueous dispersion in which fine particles with an average dispersed particle size of 0.3 to 20 μm are dispersed in an aqueous dispersion medium. The fine particles are aggregated to separate the aggregates from water, and the resulting aggregates are washed in an undried state using a hydrophilic solvent, and then the aggregates are reconstituted in a hydrocarbon-based organic solvent. It is characterized by dispersion.

As mentioned above, the modified ethylene polymer fine particle dispersion according to the present invention has a specific ethylene polymer stably dispersed in the form of fine particles in a hydrocarbon organic solvent, and has a low water content. Modified ethylene polymer fine particle dispersion,
For example, by adding it to oil-based ink, the tackiness and abrasion resistance of the ink can be improved, and properties such as transfer prevention and slip resistance can also be improved. Moreover, the modified ethylene polymer fine particles, which are dispersoids, have a fine and uniform particle size, so the modified ethylene polymer fine particle dispersion in which these dispersoids are dispersed is compared to conventional waxes. The above effects can be obtained just by adding a small amount to oil-based ink.

Furthermore, according to the production method of the present invention, a modified ethylene polymer fine particle dispersion can be efficiently produced using commonly used equipment without requiring complicated operations or special equipment. I can do it.

The modified ethylene-based fine particle dispersion according to the present invention will be described below.

The modified ethylene polymer fine particle dispersion according to the present invention basically comprises a hydrocarbon organic solvent and a fine particle resin dispersed in the solvent.

This particulate resin is formed from a modified ethylene polymer modified with an unsaturated carboxylic acid or a derivative thereof.

The modified ethylene polymer used in the present invention has an acid value of 0.
．． 3-75■-OH/, preferably 1.5-3
If the acid value is less than 0.3 part g-OH/g, the particle size of the resulting modified ethylene polymer will become large, which is undesirable. 75■
If - is larger than OH/l, the hydrophilicity of the fine particles increases, making it difficult to redisperse them in a hydrocarbon-based organic solvent, which is not preferred.

In the modified ethylene polymer fine particle dispersion according to the present invention,
The average dispersed particle diameter (median diameter) of the dispersed modified ethylene polymer fine particles is 0.3 to 20 μm, preferably 2
~10 μm. If this average dispersed particle size is less than 0.3, it is undesirable because it is too small than the ink film thickness and abrasion resistance cannot be obtained, and if it exceeds 20 μm,
This is not preferable because the gloss of the ink surface deteriorates.

Further, the concentration of the above-mentioned functional ethylene polymer in the modified ethylene polymer fine particle dispersion according to the present invention is 15
~60% by weight, preferably 30-50% by weight. If this concentration is less than 1% by weight, the amount of the dispersion added to the ink will increase, and the amount of accompanying dispersion medium will be a non-negligible amount in the ink, making it necessary for the ink medium and the dispersion medium to be of the same type. , is undesirable because it reduces versatility.
Moreover, if it exceeds 60% by weight, the viscosity of the dispersion becomes hollow and workability becomes poor, which is not preferable.

The water content of the fine particle dispersion of the present invention is 3% by weight or less,
Preferably 2.0% by weight or less, particularly preferably 0 to 1.0% by weight.
It is within the 0 star% range. By controlling the moisture content to 3% by weight or less, it can be effectively used as a compounding agent for ink, for example. Another advantage is that the storage container can be easily rust-proofed. Therefore, if the moisture content exceeds Miesha%, for example, when used as an ink compounding agent, properties such as tackiness or abrasion resistance will not be sufficiently improved, and when used in gravure ink, color will come out. There is a tendency for this to occur.

The applicant has already filed an application for the invention of "Modified ethylene-based fine particle dispersion and method for producing the same" (
(Japanese Patent Application No. 62-201848), the invention according to this application generally involves adding an acid to an aqueous dispersion of fine particles made of a specific modified ethylene polymer to agglomerate the fine particles, and then removing water. This is a method for producing a modified ethylene-based fine particle dispersion by adding a hydrocarbon organic solvent to the aggregate to transfer the fine particles into the solvent phase without removing the aggregate, and then removing the aqueous phase.

Therefore, when the modified ethylene copolymer is transferred from the aqueous dispersion to the hydrocarbon dispersion medium, a small amount of water is also transferred, so the water content in the resulting dispersion is controlled to be below a certain level. The water content in this dispersion was usually about 5 to 20% by weight.

In the fine particle dispersion of the present invention, the dispersed particle size distribution of the fine particles is extremely sharp, and the fluctuation f and deviation value (σ) of the dispersed particle size are usually 20 μm or less, and particularly suitable manufacturing conditions must be set. The thickness can be reduced to 5 μm or less.

Further, in this modified ethylene polymer fine particle dispersion, the particle size of the fine particles is fine, and the ethylene polymer concentration can be varied within a certain range. Furthermore, even when the concentration is high, the viscosity of the dispersion hardly increases significantly.

For example, for a dispersion with a concentration of 40% by weight, the viscosity measured at a temperature of 25°C (measured using a B-type viscometer) is usually 1 to 1.
io, ooo centiboise, especially 20 to i, ooo centiboise.

Next, a method for producing a modified ethylene polymer fine particle dispersion according to the present invention will be explained.

゛Elene\mu゛The modified ethylene polymer used in the present invention is obtained by modifying the ethylene polymer with an unsaturated carboxylic acid or a derivative thereof.

The ethylene polymer modified in the present invention includes:
Homopolymer of ethylene, or ethylene and propylene,
1-butene, 3-methyl-1-butene, 4-methyl-1
-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-decene, 1-dodecene and other copolymers with α-olefins. Specifically, low density polyethylene, medium density polyethylene or high density polyethylene, linear low density polyethylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-propylene-butene-1 ternary copolymer. Polymer, ethylene-pentene-1 copolymer, ethylene-4-
Examples include methylpentene-1 copolymer, ethylene-(meth)acrylic acid ester copolymer, and ethylene-vinyl acetate copolymer.

The intrinsic viscosity "η" of such an unmodified ethylene polymer
is generally 5 dJ/r or less, preferably 0.04 to 1 d
It is desirable that it be within the range of J/g.

Among such unmodified ethylene polymers, polyethylene or By blending a modified fine particle dispersion of ethylene-propylene copolymer into a printing ink, it acts as a good wax.

Modified ethylene polymers obtained by modifying the above ethylene polymers include carboxyl-modified ethylene polymers modified to a predetermined concentration using unsaturated carboxylic acids or derivatives thereof, and carboxyl-modified ethylene polymers modified to high concentrations. There are compositions of a carboxyl-modified ethylene polymer and the above-mentioned unmodified ethylene polymer, and in the present invention, any of the above-mentioned modified ethylenes can be used.

In the present invention, the unsaturated carboxylic acid or its derivative used is a compound having a copolymerizable double bond and at least one carboxyl group, an acid anhydride of this compound, and a copolymerizable double bond. and a group capable of producing an ionized carboxyl group by reaction with a base (hereinafter referred to as
These may be collectively referred to as "ethylenically unsaturated carboxylic acid monomers").

Specifically, such ethylenically unsaturated carboxylic acid monomers include (meth)acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid. ■(endocys-bicyclo(2,2,1]hept-5-ene-
2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, ethylenically unsaturated carboxylic acids or their anhydrides, and methyl, ethyl,
Examples include monoesters such as globil, unsaturated carboxylic acid esters such as diesters, and among them, acrylic acid, methacrylic acid, or maleic anhydride is preferably used.

The modified ethylene polymer used in the present invention can be obtained by graft polymerizing, block polymerizing, or random polymerizing such an ethylenically unsaturated carboxylic acid monomer onto an ethylene polymer.

Such an ethylenically unsaturated carboxylic acid monomer is used in an amount such that the acid value of the resulting modified ethylene polymer falls within the above-mentioned range. In addition, when the ethylene polymer is modified at a high concentration as mentioned above, the modified ethylene polymer should be diluted with an unmodified ethylene polymer so that the acid value is within the above range. I can do it. For example, when using a mixture of a carboxyl-modified ethylene polymer and an unmodified ethylene polymer, the ratio of the carboxyl-modified ethylene polymer and the unmodified polymer is usually 1:99.
~50:50, preferably 3:97~20:8
They are mixed in a weight ratio of 0.

In addition, since the crystallinity of the resulting modified ethylene polymer changes depending on the amount of ethylenically unsaturated carboxylic acid monomer used, the solubility of the modified ethylene copolymer in the redispersion solvent described below should be considered. Accordingly, the amount of the ethylenically unsaturated carboxylic acid monomer to be used is determined.

In addition, when reacting the ethylenically unsaturated carboxylic acid monomer with the above copolymer, the amount of ethylenically unsaturated carboxylic acid monomer relative to the copolymer is usage amount is determined.

By doing so, it is possible to prevent the obtained modified ethylene polymer from being dissolved in the organic solvent, which will lead to redispersion as described later.

For example, when using a hydrocarbon organic solvent such as toluene or hexane as a redispersion agent, it is preferable to use an ethylenically unsaturated carboxylic acid monomer so that the degree of crystallinity is 45% or more. The intrinsic viscosity [η] (decalin solvent 1. measured at 35°C) of the copolymer obtained is generally 5 dN/sr or less, preferably 0.04
~1d, ll/r.

The carboxyl-modified ethylene polymer used in the present invention is preferably a modified ethylene polymer grafted with acrylic acid, methacrylic acid, or maleic anhydride.
Furthermore, the intrinsic viscosity [η
] is preferably within the range of 0.04 to 0.5 dJ/i.

The aqueous dispersion used in the present invention is prepared by melting the above-mentioned modified ethylene polymer, and then dissolving at least a portion of the carboxyl groups in the modified ethylene polymer into an aqueous dispersion containing a basic substance. It is obtained by neutralization in a medium and phase inversion of this polymer into an oil-in-water dispersion.

In this way, the modified ethylene polymer is melted, and then
By neutralizing at least a portion of the carboxyl groups of the modified ethylene polymer, the carboxyl groups are highly ionized in the aqueous dispersion medium, and as a result, water is drawn into the molten resin and there is no interaction with the aqueous phase. Anionic carboxyl groups are oriented at the interface to form an anionic emulsified fine particle dispersion. These fine particles exhibit self-emulsifying and self-dispersing properties due to the anionic carboxyl group, so
The average dispersed particle size of the fine particles is as fine as 0.03 to 20 μm, preferably 2 to 10 μm.

Further, the standard deviation value of the particle size is 20 μm or less, preferably 5 μm or less, and the particle size distribution is extremely sharp.

In the present invention, the basic substances used for neutralization to disperse the modified ethylene polymer in the form of fine particles include substances that act as bases in water, such as alkali metals, alkaline earth metals, ammonia, and amines. Substances that act as bases in water, such as alkali metal oxides, hydroxides, weak acid salts, and hydrides, alkaline earth metal oxides, hydroxides, weak acid salts, and hydrides; Examples include alkoxides. Specific examples of such substances are shown below.

Examples of alkali metals include sodium and potassium, and alkaline earth metals include:
Examples of amines include inorganic amines such as hydroxylamine and hydrazine, organic amines such as methylamine, ethylamine, ethanolamine and cyclohexylamine, and alkali metals and barium. Examples of alkaline earth metal oxides, 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 hydroxide, potassium hydride, calcium hydride, alkali metals and alkaline earth metals Examples of weak acid salts include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate, sodium acetate, potassium acetate, and calcium acetate, and examples of ammonia and amine compounds include, for example, Ammonium hydroxide, quaternary ammonium compounds, etc. can be mentioned, and examples of the quaternary ammonium compounds include tetramethylammonium hydroxide,
Examples include hydrazine hydrate.

The basic substance used for neutralization is desirably used in an amount such that at least a portion, preferably 20% or more, of the carboxyl groups are neutralized.

The water that forms the aqueous dispersion together with the modified ethylene polymer generally has a molecular weight of 100 to 9900, based on the modified ethylene polymer.
It is used in an amount of 400-900% by weight, preferably 400-900% by weight. The modified ethylene polymer and the water in which the basic substance is dissolved are preferably mixed at a temperature higher than the melting temperature of the modified ethylene polymer, preferably 130 to 200°C. The aqueous substance solution is preferably mixed under high shear stirring, and usually a kneader-1 pressurized homomixer or a single-screw or multi-screw extrusion kneader is used.

In the present invention, the aqueous dispersion obtained as described above preferably contains a surfactant.

The surfactant can be added to water when dispersing the modified ethylene polymer into fine particles, or can be added to the aqueous dispersion after dispersion.

By adding a surfactant in this manner, the aggregated modified ethylene polymer fine particles can be easily redispersed in the organic solvent.

In the present invention, when a surfactant is used, the surfactant has a hydrophilicity/lipophilicity balance (HL B').
nonionic surfactants with a low HL B of 12.
or less, more preferably 10 or less, particularly preferably 5 or less
A range of 10 nonionic surfactants is used. Specifically, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, fatty acid sucrose Among esters, alkylolamides, polyoxyalkylene block copolymers, and the like, surfactants having an HLB within the above range are used.

In these nonionic surfactants, H[ and B generally decrease as the content of polyoxyethylene units decreases, so by adjusting the number of moles of ethylene oxide added, the desired I-I L B nonionic interface An activator is obtained. The amount of nonionic surfactant added is 0.1 to 10% by weight, preferably 0.3% by weight based on the modified ethylene polymer.
A range of 2.0% by weight is desirable.

11 In the present invention, a dispersed modified ethylene-based Agglomerate the polymer particles.

In other words, when an acid is added to an aqueous dispersion, the base serving as the counter ion of the carboxyl anion is neutralized by the acid.
The carboxyl group becomes a hydrogen ion type with a low degree of ionization. For this reason, the modified ethylene polymer fine particles have a greatly reduced self-emulsifying property or self-dispersing property in water, and are agglomerated.

As the acid used for neutralizing the base, for example, 8Ii organic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, or organic acids such as various sulfonic acids are used. When such acids are used, the salts formed as a result of the neutralization reaction exhibit water solubility; such acids have I)H in the aqueous phase of usually 6 or less, preferably 2 to 2;
It is used in an amount such that 4.

In the present invention, the temperature of the aqueous dispersion during neutralization is sufficient at room temperature, but if desired, it may be heated to about 60'C. , a range of 5 to 50% by weight is preferred.

In the present invention, the thus aggregated modified ethylene polymer fine particles and water are separated.

The separation method is not particularly limited, but in the present invention, for example, methods such as filter filtration, centrifugation, and flotation separation are used. Note that if a centrifugal separator equipped with a filter is used, the water removal operation and the later-described washing operation of the wet cake with a hydrophilic solvent can be efficiently performed in the same apparatus.

In the present invention, the obtained aggregate web 1-cake is washed with a hydrophilic solvent before it is dried, thereby removing water remaining in the wet cake by replacing it with the hydrophilic solvent.

By washing the wet cake with a hydrophilic solvent in this way, most of the remaining moisture can be removed. By washing with a hydrophilic solvent in this way,
Wet cake never becomes dry, therefore
The inherent lipophilicity of the modified ethylene polymer is not impaired, and the redispersibility of the modified ethylene polymer fine particles in an organic solvent is not reduced.

In the present invention, the hydrophilic solvent used is a solvent that dissolves at room temperature in an amount of 10% by weight or more in both water and a hydrocarbon organic solvent serving as a redispersion medium. As such hydrophilic solvents, alcohols, ketones, and ethers are preferably used.

Note that when the dispersion medium used for redispersion, which will be described later, is a hydrophilic solvent, the same hydrophilic solvent as the redispersion medium can also be used for washing the wet cake. The hydrophilic solvent is used at a concentration equal to or greater than the fine particles in the wet cake.

In the present invention, the wet cake washed with a hydrophilic solvent is redispersed in a hydrocarbon organic solvent.

Any organic solvent can be used as the hydrocarbon organic solvent. For example, when using the modified ethylene-based fine particle dispersion according to the present invention as a compounding agent for gravure ink, toluene, xylene, methyl isobutyl ketone, etc. , isopropyl alcohol, etc. are preferable, and when used as a compounding agent for offset ink, etc., it is preferable to use n-decane, light oil, or a fractional distillation solvent of light oil, etc., which have a higher boiling point than the above-mentioned solvents.

For redispersion, a stirring device having a stirring means is usually used,
The redispersion can be performed more efficiently by stirring for 10 minutes to 300 minutes, especially by using a high-performance dispersion device such as a homomixer.

By redispersing the wet cake in a hydrocarbon organic solvent in this manner, a dispersion in which modified ethylene polymer fine particles are dispersed in an organic solvent (modified ethylene polymer fine particle dispersion) can be obtained.

In the thus obtained modified ethylene polymer fine particle dispersion, the water content is 3% or less, preferably 2 equivalent% or less, and particularly preferably in the range of 0 to 1.0 equivalent%.

This modified ethylene polymer fine particle dispersion may contain a dispersant or viscosity modifier such as an oil-soluble polymer or organic bentonite in order to improve its storage stability.

Although such a modified ethylene polymer fine particle dispersion can be used for various purposes, it is particularly useful as a compounding agent for ink.

The modified ethylene polymer fine particle dispersion of the present invention has a particularly low water content, and the fine particles in the dispersion have fine and uniform particle sizes. By using such a dispersion as an additive for alcohol-based gravure inks or MIr3K (methyl isobutyl ketone)-based gravure inks in small amounts (for example, 0.3 to 5 gravure weights as solid content), tackiness can be improved. Furthermore, it is possible to obtain an ink having excellent properties such as II stain resistance and slip resistance.

A modified ethylene polymer fine particle dispersion having such crushed characteristics can be easily produced by employing the production method of the present invention as described above.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

As a modified ethylene polymer, the intrinsic viscosity [η] is 0.1.
A maleic anhydride-modified ethylene-propylene copolymer having an acid value of 3.0 dj/g, a propylene content of 7% by weight, and a crystallinity of 65% was used.

1500 cc of water and 0.96 g of potassium hydroxide (0.8 equivalent to the carboxyl group in the maleic anhydride-modified ethylene-propylene copolymer) were placed in a pressure-resistant homomixer with an internal capacity of 41, and heated to 140°C. la but 5
While stirring at 000 rpm"cm, 400 g of the above-mentioned modified ethylene-based polymer was fed into the above mixer in a 140°C molten state by a gear pump over 1 hour. After further stirring for 30 minutes, it was cooled to room temperature and the modified ethylene-based polymer An aqueous dispersion of polymer fine particles was obtained.The average dispersed particle size was 4 μm.
Met.

! ] In Reference Example 1, the modified ethylene polymer had an intrinsic viscosity [η of 0.22 dJ/lr and an acid value of 3.4 #
An aqueous dispersion was obtained in the same manner as in Reference Example 1, except that a maleic anhydride-modified low-pressure polyethylene copolymer having -OH/g and a crystallinity of 80% was used.

The average dispersed particle size of the modified ethylene polymer fine particles is 3.5
It was μm.

In Reference Example 1, the modified ethylene polymer had an intrinsic viscosity [ηJ of 0.7 (N/) and an acid value of 20 ax −
Modified ethylene polymer fine particles were prepared in the same manner as in Reference Example 1, except that acrylic acid-grafted high-pressure low-density polyethylene with KOH/g and crystallinity of 57% was used, and the heating temperature was 200°C. A dispersion was obtained.

The average dispersed particle size of the modified ethylene polymer fine particles is 10μ
It was m.

Good 11 In Reference Example 1, the modified ethylene polymer had an intrinsic viscosity [η] of 0.86 J/g and an acid value of 3.0 -KO
Using maleic anhydride-modified high-pressure low-density polyethylene with a crystallinity of 58% and a heating temperature of 20%
An aqueous dispersion of modified ethylene polymer fine particles was obtained in the same manner as in Reference Example 1 except that the temperature was 0°C.

The average dispersed particle size of the modified ethylene polymer fine particles is 10μ
It was m.

In Reference Example 1, the modified ethylene polymer had an intrinsic viscosity [η of 1.0 dJl/, and an acid value of 3.01 v-
A modified ethylene-based copolymer was prepared in the same manner as in Reference Example 1, except that a maleic anhydride-modified ethylene-1-butene copolymer having a crystallinity of 15% and a crystallinity of 15% was used, and the heating temperature was 200°C. An aqueous dispersion of polymer fine particles was obtained.

The average dispersed particle size of the modified ethylene polymer fine particles is 4 μm.
Met.

In Reference Example 1, the modified ethylene polymer had an intrinsic viscosity [η] of 0.6dj/ir, an acid value of 3.0dj/g, and a crystallinity of 20%. An aqueous dispersion of modified ethylene polymer fine particles was obtained in the same manner as in Reference Example 1, except that a certain maleic anhydride-modified ethylene-vinyl acid copolymer was used and the heating temperature was 200°C.

The average dispersed particle size of the modified ethylene polymer fine particles is 7 μm.
Met.

The aqueous dispersion of modified ethylene polymer fine particles obtained in Reference Example 1 was diluted with distilled water until the solid content concentration was 10% by weight, and used as a raw material.

200 g of the raw material was placed in a 500 cc beaker equipped with a stirring blade. In the following operations, "part" means parts by weight of the additive when the solid content in the raw material is 100 parts by weight.

0.5 part of a surfactant (polyoxyethylene-nonylphenyl ether, HLB=7.8) was added to this raw material,
Stirred at 500 rpl for 10 minutes.

Then add 0.0% to this raw material. 40 parts of IN sulfuric acid was added and neutralized by stirring at 500 rpl for 10 minutes.This neutralization caused the modified ethylene polymer fine particles to aggregate.

Next, the aggregated modified ethylene polymer fine particles were suction-filtered using a vapor filter to remove most of the water, and a wet cake was obtained.

500 parts of Ingrovil alcohol was added to this wet cake, and after stirring and washing on a filter, the mixture was again passed through suction to obtain a wet cake.

This wet cake was placed in a beer tank containing 120 parts of n-decane and stirred at 500 ml for 30 minutes to obtain a modified ethylene-based fine particle dispersion (n-decane dispersion).

When the obtained dispersion was analyzed, the water content was 0.5.
The solid content is 44% by weight, the average dispersed particle size is 4 μm, and the residue when passed through a wire mesh with a 100-mesh opening is 0.5% by weight per solid content. there were.

A modified ethylene-based fine particle dispersion (n-decane dispersion) was obtained by carrying out the same operation as in Example 1 except that the surfactant was not used in Example 1.

When the resulting dispersion was analyzed, the water content was 2.5.
The solid content was 44% by weight, the average dispersed particle size was 4 μm, and the residual liquid when passed through a wire mesh with 100 mesh openings was 1.5% by weight.

In Example 1, the aqueous dispersion obtained in Reference Example 2 was used instead of the aqueous dispersion obtained in Reference Example 1 as the aqueous dispersion of modified ethylene polymer fine particles, and 0.
A modified ethylene-based fine particle dispersion (acetone dispersion) was obtained by carrying out the same operation as in Example 1, except that 1NH (l) was used as a hydrophilic solvent, and toluene was used as an organic solvent.

When the obtained dispersion was analyzed, the water content was 0.4.
The solid content was 44% by weight, the average dispersed particle size was 3.5 μm, and the residue when filtered through a wire mesh with 100 mesh openings was 0.6% by weight.

Fire 1 Blood 1 In Example 1, the aqueous dispersion of Reference Example 4 was diluted with water,
A modified 2-ethylene fine particle dispersion (n-decane dispersion) was obtained by carrying out the same operation as in Example 1, except that the raw material had a concentration of 20%.

When the obtained dispersion was analyzed, the water content was 0.6.
The solid content was 44% by weight, the average dispersed particle size was 10 μm, and the residue after passing through a wire mesh with 100 meshes was 0.8% by weight.

K Stand 1 A modified ethylene-based fine particle dispersion (n-decane dispersion) was obtained by carrying out the same operation as in Example 1, except that the aqueous dispersion of Reference Example 3 was used in Example 1.

Analysis of the resulting dispersion revealed that the water content was 0.7% by weight.
The solid content is 44 layers, and the average dispersed particle size is 1
The residue was 0.8% by weight when passed through a wire mesh with an opening of 100 µm.

In Example 1, the aqueous dispersion of Reference Example 5 was diluted with water,
A modified ethylene-based fine particle dispersion (n-decane dispersion) was obtained by performing the same operation as in Example 1, except that an aqueous dispersion having a concentration of 10% was used as the raw material.

When the obtained dispersion was analyzed, the water content was 1.0.
% by weight, the solid content is 43% by weight, the average dispersed particle size is 4.0 μm, and the residue when subjected to 7N with a wire mesh with a mesh opening of 100 is 0.9! It was 1E amount%.

In Example 1, the aqueous dispersion of Reference Example 6 was diluted with water,
A modified ethylene-based fine particle dispersion (n-decane dispersion) was obtained by carrying out the same operation as in Example 1, except that an aqueous dispersion having a concentration of 10% was used as the raw material.

Analysis of the resulting dispersion revealed that the water content was 1.0.
The solid content was 43% by weight, the average dispersed particle size was 7 μm, and the residue when filtered through a wire mesh with 100 mesh openings was 0% by weight.

K1■1 A modified ethylene-based fine particle dispersion (MIBK
A dispersion) was obtained.

When the obtained dispersion was analyzed, the water content was 0.3.
The solid content was 40% by weight, the average dispersed particle size was 4.0 μm, and the residue when filtered through a wire mesh with 100 mesh openings was 0.14% by weight.

A modified ethylene-based fine particle dispersion (ethyl acetate dispersion) was obtained by carrying out the same operation as in Example 1, except that ethyl acetate was used instead of n-decane in Example 1.

When the obtained dispersion was analyzed, the water content was 0.4.
The solid content was 40% by weight, the average dispersed particle size was 4.0 μm, and the residue after passing through a wire mesh with 100 mesh was 0.2% by weight.

A modified ethylene fine particle dispersion (tetrachlorethylene dispersion) was obtained by carrying out the same operations as in Example 1, except that tetrachlorethylene was used instead of n-decane.

When the obtained dispersion was analyzed, the water content was 0.2
The solid content was 34% by weight, the average dispersed particle size was 4.0 μm, and the residue when filtered through a wire mesh with 100 mesh openings was 0.2% by weight.

Claims (1)

[Scope of Claims] 1) A fine particle dispersion consisting of a hydrocarbon-based organic solvent and a fine particle resin dispersed in the solvent, wherein the resin is modified with an unsaturated carboxylic acid or a derivative thereof. consisting of an ethylene polymer, the resin has an average dispersed particle size of 0.3 to 20 μm, the modified ethylene polymer has an acid value of 0.3 to 75 mg-KOH/g, and the fine particle dispersion contains A modified ethylene polymer fine particle dispersion, wherein the concentration of the modified ethylene polymer is 15 to 60% by weight, and the water content in the fine particle dispersion is 3 weight% or less. 2) modified with an unsaturated carboxylic acid or its derivative;
A modified ethylene polymer having an acid value of 0.3 to 75 mg-KOH/g has an average dispersed particle size of 0 by neutralizing at least a part of the carboxyl groups constituting the polymer with a basic substance. .To an aqueous dispersion in which fine particles of 3 to 20 μm are dispersed in an aqueous dispersion medium, an amount of acid necessary to neutralize at least the basic substance consumed in neutralization is added to aggregate the fine particles. The method is characterized in that the aggregates and water are separated, the obtained aggregates are washed in an undried state using a hydrophilic solvent, and then the aggregates are redispersed in a hydrocarbon-based organic solvent. A method for producing a modified ethylene polymer fine particle dispersion. 3) The aqueous dispersion has a hydrophilic/lipophilic balance (HL
3. The method for producing a modified ethylene polymer fine particle dispersion according to claim 2, which comprises a surfactant in which B) is 12 or less.