JP2007031639A - Aqueous dispersion system of polyolefin oligomer, and application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion system of a polyolefin oligomer exhibiting excellent lubricity including friction resistance, mold releasability and sticking resistance when used as an antifriction agent of an ink or a coating material, and further having excellent gloss and transparency; and to provide an ink composition and a coating agent. <P>SOLUTION: The aqueous dispersion system of the polyolefin oligomer contains at least (B) a maleic acid-modified polyolefin oligomer and (C) a polyethylene glycol alkyl ether, and is regulated so that the average particle diameter at 50 vol.% of emulsion particles in the aqueous dispersion system is 0.05-0.5 μm. The ink composition and the coating agent contains the aqueous dispersion system. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an aqueous dispersion of a polyolefin-based oligomer and its use, and more particularly to an aqueous dispersion of a polyolefin-based oligomer that improves friction resistance and lubricity when added to an ink or a coating agent, and its use.

  Conventionally, aqueous dispersions of polyolefin oligomers have been used as antiwear agents for inks and coating materials (Patent Documents 1, 3, and 4).

  Emulsions composed of polyolefin oligomers and maleic acid-modified polyolefin oligomers have already been reported (Patent Document 2), but since the average particle diameter of emulsion particles is large, when added to inks and coating materials, friction resistance and lubrication Although the properties are improved, the gloss is lowered, and the film forming property and transparency are impaired.

  In addition, aqueous dispersions of oxidized polyethylene wax and aqueous dispersions of ethylene / unsaturated carboxylic acid copolymers are also used as anti-wear agents for inks and coating materials. Although excellent, the friction resistance and lubricity are not sufficient.

  Thus, there has been a demand for an aqueous dispersion system having both design properties such as glossiness and transparency, and friction resistance and lubricity.

Japanese Patent Laid-Open No. 01-133783 Japanese Patent Laid-Open No. 05-056162 Japanese Patent Application Laid-Open No. 06-184988 Japanese Patent Application Laid-Open No. 08-073814

  The object of the present invention is, when used as an anti-wear agent for inks and coating materials, is an aqueous polyolefin oligomer having excellent lubricity including friction resistance, releasability and anti-sticking, and also excellent gloss and transparency. To provide a distributed system.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the use of a specific emulsifier reduces the size of emulsion particles of an aqueous polyolefin-based oligomer dispersion, thereby completing the present invention.

  That is, the present invention is an aqueous dispersion of a polyolefin oligomer containing at least (B) a maleic acid-modified polyolefin oligomer and (C) a polyethylene glycol alkyl ether, and the emulsion particles of the aqueous dispersion have an average particle size of 50% in volume. This is an aqueous dispersion of a polyolefin-based oligomer having a size of 0.05 μm to 0.5 μm, and its use.

  When used as an anti-wear agent for inks or coating materials, the aqueous dispersion of polyolefin oligomer of the present invention is excellent in lubricity including friction resistance, releasability, and anti-sticking, and also excellent in gloss and transparency. ing.

  Hereinafter, the present invention will be described in detail.

  The polyolefin oligomer in the present invention is ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene. Α-olefins such as 1-decene and 1-dodecene; conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene and 1,5-hexadiene, homopolymers of non-conjugated dienes or oligomers of these copolymers Furthermore, homopolymers such as styrene, vinyl acetate, and vinyl alcohol, and copolymers of these olefinic monomers with these monomers. Specifically, polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl alcohol copolymer, ethylene / styrene copolymer, etc. An oligomer is mentioned.

  Furthermore, modified products obtained by grafting an ethylenically unsaturated monomer onto the above polymer, oxidizing in a molten state using oxygen or an oxygen-containing gas, or halogenating using an alkali metal halide are also included. It is.

The polyolefin oligomer in the present invention includes vegetable wax, animal wax, mineral wax and petrochemical wax in addition to the polyolefin oligomer.
Examples of preferred waxes are candelilla wax and carnauba wax. Wood wax, esparto glass wax, cork wax, guaruma wax, rice bran oil wax, sweet potato wax, berry wax, uricuric wax, montan wax, jojoba wax, shea butter, beeswax, shellac wax, whale wax, lanolin, ceresin, paraffin A wax, a synthetic polyethylene wax, a synthetic polypropylene wax, a synthetic ethylene-vinyl acetate copolymer wax and the like can be mentioned, and these can be used alone or in combination.

  The number average molecular weight (Mn) of the polyolefin oligomer is usually 600 to 10,000. In addition, a number average molecular weight (Mn) can be calculated | required by measuring by gel permeation chromatography (GPC).

  The (B) maleic acid-modified polyolefin oligomer in the present invention is a polymer obtained by graft copolymerizing maleic acid or a derivative thereof with the above polyolefin oligomer, and specifically, Mitsui High Wax 1105A, 2203A, NPO555A (manufactured by Mitsui Chemicals, Inc.). ) And Umex 1010 (manufactured by Sanyo Chemical Co., Ltd.).

  (B) As a manufacturing method of maleic acid-modified polyolefin oligomer, for example, (A) polyolefin oligomer is melted or dissolved in a solvent such as hexane, and radical initiators such as peroxides and maleic acid or derivatives thereof are gradually added. It is obtained by dripping in

  The radical initiator to be used is not particularly limited, and examples thereof include di-tert-butyl peroxide, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, dicumyl peroxide, and lauroyl peroxide. Organic peroxides such as oxide, tert-butylperoxybenzoate, cumene hydroperoxide, azobisisobutyronitrile, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2- And azo compounds such as methyl-N- (2-hydroxyethyl) propioamide). These can be used alone or in combination of two or more.

  Further, the radical generation method in the case of performing the reaction by further generating radicals uses a known method such as a method of irradiating light in the presence of a photopolymerization initiator or a method of adding an organic peroxide. can do.

  Examples of the photopolymerization initiator include benzophenone, diacetyl, benzyl, benzoin, 2-methylbenzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone. 2-hydroxy-2-methylpropiophenone, 2-chlorobenzophenone, p-dimethylaminopropiophenone, p-dimethylaminoacetophenone, p, p'-bisdiethylaminobenzophenone, 3,3'-4,4'- Tetra-benzophenone, Michler's ketone, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, 2,4,6-trimethylbenzoyldiphenylphosphineoxy Carbonyls such as benzyl dimethyl ketal and methyl benzoyl formate, sulfides such as diphenyl disulfide, dibenzyl disulfide, tetramethyl thiuram monosulfide, quinones such as benzoquinone, anthraquinone, chloroanthraquinone, ethyl anthraquinone, butyl anthraquinone, thioxanthone, Examples thereof include thioxanthones such as 2-methylthioxanthone and 2-chlorothioxanthone, but these may be used alone or in combination of two or more. These photopolymerization initiators include amines such as triethylamine, trimethylamine, triethanolamine, dimethylaminoethanol, pyridine, quinoline, and trimethylbenzylammonium chloride, alkylphosphines such as triphenylphosphine, and β-thiodi. A thiol ether such as glycol may be used in combination.

  The photopolymerization initiator is preferably used in an amount of 10 to 50% by weight, more preferably 20 to 40% by weight based on the added maleic acid.

  Moreover, it is preferable to add these reaction initiators and maleic acid or derivatives thereof little by little as much as possible. Depending on the amount used, in general, when organic peroxides are added all at once, the reaction solution is relatively susceptible to gelation. It is preferable to add little by little.

  (B) The maleic acid content in the maleic acid-modified polyolefin oligomer is preferably 0.5 to 5% by weight.

  The polyethylene glycol alkyl ether in the present invention is a compound having an alkyl group having 12 to 22 carbon atoms and having 4 to 50,000 repeating units of an oxyethylene group, and an oxyalkylene group such as an oxypropylene group. These copolymers are also included. Examples of such compounds include polyoxyethylene dodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene octyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, octaethylene glycol mono- and n-dodecyl ether.

  HLB in the present invention refers to a hydrophilic / lipophilic balance representing the effect of a surfactant. For example, Griffin's formula: HLB = 20 × (number of hydrophilic groups) or Davis' formula: HLB = 7 + Σ (of hydrophilic groups) Number of radicals) -Σ (the number of hydrophobic groups).

  The preferred HLB of the polyoxyethylene alkyl ether is 8 or more, more preferably 12-18. Specific examples include Emulgen 120P, Emulgen 320P, Emulgen 420, Emulgen 1108, Emulgen 2020G-HA, Emulgen LS110 (manufactured by Kao Corporation), Neugen XL-80 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the like.

  In the aqueous dispersion of the present invention, (B) maleic acid-modified polyolefin oligomer and (C) polyethylene glycol alkyl ether, or (A) polyolefin oligomer and (B) maleic acid-modified polyolefin oligomer, and (C) polyethylene glycol alkyl. The weight ratio with ether is preferably 100/2 to 100/30, more preferably 100/5 to 100/20.

  The aqueous dispersion system in the present invention is an aqueous dispersion system in which emulsion particles having a particle size of about 0.01 nm to 1.5 μm are dispersed in water, and emulsion particles having a volume 50% average particle size of 0.05 to 0.5 μm. A composition dispersed in water. When the 50% volume average particle diameter exceeds 0.5 μm, there are problems such as deterioration of gloss and color reproducibility, and when the 50% volume average particle diameter is less than 0.05 μm, the friction resistance and lubricity are poor. When stored for a long time, there are problems such as aggregation and concentration gradient. Therefore, in order to maintain gloss and color reproducibility, have good storage stability, and exhibit friction resistance and lubricity, the 50% average particle size is preferably 0.05 μm or more and 0.5 μm or less.

  In addition, the particle diameter in this invention means the diameter of particle | grains, It can measure using a dynamic light scattering type particle size distribution measuring apparatus and a micro track particle size distribution measuring apparatus.

  The method for producing an aqueous dispersion of polyolefin oligomer in the present invention includes (B) maleic acid-modified polyolefin oligomer and (C) polyethylene glycol alkyl ether, or (A) polyolefin oligomer, (B) maleic acid-modified polyolefin oligomer and (C) polyethylene. It comprises a melting step in which glycol alkyl ether is melt-mixed and an emulsifying step in which water-dispersed particles are produced by emulsifying and dispersing.

  The melting step in the present invention is a mixture of (B) maleic acid modified polyolefin oligomer and (C) polyethylene glycol alkyl ether, or (A) polyolefin oligomer, (B) maleic acid modified polyolefin oligomer and (C) polyethylene glycol alkyl ether. It is a step of melting and uniformly mixing at a temperature higher than the melting point of the steel, and more specifically, stirring at 80 to 200 ° C. for 10 minutes or more is desirable. In addition, an organic solvent may be used when performing melt mixing below the melting point of the above mixture.

  Specific examples of the organic solvent include aromatic hydrocarbons such as xylene, toluene and ethylbenzene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclohexane, cyclohexene and methylcyclohexane, and ethyl acetate. N-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ester solvents such as 3-methoxybutyl acetate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Moreover, the mixture which consists of these 2 or more types may be sufficient.

  The emulsification step in the present invention is a method of physically emulsifying and dispersing by mechanical shearing force. Specifically, (B) maleic acid-modified polyolefin oligomer and (C) polyethylene glycol alkyl ether, or (A ) A method of removing a solvent after dissolving a mixture of a polyolefin oligomer, (B) maleic acid-modified polyolefin oligomer and (C) polyethylene glycol alkyl ether in a solvent and then emulsifying with a high-pressure homogenizer, high-pressure homomixer, etc., (B) maleic acid-modified polyolefin The mixture of the oligomer and (C) polyethylene glycol alkyl ether, or (A) polyolefin oligomer, (B) maleic acid-modified polyolefin oligomer and (C) polyethylene glycol alkyl ether in a molten state A method of emulsifying with a generator, high-pressure homomixer, extrusion kneader, a method of emulsifying a copolymer of α-olefin and (meth) acrylic acid and an alkaline substance such as potassium, sodium and ammonium in an autoclave, and other mechanical grinding. A method of spraying and pulverizing at high pressure, a method of spraying from pores, and the like.

  The ink composition in the present invention is a water-based printing ink composition, and in addition to a vehicle component, a fatty acid or a fatty acid salt, a colorant such as a pigment, and an additive such as a filler as necessary, are known. Manufactured by the method.

  Moreover, a printed matter is obtained by printing the water-based printing ink composition of the present invention on a known substrate such as plastic or paper by a gravure printing or flexographic printing method.

  Examples of the aqueous resin used as the vehicle resin of the ink composition include water-soluble resins used in general inks, paints, and recording agents, and water-dispersible resins such as emulsions and dispersions. One of these or a mixture of these resins may be used.

  Specifically, polyurethane resin, polyurethane urea resin, acrylic modified urethane resin, acrylic modified urethane urea resin, acrylic resin, styrene-acrylic acid copolymer resin, styrene-maleic acid copolymer resin, ethylene-acrylic acid copolymer resin, Examples include polyester resin, shellac, rosin-modified maleic acid resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic acid copolymer resin, chlorinated polypropylene resin, hydroxyethyl cellulose, hydroxypropyl cellulose, butyral and the like. These may be used alone or in combination of two or more.

  Examples include protective paints, lubricating paints for various steel sheets, overprint varnishes for various printed materials, overcoat varnishes for thermal paper, floor polish paints, architectural paints, and car body paints.

The coating agent in the present invention is applied to resin, metal, paper, wood, fiber, leather, glass, rubber, etc. by various methods such as spray, curtain, flow coater, roll coater, gravure coater, brush coating and dipping. By doing so, a laminated body can be constituted. Specific examples include overprint varnishes, protective coating agents, etc., which are generally highly transparent, highly glossy, and excellent in lubricity including friction resistance and sticking resistance.

The present invention will be specifically described below with reference to preferred examples and comparative examples of the present invention, but these examples do not limit the scope of the present invention in any way. In the examples, “parts” means “parts by weight”.
Various characteristic values were measured by the following methods.
1. The dispersion state of the dispersion was examined by passing the dispersion through a 100-mesh wire mesh. The evaluation results are shown in Table 1.
2. Emulsion particle diameter (μm)
The average particle diameter of 50% volume was measured with Microtrac UPA (manufactured by HONEYWELL). The evaluation results are shown in Table 1.
3. Glossiness 10 parts of an aqueous polyolefin oligomer dispersion of 10% active ingredient, 65 parts of an acrylic emulsion (manufactured by Joncryl 77 Johnson Polymer) and 30 parts of an acrylic aqueous solution (manufactured by Joncryl 60 Johnson Polymer) were mixed to prepare a coating composition. This composition was coated on a hidden pay rate test paper so as to have a film thickness of 5 μm, and dried at 25 ° C. for 24 hours. Thereafter, the reflectance at 60 ° C. was observed with a gloss meter (VG10, Nippon Denshoku Industries Co., Ltd.). The measured evaluation results are shown in Table 1.
4). Friction resistance A (ink composition)
10 parts of the emulsion composition described in Examples 1 to 9 and Comparative Examples 1 to 6, 100 parts of styrene acrylic emulsion (Almatex, Mitsui Chemicals) and 30 parts of phthalocyanine pigment dispersion are mixed to prepare an ink composition. did. This composition was applied on a 30 × 150 mm liner paper so as to have a film thickness of 5 μm, and dried at 120 ° C. for 1 minute. Using a Gakushin type fastness friction tester, the load was set to 20 gf, the same part was rubbed 100 times, and the ink peeling state was observed. The measured evaluation results are shown in Table 1.
5. Abrasion resistance B (Coating agent: Overprint varnish)
A coating composition was prepared by mixing 10 parts of an aqueous polyolefin oligomer dispersion of 10% active ingredient, 65 parts of an acrylic emulsion (manufactured by Joncryl 77 Johnson Polymer) and 30 parts of an acrylic aqueous solution (manufactured by Joncryl 60 Johnson Polymer). The weight of the coating composition was set to 500 gf using a Gakushin type abrasion resistance tester, the same part was rubbed back and forth 1000 times, and the damage was visually observed. The measured evaluation results are shown in Table 1.
6). Friction resistance C (Coating agent: Paint for lubricating steel plate)
A lubricant coating agent was prepared by mixing 10 parts of the emulsion composition described in Examples 1 to 9 and Comparative Examples 1 to 6 below and 100 parts of a styrene acrylic emulsion (Almattex, Mitsui Chemicals). This composition was applied onto a 70 × 150 mm metal plate (manufactured by Gincoat Test Piece) so as to have a film thickness of 3 μm, and dried at 120 ° C. for 1 minute. A stainless steel ball having a diameter of 10 mm was used, the load was set to 500 gf, the same portion was rubbed 50 times, and the coefficient of friction resistance was measured. The evaluation results are shown in Table 1.
7). Sticking resistance (coating agent: overcoat varnish for thermal paper)
In a separable flask, 195 parts of deionized water and 0.3 part of sodium dodecylbenzenesulfonate were charged, and the temperature was raised to 70 ° C. after substitution with nitrogen gas. After heating, 1.0 part of potassium persulfate was added, and then 30 parts of acrylonitrile, 50 parts of n-butyl acrylate, 10 parts of methacrylic acid, and 10 parts of 2-hydroxyethyl methacrylate were continuously added over about 4 hours. After that, the temperature was raised to 80 ° C. and maintained for 2 hours to complete the polymerization. After completion, the mixture was cooled to room temperature and neutralized with aqueous ammonia to obtain a resin emulsion having a solid content of about 30% and having a pH adjusted to about 8.0. After adding 6.0 g of a 40% solid content polyolefin oligomer dispersion to 100 g of the resin emulsion, the mixture was sufficiently stirred and mixed to obtain a thermal overcoat varnish. Apply to a commercially available surface untreated heat-sensitive word processor paper with a bar coater to a dry weight of 3 g / m ² , then dry (forced drying at 60 ° C. for 30 seconds, then cured under 20 ° C./60% RH atmosphere for 24 hours ) To obtain a thermosensitive recording material. The thermal recording material was subjected to pattern recording with a thermal printer (TH-PMD, manufactured by Okura Electric Co., Ltd.), and the degree of sticking in the recording portion was visually determined. The determination results are shown in Table 1.

[Example 1]
(A) 70 parts of polyethylene wax (Mitsui High Wax 210P, Mitsui Chemicals) as the polyolefin oligomer and (B) maleic acid-modified polyethylene wax (Mitsui High Wax 1105A, Mitsui Chemicals) as the maleic acid-modified polyolefin oligomer 30 parts and (C) 10 parts of polyoxyethylene lauryl ether (Emulgen 120, manufactured by Kao Corporation) having an HLB of 15.3 as polyoxyethylene alkyl ether are heated at 160 ° C. and stirred and mixed for 2 hours. While stirring at 8000 rpm in a mixer (Homomixer MARKII: manufactured by Tokushu Kika Co., Ltd.), 1800 g / hour of a potassium hydroxide solution in which 9880 cc of water and 120 g of 85% potassium hydroxide were dissolved in advance and the above-mentioned (A) polyolefin oil (B) maleic acid-modified polyolefin oligomer and (C) polyoxyethylene alkyl ether are fed to the mixer by a gear pump at a rate of 1200 g / hour while being melted at 140 ° C., and the storage stability is good. An aqueous dispersion having a 50% average particle size of 0.25 μm was obtained. The evaluation results are shown in Table 1.

[Example 2]
In Example 1, instead of adding 10 parts of polyoxyethylene lauryl ether (Emulgen 120) having 15.3 HLB as (C) polyoxyethylene alkyl ether, (C) 13.13 HLB as polyoxyethylene alkyl ether was added. No. 9 polyoxyethylene stearyl ether (Emulgen 320P, manufactured by Kao Corporation) was added and melt-mixed, and then supplied to a pressure-resistant homomixer to obtain an aqueous dispersion having a volume 50% average particle size of 0.27 μm. The evaluation results are shown in Table 1.

[Example 3]
In Example 1, instead of adding 10 parts of polyoxyethylene lauryl ether (Emulgen 120) having 15.3 HLB as (C) polyoxyethylene alkyl ether, (C) 13.13 HLB as polyoxyethylene alkyl ether was added. No. 6 polyoxyethylene oleyl ether (Emulgen 420, manufactured by Kao Corporation) was added, melted and mixed, and then supplied to a pressure-resistant homomixer to obtain an aqueous dispersion having a volume 50% average particle size of 0.25 μm. The evaluation results are shown in Table 1.

[Example 4]
In Example 1, instead of adding 10 parts of polyoxyethylene lauryl ether (Emulgen 120) having 15.3 HLB as (C) polyoxyethylene alkyl ether, (C) 13.13 HLB as polyoxyethylene alkyl ether was added. 10 parts of polyoxyethylene octyldodecyl ether (Emulgen 2020G-HA, manufactured by Kao Corporation), which is 0, is melt-mixed and then supplied to a pressure-resistant homomixer to produce an aqueous dispersion having a volume 50% average particle size of 0.30 μm. Obtained. The evaluation results are shown in Table 1.

[Example 5]
In Example 1, instead of adding 10 parts of polyoxyethylene lauryl ether (Emulgen 120) having 15.3 HLB as (C) polyoxyethylene alkyl ether, (C) 13.13 HLB as polyoxyethylene alkyl ether was added. 10 parts of polyoxyethylene alkyl (C = 11) ether (Emalgen 1108, manufactured by Kao Corporation) 5 is added, melted and mixed, and then supplied to a pressure-resistant homomixer. An aqueous dispersion having a volume 50% average particle size of 0.22 μm Got the system. The evaluation results are shown in Table 1.

[Example 6]
In Example 1, instead of adding 10 parts of polyoxyethylene lauryl ether (Emulgen 120) having 15.3 HLB as (C) polyoxyethylene alkyl ether, (C) 13.13 HLB as polyoxyethylene alkyl ether was added. No. 8 polyoxyethylene alkyl decyl ether (Neugen XL-80: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and melt mixed, and then supplied to a pressure-resistant homomixer. A dispersion was obtained. The evaluation results are shown in Table 1.

[Example 7]
In Example 1, instead of adding 10 parts of polyoxyethylene lauryl ether (Emulgen 120) having 15.3 HLB as (C) polyoxyethylene alkyl ether, (C) 13.13 HLB as polyoxyethylene alkyl ether was added. After adding 10 parts of polyoxyethylene polyoxypropylene alkyl decyl ether (Emulgen XS110: manufactured by Kao Corporation) 4 and melt mixing, the mixture is supplied to a pressure-resistant homomixer, and an aqueous dispersion having a volume 50% average particle size of 0.26 μm Got. The evaluation results are shown in Table 1.

[Example 8]
(A) 40 parts of polyethylene wax (Mitsui High Wax 210P, Mitsui Chemicals) as the polyolefin oligomer on the melting drum and (B) maleic acid-modified polyethylene wax (Mitsui High Wax 1105A, Mitsui Chemicals) as the maleic acid-modified polyolefin oligomer 60 parts and 10 parts of (C) polyoxyethylene alkyl (C = 11) ether (Emulgen 1108, manufactured by Kao Corporation) having an HLB of 13.5 as polyoxyethylene alkyl ether are heated at 160 ° C. and stirred for 2 hours. Then, in a pressure-resistant homomixer (Homomixer MARKII: manufactured by Tokushu Kika Co., Ltd.), while stirring at 8000 rpm, 1800 g / hour of potassium hydroxide solution in which 9880 cc of water and 120 g of 85% potassium hydroxide were dissolved in advance and (A ) Poly Refine oligomer, (B) maleic acid-modified polyolefin oligomer and (C) polyoxyethylene alkyl ether are fed to the mixer by a gear pump while being melted at 140 ° C. at a rate of 1200 g / hour, and the storage stability is good. An aqueous dispersion having a volume 50% average particle size of 0.16 μm was obtained. The evaluation results are shown in Table 1.

[Example 9]
(B) 100 parts of maleic acid-modified polyethylene wax (Mitsui High Wax 2203A, manufactured by Mitsui Chemicals) as the maleic acid-modified polyolefin oligomer and (C) polyoxyethylene having an HLB of 15.3 as the polyoxyethylene alkyl ether 10 parts of lauryl ether (Emulgen 120, manufactured by Kao Corporation) is heated at 160 ° C. and stirred and mixed for 2 hours, and then 9760 cc of water in advance with stirring at 8000 rpm in a pressure-resistant homomixer (Homomixer MARKII: manufactured by Tokushu Kika Co., Ltd.). 1800 g / hr of potassium hydroxide solution in which 240 g of 85% potassium hydroxide was dissolved and 120 parts of the above-mentioned (A) polyolefin oligomer, (B) maleic acid-modified polyolefin oligomer and (C) polyoxyethylene alkyl ether. g / fed by a gear pump to the mixer remains at 140 ° C. a molten state at a rate of time, good storage stability, the 50% volume average particle diameter to give an aqueous dispersion of 0.40 .mu.m. The evaluation results are shown in Table 1.

[Comparative Example 1]
In Example 1, without adding 10 parts of (C) polyoxyethylene lauryl ether (Emulgen 120) having an HLB of 15.3 as polyoxyethylene alkyl ether, (A) polyethylene wax (Mitsui High Wax 210P, 50 parts of Mitsui Chemicals Co., Ltd.) and (B) 50 parts of maleic acid-modified polyethylene wax (Mitsui High Wax 1105A, Mitsui Chemicals Co., Ltd.) as a maleic acid-modified polyolefin oligomer are melt-mixed and then supplied to a pressure-resistant homomixer. An aqueous dispersion having an average particle size of 0.59 μm was obtained. The evaluation results are shown in Table 2.

[Comparative Example 2]
In Example 8, (B) 100 parts of maleic acid-modified polyethylene wax (Mitsui High Wax 1105A, manufactured by Mitsui Chemicals) as a maleic acid-modified polyolefin oligomer was melt-mixed and then supplied to a pressure-resistant homomixer, and the volume average particle diameter was 50%. Obtained an aqueous dispersion of 0.62 μm. The evaluation results are shown in Table 2.

[Comparative Example 3]
In Example 1, (C) Polyethylene glycol monolaurate having an HLB of 13.7 instead of adding 10 parts of polyoxyethylene lauryl ether (Emulgen 120) having an HLB of 15.3 as a polyoxyethylene alkyl ether ( Emanon 1112 (manufactured by Kao Corporation) was added, melted and mixed, and then supplied to a pressure-resistant homomixer to obtain an aqueous dispersion having a volume 50% average particle size of 0.55 μm. The evaluation results are shown in Table 2.

[Comparative Example 4]
In Example 1, stearic acid (Wako Pure Chemical Industries, Ltd.), an anionic surfactant, was added instead of 10 parts of (C) polyoxyethylene lauryl ether (Emulgen 120) having an HLB of 15.3 as polyoxyethylene alkyl ether. 10 parts) and melt-mixed, and then supplied to a pressure-resistant homomixer to obtain an aqueous dispersion having a volume 50% average particle size of 0.61 μm. The evaluation results are shown in Table 2.

[Comparative Example 5]
70 parts of polyethylene wax oxidized with oxygen in the air (Mitsui High Wax 4202E: manufactured by Mitsui Chemicals) and 30 parts of potassium oleate were heated at 120 ° C. and mixed with stirring for 2 hours. Then, with stirring at 8000 rpm, a potassium hydroxide solution was heated at 95 ° C. in advance in a pressure-resistant homomixer (Homomixer MARKII: manufactured by Tokushu Kika Co., Ltd.), and the mixture of the oxidized polyethylene wax and potassium oleate was added. The mixture was gradually supplied to the mixer to obtain an aqueous dispersion having good storage stability and a volume 50% average particle size of 0.03 μm. The evaluation results are shown in Table 2.

[Comparative Example 6]
When 25 parts of an ethylene / acrylic acid copolymer (AC5120: manufactured by Clariant) was stirred for 2 hours in an autoclave having a pressure stirrer with 75 parts of an aqueous solution containing a carboxyl group of acrylic acid and an equimolar amount of potassium hydroxide, A 1.01 μm aqueous dispersion was obtained. The evaluation results are shown in Table 2.

  According to the present invention, when used as an anti-wear agent for inks and coating materials, the polyolefin oligomer aqueous solution is excellent in lubricity including friction resistance, mold release property, anti-stinking property, and excellent in gloss and transparency. A dispersion can be provided.

Moreover, the ink composition and coating agent containing the aqueous dispersion of the polyolefin-based oligomer of the present invention are excellent in lubricity, friction resistance, transparency and high gloss, and are industrially useful.

Claims (8)

(B) An aqueous dispersion of a polyolefin oligomer containing at least a maleic acid-modified polyolefin oligomer and (C) a polyethylene glycol alkyl ether, wherein the emulsion particles of the aqueous dispersion have a volume 50% average particle size of 0.05 μm to 0.00. An aqueous dispersion of a polyolefin oligomer having a size of 5 μm. The aqueous dispersion of a polyolefin-based oligomer according to claim 1, wherein the polyolefin-based oligomer comprises (A) a polyolefin oligomer, (B) a maleic acid-modified polyolefin oligomer, and (C) a polyethylene glycol alkyl ether. 2. The aqueous dispersion of polyolefin oligomer according to claim 1, wherein the maleic acid-modified polyolefin oligomer has a maleic acid content of 0.5 to 5% by weight. (C) The aqueous dispersion of polyolefin-based oligomer according to claim 1, wherein the polyethylene glycol alkyl ether has an HLB of 8 or more. The aqueous dispersion of polyolefin-based oligomer according to claim 2, wherein the weight ratio of (A) polyolefin oligomer and (B) maleic acid-modified polyolefin oligomer to (C) polyethylene glycol alkyl ether is 100/2 to 100/30. . (A) polyolefin oligomer, (B) maleic acid-modified polyolefin oligomer and (C) polyethylene glycol alkyl ether, or (B) maleic acid-modified polyolefin oligomer and (C) polyethylene glycol alkyl ether are melt-mixed in the melting step, A method for producing an aqueous dispersion of a polyolefin-based oligomer that is emulsified and dispersed in an emulsification step. An ink composition comprising the aqueous dispersion of a polyolefin-based oligomer according to claim 1 or 2. The coating agent containing the aqueous dispersion of the polyolefin-type oligomer of Claim 1 or 2.