JP2019119857A - Manufacturing method of polyolefin resin composition particle - Google Patents

Abstract

To provide a manufacturing method providing a polyolefin resin composition excellent in circularity, strength and powder flowability of particles, and narrow in particle diameter distribution.SOLUTION: There is provided a manufacturing method of a polyolefin resin composition particle (P) containing a polyolefin resin (A) and an inorganic particle (B) and having average of circularity of 0.80 or more, by melting and mixing a polyolefin resin composition containing (A) and (B), acid modified polyolefin (C) as a dispersant, polyoxyalkylene polyol containing an oxyethylene group of 60 wt.% or more (D), and polyurethane (E) by reaction of polyoxyalkylene polyol containing the oxyethylene group of 60 wt.% or more and organic polyisocyanate to obtain a resin composition (G) in which (P) is dispersed in a mixture of (D) and (E), and then mixing (G) and water to dissolve (D) and (E) into water to separate (P).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing polyolefin resin composition particles.

Fine resin particles are used in a wide range of applications such as powder coatings, matting agents, antiblocking agents, carriers for chromatography, carriers for drugs, gap regulators, electrorheological fluids and cosmetics. As a method for producing resin fine particles, there are a method of forming particles from a polymerizable monomer in the polymerization process (polymerization granulation method) and a method of forming particles from a polymer solution formed into fine droplets (dispersion granulation method) Are known.
In the polymerization granulation method, soap-free emulsion polymerization, seed polymerization, in order to produce fine particles having a target particle diameter and uniform particle size distribution basically based on the emulsion polymerization method and the suspension polymerization method. Dispersion polymerization and a two-step swelling method have been developed.
In the dispersion granulation method, the spray drying method, the in-liquid curing method (solidification method), the poor solvent precipitation method (phase separation method), the solvent evaporation method and the reprecipitation method, etc. are used to produce microdroplets mechanically or physically. The way to do it is known.
In recent years, resin fine particles having high strength, narrow particle size distribution (monodispersity), and excellent powder flowability are required in the fields of powder coatings, cosmetics, electronic information and the like.
Heretofore, as a method for obtaining resin fine particles having a small particle size distribution, a poor solvent precipitation method using a specific high boiling point solvent in the presence of a polymer surfactant has been proposed (see Patent Document 1). However, this method has a problem that the shape of the resin fine particles can not be controlled and the powder flowability is not sufficient. In addition, since the polymeric active agent remains, there is also a disadvantage such as a decrease in strength.

Patent No. 5403065

  The present invention has been made in view of the above problems of the prior art, and an object of the present invention is to obtain polyolefin resin composition particles excellent in circularity, strength and powder flowability of particles and having a narrow particle size distribution. It is in providing a manufacturing method.

The present inventors arrived at the present invention as a result of earnestly examining in order to solve the above-mentioned subject. That is, the present invention contains a polyolefin resin (A) and an inorganic particle (B), and manufacture of a polyolefin resin composition particle (P) having an average value of circularity of 0.80 or more as defined by the formula (1). A polyolefin resin composition containing a polyolefin resin (A) and inorganic particles (B), an acid-modified polyolefin (C) as a dispersant, and a polyoxyalkylene containing 60% by weight or more of an oxyethylene group The polyol (D) and a polyurethane (E) formed by reacting an polyoxyalkylene polyol containing 60% by weight or more of an oxyethylene group and an organic polyisocyanate are melt-kneaded to obtain a mixture of the above (D) and the above (E). After obtaining a resin composition (G) in which polyolefin resin composition particles (P) are dispersed in a mixture, the above (G) and water are mixed to obtain (D) 及前 Symbol a (E) is dissolved in water, is a manufacturing method of the (P) a polyolefin resin composition particles to separate (P).

  According to the production method of the present invention, polyolefin resin composition particles excellent in the degree of circularity, the strength and the powder flowability of particles and having a narrow particle size distribution can be obtained.

  The method for producing the polyolefin resin composition particles (P) of the present invention comprises the steps of preparing the polyolefin resin composition containing the polyolefin resin (A) and the inorganic particles (B) in the presence of the acid-modified polyolefin (C) as a dispersant. A polyurethane obtained by reacting a polyoxyalkylene polyol (D) containing 60% by weight or more of an oxyethylene group as a dispersion medium with a polyoxyalkylene polyol containing 60% by weight or more of an oxyethylene group and an organic polyisocyanate The dispersion of the resin composition particles (P) is separated from the dispersion obtained by mixing with water and dissolving (D) and (E) as dispersion medium in water.

  As a polyolefin resin (A) in this invention, the polymer of a C2-C30 (preferably 2-12, still more preferably 2-10) olefin is mentioned. The polyolefin resin (A) may be used alone or in combination of two or more.

As a C2-C30 olefin, C2-C30 alpha-olefin, C4-C30 diene, etc. are mentioned.
Examples of the α-olefin having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icosene and 1- Tetrakosene etc. are mentioned.
Examples of the diene having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene and 1,11-dodecadiene.

Among the olefins having 2 to 30 carbons, ethylene, propylene, α-olefins having 4 to 12 carbons, butadiene and isoprene are preferable from the viewpoint of molecular weight control, and ethylene, propylene and carbon number are more preferable. 4 to 10 α-olefins and butadiene, particularly preferably ethylene, propylene and butadiene.
The olefin having 2 to 30 carbon atoms may be used alone or in combination of two or more.

The melt flow rate (hereinafter abbreviated as MFR, unit is g / 10 min) of the polyolefin resin (A) is preferably 0.5 to 200 from the viewpoint of moldability of the polyolefin resin composition particles (P), and further Preferably it is 1-150.
Here, MFR is a numerical value that represents the melt viscosity of the resin, and the larger the numerical value, the lower the melt viscosity. For the measurement of MFR, the extrusion type plastometer specified in JIS K 6760 is used, and the measurement method is based on the method specified in JIS K 7210 (1976). For example, in the case of polypropylene, it is measured at 230 ° C. under a load of 2.16 kgf.

The polyolefin resin (A) can be produced by a known method such as a method of polymerizing an olefin having 2 to 30 carbon atoms.
The polyolefin resin (A) can be obtained from the market as Sun Aroma PM 600 A, Sun Aroma PM 900 A, Sun Aroma PM 472 W, Sun Aroma VMD 81 M, Sun Aroma PM 731 M, Sun Aroma PMA 20 V (all are polypropylene polymers manufactured by Sun Aroma Co., Ltd.) and the like.

  The strength of the polyolefin resin composition particles (P) in the present invention is improved by containing the inorganic particles (B).

As the inorganic particles (B), metal oxides (silica, alumina and titania etc.), metal carbonates (calcium carbonate and magnesium carbonate etc.), phosphates (tricalcium phosphate etc.) and silicates (talc, And kaolin, clay, diatomaceous earth, bentonite, etc.
Among these, metal oxides and silicates are preferred in view of strength, and talc and kaolin are more preferred.
The inorganic particles (B) may be used alone or in combination of two or more.

  The volume average particle diameter of the inorganic particles (B) is preferably 1 to 20,000 nm, more preferably 5 to 10,000 nm, particularly preferably 1, from the viewpoint of the dispersibility of the inorganic particles (B). It is 000-8,000 nm.

Examples of the acid-modified polyolefin (C) in the present invention include acid-modified polyolefins in which a carboxyl group or an acid anhydride group is introduced into the polyolefin.
When dispersing a polyolefin resin composition containing a polyolefin resin (A) and inorganic particles (B) to obtain polyolefin resin composition particles (P), circularity can be obtained by using an acid-modified polyolefin (C) as a dispersant And the particle size distribution is narrow (P) can be obtained.

  As polyolefins used in (C), those obtained by the polymerization method of one or two or more mixtures of olefins having 2 to 12 or more carbon atoms (preferably propylene and / or ethylene) and polyolefins of high molecular weight Mention may be made of low molecular weight polyolefins obtained by thermal degradation methods (preferably polypropylene and / or polyethylene). Among these, polypropylene is preferable from the viewpoint of the dispersibility of the polyolefin resin composition particles (P). The acid-modified polyolefin (C) may be used alone or in combination of two or more.

  The number average molecular weight (hereinafter abbreviated as Mn) of the polyolefin used in (C) is preferably 500 to 20,000, more preferably 800 to 18,000, and particularly preferably 1,000 to 16,000. As polyolefin used for (C), what has 1-40 (more preferably 2-30, especially preferably 3-20) terminal double bond per 1000 carbon is preferable. From the viewpoint of ease of modification, low molecular weight polyolefins by thermal decomposition (especially polyethylene and polypropylene having a Mn of 1,000 to 5,000) are preferred. The low molecular weight polyolefin by the thermal decomposition method can be obtained, for example, by the method described in JP-A-3-62804.

  Introduction of a carboxyl group or an acid anhydride group may be carried out by modification with an α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid and / or an anhydride thereof; the same shall apply hereinafter) or oxygen It can be carried out by oxidation with ozone and / or it may be further denatured with lactams or aminocarboxylic acids. Examples of α, β-unsaturated carboxylic acids (anhydrides) used for modification include monocarboxylic acids, dicarboxylic acids and their anhydrides, such as (meth) acrylic acid, (anhydride) maleic acid, fumaric acid (anhydride) Examples thereof include itaconic acid and (anhydrous) citraconic acid. Preferred among these are (maleic anhydride) and fumaric acid, in particular (maleic anhydride). The amount of acid (anhydride) used for modification is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight based on the weight of the polyolefin.

  The modification with α, β-unsaturated carboxylic acid (anhydride) is carried out by either solution method or melting method (for example, the method described in JP-A-3-91547) at the terminal double bond of polyolefin. It can be carried out by thermally adding (ene reacting) an α, β-unsaturated carboxylic acid (anhydride) or reacting in the presence of a radical initiator. The temperature at which the polyolefin is reacted with the α, β-unsaturated carboxylic acid (anhydride) is preferably 170 to 230 ° C. Introduction of a carboxyl group by oxidation can be carried out, for example, by the method described in US Pat. No. 3,692,877.

  In the present invention, when forming the polyolefin resin composition particles (P), the degree of circularity is high by using a polyoxyalkylene polyol (D) containing 60% by weight or more of an oxyethylene group as a dispersion medium of (P). And the particle size distribution is narrow (P).

  The polyoxyalkylene polyol (D) containing 60% by weight or more of an oxyethylene group is a C2 to C12 alkylene oxide (hereinafter abbreviated as AO) adduct to a C2 to C20 polyhydric alcohol, And those containing 60% by weight or more of oxyethylene group.

  As a C2-C20 polyhydric alcohol, a C2-C12 linear or branched aliphatic dihydric alcohol [ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol and tetraethylene glycol Chain alcohols; 1,2-, 1,3- or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2- Methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,6-hexa Diol, 3-methyl-1,6-hexanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptanediol, 4-methyl-1,7-heptanediol, 2-methyl- 1, 8-octanediol, branched alcohols such as 3-methyl-1, 8-octanediol and 4-methyloctanediol, etc.]; alicyclic dihydric alcohol having 6 to 20 carbon atoms [1, 4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7 -Norbornane diol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, 1,4 Bis (hydroxymethyl) cyclohexane and 2,2-bis (4-hydroxycyclohexyl) propane and the like]; C 8-20 aromatic aliphatic dihydric alcohol [m- or p-xylylene glycol, bis (hydroxyethyl) benzene And bis (hydroxyethoxy) benzene etc .; trihydric alcohols having 3 to 20 carbon atoms [aliphatic triols (glycerin and trimethylolpropane etc. etc)]; tetravalent alcohols having 5 to 20 carbon atoms [aliphatic polyols Pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin and dipentaerythritol etc .; sugars (sucrose, glucose, mannose, fructose, methyl glucoside and derivatives thereof)] and the like.

  Examples of AO having 2 to 12 carbon atoms include ethylene oxide (hereinafter, abbreviated as EO), propylene oxide (hereinafter, abbreviated as PO), 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, α-olefin oxide, styrene oxide, epihalohydrin (epichlorohydrin etc.) and combinations of two or more of these can be mentioned.

  As the polyoxyalkylene polyol (D), polyethylene glycol and EO / PO copolymer diol are preferable from the viewpoint of solubility in water, and polyethylene glycol is more preferable.

  The content of the oxyethylene group in the polyoxyalkylene polyol (D) is 60% by weight or more, preferably 80% by weight or more, and more preferably 100% by weight from the viewpoint of solubility in water.

  The Mn of the polyoxyalkylene polyol (D) is preferably 5,000 to 30,000, and more preferably 10,000 to 30,000 from the viewpoint of the dispersibility of the polyolefin resin composition particles (P) and the solubility of (D) in water. It is.

The Mn of the polyol in the present invention can be measured by gel permeation chromatography. The measurement conditions of Mn are as follows.
Device: "Waters Alliance 2695" (manufactured by Waters)
Column: One “Guard column Super H-L” (one), “TSK gel Super H 2000, TSK gel Super H 3000, TSK gel Super H 4000 (each manufactured by Tosoh Corporation)”
Sample solution: 0.25% by weight of tetrahydrofuran solution Injection amount: 10 μl
Flow rate: 0.6 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polyethylene glycol

  By using the polyurethane (E) as the dispersion medium of (P) when forming the polyolefin resin composition particles (P) in the present invention, it becomes possible to apply a stronger shearing force to the dispersion system, The circularity can be further increased and the particle size distribution can be further narrowed.

  The polyurethane (E) in the present invention is obtained by reacting a polyoxyalkylene polyol containing 60% by weight or more of an oxyethylene group and an organic polyisocyanate.

  As a polyoxyalkylene polyol which contains 60 weight% or more of oxyethylene groups used for polyurethane (E), the thing similar to the above-mentioned polyoxyalkylene polyol (D) is mentioned, A preferable thing is also the same.

  As the organic polyisocyanate, a linear aliphatic polyisocyanate having 4 to 22 carbon atoms having 2 to 3 or more isocyanate groups, an alicyclic polyisocyanate having 8 to 18 carbon atoms, an aromatic having 8 to 26 carbon atoms Group polyisocyanate and aromatic aliphatic polyisocyanate having 10 to 18 carbon atoms, and the like. The organic polyisocyanate may be used alone or in combination of two or more.

  Examples of the linear aliphatic polyisocyanate having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 2,2 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2, 6-diisocyanatohexanoate is mentioned.

  As an alicyclic polyisocyanate having 8 to 18 carbon atoms, for example, isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4'-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate can be mentioned.

  Examples of the aromatic polyisocyanate having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter referred to as TDI abbreviation), crude TDI, and 4,4. '-Or 2,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), crude MDI, polyaryl polyisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanate Biphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthyl diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate and m- or p-isocyanatophenylsulfonyl And isocyanates.

  Examples of the aromatic aliphatic polyisocyanate having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethyl xylylene diisocyanate.

  Among these, diisocyanates are preferred, and MDI, TDI, IPDI and HDI are particularly preferred.

  The method for producing the polyurethane (E) is not limited to the above, and a polyoxyalkylene polyol containing 60% by weight or more of an oxyethylene group and an organic polyisocyanate can be reacted by a commonly used method. The reaction temperature is preferably 30 to 200 ° C, more preferably 50 to 180 ° C. The reaction time is preferably 0.1 to 30 hours, more preferably 0.1 to 8 hours.

  By using the organic fine particles (F) when forming the polyolefin resin composition particles (P) in the present invention, it is possible to reduce the surface viscosity at the interface of the dispersion system, and the circularity of (P) is further increased. Also, the particle size distribution can be further narrowed.

  The volume average particle diameter of the organic fine particles (F) is preferably 0.01 μm to 2 μm, and more preferably 0.05 μm to 1 μm from the viewpoint of the degree of circularity and the particle size distribution of (P).

  As the organic fine particles (F), Finesphere FS-102 (volume average particle size 0.1 μm, styrene-acrylic resin), FS-106 (volume average particle size 0.1 μm, acrylic resin), FS-107 (volume average Particle size 0.1 μm, acrylic resin), FS-201 (volume average particle size 0.5 μm, styrene / acrylic resin), FS-301 (volume average particle size 1.0 μm, styrene / acrylic resin), FS-501 (volume average particle size 1.0 μm, styrene / acrylic resin) Volume average particle diameter 0.5 μm, acrylic resin), FS-701 (volume average particle diameter 0.1 μm, fluorinated acrylic resin), MG- 351 (volume average particle diameter 1.0 μm, styrene acrylic resin), and MG- 451 (volume-average particle size 0.1 μm, styrene / acrylic resin) [manufactured by Nippon Paint Industrial Coatings Co., Ltd.] That.

  The amount of the organic fine particles (F) to be used is preferably 0.1% by weight to 10% by weight, more preferably 0.2% by weight to 5% by weight, based on the total weight of (A) and (B).

  In the method for producing polyolefin resin composition particles (P) of the present invention, first, a polyolefin resin composition containing a polyolefin resin (A) and inorganic particles (B) is produced. The polyolefin resin composition is obtained by melt-kneading (A) and (B) under commonly used conditions. The shape of the polyolefin resin composition may be block, pellet or powder.

  The weight ratio of the polyolefin resin (A) to the inorganic particles (B) [(A) :( B)] is preferably 50:50 to 98: 2, more preferably 60:40 to 95: 5 from the viewpoint of strength. It is.

  A polyolefin resin composition containing a polyolefin resin (A) and inorganic particles (B), an acid-modified polyolefin (C) as a dispersant, a polyoxyalkylene polyol (D) as a dispersion medium, and a polyurethane (dispersion medium) E) and, if necessary, melt-kneading the organic fine particles (F) at a temperature of the highest melting point among the melting points of (A), (C), (D) and (E), (A) and A resin composition (G) is formed in which polyolefin resin composition particles (P) containing (B) are dispersed in (D) and (E) as a dispersion medium.

  The apparatus for melt-kneading is not particularly limited, and, for example, a roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, etc. can be used.

  The weight ratio of the total weight of the polyolefin resin composition containing (A) and (B) to the polyoxyalkylene polyol (D) and the polyurethane (E) is from the viewpoint of volume average particle diameter, circularity and particle size distribution, Preferably it is 10: 90-50: 50, More preferably, it is 20: 80-45: 55.

  The weight ratio of the polyoxyalkylene polyol (D) to the polyurethane (E) is preferably 50:50 to 99: 1, more preferably 70:30 from the viewpoint of handling property, volume average particle diameter, circularity and particle size distribution. ~ 97: 3.

  By appropriately selecting the amounts of (C), (D) and (E) used and the conditions of the kneader, it is possible to adjust the degree of circularity, volume average particle diameter and particle size distribution of (P).

  The shape of the resin composition (G) is not particularly limited, and may be in the form of block, pellet or powder, but in the later step, the viewpoint of efficiency of dissolving (D) and (E) in (G) From the above, pellet or powder is preferable.

  (D) and (E) are dissolved in water by mixing the resin composition (G) with water to dissolve (D) and (E) in (G); A dispersion in which P) is dispersed is obtained.

  The weight ratio of the resin composition (G) to water is preferably 10:90 to 50:50, more preferably 15:85, from the viewpoint of handling property and solubility of (D) and (E) in water. 40:60.

The temperature at which the resin composition (G) and water are mixed is preferably 20 to 100 ° C., more preferably 50 to 100, from the viewpoint of handling properties and solubility of (D) and (E) in water. ° C.
The time for mixing the resin composition (G) and water is preferably 0.5 to 10 hours, more preferably 1 to 5 hours, from the viewpoint of handling property and solubility of (D) and (E) in water. It's time.

By solid-liquid separation of the dispersion in which the polyolefin resin composition particles (P) are dispersed, polyolefin resin composition particles (P) are obtained.
As a method of solid-liquid separation, filtration, vacuum filtration, pressure filtration, centrifugation, spray drying and the like can be mentioned. After solid-liquid separation, the polyolefin resin composition particles (P) can be washed with water, dried, sieved, and the like.

  The average value of the circularity of the polyolefin resin composition particles (P) defined by the formula (1) is 0.80 or more, preferably 0.85 or more, more preferably 0 from the viewpoint of powder flowability. .90 or more.

  The circularity of the polyolefin resin composition particles (P) in the present invention is the average value of the circularity determined for 3000 particles using a flow type particle image analyzer [FPIA-3000, manufactured by Sysmex Corporation]. is there.

The volume average particle diameter of the polyolefin resin composition particles (P) is preferably from 1,000 to 200,000 nm (1 to 200 μm), more preferably from 10,000 to 100 nm, from the viewpoint of powder flowability and aggregation between particles. And 1000 nm (10 to 100 μm).
The volume average particle diameter in the present invention can be measured using a flow type particle image analyzer [FPIA-3000, manufactured by Sysmex Corporation].

The coefficient of variation (CV) of the particle size distribution of the polyolefin resin composition particles (P) is preferably 80% or less, more preferably 70% or less, from the viewpoint of fluidity.
The particle size distribution in the present invention can be measured using a laser diffraction scattering type particle size distribution measuring apparatus [LA-700, manufactured by Horiba, Ltd.].

  The polyolefin resin composition particles (P) may be internally or externally added with one or more additives such as a coloring agent and a fluidizing agent.

  The additive can be internally added by adding the additive when melt-kneading the polyolefin resin (A) and the inorganic particles (B). In addition, the additive is removed by mixing the polyolefin resin composition particles (P) and the additive using a known powder mixing apparatus such as a container rotation type mixer, a fixed container type mixer, and a fluid motion type mixer. It can be accompanied.

As colorants, all commonly used dyes and pigments can be used. Specifically, carbon black, iron black, sudan black SM, fast yellow G, benzidine yellow, pigment yellow, indofirst orange, irgasine red, paranitroaniline red, toluidine red, carmine FB, pigment orange R, lake red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayset YG, Orazol Brown B, Oil Pink OP and the like.
If necessary, magnetic powders (powders of ferromagnetic metals (iron, cobalt, nickel, etc.) and powders of magnetite, hematite, ferrite, etc.) can be used as a coloring agent.

  As a fluidizing agent, colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder and the like can be mentioned.

  EXAMPLES The present invention will be further described by way of examples, but the present invention is not limited thereto.

Production Example 1 [Production of Acid-Modified Polyolefin (C-1)]
A low-molecular-weight polypropylene [polypropylene (based on the method specified in JIS K 7210) obtained by the thermal decomposition method in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introducing pipe and pressure reducing device Melt flow rate measured under conditions of 230 ° C. and a load of 2.16 kgf: 10 g / 10 min) obtained by thermal degradation at 410 ± 0.1 ° C. under nitrogen gas flow (80 mL / min). One hundred parts by weight of Mn = 15,000 and the number of double bonds per 1,000 carbon atoms = 1.7 were charged, and heated to 180 ° C. to be uniformly melted. After 5 parts by weight of maleic anhydride was added and dissolved therein, a solution of 2 parts by weight of dicumyl peroxide in 4 parts by weight of xylene was added dropwise over 10 minutes, and stirring was continued at 180 ° C. for 3 hours. Thereafter, xylene and unreacted maleic anhydride were distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (C-1) to which 4.5% by weight of maleic anhydride was added. The Mn of (C-1) was 15,000.

Production Example 2 [Production of Acid-Modified Polyolefin (C-2)]
A low-molecular-weight polypropylene [polypropylene (based on the method specified in JIS K 7210) obtained by the thermal decomposition method in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introducing pipe and pressure reducing device Melt flow rate measured under conditions of 230 ° C. and a load of 2.16 kgf: 10 g / 10 min) obtained by thermal degradation at 410 ± 0.1 ° C. under nitrogen gas flow (80 mL / min). 100 parts by weight of Mn = 3,400, the number of double bonds per 1,000 carbon atoms = 7.0 were charged, and the temperature was raised to 180 ° C. to melt uniformly. After 10 parts by weight of maleic anhydride was added and dissolved therein, a solution of 2 parts by weight of dicumyl peroxide in 4 parts by weight of xylene was added dropwise over 10 minutes, and stirring was continued at 180 ° C. for 3 hours. Thereafter, xylene and unreacted maleic anhydride were distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (C-2) to which 9 wt% of maleic anhydride was added. The Mn of (C-2) was 3500.

Production Example 3 [Production of Pentaerythritol EO Adduct (D-4)]
3.9 parts by weight of pentaerythritol [Perstorp Co., Ltd.], 2 parts by weight of pentaerythritol EO 4 mol adduct [“PNT-40” manufactured by Japan Emulsifier Industry Co., Ltd.] and 0.027 parts by weight of sodium hydroxide are charged in an autoclave, After substituting with argon gas, the pressure was reduced and the temperature was raised to 95.degree.
After dewatering at 0.001 to 0.003 MPa and 95 ° C. for 1 hour, the temperature is lowered to 130 ° C. and 996 parts by weight of ethylene oxide is kept at an autoclave internal pressure of not more than 0.2 MPa. Over the course of 18 hours, the solution was dropped gradually. After completion of the dropwise addition, aging was carried out at 145 to 155 ° C. for 2 hours until the internal pressure of the autoclave showed the same pressure as at the start of dropwise addition to obtain 1000 parts by weight of pentaerythritol EO adduct (D-4). The Mn of (D-4) was 29,000.

Production Example 4 [Production of Polyurethane (E-1)]
120 parts by weight of polyethylene glycol having a Mn of 20000, 32 parts by weight of EO / PO copolymer diol [polypropylene glycol having a Mn of 1600 with EO added thereto; Mn = 8,000, EO content = 80% by weight] and tolylene 1.8 parts by weight of isocyanate (urethane group concentration 0.22%) was reacted at 180 ° C. for 2 hours to obtain polyurethane (E-1) having a weight average molecular weight of 72000.
Production Example 5 [Production of Polyurethane (E-2)]
120 parts by weight of polyethylene glycol having an Mn of 8300, EO / PO copolymer diol [polypropylene glycol having an Mn of 1600 added with EO; Mn = 8,000, EO content = 80% by weight] 32 parts by weight and tolylene An isocyanate 1.8 parts by weight (urethane group concentration 0.22%) was reacted at 180 ° C. for 2 hours to obtain polyurethane (E-2) having a weight average molecular weight of 52000.

Example 1
Polypropylene homopolymer (A-1) as a polyolefin resin (A) [trade name: Sun Aroma PM600A, manufactured by Sun Aroma Co., Ltd.] 95 parts by weight and talc fine particles (B-1) as inorganic particles (B) [trade name: After dry blending 5 parts by weight of Microace P-8, Nippon Talc Co., Ltd., volume average particle diameter: 3.3 μm with a hand mixer, the mixture is kneaded at 190 ° C. and rotational speed 100 rpm using a kneader to give pellets To obtain a polyolefin resin composition. 100 parts by weight of the obtained pellet-like polyolefin resin composition, 5 parts by weight of acid-modified propylene (C-1) obtained in Production Example 1, polyethylene glycol (D-1) [trade name: PEG 20000, Sanyo Chemical Industries, Ltd. Manufactured by Co., Ltd., and 30 parts by weight of the polyurethane (E-1) obtained in Production Example 3 were dry-blended with a hand mixer, and then a kneader with heating equipment at a rate of 10 g / min using a feeder The mixture was kneaded at 190 ° C. and a rotational speed of 100 rpm and pelletized to obtain a resin composition (G-1) in which particles of the polyolefin resin composition were dispersed. 285 parts by weight of the resin composition (G-1) and 560 parts by weight of water were mixed and stirred under reflux to obtain a dispersion liquid of polyolefin resin composition particles (P-1). The obtained dispersion is suction filtered using filter paper, and 200 parts by weight of water is further added to the filtrate and stirred, and the slurry obtained is suction filtered using filter paper, and residual water is removed at 100 ° C. It removed and obtained polyolefin resin composition particles (P-1).

Examples 2 to 16 and Comparative Examples 1 to 2
Polyolefin resin composition particles (P-2) to (P-16) of the present invention and polyolefin resins for comparison in the same manner as in Example 1 except that the raw materials used and the amount used thereof are replaced with those described in Table 1 Composition particles (P'-1) to (P'-2) were obtained. The organic fine particles (F) in Examples 11 and 12 were used as a dry blend together with a polyolefin resin composition, an acid-modified polyolefin (C), a polyoxyalkylene polyol (D) and a polyurethane (E).

Comparative Example 3 [Production of Composite Particle (Y1)]
Polypropylene homopolymer (A1) (trade name: Sun Aroma PM 600A, manufactured by Sun Aroma Co., Ltd.) 95 parts by weight, talc fine particles (C1) [trade name: Microace P in a reaction vessel equipped with a stirrer, a condenser and a thermometer] -8, manufactured by Nippon Talc Co., Ltd., volume average particle diameter: 3.5 μm] 5 parts by weight and 950 parts by weight of xylene were charged and stirred at 125 ° C. for 2 hours to uniformly dissolve polypropylene in xylene. Thereafter, it was cooled to 25 ° C. over 50 minutes (cooling rate: 2 ° C./min) to obtain a suspension of composite particles.
A slurry obtained by adding 50 parts by weight of acetone to the obtained suspension and stirring was wrapped using a 300 mesh wire mesh and squeezed to obtain a residue. Thereafter, with respect to a slurry obtained by adding 50 parts by weight of acetone to the filtrate and stirring, the operation of obtaining the filtrate by repeating the above operation using a 300 mesh wire mesh is repeated twice to obtain a filtrate. The Next, with respect to the finally obtained filtrate, the residual solvent was distilled off at 70 ° C. to obtain composite particles (P3).

  Volume average particle diameter, particle size distribution, average value of circularity, and the following tests of the obtained polyolefin resin composition particles (P-1) to (P-16) and (P'-1) to (P'-3) The tensile yield stress and elongation of the test plate molded from the polyolefin resin composition particles measured by the method are shown in Table 1.

[Measurement method of tensile yield stress and elongation]
The tensile yield stress and the elongation were measured according to JIS K 7161-1, using a dumbbell-shaped test piece of type A1 of JIS K 7139 obtained by injection molding polyolefin resin composition particles. In addition, the average value of three test pieces was made into the measured value, and the thickness of each test piece took the minimum value of five places of a parallel part.

The compositions of the raw materials represented by symbols in Table 1 are as follows.
(A-1): "Sun Aroma PM600A" [polypropylene homopolymer: manufactured by Sun Aroma Co., Ltd.]
(A-2): "Sun Aroma PM 900 A" [polypropylene homopolymer: manufactured by Sun Aroma Co., Ltd.]
(A-3): "Sun Aroma PM-472 W" [polypropylene ethylene block copolymer: manufactured by Sun Aroma Co., Ltd.]
(A-4): “Sun Aroma VMD 81 M” [polypropylene ethylene block copolymer: manufactured by Sun Aroma Co., Ltd.]
(A-5): “Sun Aroma PM 731 M” [polypropylene ethylene random copolymer: manufactured by Sun Aroma Co., Ltd.]
(A-6): "Sun Aroma PMA 20 V" [polypropylene ethylene random copolymer: manufactured by Sun Aroma Co., Ltd.]
(B-1): “Micro Ace P-8” [talc powder: Nippon Talc Co., Ltd., volume average particle diameter = 3.3 μm]
(B-2): "Micro Ace P-2" [talc powder: Nippon Talc Co., Ltd., volume average particle diameter = 7.0 μm]
(B-3): "Satinton SP33" [Kaolin: manufactured by BASF, volume average particle diameter = 1.3 μm]
(B-4): "Sunlight SL-100""calcium carbonate: manufactured by Takehara Chemical Industry, volume average particle diameter = 6.0 μm"
(C-1): Acid-modified polyolefin obtained in Production Example 1 (C-1)
(C-2): Acid-modified polyolefin obtained in Production Example 2 (C-2)
(D-1): "PEG 20000" [Mn = 20000 polyethylene glycol: Sanyo Chemical Industries, Ltd. product]
(D-2): "PEG 13000" [polyethylene glycol of Mn = 13000: manufactured by Sanyo Chemical Industries, Ltd.]
(D-3): "Neupol PE108" [polyethylene glycol propylene glycol copolymer of Mn = 16000: manufactured by Sanyo Chemical Industries, Ltd., weight 60% by weight or more of oxyethylene group]
(D-4): pentaerythritol EO adduct [60% by weight or more of oxyethylene group]
(F-1): “Finesphere FS-106” [acrylic resin fine particles: Nippon Paint Industrial Coatings Co., Ltd., volume average particle diameter = 0.1 μm]
(F-2): “Finesphere MG-451” [Styrene / Acryl resin fine particles: Nippon Paint Industrial Coatings Co., Ltd., volume average particle diameter = 0.1 μm]

The polyolefin resin composition particles (P) obtained by the production method of the present invention can be extremely useful and practically used in industrial applications and various applications. Specifically, skin care product additives such as facial cleanser, sunscreen agent, cleansing agent, lotion, milk, serum, cream, cold cream, after shaving lotion, shaving soap, oil dripping paper, matifant agent, etc. Cosmetics such as foundation, lotion, lotion, mascara, face powder, oran, black ink, mascara, eye line, eye shadow, eye shadow base, nose shadow, lipstick, gloss, gloss, onion, manicure, top coat, etc. Or its modifiers, shampoos, dry shampoos, conditioners, rinses, rinse-in shampoos, treatments, hair tonics, hair setting agents, additives for hair care products such as hair oils, pomades, hair coloring agents, perfumes, eau de cologne, deodorants, bees -Additives for amenity products such as powders, tooth powders, mouthwashes, lip balms, soaps, etc., rheology modifiers such as paints, diagnostic test agents for medical use, mechanical property improvers for molded articles such as automobile materials and building materials, Materials for improving mechanical properties such as films and fibers, raw materials for resin moldings such as rapid prototyping and rapid manufacturing, materials for flash molding, paste resins for plastic sol, powder blocking materials, flow improvers for powders, lubrication Agents, rubber compounding agents, abrasives, thickeners, filter agents and filter aids, gelling agents, flocculants, additives for paints, oil absorbing agents, mold release agents, slip improvers for plastic films and sheets, blocking Various modifiers such as anti-slip agent, gloss adjustor, matte finish, light diffusing agent, surface high hardness improver, toughness improver, spacer for liquid crystal display, black Fillers for cosmetics, base materials and additives for cosmetic foundations, adjuvants for microcapsules, medical materials such as drug delivery systems and diagnostic agents, retention agents for perfumes and agrochemicals, catalysts for chemical reactions and their carriers, gases It can be used for adsorbents, sintered materials for ceramic processing, standard particles for measurement and analysis, particles for the food industry field, materials for powder coatings, and the like.
Specific examples of resin molded products, films, fibers, etc. include housings of electric devices, housings of OA devices, various covers, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases , Switches, various terminal boards, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, Electrical and electronic parts represented by computer related parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio and laser disc (registered trademark) and compact discs Homes represented by camera, VTR, lens for shooting such as projection TV, finder, image device related parts such as finder, filter, prism, Fresnel lens, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts etc. Business electronic products parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, various disc substrate protective films, optical disc player pickup lenses, optical fibers, optical switches, optical connectors and other information equipment related parts, liquid crystal display , Flat panel display, light guide plate of plasma display, Fresnel lens, polarizing plate, polarizing plate protective film, retardation film, light diffusion film, viewing angle widening film, reflective film, antireflection film, Glare films, brightness enhancement films, prism sheets, light guide films for touch panels, jigs for cleaning, motor parts, machine related parts represented by lighters, typewriters etc., optical devices represented by microscopes, binoculars, watches etc. Precision machine related parts, Fuel, exhaust, intake various pipes, air intake nozzle snorkel, intake manifold, fuel pump, connector for fuse, horn terminal, electrical component insulation plate, lamp socket, lamp reflector, lamp housing, engine oil These include filters and igniter cases, which are extremely effective for these various applications.

Claims (3)

It is a manufacturing method of polyolefin resin composition particles (P) which contain polyolefin resin (A) and inorganic particles (B), and whose average value of the degree of circularity defined by Numerical formula (1) is 0.80 or more,
A polyolefin resin composition containing a polyolefin resin (A) and inorganic particles (B),
Acid-modified polyolefin (C) as a dispersant,
A polyoxyalkylene polyol (D) containing 60% by weight or more of an oxyethylene group,
Polyolefin resin composition in the mixture of the above (D) and the above (E) by melt-kneading the polyoxyalkylene polyol containing 60% by weight or more of oxyethylene group and the polyurethane (E) formed by reacting an organic polyisocyanate. After the resin composition (G) in which substance particles (P) are dispersed is obtained, the (G) and water are mixed, and the (D) and the (E) are dissolved in water to obtain the resin composition (G). The manufacturing method of the polyolefin resin composition particle (P) which isolate | separates P).

  The number average molecular weight of the polyoxyalkylene polyol (D) containing 60% by weight or more of the oxyethylene group and the polyoxyalkylene polyol containing 60% by weight or more of the oxyethylene group used for the polyurethane (E) is 5,000 to 30,000 The method according to claim 1.   The method according to claim 1 or 2, wherein the inorganic particles (B) are at least one inorganic particle selected from the group consisting of metal oxides, metal carbonates, phosphates and silicates.