JP6735252B2 - Resin batch masterbatch and method for producing the same, liquid colorant, colored resin composition, and colored resin molded product - Google Patents

Description

The present invention relates to a resin coloring masterbatch, a method for producing a resin coloring masterbatch, a liquid coloring agent, a coloring resin composition, and a coloring resin molded product.

In recent years, various synthetic resins such as thermoplastic resins such as polyethylene and polyvinyl chloride and thermosetting resins such as phenol resin and urea resin are convenient and useful not only in industrial materials but also in daily home life. Widely used as a material.

As a method of coloring these resins, conventionally, a resin and a pigment are melt-kneaded using an extruder or the like, and a method of molding the obtained colored resin pellets; an uncolored resin pellet and a pigment are kneaded at the time of molding, There is a method of coloring at the same time as the molding process. In these methods, a dry color obtained by mixing a pigment and a metallic soap, a colored pellet obtained by kneading a resin pellet with a final coloring concentration of a pigment by an extruder, and the like are used. Further, in recent years, in order to make the pigment more uniformly present in the resin, a so-called masterbatch in which a pigment having a higher concentration than the final coloring concentration is previously dispersed in the resin or the resin mixture is mainly used. The masterbatch is produced, for example, by kneading a resin and a pigment to which various additives are added, if necessary, using a kneader or the like.

Most pigments are powders and are primarily synthesized in water. The produced pigment is present in the form of fine primary particles in water, but the primary particles agglomerate due to heat during drying, and a large number of hard and coarse secondary particles are contained. It is difficult to redisperse fine primary particle pigments in a resin using a pigment containing agglomerated secondary particles. Therefore, when a pigment containing agglomerated secondary particles is used, a large number of coarse pigment particles remain in the obtained masterbatch. When a colored resin molded product (particularly a film or fiber) is manufactured by using a masterbatch containing a large number of coarse pigment particles, the surface of the molded product has a spot, the transparency of the film decreases, and the fiber is spun. Problems such as yarn breakage tend to occur during or during processing.

Further, as a conventional method for producing a masterbatch, an aqueous paste of a pigment synthesized in water and a resin were kneaded at a temperature not lower than the softening point of the resin and not higher than the boiling point of water to transfer the pigment in the water phase to the resin phase. There is a method of removing water later (so-called flushing method). According to this flushing method, the pigment can be finely dispersed in the resin without secondary aggregation.

However, the flushing method cannot be applied to pigments that cannot exist in the form of aqueous pastes such as carbon black and titanium dioxide. Further, the flushing method can be applied only when the softening point of the resin is not higher than the boiling point of water. Therefore, the softening points of 6-nylon, 6,6-nylon, polyethylene terephthalate and the like are remarkably higher than the boiling point of water, and therefore cannot be applied to the flushing method.

As a method other than the above for producing the masterbatch, for example, there is a method of adding an internal lubricant such as various waxes, plasticizers, and surfactants; wetting agent, dispersant, etc. when kneading the resin and the powder pigment. .. In this method, the hard secondary particles formed by aggregating the powder pigment are easily disentangled, so that the dispersibility of the pigment in the master batch can be improved. This method is known as a masterbatch using a resin such as a vinyl chloride resin or a polyolefin resin, or a method for coloring these resins (Patent Document 1).

Further, in recent years, in order to improve the compatibility between the resin and the pigment, the same resin as the molding resin or a similar resin and the pigment are kneaded with a dispersant such as polyethylene wax to prepare a colorant composition. A coloring method in which the colorant composition and a molding resin are kneaded to uniformly disperse the pigment is widely used industrially. This colorant composition is a pellet-shaped, plate-shaped, or flake-shaped colorant (masterbatch) in which a pigment is dispersed in a resin at a high concentration. In addition, a dispersant such as polyethylene wax is blended as an essential component for improving the dispersibility of the pigment in the molded body (Patent Document 2).

JP, 2003-183447, A JP, 2002-179891, A

However, when a masterbatch containing a wax-based dispersant is used, the wax-based dispersant oozes out onto the surface of colored molded products such as films and fibers, and the physical properties of the resin deteriorate due to the effect of the wax-based dispersant. There is something to do. When the physical properties of the resin deteriorate, breakage or yarn breakage may occur during processing such as stretching.

Furthermore, depending on the type of resin, the compatibility with the wax-based dispersant may be poor. Therefore, if other additives are added to improve the compatibility, it may be difficult to incorporate the pigment in a high concentration in the masterbatch.

The present invention has been made in view of such problems of the prior art, and the problem is that the pigment does not contain coarse secondary particles aggregated, and the dispersibility of the pigment is good. Therefore, it is to provide a masterbatch for resin coloring that is colored well without uneven color. Further, the object of the present invention is to provide a method for producing the resin coloring masterbatch, a liquid colorant for producing the resin coloring masterbatch, and a colored resin composition obtained by using the resin coloring masterbatch. The object is to provide an article and a colored resin molded article.

That is, according to the present invention, there is a step of melt-kneading a resin component containing a resin and a liquid colorant containing a colorant containing a pigment and a vegetable oil having an iodine value of 90 or more. And at least one of the liquid colorants further comprises a surfactant having a surface tension of an aqueous solution of 0.1% by mass of 50 mN/m or less and a sedimentation time of 300 seconds or less as measured by a felt natural sedimentation method. Provided is a method for producing a masterbatch for resin coloring, which contains at least one of the resin component and the liquid colorant and further contains metal soap.

Further, according to the present invention, there is provided a resin coloring masterbatch manufactured by the above manufacturing method.

Furthermore, according to the present invention, a coloring agent containing a pigment, a vegetable oil having an iodine value of 90 or more, a surface tension of a 0.1% by mass aqueous solution of 50 mN/m or less, and a sedimentation measured by a felt natural sedimentation method. A liquid colorant containing a surfactant having a time of 300 seconds or less and a metal soap and having a vegetable oil content of 60 to 2,000 parts by mass with respect to 100 parts by mass of the coloring agent is provided. ..

Further, according to the present invention, there is provided a colored resin composition containing a base resin and the resin coloring masterbatch. Further, according to the present invention, there is provided a colored resin molded product comprising the above colored resin composition.

According to the present invention, it is possible to provide a masterbatch for resin coloring in which coarse secondary particles in which pigments are aggregated are scarcely contained, the dispersibility of the pigment is good, and the pigment is favorably colored without color unevenness. Further, according to the present invention, a method for producing the resin coloring masterbatch, a liquid colorant for producing the resin coloring masterbatch, a colored resin composition obtained using the resin coloring masterbatch, and A colored resin molding can be provided.

The resin-coloring masterbatch of the present invention does not substantially require the use of a wax-based dispersant. Therefore, even if the resin has poor compatibility with the wax-based dispersant, it can be used as a resin for a masterbatch, and a resin-coloring masterbatch containing a coloring agent such as a pigment at a high concentration is prepared. be able to. Furthermore, by using the resin-coloring masterbatch of the present invention which does not substantially require the use of a wax-based dispersant, the wax-based dispersant exudes on the surface of the resulting colored molded article, and the physical properties of the resulting colored molded article are improved. It is difficult for problems such as decrease in

<Resin coloring masterbatch and method for producing the same>
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. The method for producing a resin-coloring masterbatch (hereinafter, also simply referred to as “masterbatch”) of the present invention includes a resin component containing a resin, a coloring agent (coloring material) containing a pigment, and a vegetable oil having an iodine value of 90 or more. And a liquid colorant containing (1) is melt-kneaded (melt-kneading step). At least one of the resin component and the liquid colorant is a surfactant having a surface tension of a 0.1% by mass aqueous solution of 50 mN/m or less and a sedimentation time of 300 seconds or less measured by a felt natural sedimentation method. Further contains. Then, at least one of the resin component and the liquid colorant further contains metal soap. Further, the masterbatch of the present invention is manufactured by the above-described masterbatch manufacturing method. Hereinafter, the details of the masterbatch of the present invention and the manufacturing method thereof will be described.

(resin)
Examples of the resin used for the masterbatch (resin for the masterbatch) include thermoplastic resins. As the thermoplastic resin, polyethylene resin (PE resin), polypropylene resin (PP resin), polystyrene resin (PS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile-styrene copolymer resin (AS resin) Examples include general-purpose resins such as acrylonitrile-EPDM-styrene copolymer resin (AES resin). These resins can be used alone or in combination of two or more.

(Colorant)
The colorant includes a pigment. A dye may be used in combination for the purpose of toning. As the pigments and dyes, known organic pigments, inorganic pigments, and dyes conventionally used for coloring printing inks, paints, and thermoplastic resins can be used.

Examples of organic pigments include monoazo pigments, disazo pigments, condensed azo pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, isoindolinone pigments, dioxane pigments, and indigo pigments. More specifically, insoluble azo pigments such as disazo yellow, toluidine red, toluidine maroon, hansa yellow, benzidine yellow, and pyrazolone red; soluble azo pigments such as litol red, heliobordeaux, pigment yellow, pigment scarlet, permanent red 2B; Phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; quinacridone pigments such as quinacridone red and quinacridone magenta; perylene pigments such as perylene red and perylene scarlet; isoindolinone pigments such as isoindolinone yellow and isoindolinone orange; Pyranthrone pigments such as pyranthrone red and pyranthrone orange; thioindigo pigments; condensed azo pigments; benzimidazolone pigments; quinophthalone yellow; nickel azo yellow; perinone orange; anthrone orange; dianthraquinonyl red; dioxazine Examples include violet.

Examples of the inorganic pigment include extender pigments, titanium oxide pigments, iron oxide pigments, spinel pigments and the like. More specifically, carbon black, titanium oxide, red iron oxide, yellow iron oxide, black iron oxide, ferrite, chromium oxide, aluminum oxide, zirconium oxide, manganese oxide, cobalt oxide, nickel oxide, antimony oxide, lanthanum oxide, Cerium oxide, copper oxide, magnesium oxide, bismuth oxide, barium sulfate, zinc oxide, zinc sulfide, zinc hydroxide, cerium hydroxide, lanthanum hydroxide, cobalt hydroxide, nickel hydroxide, manganese hydroxide, vanadium oxide, zinc carbonate , Cobalt carbonate, barium carbonate, calcium carbonate, magnesium carbonate, titanium yellow, cobalt green, titanium cobalt green, cobalt blue, cobalt aluminum chrome blue, cobalt chrome green, cerulean blue, cobalt zinc silica blue, copper chrome black, copper-iron Examples thereof include manganese black, chrome tin pink, chrome alumina pink, vanadium blue, praseodymium yellow, bismuth yellow vanadate, Victoria green, cobalt silicate, zirconium silicate, talc, kaolin and zeolite.

The primary average particle diameter of the pigment is usually 10 μm or less, preferably 1 to 1,000 nm, more preferably 10 to 100 nm. The colorants may be used alone or in combination of two or more. Examples of dyes include direct dyes, basic dyes, cationic dyes, acid dyes, mordant dyes, acid mordant dyes, sulfur dyes, naphthol dyes, disperse dyes, and reactive dyes.

It is preferable to select the pigment, the particle size, and the treatment method, depending on the intended use. For example, when hiding power is required or when transparency is imparted to a colored product, the type of pigment, particle size, etc. may be appropriately selected. The brightening agent is a pigment which is effective as a material that imparts retroreflective properties and light scattering properties to the surface of the obtained molded product and changes the color tone depending on the viewing angle. As a pearl mica pigment, natural mica (mica) or synthetic mica is coated with metal oxides such as titanium oxide, zinc oxide, tin oxide, aluminum oxide, silicon oxide, iron oxide, copper oxide, nickel oxide and cobalt oxide. What was done can be used.

(vegetable oil)
The iodine value of the vegetable oil is 90 or more, preferably 90 to 200. As the vegetable oil, non-drying oil, semi-drying oil, and drying oil can be used. These vegetable oils and fats can be used alone or in combination of two or more. Specific examples of vegetable oils and fats include flaxseed oil, rapeseed oil, soybean oil, cottonseed oil and the like. As the vegetable oils and fats, suitable ones can be selected and used according to the ease of dispersion of the colorant, the addition amount of the colorant, and the like. Among them, it is preferable to use a semi-drying oil or a drying oil having an iodine value of 100 to 140, and it is more preferable to use a vegetable oil (for example, soybean oil) having an iodine value of 120 to 135. The amount of vegetable oil/fat used is preferably 35% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less, based on all components.

(Metal soap)
Metal soap is a component that enhances the affinity of vegetable oils and fats for resins. As the metal soap, a metal salt of fatty acid can be used. Examples of the metal constituting the fatty acid metal salt include magnesium, calcium, barium, manganese, iron, cobalt, nickel, copper, silver, zinc, aluminum and thallium. Specific examples of the metal soap, cobalt octylate, zinc octylate, vanadium octylate, cobalt naphthenate, copper naphthenate, barium naphthenate, lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate. , Barium stearate, zinc stearate, magnesium 12-hydroxystearate, calcium laurate, barium laurate, zinc laurate, barium 2-ethylhexanoate, zinc 2-ethylhexanoate, barium ricinoleate, zinc ricinoleate, etc. Can be mentioned. Of these, a metal salt of stearic acid (having 18 carbon atoms) is preferable from the viewpoint of affinity with colorants such as pigments and resins.

The amount of metal soap is preferably set appropriately according to the amounts of colorant and vegetable oil. If the amount of metal soap is too small, the affinity of fats and oils for the resin tends to decrease, and the dispersibility of the colorant may decrease slightly. On the other hand, if the amount of the metal soap is too large, the shearing is less likely to occur during kneading, and the dispersibility of the colorant in the resin may be reduced. In addition, the ability to meet with each other tends to decrease, which may cause color separation during dilution.

The amount of the metal soap used is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2.5 parts by mass, and even more preferably 0.25 to 1 part by mass relative to 1 part by mass of the colorant. Is particularly preferable.

(Surfactant)
The surface tension of a 0.1 mass% aqueous solution of a surfactant is 50 mN/m or less, preferably 20 to 40 mN/m. If the surface tension of the 0.1% by mass aqueous solution of the surfactant is more than 50 mN/m, the penetrating power into the resin will decrease and the dispersibility cannot be improved. The sedimentation time of the surfactant measured by the felt natural sedimentation method is 300 seconds or less, preferably 150 seconds or less. If the sedimentation time of the surfactant measured by the felt spontaneous sedimentation method exceeds 300 seconds, the penetrating power into the pigment will be reduced.

As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be used. These surfactants may be used alone or in combination of two or more.

Examples of the anionic surfactant include alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate; dialkylsulfosuccinates such as sodium di-2-ethylhexylsulfosuccinate and sodium diisotridecylsulfosuccinate; di(polyoxyethylene 2-ethylhexyl ether). ) Sodium sulfosuccinate, di(polyoxyethylene isotridecyl ether) sodium sulfosuccinate and other dipolyoxyethylene alkyl ether sulfosuccinates; polyoxyalkylenes such as sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate Alkyl ether sulfates; alkyl sulphates such as sodium lauryl sulphate, sodium higher alcohol sulphate, triethanolamine lauryl sulphate, ammonium lauryl sulphate; fatty acid salts such as potassium oleate, sodium oleate, semi-hardened tallow fatty acid sodium etc. it can.

Examples of the cationic surfactant include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride, cetyltrimethylammonium bromide and stearyltrimethylammonium chloride; alkyls such as stearyldimethylbenzylammonium chloride, benzalkonium chloride and lauryldimethylbenzylammonium chloride. Examples thereof include dimethylbenzyl ammonium salt.

Examples of nonionic surfactants include alkylol amides such as coconut oil fatty acid monoethanolamide and lauric acid diethanolamide; polyoxyalkyl phenyl ethers such as polyoxyethylene alkylphenyl ethers; polyoxyethylene alkyls such as polyoxyethylene lauryl ether. Ethers; polyethylene glycol fatty acid esters such as polyethylene glycol distearate; sorbitan monocaprate, sorbitan monostearate, sorbitan monostearate and the like; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate; polyoxy Examples thereof include ethylene sorbit fatty acid ester; polyoxyethylene polyoxypropylene alkyl ether; glycol ether and the like.

Examples of the amphoteric surfactant include alkyl betaines such as coconut oil alkyl betaines; alkylamido betaines such as lauryldimethylaminoacetic acid betaines; imidazolines such as Z-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaines; polyoctyl. Examples thereof include glycines such as polyaminoethylglycine; acetylene-based surfactants, and the like.

It is preferable that the amount of the surfactant is appropriately set according to the amounts of the metal soap, the colorant, and the vegetable oil and fat. If the amount of the surfactant is too large, foaming is likely to occur, the dispersibility of the vegetable oil/fat in the resin may be slightly reduced, or the shearing property may be less likely to occur during kneading, resulting in reduced dispersibility of the colorant. In addition, the ability to meet with each other tends to decrease, which may cause color separation during dilution. On the other hand, when the amount of the surfactant is too small, it may be slightly difficult to disperse the metal soap, the colorant, and the vegetable oil in the resin in a good state.

The amount of the surfactant used relative to 1 part by mass of the colorant is preferably 0.05 to 5 parts by mass, more preferably 0.15 to 5 parts by mass, and 0.25 to 1 part by mass. It is particularly preferable that

(Resin component, liquid colorant)
The resin component contains the resin for the masterbatch described above. The liquid colorant is a component for coloring the resin for the masterbatch, and contains the above-mentioned colorant and a vegetable oil having an iodine value of 90 or more. The liquid colorant is usually liquid or semi-liquid under room temperature (25°C) conditions. At least one of the resin component and the liquid colorant further contains the above-mentioned metal soap. Further, at least one of the resin component and the liquid colorant further contains the above-mentioned surfactant. By using the surfactant, the dispersibility of the colorant, the metallic soap, and the vegetable oil/fat in the resin can be enhanced, and thus a masterbatch having good dispersibility can be produced.

The metal soap and the surfactant may be contained in either the resin component or the liquid colorant. Above all, it is preferable to use a liquid colorant containing a metal soap and a surfactant. That is, in the melt-kneading step, it is preferable to melt-knead the liquid colorant containing the colorant, the vegetable oil and fat, the metal soap, and the surfactant, and the resin component. This makes it possible to produce a resin-coloring masterbatch that is more excellent in the dispersibility of the pigment and is well colored without color unevenness.

As described above, the liquid colorant is usually a liquid or a semi-liquid under room temperature (25° C.) conditions, so that sampling is easy, workability can be improved, and accurate color adjustment is possible. it can. While ensuring fluidity by using vegetable oils and fats that have a high affinity with the surface of the pigment, by further using metal soap, the affinity of vegetable oil and fats for the resin during melt kneading is improved, and the pigment is highly dispersed. Can be a masterbatch. Furthermore, by adding a surfactant to the liquid composition, each component can be dispersed more uniformly. That is, by using the liquid colorant, it is possible to obtain a resin-coloring masterbatch that has good pigment dispersibility and is well-colored without color unevenness, even if the wax-based dispersant is not substantially contained. ..

(Melting and kneading process)
In the melt-kneading step, the resin component and the liquid colorant are melt-kneaded at a temperature preferably exceeding the softening point of the resin. The masterbatch of the present invention can be obtained by melt-kneading. If necessary, each component may be dispersed by using a dispersing machine such as a ball mill, a roll mill, a sand mill and a dissolver. When dispersing each component, various dispersants such as polycarboxylic acid-based dispersants, silane coupling agents, titanate-based coupling agents, silicone-based dispersants, and organic copolymer-based dispersants may be used in combination. Good.

A kneader can be used for melt-kneading the resin component and the liquid colorant. Examples of the kneader include a kneader, a Banbury mixer, a single-screw extruder, a same-direction multi-screw extruder, a different-direction multi-screw extruder, a two-roll, a three-roll, a continuous kneader, and a continuous two-roll. Can be mentioned.

When the resin component and the liquid colorant are melt-kneaded, the following modes (a) to (e) can be adopted, for example. Among them, the mode (a) is preferable in terms of cost and dispersibility.
(A) A liquid colorant containing a colorant, vegetable oil, a metallic soap and/or a surfactant is kneaded into a resin.
(B) A liquid colorant containing a colorant, vegetable oil, a metal soap and/or a surfactant is kneaded into a resin component containing a resin and a surfactant.
(C) A liquid colorant containing a colorant, a vegetable oil, a metal soap and/or a surfactant is kneaded into a resin component containing a resin and a metal soap.
(D) A liquid colorant containing a colorant, vegetable oil, a metal soap and/or a surfactant is kneaded into a resin component containing a resin, a surfactant and a metal soap.
(E) A liquid colorant containing a colorant and a vegetable oil is kneaded into a resin component containing a resin, a surfactant and a metal soap.

(Other processes)
It is preferable to cool the melt-kneaded product obtained in the above-mentioned melt-kneading step, then pulverize it using a pulverizer or the like, and knead the obtained pulverized product again. Examples of the crusher include a pin mill, a disc mill, a screen mill, a turbo mill and a jet mill. It is preferable to pre-pulverize the melt-kneaded product by using a coarse pulverizer such as a cutter mill or a hammer mill before using the pulverizer, because the load on the pulverizer can be reduced. Further, the melt-kneaded product can be granulated into a pellet-shaped master batch using a granulator. As the granulator, a single-screw or twin-screw extruder, a compression granulator, or the like can be used.

(Masterbatch for resin coloring)
The resin coloring masterbatch of the present invention is manufactured by the above-described method for manufacturing a resin coloring masterbatch. That is, the masterbatch of the present invention can be produced by melt-kneading a resin component containing a resin and a liquid colorant containing a colorant and a predetermined vegetable oil and fat.

The content of the resin in the masterbatch is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more. The content of the colorant in the masterbatch is preferably 40% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less. By setting the contents of the resin and the colorant in the masterbatch within the above ranges, each component can be met in a better state, and a masterbatch having more excellent physical properties can be obtained. When the content of the resin is less than 30% by mass, it may be difficult to maintain the shape of the resin. If the content of the colorant is more than 40% by mass, it may be difficult to obtain a kneaded product in which the resin and the colorant are integrated in a better state.

(Other ingredients)
The masterbatch of the present invention may contain other components, if necessary, within a range that does not impair the effects of the present invention. Examples of other components include various additives such as a light stabilizer, a polymerization inhibitor, an antistatic agent, an inorganic filler, an organic filler, a plasticizer, and an ultraviolet absorber.

<Colored resin composition and colored resin molded body>
The masterbatch of the present invention can be used in the same manner as a conventionally known masterbatch used for coloring a resin. That is, by combining the above masterbatch with the base resin, a colored resin composition containing the base resin and the masterbatch can be obtained. Further, by molding this colored resin composition into a desired shape, it is possible to obtain a colored resin molded product such as a fiber, a film, various molded products, and a powder coating material. The masterbatch may be suspended or dissolved in water, a solvent or the like to prepare a paint, an ink, a developer for electrophotography and the like.

A colored resin molded product can be obtained by diluting the masterbatch with a base resin such as a polypropylene resin to an appropriate concentration and then molding the product using an inflation device or a T-die device. The polypropylene resin used as the base resin is preferably of the same type (same quality) as the resin used for the masterbatch (resin for masterbatch). Further, the temperature of the cylinder and the die of the inflation device or the T-die device may be set to, for example, 180 to 320°C.

By using the masterbatch, the base resin can be colored at the same time as the molding process. The amount of the masterbatch with respect to 100 parts by mass of the base resin is preferably 0.5 to 20 parts by mass, and more preferably 1 to 5 parts by mass. By setting the amount of the masterbatch with respect to the base resin within the above range, the dispersibility of the colorant becomes better and a more stable coloring effect can be obtained. Further, the content of the colorant in the colored resin molded product is preferably 0.1 to 10% by mass, and more preferably 0.2 to 5% by mass, based on the total mass of the colored resin molded product. More preferable.

The method of molding the colored resin composition (molding method) is not particularly limited. Examples of the molding method include a general injection molding method, an injection foam molding method, a supercritical injection foam molding method, an injection compression molding method, a gas assist injection molding method, a sandwich molding method, and a sandwich foam molding method. You can

A film-shaped or sheet-shaped molded product can be produced by molding the colored resin composition using a molding machine by a general film molding method or sheet molding method. As the molding machine, an extrusion molding machine, a hollow molding machine, a vacuum molding machine, a pressure molding machine, a compression molding machine, a calender molding machine, or the like can be used. The thickness of the film-shaped molded product and the sheet-shaped molded product may be appropriately adjusted depending on the application. Specifically, the thickness is preferably 0.1 to 500 μm, more preferably 1 to 100 μm.

In addition, a fibrous molded body can be manufactured by spinning the colored resin composition using a spinning machine. The fiber diameter of the fibrous molded body may be appropriately adjusted according to the application. Specifically, the thickness is preferably 1 to 1,000 μm, more preferably 1 to 500 μm, and particularly preferably 5 to 200 μm. The fibrous molded body may be cut into an appropriate length or may be bundled into a fiber bundle. Further, it can be processed into a cloth or a non-woven fabric.

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. In addition, "part" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

<Each component>
(resin)
As the resin, low density polyethylene (trade name "Suntech LDPE M2270", manufactured by Asahi Kasei) was prepared.

(Pigment)
As a pigment, a phthalocyanine-based pigment (trade name "Cyanine Blue 4920", manufactured by Dainichiseika Chemical Industry Co., Ltd.) was prepared.

(vegetable oil)
The vegetable oils and fats of the types shown in Table 1 were prepared.

(wax)
As a wax-based dispersant (wax), a low-molecular-weight polyethylene wax (trade name "Sun Wax 151-P", manufactured by Sanyo Chemical Industry Co., Ltd.) was prepared.

(Surfactant)
The types of surfactants shown in Table 2 were prepared.

<Manufacture of masterbatch>
(Example 1)
A liquid colorant was prepared by mixing 4 parts of a pigment, 5 parts of soybean oil, 2 parts of a metal soap (Mg-St), and 4 parts of a surfactant A, and dispersing the mixture using a triple roll under room temperature conditions. After 85 parts of the resin was put in a kneader and kneaded at 120 to 140° C. to obtain a molten state, the whole amount of the liquid colorant was added and further kneaded to obtain a masterbatch.

(Examples 2 to 20, Comparative Examples 1 to 5)
A masterbatch was obtained in the same manner as in Example 1 except that the formulations shown in Tables 3-1 to 3-3 were used.

(Example 21)
A liquid colorant was prepared by mixing 4 parts of the pigment and 5 parts of soybean oil and dispersing them using a triple roll under room temperature conditions. 2 parts of metal soap (Mg-St), 4 parts of surfactant D, and 85 parts of resin were put in a kneader and kneaded at 120 to 140° C. to obtain a molten state, and then the whole amount of the liquid colorant was added. The mixture was kneaded to obtain a masterbatch.

(Example 22)
A liquid colorant was prepared by mixing 4 parts of pigment, 5 parts of soybean oil, and 2 parts of metal soap (Mg-St) and dispersing them using a triple roll under room temperature conditions. 4 parts of Surfactant D and 85 parts of resin were put in a kneader and kneaded at 120 to 140° C. to obtain a molten state. Then, the entire amount of the liquid colorant was added and further kneaded to obtain a masterbatch.

(Example 23)
A liquid colorant was prepared by mixing 4 parts of pigment, 5 parts of soybean oil, and 4 parts of surfactant D, and dispersing the mixture using a triple roll under room temperature conditions. 2 parts of metal soap (Mg-St) and 85 parts of resin were put in a kneader and kneaded at 120 to 140° C. to be in a molten state, and then the whole amount of the liquid colorant was added and further kneaded to obtain a masterbatch. ..

(Example 24)
A liquid colorant was prepared by mixing 4 parts of pigment, 5 parts of soybean oil, 1 part of metal soap (Mg-St), and 4 parts of surfactant D, and dispersing the mixture using a triple roll under room temperature conditions. 1 part of metallic soap (Zn-St) and 85 parts of resin were put in a kneader and kneaded at 120 to 140° C. to make a molten state. Then, the whole amount of the liquid colorant was added and further kneaded to obtain a masterbatch. ..

(Example 25)
A liquid colorant was prepared by mixing 4 parts of pigment, 5 parts of soybean oil, 2 parts of metal soap (Mg-St), and 2 parts of surfactant D, and dispersing the mixture using a triple roll under room temperature conditions. After putting 2 parts of the surfactant C and 85 parts of the resin into a kneader and kneading them at 120 to 140° C. to obtain a molten state, the whole amount of the liquid colorant was added and further kneading to obtain a masterbatch.

(Example 26)
A liquid colorant was prepared by mixing 4 parts of pigment, 5 parts of soybean oil, 1 part of metal soap (Mg-St), and 2 parts of surfactant D, and dispersing the mixture using a triple roll under room temperature conditions. 1 part of metallic soap (Zn-St), 2 parts of surfactant C, and 85 parts of resin were put in a kneader and kneaded at 120 to 140° C. to obtain a molten state, and then the whole amount of the liquid colorant was added. The mixture was kneaded to obtain a masterbatch.

(Example 27)
A liquid colorant was prepared by mixing 4 parts of pigment, 5 parts of soybean oil, 1 part of metal soap (Mg-St), and 2 parts of surfactant D, and dispersing the mixture using a triple roll under room temperature conditions. 2 parts of metallic soap (Zn-St), 1 part of surfactant C, and 85 parts of resin were put into a kneader and kneaded at 120 to 140° C. to be in a molten state, and then the whole amount of the liquid colorant was added. The mixture was kneaded to obtain a masterbatch.

(Comparative example 6)
4 parts of pigment and 4 parts of metal soap (Zn-St) were mixed to prepare a powdery pigment dispersion. 92 parts of the resin was put in a kneader and kneaded at 120 to 140° C. to obtain a molten state, and then an appropriate amount of water and the total amount of the pigment dispersion were added and further kneaded to obtain a masterbatch.

(Comparative Example 7)
4 parts of pigment and 4 parts of metal soap (Zn-St) were mixed to prepare a powdery pigment dispersion. 88 parts of the resin was put in a kneader and kneaded at 120 to 140° C. to obtain a molten state, and then an appropriate amount of water, 4 parts of surfactant D, and the total amount of the pigment dispersion were added and further kneaded to prepare a masterbatch. Obtained.

(Comparative Example 8)
4 parts of the pigment and 4 parts of the wax were mixed and dispersed under a temperature condition of 100° C. using a triple roll to prepare a flake pigment dispersion. After 92 parts of the resin was put in a kneader and kneaded at 120 to 140° C. to obtain a molten state, the entire amount of the pigment dispersion was added and further kneaded to obtain a masterbatch.

(Comparative Example 9)
84 parts of resin was put in a kneader and kneaded at 120 to 140° C. to obtain a molten state, and then 4 parts of pigment, 2 parts of soybean oil, 2 parts of metal soap (Zn-St), 4 parts of wax, and surfactant D. 4 parts were added and further kneaded to obtain a masterbatch.

(Comparative Example 10)
2 parts of soybean oil, 2 parts of metal soap (Mg-St), and 4 parts of surfactant D were mixed and dispersed using a triple roll under room temperature conditions to prepare a kneaded product. 4 parts of pigment, 4 parts of metal soap (Zn-St), and 84 parts of resin were put in a kneader and kneaded at 120 to 140° C. to be in a molten state, and then the entire amount of the kneaded product was added and further kneaded to obtain a master. Got a batch.

(Comparative Example 11)
A liquid colorant was prepared by mixing 4 parts of the pigment and 5 parts of soybean oil and dispersing them using a triple roll under room temperature conditions. 6 parts of metal soap (Mg-St) and 85 parts of resin were put in a kneader and kneaded at 120 to 140° C. to obtain a molten state, and then the entire amount of the liquid colorant was added and further kneaded to obtain a masterbatch. ..

(Comparative Example 12)
A liquid colorant was prepared by mixing 4 parts of the pigment and 5 parts of soybean oil and dispersing them using a triple roll under room temperature conditions. 6 parts of Surfactant D and 85 parts of resin were put in a kneader and kneaded at 120 to 140° C. to obtain a molten state, and then the whole amount of the liquid colorant was added and further kneaded to obtain a masterbatch.

(Comparative Example 13)
5 parts of soybean oil, 2 parts of metal soap (Mg-St), and 4 parts of surfactant D were mixed and dispersed using a triple roll under room temperature conditions to prepare a kneaded product. 4 parts of the pigment and 85 parts of the resin were put into a kneader and kneaded at 120 to 140° C. to obtain a molten state. Then, the entire amount of the kneaded product was added and further kneaded to obtain a masterbatch.

(Comparative Example 14)
4 parts of pigment, 5 parts of soybean oil, 2 parts of metal soap (Mg-St), 4 parts of surfactant D, and 85 parts of resin were put in a kneader and kneaded at 120 to 140°C to obtain a masterbatch.

<Evaluation>
(Dispersibility)
A small amount of the produced masterbatch was placed on a hot plate, and pressure was applied from above to form a thin film having a thickness of 0.05 mm. The formed thin film was observed with an optical microscope, and the number of particles (less than 30 μm, 30 μm or more) within a range of 1 cm×1 cm was counted. Then, the dispersibility was evaluated according to the following evaluation criteria. The results are shown in Tables 3-1 to 3-3.
A: 0 or more and less than 10 B: 10 or more and less than 25 C: 25 or more and less than 50 D: 50 or more

(Colorability)
The sensory evaluation analysis based on JIS Z 9080 was performed. Specifically, an injection molding machine (trade name “70Z”, manufactured by Meiki Seisakusho) is used to injection-mold the manufactured masterbatch to prepare a test piece (n=10) of 50 mm×90 mm×20 mm. did. Then, the occurrence of color unevenness on the surface of the produced test piece was observed, and the colorability was evaluated according to the following evaluation criteria. The results are shown in Tables 3-1 to 3-3.
A: No occurrence.
◯: Almost no occurrence.
Δ: Slightly generated
X: Occurred all over.

(Other Examples and Comparative Examples)
A masterbatch was obtained in the same manner as in Examples 1 to 27 and Comparative Examples 1 to 14 except that quinacridone pigments and azo yellow pigments were used instead of the phthalocyanine pigments. When the dispersibility and colorability of the obtained masterbatch were evaluated in the same manner as above, the same results as in Examples 1 to 27 and Comparative Examples 1 to 14 using the phthalocyanine pigment were obtained.

By using the resin-coloring masterbatch of the present invention, various colored moldings such as films and fibers having no color unevenness can be produced.

Claims (10)

A step of melt-kneading a resin component containing a resin, a colorant containing a pigment, and a liquid colorant containing a vegetable oil having an iodine value of 90 or more;
At least one of the resin component and the liquid colorant has a surface tension of an aqueous solution of 0.1% by mass of 50 mN/m or less and a sedimentation time of 300 seconds or less as measured by a felt natural sedimentation method. Further contains an agent,
A method for producing a resin-coloring masterbatch, wherein at least one of the resin component and the liquid colorant further contains a metallic soap. The method for producing a masterbatch for resin coloring according to claim 1, wherein the liquid colorant further contains the surfactant and the metal soap. The method for producing a resin-coloring masterbatch according to claim 1 or 2, wherein the resin component and the liquid colorant are melt-kneaded at a temperature exceeding the softening point of the resin. Content of the said vegetable oils and fats with respect to 100 mass parts of said colorants in the said liquid colorant is 60-2,000 mass parts, The masterbatch for resin coloring as described in any one of Claims 1-3. Production method. The surfactant is at least one selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Item 8. A method for producing a masterbatch for coloring a resin according to Item. A resin-coloring masterbatch produced by the production method according to claim 1. The resin-coloring masterbatch according to claim 6, which contains substantially no wax-based dispersant. An interface in which a coloring agent containing a pigment, a vegetable oil having an iodine value of 90 or more, a surface tension of a 0.1% by mass aqueous solution of 50 mN/m or less, and a sedimentation time of 300 seconds or less measured by a felt natural sedimentation method Contains activator and metal soap,
The liquid colorant, wherein the content of the vegetable oil is 60 to 2,000 parts by mass with respect to 100 parts by mass of the colorant. A colored resin composition containing a base resin and the resin coloring masterbatch according to claim 6 or 7. A colored resin molded product comprising the colored resin composition according to claim 9.