JP2018188577A - Masterbatch for resin coloration and method for producing the same, liquid colorant, colored resin composition, and colored resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a masterbatch for resin coloration which contains almost no coarse secondary particles formed by coagulation of a pigment, has good dispersibility of the pigment, and is satisfactorily colored without color unevenness.SOLUTION: A method for producing a masterbatch for resin coloration includes a step of melt-kneading a resin component containing a resin, and a liquid colorant containing a colorant containing a pigment and vegetable oil and fat having an iodine value of 90 or more, where at least one of the resin component and the liquid colorant further contains a surface active agent which has a surface tension of 0.1 mass% aqueous solution of 50 mN/m or less and has a precipitation time measured by a felt natural precipitation method of 300 seconds or shorter, and at least one of the resin component and the liquid colorant further contains a metallic soap.SELECTED DRAWING: None

Description

  The present invention relates to a resin coloring masterbatch, a method for producing a resin coloring masterbatch, a liquid colorant, a colored resin composition, and a colored resin molding.

  In recent years, various synthetic resins, including thermoplastic resins such as polyethylene and polyvinyl chloride, and thermosetting resins such as phenolic resins and urea resins, are convenient and useful not only for industrial materials but also for 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 colored resin pellet obtained is molded; 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 molding. In these methods, a dry color obtained by mixing a pigment and a metal soap, or a colored pellet obtained by kneading a resin pellet with a pigment adhering to a final coloring concentration with an extruder is used. Further, in recent years, so-called master batches in which a pigment having a concentration higher than the final coloring concentration is previously dispersed in a resin or a resin mixture are mainly used so that the pigment is present more uniformly in the resin. The master batch is manufactured, for example, by kneading a resin and a pigment with various additives as necessary using a kneader.

  Most pigments are powders and are synthesized primarily in water. The formed pigment is present in the form of fine primary particles in water, but the primary particles are aggregated by heat during drying and contain a large number of hard and coarse secondary particles. It is difficult to redisperse the fine primary particle pigment in the resin using the pigment containing the agglomerated secondary particles. For this reason, when a pigment containing aggregated secondary particles is used, many coarse particles of the pigment remain in the obtained master batch. When a colored resin molded product (especially a film or fiber) is produced using a masterbatch containing a large number of coarse pigment particles, the surface of the molded product is fuzzy, the transparency of the film is lowered, and fiber spinning. Problems such as thread breakage occurring at the time or during processing are likely to occur.

  In addition, as a conventional masterbatch production method, an aqueous pigment paste and resin synthesized in water are kneaded at a temperature not lower than the softening point of the resin and not higher than the boiling point of water, so that the pigment in the aqueous phase is transferred 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 an aqueous paste such as carbon black or titanium dioxide. Moreover, the flushing method cannot be applied unless the softening point of the resin is equal to or lower than the boiling point of water. For this reason, since the softening points of 6-nylon, 6,6-nylon, polyethylene terephthalate, and the like are significantly higher than the boiling point of water, they cannot be applied to the flushing method.

  As a method other than the above for producing a masterbatch, for example, when a resin and a powder pigment are kneaded, there are methods of adding various lubricants, internal lubricants such as plasticizers, surfactants, etc .; wetting agents and dispersing agents. . In this method, since the hard secondary particles in which the powder pigment is aggregated are easily loosened, 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).

  Furthermore, in recent years, in order to improve the compatibility between the resin and the pigment, a colorant composition is prepared by kneading the same resin as the molding resin or a similar resin and pigment with a dispersant such as polyethylene wax. 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 colorant (masterbatch) in the form of pellets, plates, flakes, or the like in which a pigment is dispersed in a high concentration in a resin. 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, if a masterbatch containing a wax-based dispersant is used, it will ooze out on the surface of a colored molded article such as a film or fiber from which the wax-based dispersant is obtained, or the physical properties of the resin will decrease due to the influence of the wax-based dispersant. Sometimes. If the physical properties of the resin deteriorate, tearing or thread breakage may easily occur during processing such as stretching.

  Furthermore, depending on the type of resin, the compatibility with the wax-based dispersant may be poor. For this reason, when other additives are blended in order to improve the compatibility, it may be difficult to contain the pigment in the master batch at a high concentration.

  The present invention has been made in view of such problems of the prior art, and the problem is that almost no coarse secondary particles aggregated with the pigment are contained, and the dispersibility of the pigment is good. It is another object of the present invention to provide a resin coloring masterbatch that is favorably colored without color unevenness. Moreover, the place made into the subject of this invention is the coloring resin composition obtained by using the manufacturing method of the said resin coloring masterbatch, the liquid colorant for manufacturing the said resin coloring masterbatch, and the said resin coloring masterbatch And providing a colored resin molded body.

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

  Moreover, according to this invention, the masterbatch for resin coloring manufactured by said manufacturing method is provided.

  Furthermore, according to the present invention, the colorant containing the pigment, the vegetable oil and fat having an iodine value of 90 or more, the surface tension of the 0.1% by mass aqueous solution is 50 mN / m or less, and the sedimentation measured by the 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 colorant is provided. .

  Moreover, according to this invention, the colored resin composition containing base resin and the said masterbatch for resin coloring is provided. Furthermore, according to this invention, the colored resin molding which consists of the said colored resin composition is provided.

  According to the present invention, it is possible to provide a resin coloring masterbatch that contains almost no coarse secondary particles in which pigments are aggregated, has good dispersibility of the pigment, and is favorably colored without color unevenness. Moreover, 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 molded body can be provided.

  In the master batch for resin coloring of the present invention, it is not necessary to substantially use a wax-based dispersant. For this reason, even if it is resin with poor compatibility with a wax-type dispersing agent, while being able to use as resin for masterbatch, it is set as the resin coloring masterbatch which contained colorants, such as a pigment, in high concentration. be able to. Furthermore, if the master batch for resin coloring according to the present invention, which does not require the use of a wax-based dispersant, is used, the wax-based dispersant oozes out on the surface of the resulting colored molded body, or the physical properties of the resulting colored molded body It is difficult to cause problems such as lowering.

<Masterbatch for resin coloring and its manufacturing method>
Embodiments of the present invention will be described below, 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 comprises a resin component containing a resin, a colorant (coloring material) containing a pigment, and a vegetable oil and fat having an iodine value of 90 or more. And a liquid colorant containing a step of melt-kneading (melt-kneading step). At least one of the resin component and the liquid colorant is a surfactant in which the surface tension of a 0.1% by mass aqueous solution is 50 mN / m or less and the sedimentation time measured by the felt natural sedimentation method is 300 seconds or less. Furthermore, it contains. At least one of the resin component and the liquid colorant further contains a metal soap. Moreover, the masterbatch of this invention is manufactured by said manufacturing method of a masterbatch. Hereinafter, the details of the master batch of the present invention and the production method thereof will be described.

(resin)
Examples of the resin used for the master batch (resin for master batch) include thermoplastic resins. As thermoplastic resins, 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) And 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.

(Coloring agent)
The colorant includes a pigment. A dye may be used in combination for the purpose of toning. As the pigment and dye, 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, disazo, condensed azo, phthalocyanine, quinacridone, anthraquinone, isoindolinone, dioxane, 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 lithol red, heliobordeaux, pigment yellow, pigment scarlet, and 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; Pilanthrone pigments such as pyranthrone red and pyranthrone orange; thioindigo pigments; condensed azo pigments; benzimidazolone pigments; quinophthalone yellow Nickel azo yellow; perinone orange; Anse Ron orange; Dianthraquinonyl Red; such as dioxazine violet can be mentioned.

  Examples of inorganic pigments include extender pigments, titanium oxide pigments, iron oxide pigments, and spinnel pigments. 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 manganese black, chrome tin pink, chrome alumina pink, can be mentioned vanadium blue, praseodymium yellow, bismuth vanadate yellow, Victoria green, silicate cobalt, zirconium silicate, talc, kaolin, zeolite and the like.

  The primary average particle diameter of the pigment is usually 10 μm or less, preferably 1 to 1,000 nm, and more preferably 10 to 100 nm. A coloring agent can be used individually by 1 type or in combination of 2 or more types. Examples of the dye include direct dyes, basic dyes, cationic dyes, acid dyes, mordant dyes, acid mordant dyes, sulfur dyes, naphthol dyes, disperse dyes, and reactive dyes.

  The pigment is preferably used by selecting the type, particle size, and treatment method according to the application. For example, when hiding power is required or when transparency is imparted to a colored product, the type of pigment, particle diameter, and the like may be appropriately selected. The brightening agent is a pigment that is effective as a material that imparts retroreflective properties and light scattering properties to the surface of the resulting molded product and changes the color tone depending on the viewing angle. As pearl mica pigment, natural mica or synthetic mica is coated with metal oxide such as titanium oxide, zinc oxide, tin oxide, aluminum oxide, silicon oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, etc. Can be used.

(vegetable oil)
The iodine value of vegetable oils and fats is 90 or more, preferably 90 to 200. Non-drying oil, semi-drying oil, and drying oil can be used as the vegetable oil. These vegetable oils and fats can be used singly or in combination of two or more. Specific examples of vegetable oils include linseed oil, rapeseed oil, soybean oil, cottonseed oil and the like. As vegetable oils and fats, suitable ones can be selected and used according to the ease of dispersion of the colorant, the amount of colorant added, 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 used is preferably 35% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less in all components.

(Metal soap)
Metal soap is a component that increases the affinity of vegetable oils and fats for resins. As the metal soap, a metal salt of a 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 metal soaps include 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, metal salts of stearic acid (18 carbon atoms) are preferred from the viewpoint of affinity with colorants such as pigments and resins.

  The amount of the metal soap is preferably set as appropriate according to the amount of the colorant and the vegetable oil. If the amount of the metal soap is too small, the affinity of the fats and oils for the resin tends to decrease, and the dispersibility of the colorant may decrease slightly. On the other hand, when the amount of the metal soap is too large, it becomes difficult to take a share at the time of kneading, and the dispersibility of the colorant in the resin may be lowered. In addition, the inertia tends to decrease, and it may cause color separation during dilution.

  The amount of metal soap used relative to 1 part by weight of the colorant is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 2.5 parts by weight, and 0.25 to 1 part by weight. It is particularly preferred that

(Surfactant)
The surface tension of the 0.1% by mass aqueous solution of the surfactant is 50 mN / m or less, preferably 20 to 40 mN / m. When 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 is lowered, and the dispersibility cannot be improved. Further, the settling time of the surfactant as measured by the felt natural settling method is 300 seconds or less, preferably 150 seconds or less. When the settling time of the surfactant measured by the felt natural settling method is more than 300 seconds, the penetrating power to the pigment is lowered.

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

  Examples of the anionic surfactant include alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; dialkylsulfosuccinates such as sodium di2-ethylhexylsulfosuccinate and sodium diisotridecylsulfosuccinate; di (polyoxyethylene 2-ethylhexyl ether) ) Dipolyoxyethylene alkyl ether sulfosuccinates such as sodium sulfosuccinate and di (polyoxyethylene isotridecyl ether) sodium sulfosuccinate; polyoxyalkylenes such as sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate Alkyl ether sulfate; sodium lauryl sulfate, higher alcohol sodium sulfate, lauryl sulfate triethanolamine, lauryl Alkyl sulfates such as ammonium, potassium oleate, sodium oleate, and the like fatty acid salts such as sodium partially hydrogenated tallow fatty acid.

  Cationic surfactants include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium chloride; alkyls such as stearyldimethylbenzylammonium chloride, benzalkonium chloride, and lauryldimethylbenzylammonium chloride. Examples thereof include dimethylbenzylammonium salt.

  Nonionic surfactants include alkylolamides such as coconut oil fatty acid monoethanolamide and lauric acid diethanolamide; polyoxyalkylphenyl ethers such as polyoxyethylene alkylphenyl ether; polyoxyethylene alkyls such as polyoxyethylene lauryl ether Ethers; polyethylene glycol fatty acid esters such as polyethylene glycol distearate; sorbitan fatty acid esters such as sorbitan monocaprate, sorbitan monostearate, sorbitan distearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate; polyoxy Ethylene sorbite fatty acid ester; Polyoxyethylene polyoxypropylene alkyl ether; Glycolate And the like.

  Examples of amphoteric surfactants include alkylbetaines such as coconut oil alkylbetaines; alkylamidobetaines such as lauryldimethylaminoacetic acid betaine; imidazolines such as Z-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine; polyoctyl Examples thereof include glycines such as polyaminoethylglycine; acetylene surfactants.

  The amount of the surfactant is preferably set as appropriate according to the amounts of the metal soap, the colorant, and the vegetable oil. If the amount of the surfactant is too large, foaming is likely to occur, and the dispersibility of the vegetable oil / fat to the resin may be slightly reduced, or shearing may not be easily applied during kneading, and the dispersibility of the colorant may be reduced. In addition, the inertia tends to decrease, and it may cause color separation during dilution. On the other hand, if the amount of the surfactant is too small, it may be somewhat difficult to disperse the metal soap, the colorant, and the vegetable oil in a resin in a good state.

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

(Resin component, liquid colorant)
The resin component contains the resin for the master batch described above. Moreover, a liquid colorant is a component for coloring the resin for masterbatch, and contains the above-mentioned colorant and vegetable oil and fat with 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 aforementioned metal soap. Further, at least one of the resin component and the liquid colorant further contains the aforementioned surfactant. By using the surfactant, the dispersibility of the colorant, metal soap, and vegetable oil / fat into the resin can be increased, and thus a masterbatch having good dispersibility can be produced.

  The metal soap and the surfactant may be contained in any of the resin component and the liquid colorant. Among them, 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 a liquid colorant containing a colorant, vegetable oil and fat, metal soap, and a surfactant, and a resin component. Thereby, while being excellent by the dispersibility of a pigment, the masterbatch for resin coloring colored more satisfactorily without color unevenness can be manufactured.

  As described above, since the liquid colorant is usually liquid or semi-liquid at room temperature (25 ° C.), sampling is easy, workability can be improved, and color adjustment can be accurately performed. it can. While using a vegetable oil that has a high affinity with the pigment surface, fluidity is ensured, and by using a metal soap, the affinity of the vegetable oil to the resin is improved during melt kneading, and the pigment is highly dispersed. Can be a master batch. Furthermore, each component can be more uniformly dispersed by mix | blending surfactant with a liquid composition. That is, by using a liquid colorant, it is possible to obtain a resin-colored masterbatch that has good dispersibility of the pigment and is colored well 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 preferably melt-kneaded at a temperature exceeding the softening point of the resin. It can be set as the masterbatch of this invention by melt-kneading. In addition, as needed, you may disperse | distribute each component using dispersers, such as a ball mill, a roll mill, a sand mill, and a dissolver. When dispersing each component, various dispersants such as polycarboxylic acid dispersants, silane coupling agents, titanate coupling agents, silicone dispersants, organic copolymer dispersants may be used in combination. Good.

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

When the resin component and the liquid colorant are melt-kneaded, for example, the following embodiments (a) to (e) can be employed. Especially, it is preferable from the surface of cost and a dispersibility to set it as the aspect of (a).
(A) A liquid colorant containing a colorant, vegetable oil, metal soap and / or surfactant is kneaded into the resin.
(B) A liquid colorant containing a colorant, vegetable oil, metal soap and / or surfactant is kneaded into a resin and a resin component containing a surfactant.
(C) A liquid colorant containing a colorant, vegetable oil, metal soap and / or surfactant is kneaded into a resin component containing a resin and metal soap.
(D) A liquid colorant containing a colorant, vegetable oil and fat, metal soap and / or surfactant is kneaded into a resin component containing resin, surfactant and metal soap.
(E) A liquid colorant containing a colorant and 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-described melt-kneading step, finely pulverize using a pulverizer or the like, and knead the obtained finely-ground product again. Examples of the pulverizer include a pin mill, a disk mill, a screen mill, a turbo mill, and a jet mill. It is preferable to pre-crush the melt-kneaded product 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 master batch using a granulator. As the granulator, a single-screw or twin-screw extruder, a compression granulator, or the like can be used.

(Master batch 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.

  The content of the resin in the master batch 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 master batch is preferably 40% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less. By making content of resin and a coloring agent in a masterbatch into said range, while being able to make each component hazy in a more favorable state, it can be set as the masterbatch which was excellent in the physical property. If the resin content is less than 30% by mass, it may be somewhat difficult to maintain the resin form. Moreover, when content of a coloring agent exceeds 40 mass%, it may become difficult to obtain the kneaded material which resin and the coloring agent integrated in a better state.

(Other ingredients)
The masterbatch of the present invention can contain other components as necessary within the range not impairing the effects of the present invention. Examples of the 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 molding>
The master batch of the present invention can be used in the same manner as a conventionally known master batch used for coloring a resin. That is, it can be set as the colored resin composition containing base resin and a masterbatch by combining the above-mentioned masterbatch with base resin. Furthermore, it can be set as colored resin moldings, such as a fiber, a film, various moldings, and a powder coating, by shape | molding this colored resin composition in a desired shape. In addition, a masterbatch can be suspended or dissolved in water, a solvent, or the like to prepare a paint, ink, electrophotographic developer, or the like.

  A colored resin molded body can be obtained by diluting the master batch with a base resin such as a polypropylene resin to an appropriate concentration and then molding it using an inflation apparatus, a T-die apparatus or the like. 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). Moreover, what is necessary is just to set the temperature of cylinders and dies, such as an inflation apparatus and a T-die apparatus, to 180-320 degreeC, for example.

  By using the master batch, the base resin can be colored simultaneously with the molding process. The amount of the master batch 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 making the amount of the master batch 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 body is preferably 0.1 to 10% by mass, and preferably 0.2 to 5% by mass based on the total mass of the colored resin molded body. Further preferred.

  The method (molding method) for molding the colored resin composition is not particularly limited. Examples of molding methods include general injection molding methods, injection foam molding methods, supercritical injection foam molding methods, injection compression molding methods, gas-assisted injection molding methods, sandwich molding methods, sandwich foam molding methods, and the like. Can do.

  By using a molding machine and molding a colored resin composition by a general film molding method or sheet molding method, a film-shaped or sheet-shaped molded body can be produced. As the molding machine, an extrusion molding machine, a hollow molding machine, a vacuum molding machine, a pressure forming machine, a compression molding machine, a calendar molding machine, or the like can be used. What is necessary is just to adjust the thickness of a film-form molded object and a sheet-form molded object suitably according to a use. Specifically, the thickness is preferably 0.1 to 500 μm, and more preferably 1 to 100 μm.

  Moreover, a fibrous molded body can be produced by spinning the colored resin composition using a spinning machine. What is necessary is just to adjust the fiber diameter of a fibrous molded object suitably according to a use. 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 shaped product may be cut into an appropriate length or may be bundled into a fiber bundle. Furthermore, it can be processed into a cloth or a non-woven fabric.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

<Each component>
(resin)
Low-density polyethylene (trade name “Suntech LDPE M2270”, manufactured by Asahi Kasei Co., Ltd.) was prepared as the resin.

(Pigment)
As the pigment, a phthalocyanine pigment (trade name “Cyanine Blue 4920”, manufactured by Dainichi Seika Kogyo Co., Ltd.) was prepared.

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

(wax)
A low molecular weight polyethylene wax (trade name “Sun Wax 151-P”, manufactured by Sanyo Chemical Industries, Ltd.) was prepared as a wax-based dispersant (wax).

(Surfactant)
Surfactants of the type shown in Table 2 were prepared.

<Manufacture of master batch>
Example 1
A liquid colorant was prepared by mixing 4 parts of pigment, 5 parts of soybean oil, 2 parts of metal soap (Mg-St), and 4 parts of surfactant A, and dispersing them using a three roll at room temperature. After 85 parts of the resin was put into 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 master batch.

(Examples 2-20, Comparative Examples 1-5)
A master batch 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 pigment and 5 parts of soybean oil and dispersing them using a three-roll system at room temperature. 2 parts of metal soap (Mg-St), 4 parts of surfactant D, and 85 parts of resin are put in a kneader and kneaded at 120 to 140 ° C. to obtain a molten state. The mixture was kneaded to obtain a master batch.

(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 the mixture using a three roll at room temperature. 4 parts of Surfactant D and 85 parts of resin were put into 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 master batch.

(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 three-roll system at room temperature. 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 total amount of the liquid colorant was added and further kneaded to obtain a master batch. .

(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 using three rolls to disperse at room temperature. 1 part of metal soap (Zn-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 total amount of the liquid colorant was added and further kneaded to obtain a master batch. .

(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 them using a three roll at room temperature. 2 parts of the surfactant C and 85 parts of the resin were put into 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 master batch.

(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 three roll at room temperature. 1 part of metal soap (Zn-St), 2 parts of surfactant C, and 85 parts of resin are put in a kneader and kneaded at 120 to 140 ° C. to obtain a molten state. The mixture was kneaded to obtain a master batch.

(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 three roll at room temperature. 2 parts of metal soap (Zn-St), 1 part of surfactant C, and 85 parts of resin are put into a kneader and kneaded at 120 to 140 ° C. to obtain a molten state. The mixture was kneaded to obtain a master batch.

(Comparative Example 6)
A powdery pigment dispersion was prepared by mixing 4 parts of pigment and 4 parts of metal soap (Zn-St). After 92 parts of the resin was put into a kneader and kneaded at 120 to 140 ° C. to obtain a molten state, an appropriate amount of water and the total amount of the pigment dispersion were added and further kneaded to obtain a master batch.

(Comparative Example 7)
A powdery pigment dispersion was prepared by mixing 4 parts of pigment and 4 parts of metal soap (Zn-St). 88 parts of the resin is put into a kneader and kneaded at 120 to 140 ° C. to obtain a molten state, and then an appropriate amount of water, 4 parts of the surfactant D, and the total amount of the pigment dispersion are added and further kneaded. Obtained.

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

(Comparative Example 9)
After 84 parts of resin are put into a kneader and kneaded at 120 to 140 ° C. to obtain a molten state, 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 master batch.

(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 three roll at room temperature to prepare a kneaded product. 4 parts of pigment, 4 parts of metal soap (Zn-St), and 84 parts of resin are put into a kneader and kneaded at 120 to 140 ° C. to obtain a molten state. Got a batch.

(Comparative Example 11)
A liquid colorant was prepared by mixing 4 parts of pigment and 5 parts of soybean oil and dispersing them using a three-roll system at room temperature. 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 be in a molten state, and then the total amount of the liquid colorant was added and further kneaded to obtain a master batch. .

(Comparative Example 12)
A liquid colorant was prepared by mixing 4 parts of pigment and 5 parts of soybean oil and dispersing them using a three-roll system at room temperature. 6 parts of Surfactant D and 85 parts of resin were put into 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 master batch.

(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 three roll at room temperature 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, and then the entire amount of the kneaded product was added and further kneaded to obtain a master batch.

(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 placed in a kneader and kneaded at 120 to 140 ° C. to obtain a master batch.

<Evaluation>
(Dispersibility)
A small amount of the manufactured master batch 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) in the range of 1 cm × 1 cm was counted. And dispersibility was evaluated according to the evaluation criteria shown below. 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)
Sensory evaluation analysis based on JIS Z 9080 was performed. Specifically, using an injection molding machine (trade name “70Z”, manufactured by Meiki Seisakusho Co., Ltd.), the manufactured master batch is injection molded to produce a test piece (n = 10) of 50 mm × 90 mm × 20 mm. did. And the color nonuniformity generation | occurrence | production situation of the produced test piece surface was observed, and coloring property was evaluated according to the evaluation criteria shown below. The results are shown in Tables 3-1 to 3-3.
A: Not generated.
○: Almost no occurrence.
Δ: Slightly generated.
X: Generated throughout.

(Other examples and comparative examples)
Master batches were obtained in the same manner as in Examples 1 to 27 and Comparative Examples 1 to 14 except that quinacridone and azo yellow pigments were used in place of the phthalocyanine pigments. The obtained master batch was evaluated for dispersibility and colorability in the same manner as described above. As a result, the same results as in Examples 1 to 27 and Comparative Examples 1 to 14 using phthalocyanine pigments were obtained.

  If the master batch for resin coloring of this invention is used, various colored molded objects, such as a film and a fiber without a color nonuniformity, can be manufactured.

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 with an iodine value of 90 or more,
At least one of the resin component and the liquid colorant has a surface activity of 0.1 mass% aqueous solution having a surface tension of 50 mN / m or less and a sedimentation time measured by a felt natural sedimentation method of 300 seconds or less. Further containing an agent,
The manufacturing method of the masterbatch for resin coloring in which at least any one of the said resin component and the said liquid colorant further contains a metal soap.   The manufacturing method of the masterbatch for resin coloring of Claim 1 in which the said liquid colorant further contains the said surfactant and the said metal soap.   The manufacturing method of the masterbatch for resin coloring of Claim 1 or 2 which melt-kneads the said resin component and the said liquid colorant at the temperature exceeding the softening point of the said resin.   Content of the said vegetable oil and fat with respect to 100 mass parts of said coloring agents in the said liquid coloring agent is 60-2,000 mass parts, The masterbatch for resin coloring as described in any one of Claims 1-3. Production method.   5. The surfactant according to claim 1, wherein the surfactant is at least one selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. The manufacturing method of the masterbatch for resin coloring as described in a term.   The masterbatch for resin coloring manufactured by the manufacturing method as described in any one of Claims 1-5.   The master batch for resin coloring according to claim 6, which contains substantially no wax-based dispersant. An interface having a coloring agent containing a pigment, a vegetable oil and fat having an iodine value of 90 or more, and a 0.1% by mass aqueous solution having a surface tension of 50 mN / m or less and a sedimentation time of 300 seconds or less as measured by the felt natural sedimentation method. Containing an activator and a metal soap,
The liquid coloring agent whose content of the said vegetable fats and oils is 60-2,000 mass parts with respect to 100 mass parts of said coloring agents.   The coloring resin composition containing base resin and the masterbatch for resin coloring of Claim 6 or 7.   A colored resin molded article comprising the colored resin composition according to claim 9.