JPH07247367A - Production of resin composition for coloring and resin composition for coloring - Google Patents

Abstract

PURPOSE:To obtain a method of efficiently producing a resin composition for thermoplastic resin coloring which can well disperse pigment and is capable of homogeneous coloring. CONSTITUTION:A mixture of 1-80wt.% aqueous dispersion or solution of a synthetic resin. 1-90wt.% pigment, and 1-90wt.% thermoplastic resin is fed to a twin-screw extruder to conduct phase displacement and dehydration. Thus, the resin composition having high dispersibility has come to be produced by a process characterized by, e.g. automation, energy-saving, and freedom from pigment scattering in the working atmosphere.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a resin composition for coloring a thermoplastic resin.

[0002]

BACKGROUND OF THE INVENTION Thermoplastic resin coloring compositions include powdery dry color prepared by mixing a pigment and a dispersant, liquid color or paste color prepared by dispersing a pigment in a liquid dispersant at room temperature, and room temperature. There are pellet-like, flake-like, or bead-like master batches in which a pigment is dispersed in a solid resin. These coloring compositions are properly used depending on the intended use, and among them, masterbatches are preferably used from the viewpoints of easy handling and preservation of working environment during use. The masterbatch has a high pigment concentration, has a small effect on physical properties such as heat resistance and strength of the thermoplastic resin to be colored, and refines the molding of the thermoplastic resin,
With the increase in speed, pigment dispersibility and distributability have become more demanding than before.

In order to impart pigment dispersibility to the master batch, stearic acid, zinc stearate, magnesium stearate, aluminum stearate, calcium stearate, ethylene bisamide, polyethylene wax, polypropylene wax, as a dispersant, have hitherto been used. One or more of these derivatives, for example, waxes composed of acid-modified products are used. However, for example, when a high degree of pigment dispersion is required, such as high-speed spinning of a thermoplastic resin with a diameter of a few tens of microns or film formation, the dispersant may not be satisfied.
That is, yarn breakage at the time of spinning due to poor pigment dispersion, clogging of a filter of a melt spinning machine, defective molding of a film, and the like occur. In order to solve these problems, efforts have been made to improve the processing method of the masterbatch and to improve the pigment dispersibility by using a strong kneader, but the pigment dispersibility is not sufficiently exhibited.

Further, in the field of large-sized injection molding in which colored pellets have been conventionally used, color unevenness and flow marks have become a problem in the coloring of molded products as the coloring by the master batch increases. Conventionally, in blow molding and film molding in which coloring is performed by a masterbatch, plasticization, mixing and kneading of a resin and a masterbatch are performed in an extruder part of a molding machine. In the case of an injection molding machine, the plasticizing, mixing, and kneading steps are carried out in the cylinder in which the screw moves backward, but the kneading force is not sufficient compared to the extruder, and the molding cycle can be shortened and the viscosity of the molding resin can be reduced. Along with this, the kneading power is becoming smaller. As a result, color unevenness is likely to occur on the surface of the molded product.

In addition, the pigment content of the masterbatch, which has been promoted for the purpose of reducing the cost of coloring, has been increased. With the advent of the high-concentration masterbatch, the addition amount of the masterbatch to the resin to be colored is reduced. Color unevenness and flow marks are becoming more likely to occur. This problem is recognized in various thermoplastic resins, but it is remarkable in polypropylene-based resins, which have been used increasingly in home appliances and automobile parts,
There has been an urgent need for a solution. In order to solve this problem, of the three main components of the masterbatch (pigment, dispersant and base resin), the content of the dispersant is increased, or a base resin having a viscosity lower than that of the resin to be colored is used. Color unevenness has been eliminated by lowering the melt viscosity of the masterbatch. However, for example, a polypropylene-based resin filled with an inorganic filler or a melt flow rate (hereinafter, referred to as MFR) of more than 25 for the purpose of thin-wall molding easily causes color unevenness and flow marks. I was waiting for the solution of the problem.

In the conventional masterbatch, a pigment obtained by introducing a mixture of a pigment, a dispersant and a base resin into a discontinuous kneader such as a three-roll mill or a kneader and melting and kneading for a long time is obtained. It is produced by pelletizing the dispersion using a single-screw extruder.However, once dried, the pigment powder has a large number of coarse secondary agglomerated particles. It is very difficult to disperse.

On the other hand, in the production of printing inks, paints, etc., a large-volume kneading tank is provided in order to disperse pigments in printing ink varnishes or paint vehicles or to flush water-based presscake into oily vehicles or oily varnishes. A pigment dispersion is obtained by charging the mixture in a flasher and intensifying it strongly with a large amount of power to invert the phase of the pigment to remove water, and then dehydrating it under reduced pressure with heating. However, according to this method, pelletization of a coloring resin such as a masterbatch is difficult, and an apparatus which is excessive with respect to the amount of the pigment dispersion is required. Also, it requires a great deal of time due to the complexity of the process, and the batch method causes variations in lots and complexity of handling, and it is extremely difficult to increase the concentration of the pigment in terms of work. However, it was not suitable for the production of masterbatches.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is to improve the above-mentioned various drawbacks, and to improve the physical properties of thermoplastic resin such as tensile strength, flexural strength and impact strength to 5% or more for each mechanical strength value. An object of the present invention is to provide an efficient production method of a resin composition (masterbatch) for coloring a thermoplastic resin, which does not impede, has excellent pigment dispersibility, and is capable of uniform coloring without color unevenness.

[0009]

That is, the present invention provides a synthetic resin aqueous dispersion or aqueous solution (a) of 1 to 80% by weight, a pigment.
(b) 1 to 90% by weight and 1 to 90% by weight of a thermoplastic resin (c) are fed to a twin-screw extruder, and phase substitution and dehydration are performed to produce a resin composition for coloring a thermoplastic resin. Provide a way.

The coloring resin composition of the present invention has excellent pigment dispersibility and is extremely effective in improving the coloring power. The improvement in dispersibility and coloring power is due to the affinity of the thermoplastic resin having at least one polar functional group in the molecule for the pigment, and the polar functional group exists in a molecular state in an aqueous solution. Therefore, it is considered that a polar bond is likely to be formed between the pigment and the pigment, and a polar colloidal structure surrounded by the hydrophobic portion of the thermoplastic resin is formed around it.

The synthetic resin has only to be compatible with the resin to be colored, and a polar thermoplastic resin, thermosetting resin or the like is used. Of these, polar functional group-containing thermoplastic resins are preferable. There is no particular limitation on the polar functional group, for example,
A monobasic acid or a dibasic acid or an anhydride thereof, a glycidyl group, a hydroxyl group, an amino group, an amide group, an ethyleneimine group,
Examples thereof include polar functional groups capable of being made water-based, such as an isocyanate group and an alkylene oxide bonding group. Of the polar functional group-containing thermoplastic resins, particularly in the carboxyl group-containing thermoplastic resin, the acid value is an important factor, and acid values in the range of 5 to 600, more preferably 50 to 500 are preferably used. When the acid value is less than 5, it is difficult to dissolve or disperse in water, and it is difficult to obtain good pigment dispersibility and color developability, and color unevenness and flow marks are likely to occur in the colored molded product. If the acid value exceeds 600, it tends to absorb moisture, which not only causes silver stalk and foaming on the surface of the molded product, but also adversely affects the weather resistance and heat resistance of the resin to be colored.

Among the polar functional group-containing thermoplastic resins, examples of the polyolefin resin include crystalline or amorphous polypropylene, polybutene-1, polypentene-1, poly4-methylpentene-1, low density or high density polyethylene, Random, block or graft copolymer of ethylene / propylene, copolymer of α-olefin and ethylene or propylene, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer , Ethylene / methyl methacrylate copolymers and the like to which polar functional groups are added. Furthermore, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / maleic anhydride copolymer,
Propylene / acrylic acid copolymer, α-olefin,
Examples include copolymers of a polar functional group-containing monomer with a monomer having an α, β-unsaturated double bond such as a diolefin, an allyl monomer, an N-vinyl monomer, a vinyl ether, a vinyl sulfide, and a (meth) acrylic acid ester monomer. One or more of these are used.

As α-olefins, ethylene, propylene, butylene, isobutylene, pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-dococene, 1-tetracocene,
1-hexacocene, 1-octacocene, 1-triacontene,
1-Dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetracontene and the like can be mentioned. Commercially available products are "Dialen 208" (C20-28), "Dialen 30" manufactured by Mitsubishi Kasei.
(C30 or higher), Petrolite's "VYBER260" (C30 or higher), etc.

Examples of diolefins include butadiene, isoprene, neoprene and chloroprene. Examples of the allyl monomer include allyl acetate, isopropenyl acetate, allyl chloride, isopropenyl chloride, trans-propenyl chloride, cis-propenyl chloride and the like. Examples of N-vinyl monomers include N-vinylcarbazole and N-vinyl-
Examples include 2-pyrrolidone and N-vinylphthalimide.
Examples of vinyl ethers include linear or branched aliphatic alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether and hexyl vinyl ether, and p-dioxene.

Examples of the vinyl sulfide include ethyl vinyl sulfide and phenyl vinyl sulfide. (Meth) acrylic acid ester monomers include linear or branched fats such as methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, etc. Examples thereof include acrylic acid esters of group alcohols and corresponding methacrylic acid esters. Further, other copolymerizable vinyl monomers include vinyl ester, vinyl pyridine, vinyl acetate, vinyl propionate, styrene, α-methylstyrene, β-methylstyrene, acrylonitrile, methacrylonitrile, vinylidene chloride and the like. .

Examples of the polar functional group-containing monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, crotonic acid,
Citraconic acid, hymic acid, allyl succinic acid, mesaconic acid, glutaconic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, hymic acid allyl succinic anhydride, anhydrous Examples thereof include monobasic acids and dibasic acids having unsaturated groups such as glutaconic acid, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and aconitic anhydride, or anhydrides thereof.

In addition, glycidyl acrylate, glycidyl methacrylate, diglycidyl maleate, methyl glycidyl maleate, isopropyl glycidyl maleate, tert-butyl glycidyl maleate, diglycidyl fumarate, isopropyl glycidyl fumarate Ester, itaconic acid diglycidyl ester, itaconic acid methylglycidyl ester, itaconic acid isopropylglycidyl ester, 2-methyleneglutanic acid diglycidyl ester, 2-methyleneglutanic acid methylglycidyl ester, butenedicarboxylic acid monoglycidyl ester, 3,4 -Epoxy butene, 3,4-
Examples thereof include glycidyl group-containing monomers such as epoxy-3-methyl-1-butene, vinylcyclohexene monoxide, and p-glycidylstyrene.

Further, N-methylolacrylamide, N-methylolmethacrylamide, N-methylaminoethyl acrylate, N-tributylaminoethyl acrylate, N,
N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, acrylamide, methacrylamide,
N-butoxymethylacrylamide, N-methoxymethylacrylamide, allylamine, dimethylaminopropylmethacrylamide, diallylamine, triallylamine, 4-vinylpyridine, 2-methyl-6-vinylpyridine,
Examples thereof include amino group- or amide group-containing monomers such as 4-butenylpyridine and vinylpyrrolidone.

Further, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, mono- (2-hydroxyethyl-
Examples thereof include a hydroxyl group-containing monomer such as α-chloroacrylate) acid phosphate and an ethyleneimine group- or isocyanate group-containing monomer such as 2- (1-aziridinyl) ethyl methacrylate and isocyanatoethyl methacrylate. As the polar functional group-containing monomer, at least one of these is used, but acrylic acid and maleic anhydride are industrially advantageous, and are easily made aqueous.

Examples of resins other than polyolefin resins include long-chain alcohol esters such as lauric acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, and linoleic acid, and fatty acid esters such as glycerin ester. Or thermoplastic resin such as polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-EPDM-styrene (AES) resin, acrylic resin, polyamide, polycarbonate, polyacetal, polyurethane, etc. Examples thereof include those to which a polar functional group has been imparted and in which the polar functional group necessary for water-solubilization remains, and one or more of these are used.

In order to dissolve or disperse the synthetic resin in water, a neutralizing agent is used if necessary. The polar functional group-containing thermoplastic resin can be easily dissolved or dispersed in water by neutralizing it with an organic acid, an inorganic acid, a hydroxide, an organic amine or the like as a neutralizing agent and diluting with water. Examples of the neutralizing agent include acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, sodium hydroxide, potassium hydroxide, lithium hydroxide, aqueous ammonia, monoethanolamine, N-methylethanolamine, N, N-dimethyl. Examples thereof include ethanolamine, triethylamine and triethanolamine. Also,
It is also possible to use a surfactant or the like together. The solid content of the synthetic resin aqueous dispersion or the aqueous solution (a) is 1 to 80% by weight,
Further, the range of 5 to 65% by weight is preferable.

As the pigment (b), known organic pigments and inorganic pigments conventionally used for coloring thermoplastic resins can be used. As such pigments, azo-based, anthraquinone-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, dioxane-based, berylylene-based, quinophthalone-based, verinone-based organic pigments and wet presscake thereof, cadmium sulfide, Inorganic pigments such as cadmium selenide, ultramarine blue, titanium dioxide, iron oxide, chromate oxide and carbon black can be mentioned.

As the thermoplastic resin (c), those having compatibility with the resin to be colored are preferable, and those having MFR in the range of 0.1 to 400, more preferably 10 to 250 are preferably used. MF
When R is less than 0.1, the compatibility with the thermoplastic resin to be colored becomes poor, causing color unevenness and the like, and adversely affecting the physical properties of the colored thermoplastic resin. On the other hand, MF
When R exceeds 400, the mechanical strength and heat resistance of the coloring resin composition itself become low, making it difficult to manufacture the coloring resin composition, and the heat resistance of the thermoplastic resin to be colored, It adversely affects physical properties such as strength. In addition, MF
R is MFR measured according to JIS K7210.

More specifically, as the thermoplastic resin, for example, in the case of polyolefin resin, crystalline or amorphous polypropylene, low density or high density polyethylene, ethylene / propylene random, block or graft copolymer, α- Copolymer of olefin and ethylene or propylene, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / acrylic acid copolymer, or low due to thermal decomposition thereof. Examples thereof include polymers and waxes, and one or more of these may be used.

Other than polyolefin resins, polymethylpentene, polystyrene, polyethylene terephthalate, polydiene-based polybutylene terephthalate, acrylonitrile-butadiene-styrene (AB
S) resin, acrylonitrile-EPDM-styrene (A
ES), other acrylic resins, polyamides, polycarbonates, polyacetals, polyvinyl acetates, polyvinyl chlorides, polyvinylidene chlorides, thermoplastic resins such as polyurethanes, and the like, and one or more of them are used. The thermoplastic resin (c) may be a derivative obtained by functional group modification, crosslinking modification, grafting or block modification, and may be in the form of powder or pellets.

In addition to polyolefin resins, polymethylpentene, polystyrene, polyethylene terephthalate and polydiene polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-EPDM-styrene (AES).
Resins, other acrylic resins, polyamides, polycarbonates, polyacetals, polyvinyl acetates, polyvinyl chlorides, polyvinylidene chlorides, thermoplastic resins such as polyurethanes, and the like can be mentioned, and one or more of these can be used. Resins are preferred.

As the twin-screw extruder, a twin-screw co-rotating screw extruder is preferable, and the L / D value of the screw is 25 or more, more preferably 30 or more. If the L / D value is less than 25, problems occur in terms of poor kneading and quality stability. Further, the shape of the screw is not particularly limited, but an arrangement of a strongly kneading type screw element is preferable. The screw rotation speed of the twin-screw extruder is an important factor and must be determined in consideration of the speed of phase substitution. The screw rotation speed varies depending on the L / D value and the screw shape, but it is preferably set to 150 to 450 rpm in order to improve the mixing and kneading effect and to perform high-speed processing. The temperature setting of the twin-screw extruder is not particularly limited, and it is important to perform cooling and heating in each barrel unit according to the characteristics of the pigment used and the melting characteristics of the resin. The twin-screw extruder can be provided with a vent port to which a vacuum pump is connected in order to improve the efficiency of dehydration, and can be subjected to a heating / reducing pressure dehydration treatment if necessary.

To the coloring resin composition of the present invention, various additives such as stabilizers such as antioxidants and ultraviolet absorbers and surfactants are added within a range that does not impair the effects of the present invention. You can also Further, if necessary, additives such as a filler, a plasticizer, a thickener, a preservative, an antifoaming agent and a leveling agent can be used in combination. The coloring resin composition of the present invention can color almost all thermoplastic resins, and can also color those containing a reinforcing material such as an inorganic filler or glass fiber or organic fiber for the purpose of improving physical properties. For example, uniform coloring without uneven coloration without impact on mechanical properties such as strength and heat resistance, which could not be achieved by coloring with conventional resin compositions, can be achieved with inorganic fillers and fiber reinforced materials. It can be realized by adding a small amount of 4 parts by weight or less of the coloring resin composition of the present invention to 100 parts by weight of the thermoplastic resin composition containing about 50% by weight.

The coloring resin composition of the present invention is particularly preferably used for coloring a polyolefin resin, but in addition to that, polymethylpentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS). ) Resin, acrylonitrile-EPDM-styrene (AES) resin,
It can also be blended with thermoplastic resins such as acrylic resins, polyamides, polycarbonates, polyacetals, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl acetates and polyurethanes. The coloring resin composition of the present invention can also be used for applications such as inks, paints and adhesives.

[0030]

EXAMPLES The present invention will be specifically described below based on examples. In the examples, parts and% represent parts by weight and% by weight, respectively. (Production Example 1) 200 parts of a polyethylene oxide adduct of polyolefin "Unitox 480" (manufactured by Petrolite) was dissolved in 800 parts of water to obtain a resin aqueous solution having a solid content of 20%.

(Production Example 2) Polyethylene wax "Sun Wax 171P" (manufactured by Sanyo Kasei Co., Ltd.) 838.7 parts, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3 "Perhexin 25B" (Nippon Yushi Co., Ltd.) 4.6 parts and toluene 10 parts were charged into a flask and, after nitrogen substitution, 161.3 parts of acrylic acid was added for 1 hour while heating and stirring at 180 ° C. and 2,5-dimethyl-2,5. -Di-t-butylperoxyhexyne-3 "Perhexin 25B" was dripped at 5.0 parts per hour. After completion of the dropping, the temperature of the system was kept at 200 ° C., and the reaction was further continued for 6 hours. After the reaction was completed, the contents were taken out while being hot, cooled and solidified. A resin with an acid number of 143 was obtained. Resin 30 obtained
Parts, water 70 parts, potassium hydroxide 15 parts into a flask,
The mixture was stirred at 95 ° C for 2 hours to obtain an aqueous resin dispersion having a pH of 7.9 and a solid content of 29.8%.

(Production Example 3) Polyethylene wax "High Wax 400P" (manufactured by Mitsui Petrochemical Industries, Ltd.) 905 parts, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3 "Perhexin 25B 2.2 parts and 10 parts of toluene were charged into a flask, and after nitrogen substitution, 94.9 parts of diethylaminoethyl methacrylate were heated for 1 hour while stirring and heating at 180 ° C.
Further, 2.0 parts of 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3 "Perhexin 25B" was added dropwise over 1 hour.
After completion of the dropping, the temperature of the system was kept at 200 ° C., and the reaction was further continued for 6 hours. After the reaction was completed, the contents were taken out while being hot, cooled and solidified. A resin with an amine number of 40 was obtained. The obtained resin 30 parts, water 70 parts, acetic acid 40 parts was charged into a flask, 95
The mixture was stirred at 0 ° C. for 2 hours to obtain an aqueous resin dispersion having a pH of 6.2 and a solid content of 29.5%.

(Production Example 4) Ethylene / α-olefin /
Maleic anhydride copolymer "Lucant A-6002" (Mitsui Petrochemical Industry Co., Ltd.) 600 parts, water 400 parts and potassium hydroxide
After 38 parts was charged into a flask and purged with nitrogen, the mixture was heated at 95 ° C. for 2 hours and stirred to obtain an aqueous resin dispersion having a solid content of 59.8%.

(Production Example 5) 1-octadecene 757.4 parts, di
2.7 parts of t-butyl peroxide and 10 parts of toluene were charged into a flask, and after nitrogen substitution, 294.2 parts of maleic anhydride was heated at 150 ° C. with stirring and 9.8 parts every 2 minutes.
In addition, 2.1 parts of di-t-butyl peroxide was added at 0.7 parts every 20 minutes. After the addition is complete, keep the system temperature at 160 ° C and
The reaction was continued for 6 hours. After the reaction was completed, the contents were taken out while being hot, cooled and solidified. A resin with an acid number of 320 was obtained. 30 parts of the obtained resin, 70 parts of water, ammonia water (28%)
Charge 12.5 parts into a flask and stir at 70 ° C for 2 hours to adjust the pH.
An aqueous resin dispersion having a solid content of 7.9 and a solid content of 29.7% was obtained.

(Production Example 6) 312 parts of styrene, 2.7 parts of di-t-butyl peroxide, and 10 parts of toluene were charged into a flask, and after nitrogen substitution, 294.2 parts of maleic anhydride were added while heating and stirring at 150 ° C. 9.8 copies per minute, again t-
2.1 parts of butyl peroxide were added in 0.7 parts every 20 minutes. After the addition is complete, maintain the system temperature at 160 ° C and
Reacted for hours. After the reaction was completed, the contents were taken out while being hot, cooled and solidified. A resin with an acid number of 555 was obtained. 200 parts of the obtained resin and 34.0 parts of cyclohexylamine were charged into the flask again, melted in a nitrogen stream while stirring, and reacted at a reaction temperature of 180 ° C. for 5 hours. After completion of the reaction, the content was taken out while hot, cooled and solidified to obtain a resin having an acid value of 108. 40 parts of the obtained resin, 60 parts of water, potassium hydroxide
Charge 33.6 parts into a flask and stir at 95 ° C for 2 hours to adjust the pH.
An aqueous resin dispersion having a solid content of 7.6 and a solid content of 39.8% was obtained.

(Production Example 7) Phenyl vinyl sulfide 5
04 parts, 200 parts of methyl methacrylate, 3.6 parts of di-t-butyl peroxide, and 14 parts of toluene were charged into a flask and, after purging with nitrogen, 412 parts of maleic anhydride was added at 13.7 every 2 minutes while heating and stirring at 150 ° C. Parts and 1.8 parts of di-t-butyl peroxide were added every 20 minutes at 0.9 parts. After the addition was completed, 1 part of di-t-butyl peroxide was further added, the temperature of the system was kept at 160 ° C., and the reaction was further continued for 6 hours. After the reaction was completed, the contents were taken out while being hot, cooled and solidified. A resin with an acid value of 322 was obtained. Resin 40 obtained
Parts, 60 parts of water, and 33.6 parts of sodium hydroxide were charged into a flask and stirred at 95 ° C. for 2 hours to obtain an aqueous resin dispersion having a pH of 7.5 and a solid content of 39.7%.

(Production Example 8) Styrene / maleic anhydride copolymer "GSM603" (manufactured by Gifu Shellac Manufacturing Co., acid value: 27)
0) 200 parts, water 300 parts, potassium hydroxide 80 parts were charged into a flask and stirred at 95 ° C. for 2 hours, pH 8.0, solid content 38.7%
A water-based resin dispersion of was obtained. (Production Example 9) 200 parts of modified polyamide "AQ nylon A-90" (manufactured by Toray Industries, Inc.) was dissolved in 800 parts of water to obtain a resin aqueous solution having a solid content of 20%.

[Example 1] 27% aqueous dispersion of ethylene / methacrylic acid copolymer 74 parts "Chemipearl S-650" (manufactured by Mitsui Petrochemical Industries, Ltd.) Polyethylene "NUC G5391" (manufactured by Nippon Unicar, MFR: 50) 40 parts Phthalocyanine blue "Rionol blue 7110V" 40 parts (manufactured by Toyo Ink Mfg. Co., Ltd.)

The above three components were premixed with a Henschel mixer, and the twin screw co-rotating screw extruder having a screw diameter of 30 mm and an L / D value of 38 was used, and the rotation speed was 350 rpm and the set temperature was 140 ° C.
After kneading and extruding under the processing conditions of No. 1, the mixture was cut with a pelletizer to obtain a master batch. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Furthermore, polypropylene "Mitsui Noblen J4
00 ”(MFR, 3 manufactured by Mitsui Petrochemical Co., Ltd.) is mixed with 3 parts of the obtained masterbatch, and the vertical test spinning machine“ Spinning Tester ”(manufactured by Fuji Filter Co., Ltd.) is used under the hopper. After spinning at a temperature of 230 ° C., a kneading part and a die part temperature of 230 ° C., and stretching was performed 3 times to obtain a polypropylene fiber of 5 denier. The spinnability, the clogging property, and the stretchability exhibited good dispersibility without problems.

[Comparative Example 1] A masterbatch was obtained in the same manner as in Example 1 except that 74 parts of "Chemipearl S-650" was replaced with 20 parts of polypropylene wax "Viscol 550P" (manufactured by Sanyo Kasei Co., Ltd.). . At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Further, spinning was performed in the same manner as in Example 1, but yarn breakage due to clogging occurred. [Comparative Example 2] With the same composition as in Example 1, the three components after premixing were kneaded in a three-roll mill and pelletized with an extruder having a screw diameter of 65 mm. Occurred and the masterbatch could not be obtained.

Example 2 100 parts of the aqueous resin solution obtained in Production Example 1 100 parts polypropylene / polyethylene block copolymer 35 parts “Mitsui Noblen J740P” (Mitsui Petrochemical Co., Ltd., MFR: 25) Quinacridone Red “Fastgen Super Magenta” RE03 ”45 parts (manufactured by Dainippon Ink and Chemicals, Inc.) The above three components are premixed with a Henschel mixer, a twin screw co-rotating screw extruder with a screw diameter of 30 mm and an L / D value of 42, rotation speed 350 rpm, set temperature After kneading and extruding under a processing condition of 140 ° C., it was cut with a pelletizer to obtain a masterbatch. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Further, spinning was performed in the same manner as in Example 1 to obtain polypropylene fibers. The spinnability, the clogging property, and the stretchability exhibited good dispersibility without problems.

Comparative Example 3 A masterbatch was prepared in the same manner as in Example 2 except that 100 parts of the aqueous resin solution obtained in Production Example 1 was replaced with 20 parts of polymerized rosin ester “Pentaline CJ” (manufactured by Rika Hercules). Got At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Further, spinning is performed in the same manner as in Example 1,
A polypropylene fiber was obtained. The spinnability was not a problem.

Example 3 Water-based resin dispersion obtained in Production Example 2 50.3 parts Polyethylene “NUC G5391” (MFR: 50) 50 parts Phthalocyanine blue “Rionol Blue FG7330” 35 parts (Toyo Ink Mfg. Co., Ltd.) Manufacture) A masterbatch was obtained in the same manner as in Example 2 using the above three components. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Further, spinning was performed in the same manner as in Example 1 to obtain polypropylene fibers. The spinnability, the clogging property, and the stretchability exhibited good dispersibility without problems.

Comparative Example 4 50.3 parts of the water-based resin dispersion obtained in Production Example 2 was mixed with polypropylene wax “Viscole 55”.
A masterbatch was obtained in the same manner as in Example 1 except that 15 parts of "0P" was used. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow.
Further, spinning was performed in the same manner as in Example 1, but yarn breakage due to clogging occurred. [Comparative Example 5] With the same composition as in Example 3, the three components after premixing were kneaded with a kneader and pelletized with an extruder having a screw diameter of 65 mm. , Could not get a masterbatch.

[Example 4] Aqueous resin dispersion obtained in Production Example 3 67.8 parts Polyethylene "Mitsubishi Polyethylene MV-31" (MFR: 45, manufactured by Mitsubishi Petrochemical Co., Ltd.) 20 parts Polyethylene wax "High Wax 420P" 10 parts (manufactured by Mitsui Petrochemical Industry Co., Ltd.) Condensed Azo Yellow “Chromophtal yellow GR” (manufactured by Ciba Geigy) 50 parts A masterbatch was obtained in the same manner as in Example 1 using the above 4 components. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Further, it was spun in the same manner as in Example 1 to obtain polypropylene fiber. The spinnability, the clogging property, and the stretchability exhibited good dispersibility without problems.

Comparative Example 6 67.8 parts of the aqueous resin dispersion obtained in Production Example 3 was dissolved in sodium dodecylbenzene sulfonate.
A masterbatch was obtained in the same manner as in Example 4 except that 50 parts of a 40% aqueous solution was used. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Further, spinning was performed in the same manner as in Example 1 to obtain polypropylene fibers. The spinnability was not a problem. [Comparative Example 7] The same components as in Example 4 but with the four components after premixing were kneaded with a three-roll mill and pelletized with an extruder having a screw diameter of 65 mm to obtain a masterbatch.
At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Furthermore, Example 1
Spinning was performed in the same manner as in to obtain polypropylene fiber. The spinnability was not a problem.

Example 5 27% Aqueous Dispersion of Ethylene / Methacrylic Acid Copolymer 37 Parts "Chemipearl SA-300" (manufactured by Mitsui Petrochemical Co., Ltd.) Copolyester "Byron GM900" (manufactured by Toyobo Co., Ltd., MFR: 2) 10 parts Polyethylene terephthalate "Unipet RT543" 37 parts (Nippon Unipet, MFR: 0.5) Partially saponified montanic acid "Luwax OP" 3 parts (BASF, saponification value: 150 mgKOH / g) ) Phthalocyanine blue "Rionol Bull-POBS" 30 parts (manufactured by Toyo Ink Mfg. Co.) Titanium oxide "Taipec CR-80" (manufactured by Ishihara Sangyo Co., Ltd.) 10 parts

The above 6 components were premixed with a Henschel mixer, and the same twin-screw co-rotating screw extruder as in Example 2 was used to knead and extrude at a set temperature of 230 ° C., and then cut with a pelletizer to obtain a master. Got a batch. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. 100 parts of polyethylene terephthalate "Unipet RT543" (MFR: 0.5) was mixed with 3 parts of the obtained masterbatch, and spinning was carried out in the same manner as in Example 1 and then stretched 4 times, followed by heat treatment at 140 ° C. To obtain 3 denier polyester fiber. Spinnability,
Good dispersibility was exhibited without any problems in clogging and stretchability.
The intrinsic viscosity of the fiber obtained is 0.872 dl / g for the polyethylene terephthalate without masterbatch.
It was 0.850 dl / g, and the intrinsic viscosity retention was 97.5%.

Comparative Example 8 A masterbatch was obtained in the same manner as in Example 5 except that 37 parts of "Chemipearl SA-300" was replaced with 10 parts of copolyester "Vylon GM900". At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Further, when spinning was performed in the same manner as in Example 5, yarn breakage due to clogging occurred. The intrinsic viscosity of the obtained fiber is 0.550 dl / g, while the intrinsic viscosity of polyethylene terephthalate without masterbatch is 0.872 dl / g, and the intrinsic viscosity retention rate is 63.1%.
Met. [Comparative Example 9] Six components after premixing having the same composition as in Example 5 were kneaded with a three-roll mill and pelletized with an extruder having a screw diameter of 65 mm. And a masterbatch could not be obtained.

Example 6 25% Aqueous Dispersion of Nylon / Olefin Copolymer 40 Parts “Hitech N-2010” (Toho Chemical Industry Co., Ltd.) Nylon 6 “Unitika Nylon A1020” (Unitika, MFR: 20) ) 10 parts Nylon 6 "Unitika Nylon A1030BRL" (Munitika, MFR: 1) 40 parts Phthalocyanine blue "Rionol Bull-FG7330" 30 parts Titanium oxide "Taipec CR-80" 10 parts Premix the above 5 ingredients with a Henschel mixer. Using the same twin-screw, co-rotating screw extruder as in Example 2, after kneading and extruding at a preset temperature of 250 ° C., the mixture was cut with a pelletizer to obtain a masterbatch. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Nylon 6 "Unitika Nylon A1
030BRL ”100 parts was mixed with 3 parts of the obtained masterbatch, and 3 denier nylon fiber was obtained in the same manner as in Example 5. The spinnability, the clogging property, and the stretchability exhibited good dispersibility without problems.

Comparative Example 10 A masterbatch was obtained in the same manner as in Example 6 except that 40 parts of "Hitech N-2010" was replaced with 10 parts of nylon 6 "Unitika Nylon A1020".
At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Furthermore, Example 6
When spinning was performed in the same manner as above, yarn breakage due to clogging occurred. [Comparative Example 11] 5 after premixing with the same composition as in Example 6
When the components were kneaded with a three-roll mill and pelletized with an extruder having a screw diameter of 65 mm, strand breakage and pulsating flow occurred due to poor supply, and a masterbatch could not be obtained.

In order to evaluate the clogging property of the undispersed pigment of the masterbatch, Examples 1 to 4 and Comparative Examples 1 and 3,
Ten parts of each of the master batches obtained in 4, 6, and 7 were added to 100 parts of polypropylene "Mitsui Noblen J400", and 10 parts of each of the master batches obtained in Example 5 and Comparative Example 8 were respectively added to polyethylene terephthalate "Unipet RT54".
10 parts of each of the master batches obtained in Example 6 and Comparative Example 10 was mixed with 100 parts of nylon 6 "Unitika Nylon A1030BRL" 100 parts, and a screw diameter of 30 mm equipped with a 500 mesh wire mesh at the tip was mixed. A single-screw extruder was used to extrude 3 kg of the mixture, and the pressure increase at the tip was compared. The results are shown in Table 1. The larger the pressure rise value is, the more undispersed pigment is and the poorer the dispersibility is.

Further, in order to evaluate the dispersive coloring property of the pigments, Examples 1, 2, 3, 4 and Comparative Examples 1, 3, 4,
1 part of each of the master batches obtained in 6 and 7 was added to 100 parts of polypropylene "Mitsui Noblen J400", and Example 5
And 1 part each of the master batches obtained in Comparative Example 9 were respectively treated with polyethylene terephthalate "Unipet RT543".
1 part of each of the master batches obtained in Example 6 and Comparative Example 10 was added to 100 parts of nylon 6 "Unitika Nylon".
A1030BRL ”was mixed with 100 parts, and further, 5 parts of titanium oxide“ Taipaque CR-80 ”was mixed and kneaded with a two-roll mill, and molded into a 2 mm thick plate by a cooling press. Table 1 shows the results of measuring the reflection intensity at 600 nm with a color difference meter (manufactured by Hunter, USA). The reflection intensity is 100% in the example.
And compared with the corresponding comparative example.

[0054]

[Table 1]

[Example 7] Water-based resin dispersion obtained in Production Example 2 25.1 parts Polyethylene "Mitsubishi Polyethylene MV-31" (MFR: 45) 20 parts Polyethylene wax "Sun Wax 165P" (Sanyo Chemical Co., Ltd.) 15 parts (manufactured by Mitsui Petrochemical Industry Co., Ltd.) Titanium oxide "Taipaque CR-80" 45 parts Carbon black "Mitsubishi Carbon MA-100" (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 5 parts The same 5 components as in Example 2 Using a twin-screw co-rotating screw extruder, the kneading / extruding was performed at a rotation speed of 400 rpm and a preset temperature of 160 ° C., and the mixture was cut with a pelletizer to obtain a masterbatch. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow.
In addition, 100 parts of polyethylene "HIZEX 2100J" (MFR, 6.5) manufactured by Mitsui Petrochemical Co., Ltd.
Three parts were mixed and molded into a plate with a back pressure of 0 Kg / cm ² using an injection molding machine.

[Comparative Example 12] 25.1 parts of the aqueous resin dispersion obtained in Production Example 4 was mixed with metal soap (calcium stearate).
A masterbatch was obtained in the same manner as in Example 6 except that the amount was changed to 15 parts. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 7.

[Example 8] Aqueous resin dispersion obtained in Production Example 5 67.3 parts Polyethylene "NUC G5391" (MFR: 50) 20 parts Polyethylene wax "High Wax 420P" 10 parts Condensed azo yellow "chromophthalm" Yellow GR ”15 parts Quinacridone red“ Fastgen Super Magenta RE03 ”20 parts Titanium oxide“ Taipaque CR-80 ”10 parts Carbon black“ Mitsubishi Carbon MA-100 ”5 parts Using the above 7 components and in the same manner as in Example 7. A masterbatch was obtained. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 7.

Comparative Example 13 Example 8 was repeated except that 67.3 parts of the aqueous resin dispersion obtained in Production Example 5 was replaced with 50 parts of a 40% aqueous solution of sodium lauryl sulfate "Emar O" (manufactured by Kao Corporation). A masterbatch was obtained in the same manner. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 7.

[Example 9] Water-based resin dispersion obtained in Production Example 6 50.3 parts ABS resin "Styrac 191F" (MFR: 55, Asahi Kasei Corp.) 40 parts Phthalocyanine blue "Rionol Bull-7110V" 30 parts Titanium oxide "Taipaque CR-80" 10 parts A masterbatch was obtained in the same manner as in Example 7 using the above-mentioned 4 components. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. ABS
100 parts of the resin "JSR ABS10" (MFR: 0.5 manufactured by Japan Synthetic Rubber Co., Ltd.) was mixed with 3 parts of the obtained masterbatch, and plate molding was carried out in the same manner as in Example 7.

[Comparative Example 14] 50.3 parts of the aqueous resin dispersion obtained in Production Example 6 was converted into polystyrene wax "Haimer ST9".
A masterbatch was obtained in the same manner as in Example 9 except that 20 parts of "5" (manufactured by Sanyo Kasei Co., Ltd.) was used. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 9.

Example 10 Water-based resin dispersion obtained in Production Example 7 50.4 parts Acrylic resin “Dianal BR-73” (Mitsubishi Rayon Co., Ltd., MFR: 20) 30 parts Acrylic resin “Dianal BR -117 "(MFR: 95, manufactured by Mitsubishi Rayon Co., Ltd.) 10 parts Condensed Azo Yellow" Chromophtal Yellow GR "5 parts Quinacridone Red" Fastgen Super Magenta RE03 "45 parts Using the above 5 components and in the same manner as in Example 7. A masterbatch was obtained. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. 3 parts of the obtained masterbatch was mixed with 100 parts of the acrylic resin "Dynar BR-73", and plate molding was carried out in the same manner as in Example 7.

[Comparative Example 15] 50.4 parts of the water-based resin dispersion obtained in Production Example 7 was mixed with an acrylic resin "Dianal BR-117".
A masterbatch was obtained in the same manner as in Example 10 except that 10 parts were replaced. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 10.

Example 11 Vinyl chloride 55% latex “PVC LATEX G-576” 36.4 parts (manufactured by Zeon Corporation) Vinyl chloride resin “Vinica P540” (manufactured by Mitsubishi Kasei Vinyl Co., MFR: 1.5) 39 parts Plasticizer "Dioctyl phthalate" (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 1 part Phthalocyanine blue "Rionol Bull-FG7330" 30 parts Titanium oxide "Taipec CR-80" 10 parts Master batch was carried out in the same manner as in Example 7 using the above 5 components. Got At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. 100 parts of vinyl chloride resin "Binica P540" was mixed with 3 parts of the obtained masterbatch, and plate molding was carried out in the same manner as in Example 7.

[Comparative Example 16] In the same manner as in Example 11 except that 36.4 parts of "PVC LATEX G-576" was replaced with 20 parts of vinyl chloride resin "Vinica 75BX" (MFR: 20 manufactured by Mitsubishi Kasei Vinyl Co., Ltd.). A masterbatch was obtained. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 11.

Example 12 Water-based resin dispersion obtained in Production Example 8 25.8 parts Polystyrene resin “Styron 683” (MFR: 2.8 manufactured by Asahi Kasei Corporation) 30 parts Polystyrene resin “Styron 666” (Asahi Kasei Industry Co., Ltd. (MFR: 7.5) 10 parts Condensed Azo Yellow "Chromophtal Yellow GR" 20 parts Quinacridone Red "Fastgen Super Magenta RE03" 25 parts Titanium Oxide "Taipec CR-80" 5 parts Using the above 6 components, Example 7 A masterbatch was obtained in the same manner as. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. 100 parts of the polystyrene resin "Stylon 683" was mixed with 3 parts of the obtained masterbatch, and plate molding was carried out in the same manner as in Example 7.

[Comparative Example 17] A masterbatch was obtained in the same manner as in Example 12 except that 10 parts of the polystyrene wax "Haimer ST95" was used instead of the aqueous resin dispersion obtained in Production Example 8. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 12.

[Example 13] 30% aqueous dispersion of urethane / olefin copolymer 50 parts "Hitech U-3002" (manufactured by Toho Chemical Industry Co., Ltd.) Polyurethane resin "Desmocoll 540" 35 parts (manufactured by Sumitomo Bayer Urethane Co., Ltd.) , MFR: 65) Polyurethane resin "Desmocol U42" 10 parts (Sumitomo Bayer Urethane Co., MFR: 120) Condensed azo yellow "Chlomophthal yellow GR" 35 parts Titanium oxide "Taipec CR-80" 5 parts The above 6 components A masterbatch was obtained in the same manner as in Example 7. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. 100 parts of the polyurethane resin "Desmocol 540" was mixed with 3 parts of the obtained masterbatch, and plate molding was carried out in the same manner as in Example 7.

[Comparative Example 18] A masterbatch was obtained in the same manner as in Example 13 except that 50 parts of "Hitech U-3002" was replaced with 15 parts of polyurethane "Desmocoll U42". At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 13.

Example 14 SBR 67% Latex “Nipol LX139” (manufactured by Zeon Corporation) 15 parts Polycarbonate “UPILON S1000” (Mitsubishi Gas Chemical Co., MFR: 5) 10 parts Polycarbonate “UPILON S3000” 40 parts ( Mitsubishi Gas Chemical Co., Ltd., MFR: 0.7) ABS resin "JSR ABS35" (Nippon Synthetic Rubber Co., Ltd., MFR: 60) 10 parts Phthalocyanine blue "Rionol Bull-FG7330" 35 parts Titanium oxide "Taipec CR-80" 5 parts Above 6 Using the same twin-screw co-rotating screw extruder as in Example 2, the components were kneaded and extruded at a rotation speed of 400 rpm and a set temperature of 250 ° C., and then cut with a pelletizer to obtain a masterbatch. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. 100 parts of polycarbonate "Iupilon S3000" was mixed with 3 parts of the obtained masterbatch, and plate molding was carried out in the same manner as in Example 7.

[Comparative Example 19] A masterbatch was obtained in the same manner as in Example 14 except that 15 parts of "Nipol LX139" was replaced with 10 parts of polycarbonate "Iupilon S1000". At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 14.

Example 15 SBR 69% Latex “JSR0561” (manufactured by Japan Synthetic Rubber Co., Ltd.) 14.5 parts Nitrile rubber “Hycar1411” (manufactured by Zeon Corporation, MFR: 10) 40 parts Nitrile rubber “Nipol DN502” ( ZEON CORPORATION, MFR: 120) 10 parts Condensed Azo Yellow "Chromophtal Yellow GR" 10 parts Phthalocyanine Blue "Rionol Bull-FG7330" 20 parts Titanium Oxide "Taipec CR-80" 5 parts Carbon Black "Mitsubishi Carbon MA-100" 5 parts A masterbatch was obtained in the same manner as in Example 7 using the above 7 components. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. 100 parts of the nitrile rubber "Hycar 1411" was mixed with 3 parts of the obtained masterbatch, and plate molding was carried out in the same manner as in Example 7.

Comparative Example 20 Example 15 was repeated except that 14.5 parts of "JSR0561" was replaced with 10 parts of nitrile rubber "Nipol DN502".
A masterbatch was obtained in the same manner as. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 15.

[Example 16] 18% aqueous solution of polyvinyl acetal "ESREC KW-1" 55.6 parts (manufactured by Sekisui Plastics Co., Ltd.) Polyvinyl butyral "denka butyral 4000-1" 10 parts (manufactured by Denki Kagaku Kogyo, MFR: 80) Vinyl chloride / vinyl acetate copolymer resin "NPR TSH" 40 parts (manufactured by Nissin Chemical Industry Co., Ltd., MFR: 50) Titanium oxide "Taipec CR-80" 35 parts Carbon black "Mitsubishi Carbon MA-100" 5 parts A masterbatch was prepared in the same manner as in Example 7 except that the above 5 components were used. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. 3 parts of the obtained masterbatch was mixed with 100 parts of polyvinyl acetate resin "Ethnyl C-5" (MFR: 20 manufactured by Sekisui Plastics Co., Ltd.), and plate molding was carried out in the same manner as in Example 7.

[Comparative Example 21] Example 16 was repeated, except that 55.6 parts of "ESREC KW-1" was replaced with 10 parts of polyvinyl acetate resin "Esnile C-2A" (manufactured by Sekisui Plastics Co., Ltd., MFR: 100). A masterbatch was obtained in the same manner as. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Example using the obtained masterbatch
Plate molding was performed in the same manner as 16.

Example 17 Resin aqueous solution obtained in Production Example 9 50 parts Polyamide "Versamide DPX640" (manufactured by Henkel Hakusui, MFR: 120) 10 parts Special nylon resin "Macromelt 6900" (manufactured by Henkel Hakusui, MFR: 10) 40 parts Titanium oxide "Taipeque CR-80" 35 parts Carbon black "Mitsubishi Carbon MA-100" 5 parts A masterbatch was prepared in the same manner as in Example 7 using the above 5 components. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Special nylon resin "Macromelt 6902" (Made by Henkel Hakusui, M
FR: 3) Mix 100 parts with 3 parts of the obtained masterbatch,
Plate molding was performed in the same manner as in Example 7.

Comparative Example 22 An example except that 50 parts of the resin aqueous solution obtained in Production Example 9 was replaced with 10 parts of a special nylon resin “Macromelt 6903” (MFR: 100 manufactured by Henkel Hakusui Co., Ltd.)
A masterbatch was obtained in the same manner as in 17. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch,
Plate molding was performed in the same manner as in Example 17.

[Example 18] 50% aqueous solution of ethylene / vinyl acetate copolymer resin 40 parts "Sumikaflex 473" (manufactured by Sumitomo Chemical Co., Ltd.) Polypropylene "Mitsui Noblene J900P" 35 parts Phthalocyanine green "Rionol green Y-" 102 "40 parts (manufactured by Toyo Ink Mfg. Co., Ltd.) Titanium oxide" Taipaque CR-80 "5 parts A masterbatch was obtained in the same manner as in Example 7 using the above 5 components. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. 100 parts of polypropylene "Mitsui Noblen J400" was mixed with 3 parts of the obtained masterbatch, and plate molding was carried out in the same manner as in Example 7.

[Comparative Example 23] "Sumikaflex 473"
A masterbatch was obtained in the same manner as in Example 18, except that 40 parts were replaced with 20 parts of polypropylene wax "Viscor 660P". At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 18.

Table 2 shows the results of evaluation of mechanical properties, surface color unevenness and pigment dispersity of the molded plates obtained in Examples 7 to 18 and Comparative Examples 12 to 23, and the productivity of the masterbatch.

[0080]

[Table 2]

* 1 Retention ratio of the mechanical properties of the resin colored with the masterbatch to the mechanical properties <100%> of the uncolored resin. ◯: 96% or more Δ: 90 to 96% ×: 90% or less * 2 Color unevenness on the surface of the molding plate was visually evaluated. ◯: No color unevenness Δ: Slight color unevenness ×: Significant color unevenness * 3 A part of the molding plate was pressed with a pressing device at a temperature of 170 ° C. to obtain a film having a thickness of 0.1 mm. This was magnified twice with a microscope, and the size and number of coarse pigment particles were measured with an image processor "Luzex 450" (manufactured by Toyo Ink Mfg. Co., Ltd.). 5: Number of particles of 50μ or less 1.0 × 10 ³ particles / cm ² or less 4: Number of particles of 50μ or less 1.0 × 10 ³ to 7.0 × 10 ³ particles / cm ² 3: Number of particles of 50μ or less 7.0 × 10 ³ to 2.7 × 10 ⁴ particles / cm ² 2: Number of particles less than 50μ 2.7 × 10 ⁴ to 7.0 × 10 ⁴ particles / cm ² 1: Number of particles less than 50μ 7.0 × 10 ⁴ particles / cm ² or more * 4 Extruder with screw diameter of 30mm Masterbatch productivity by. ○: good ×: bad

[0082]

EFFECTS OF THE INVENTION According to the present invention, a highly dispersible resin composition for coloring can be provided by a method characterized by omitting the conventional three-roll mill process, automation of the process, labor saving, a working environment without pigment scattering, and the like. It can be manufactured. The thermoplastic resin coloring resin composition produced by the method of the present invention has excellent pigment dispersibility despite having a very high pigment content, and in coloring a textile product which requires a high degree of pigment dispersion, It exerts a great effect on its coloring power and workability. Further, conventionally, for the coloring of a polyolefin-based resin composition containing a high content of an inorganic filler or a fiber reinforcement in which physical properties such as mechanical properties and heat resistance, which were difficult to be uniformly colored by a masterbatch, are particularly important. However, it is extremely effective and enables coloring without color unevenness.

Claims (6)

[Claims] 1. A synthetic resin aqueous dispersion or aqueous solution (a) 1-80.
% By weight, pigment (b) 1-90% by weight and thermoplastic resin (c) 1-
A method for producing a resin composition for coloring a thermoplastic resin, which comprises supplying 90% by weight to a twin-screw extruder to perform phase substitution and dehydration. 2. The method for producing a coloring resin composition according to claim 1, wherein the synthetic resin is a polar functional group-containing thermoplastic resin. 3. The method for producing a coloring resin composition according to claim 2, wherein the polar functional group-containing thermoplastic resin has an oxide or an active hydrogen which accompanies an aqueous solution. 4. The method for producing a coloring resin composition according to claim 1, wherein the synthetic resin aqueous dispersion or the aqueous solution (a) has a solid content in the range of 1 to 80% by weight. . 5. The melt flow rate of the thermoplastic resin (c) is
The method for producing a coloring resin composition according to any one of claims 1 to 4, which is in the range of 0.1 to 400. 6. A resin composition for coloring, which is produced by the method according to any one of claims 1 to 5.