JP3183018B2 - Method for producing resin composition for coloring and resin composition for coloring - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art A composition for coloring a thermoplastic resin includes a powdery dry color in which a pigment and a dispersant are mixed, a liquid color or a paste color in which a pigment is dispersed in a liquid dispersant at room temperature, and a room temperature. Pellet, flake, or bead-shaped master batches in which a pigment is dispersed in a solid resin are also available. These coloring compositions are selectively used by taking advantage of their characteristics depending on the use. Of these, masterbatches are preferably used in terms of ease of handling and preservation of working environment during use. The masterbatch has a high pigment concentration, a small effect on various physical properties such as the heat resistance and strength of the thermoplastic resin to be colored, and the precision of molding of the thermoplastic resin,
With the increase in speed, pigment dispersibility and dispersibility have been required more than before.

In order to impart pigment dispersibility to a masterbatch, conventionally, as a dispersant, stearic acid, zinc stearate, magnesium stearate, aluminum stearate, calcium stearate, ethylene bisamide, polyethylene wax, polypropylene wax, And one or more of these derivatives, for example, a wax made of an acid-modified product, and the like. However, when a high degree of pigment dispersion is required, for example, when a thermoplastic resin is spun at a high speed of several tens of microns or formed into a film, the dispersant may not be satisfied.
That is, yarn breakage during spinning due to poor pigment dispersion, clogging of a filter of a melt spinning machine, and poor molding in a film are caused. In order to solve these problems, efforts have been made to improve the processing method of the master batch and to improve the pigment dispersibility by using a powerful kneader, but they have not been able to exhibit sufficient pigment dispersing ability.

[0004] In the field of large-sized injection molding in which colored pellets have been conventionally used, uneven coloring and flow marks have become a problem in the coloring of molded articles with an increase in coloring with master batches. 2. Description of the Related Art Conventionally, in blow molding or film molding which has been colored by a master batch, plasticization, mixing and kneading of a resin and a master batch are performed in an extruder portion of a molding machine. In the case of an injection molding machine, the plasticizing, mixing, and kneading steps are performed in a cylinder that retreats the screw, but the kneading force is not enough compared with the extruder, and the molding cycle is shortened and the viscosity of the molding resin is reduced. Accordingly, the kneading power has become smaller. As a result, color unevenness tends 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. The occurrence of color unevenness and flow marks has become more likely to occur. This problem is observed in various thermoplastic resins, but is remarkable in polypropylene-based resins that have been increasingly used in home appliances and automotive parts.
An immediate solution has been required. In order to solve this problem, among the three main components of the master batch (pigment, dispersant and base resin), the content of the dispersant is increased, and the base resin having a viscosity smaller than the viscosity of the resin to be colored is used. Color unevenness has been eliminated by lowering the melt viscosity of the master batch. However, for example, in the case where the inorganic filler is filled with a polypropylene resin or the melt flow rate (hereinafter, referred to as MFR) exceeds 25 for the purpose of thin-wall molding, color unevenness or flow mark Is likely to occur, and the solution of this problem has been awaited.

A conventional masterbatch is prepared by introducing a blend of a pigment, a dispersant, and a base resin into a non-continuous kneader such as a three-roll mill or a kneader and melting and kneading the mixture for a long time. The dispersion is produced by pelletizing using a single screw extruder. However, once the pigment powder has been dried, there are many coarse secondary aggregated particles. It was very difficult to disperse .

On the other hand, in the production of printing inks and paints, a large-volume kneading tank is provided for dispersing pigments in a printing ink varnish or paint vehicle or for flushing an aqueous press cake into an oily vehicle or oily varnish. The pigment is charged into a flasher and vigorously stirred with a large power to invert the phase of the pigment to remove water, which is then heated and dehydrated under reduced pressure to obtain a pigment dispersion. However, in this method, it is difficult to pelletize a coloring resin such as a masterbatch or the like, and furthermore, an apparatus having an excessive amount for the amount of the pigment dispersion is required . In addition, a large amount of time is required due to the complexity of the process, and variation in each lot and complicated handling are problems due to the batch method. And the like, which is not suitable for the production of a master batch.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned various drawbacks and to provide a thermoplastic resin having a mechanical property such as tensile strength, bending strength, impact strength, etc., of 5% or more for each strength value. An object of the present invention is to provide a method for efficiently producing a resin composition (master batch) for coloring a thermoplastic resin, which does not hinder, has excellent pigment dispersibility, and enables uniform coloring without color unevenness.

[0009]

[SUMMARY OF Namely, the present invention is the field
Aqueous compound (a) having surface activity performance 1-30 parts by weight, pigment
(b) 1 to 90 parts by weight, thermoplastic resin (c) 1 to 90 parts by weight and water
(d) A method for producing a resin composition for coloring a thermoplastic resin, wherein 1 to 360 parts by weight is supplied to a twin-screw extruder to carry out phase replacement and dehydration.

The aqueous compound (a) having a surface active property is
It is a water-soluble or water-dispersible compound, as long as it is compatible with the resin to be colored. Aqueous compound having surface active performance
(a) can be used as an aqueous solution or dispersion having a concentration of 1 to 80% by weight, preferably 5 to 65% by weight. Further, a general surfactant can be used in combination. As an example of an aqueous compound (a) having surface active performance
Te is boric acid ester compound, phosphate compound, an organic silicon compound having a hydrophilic group, an organic fluorine compound and the like having a hydrophilic group, can be used alone or two or more thereof, with respect to pigment particles High affinity
Are preferably used.

The boric acid ester compound or the phosphoric acid ester compound is an esterified product of boric acid or phosphoric acid and an alcohol, and may be a mono-, di- or triester, or a mixture thereof. As the alcohols, polyhydric alcohols, monoalcohols, derivatives such as alkylene oxide adducts of these alcohols, and oxyacids are used. Of these, polyhydric alcohols such as glycols and glycerins having adjacent OH groups and alkylene oxide adducts of these alcohols are particularly preferred.

Examples of the above-mentioned alcohols include polyhydric alcohols such as 1,3-butylene glycol and tetrabutyl alcohol.
Methylene glycol , neopentyl glycol, hexamethylene glycol, diethylene glycol , propylene glycol, dipropylene glycol, triethylene glycol, poly (ethylene ether) glycol, poly (propylene ether) glycol, poly (tetramethylene ether) glycol, polyformal glycol, Copolymer of ethylene oxide and propylene oxide, hydrogenated bisphenol A, trimethylolpropane, tris (hydroxylethyl) isocyanate,
Glycerin, glycerol monolaurate, glycerol monopalmitate, glycerol monostearate,
Diglycerin monostearate, glycerol monooleate, polyoxyethylene glycerol stearate,
Sorbitol and the like.

The monoalcohols include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol,
Examples include decyl alcohol, dodecyl alcohol, tetracosyl alcohol, hexacosyl alcohol, octadecenyl alcohol, cyclohexyl alcohol, oleyl alcohol, palmityl alcohol, isostearyl alcohol, benzyl alcohol and the like. Examples of the oxyacid include 12-hydroxystearic acid, linosic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, delta-hydroxyvaleric acid, ε-hydroxycaproic acid, and p-hydroxyethyloxybenzoic acid.

The organic silicon compound having a hydrophilic group in the aqueous compound (a) having a surface active property includes a nonionic type such as a polyalkylene oxide adduct of methylpolysiloxane, and an acid-neutralized product of amino-modified methylpolysiloxane. Examples thereof include an isocationic type and an anionic type obtained by neutralizing a basic substance of acid-modified methylpolysiloxane, and a nonionic type is preferable. In particular,
Examples include a side chain-modified organosilicon compound represented by the following general formula 1 and a terminal-modified organosilicon compound represented by the following general formula 2.

[0015]

Embedded image

Embedded image (However, m, n, a, and b are arbitrary integers, R is a hydrogen atom or an alkyl group, and R 'is a hydrogen atom or a methyl group.)

The organic fluorine compound having a hydrophilic group among the aqueous compounds (a) having a surface activity has a fluoroalkyl group (CF _3- (CF ₂ ) _m- ) in the molecule and has an extremely low surface tension. The compound shown below has a hydrophilic part in which an anionic type such as a carboxylate, a sulfonate or a phosphate, a cationic type such as a trimethylammonium salt, an amphoteric type such as an alkyl betaine or an alkylamino sulfonate, or a polyalkylene oxide is added. The nonionic type of the product is exemplified.

As the pigment (b), known organic pigments and inorganic pigments conventionally used for coloring thermoplastic resins can be used. Examples of such pigments include azo-based, anthraquinone-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, dioxane-based, perylene-based, quinophthalone-based, and perinone-based organic pigments and their wet press cakes, cadmium sulfide, and selenium. Inorganic pigments such as cadmium oxide, ultramarine, titanium dioxide, iron oxide, chromate oxide, and carbon black.

As the thermoplastic resin (c), those which are compatible with the resin to be colored are preferred, and those having an 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 is deteriorated, causing color unevenness and the like, and adversely affecting various physical properties of the colored thermoplastic resin. On the other hand, MF
When R exceeds 400, the mechanical strength and heat resistance of the resin composition itself become low, making the production of the resin composition difficult, and various properties such as heat resistance and strength of the thermoplastic resin to be colored. It adversely affects physical properties. MFR is JIS
It is an MFR measured according to K7210.

Specific examples of the thermoplastic resin (c) include, for example, polyolefin-based resins such as crystalline or amorphous polypropylene, low-density or high-density polyethylene, and random, block or graft copolymers of ethylene / propylene; α-olefin and ethylene or propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / acrylic acid copolymer, or its thermal decomposition And one or more of these are used.

In addition to polyolefin resins, polymethylpentene, polystyrene, polyethylene terephthalate and polydiene polybutylene terephthalate, acrylonitrile-butadiene-styrene (AB
S) Resin, acrylonitrile-EPDM-styrene (A
ES) resins, and other thermoplastic resins such as acrylic resins, polyamides, polycarbonates, polyacetals, polyvinyl acetates, polyvinyl chlorides, polyvinylidene chlorides, and polyurethanes, and one or more of these are used. The thermoplastic resin (c) may be a derivative by functional group modification, cross-linking modification, grafting and blocking modification, and may be in the form of powder or pellet.

As the twin-screw extruder, a twin-screw co-rotating screw extruder is preferable.
It is preferably at least 25, more preferably at least 30. If the L / D value is less than 25, problems arise in terms of poor kneading and stability of quality.
The screw shape is not particularly limited, but a strong kneading type screw element arrangement 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 replacement. The screw rotation speed varies depending on the L / D value and the screw shape, but is preferably set at 150 to 450 rpm from the viewpoint of improving the mixing and kneading effects and performing high-speed processing.

The temperature setting of the twin screw extruder is not particularly limited, and it is important to perform cooling and heating for each barrel in accordance with the characteristics of the pigment used and the melting characteristics of the thermoplastic resin. For twin screw extruders,
In order to increase the efficiency of dehydration, a vent port connected to a vacuum pump can be provided, and a heating decompression dehydration treatment can be performed if necessary.

A small amount of various additives such as an antioxidant, a stabilizer such as an ultraviolet absorber, and a surfactant are added to the coloring resin composition of the present invention as long as the effects of the present invention are not impaired. You can also. 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 reinforcing materials such as inorganic fillers, glass fibers, and organic fibers for the purpose of improving physical properties. For example, inorganic fillers without affecting mechanical properties such as strength and heat resistance, which were not feasible with coloring using conventional resin compositions.
Resin composition containing up to 50% by weight of fiber and fiber reinforcement
4 parts by weight of the coloring resin composition of the present invention based on 100 parts by weight of the product
Coloring without color unevenness can be achieved by adding a small amount of
Noh.

The coloring resin composition of the present invention can be particularly preferably used for coloring a polyolefin resin.
Polymethylpentene, polystyrene, polyvinyl chloride,
Polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene (AB
S) Resin, acrylonitrile-EPDM-styrene (A
ES) Resins, acrylic resins, polyamides, polycarbonates, polyacetals, polyurethanes, and other thermoplastic resins can also be blended.

The coloring resin composition of the present invention is extremely effective for improving the dispersibility and coloring power of a pigment. Incidentally, the improvement of this amount <br/> dispersibility and coloring power are due to affinity for the pigment in an aqueous compound having at least one or more polar groups in a molecule, molecular state the polar group in an aqueous solution It is presumed that a polar bond is easily formed between the pigment and the pigment, and a flushing action accompanying the elimination of water is caused. The coloring resin composition of the present invention can also be used for applications such as inks, paints, and adhesives.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically based on embodiments. In the examples, parts and% represent parts by weight and% by weight, respectively. Example 1 100 parts of a 5% aqueous solution of polyoxyethylene glycerol borate-stearate "Emalbon T-83" (manufactured by Toho Chemical Industry) 55 parts of polyethylene "NUC G5391" (manufactured by Nippon Unicar, MFR: 50) 40 parts of phthalocyanine blue "Lionol Blue FG7330" (Toyo Ink Mfg. Co., Ltd.)

The above three components were premixed with a Henschel mixer, and a twin-screw co-rotating screw extruder with a screw diameter of 30 mm and an L / D value of 38 was used at a rotational speed of 350 rpm and a set temperature of 140 ° C.
After extruding and extruding under the conditions described above, the mixture was cut with a pelletizer to obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Furthermore, 100 parts of polypropylene “Mitsui Noblen J400” (manufactured by Mitsui Petrochemical Industries, Ltd., MFR: 3) was mixed with 3 parts of the obtained master batch, and a vertical test spinning machine “Spinning Tester” (manufactured by Fuji Filter Co., Ltd.) ), The fiber was spun at 230 ° C. under the hopper, the kneading part and the die part at 230 ° C., and then stretched three times to obtain a 5-denier polypropylene fiber.
Good dispersibility was exhibited without any problem in spinnability, clogging and stretching.

Comparative Example 1 The procedure of Example 1 was repeated except that 100 parts of a 5% aqueous solution of “Emalbon T-83” was replaced with 5 parts of polyethylene wax “Sunwax 131P” (manufactured by Sanyo Chemical Industries, Ltd.). Master batch was obtained. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. further,
The spinning was performed in the same manner as in Example 1, but the yarn was broken due to clogging. [Comparative Example 2] The three components after premixing with the same composition as in Example 1 were kneaded with a three-roll mill at a temperature of 140 ° C, and the kneaded material was cooled and pulverized.
Pelletization was performed with an extruder with a screw diameter of 65 mm,
Due to poor supply, strand breaks and pulsation occurred, and a master batch could not be obtained.

Example 2 Polyoxyethylene glycol ether phosphate ester 5% aqueous solution of "Phosphanol RE960" (produced by Toho Chemical Industry Co., Ltd.) 112 parts Polyethylene "Mitsubishi Polyethylene MV-31" (produced by Mitsubishi Yuka Co., Ltd. MFR: 45) 40 parts Polyethylene wax “Sunwax 165P” (manufactured by Sanyo Chemical Industries) 15 parts Kinacridone red “Fast Gen Super Magenta RE03” 40 parts (manufactured by Dainippon Ink and Chemicals, Inc.) Mix, extrude and extrude using a twin-screw co-rotating screw extruder with a screw diameter of 30 mm and an L / D value of 42 at a rotation speed of 400 rpm and a set temperature of 150 ° C, then cut with a pelletizer to obtain a masterbatch Was. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Furthermore, spinning was performed in the same manner as in Example 1, to obtain a polypropylene fiber. Good dispersibility was exhibited without any problem in spinnability, clogging and stretching.

Comparative Example 3 A 5% aqueous solution of “Phosphanol RE960” was replaced with 112 parts of a 5% metal soap (calcium stearate).
A master batch was obtained in the same manner as in Example 2. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Furthermore, spinning was performed in the same manner as in Example 1, to obtain a polypropylene fiber. There was no problem in spinnability. [Comparative Example 4] The four components having the same composition as in Example 2 were kneaded with a pressure kneader, and pelletized with an extruder having a screw diameter of 65 mm. Could not get a batch.

Example 3 100 parts of a 5% aqueous solution of side chain-modified methylpolysiloxane polyethylene oxide "Silwet L-7602" (manufactured by Nippon Unicar) 100 parts polypropylene "Mitsubishi Polypro BC05B" (manufactured by Mitsubishi Yuka Co., Ltd., MFR) : 50) 40 parts Phthalocyanine blue "Lionol Blue 7110V" 30 parts (Toyo Ink Mfg. Co., Ltd.) Condensed azo yellow "Chromophthal Yellow GR" (Ciba Geigy) 10 parts Titanium oxide "Taipek CR-80" (Ishihara Sangyo Co., Ltd.) 5 parts) A masterbatch was obtained in the same manner as in Example 2 using the above five components. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Furthermore, spinning was performed in the same manner as in Example 1 to obtain a polypropylene fiber. Good dispersibility was exhibited without any problem in spinnability, clogging and stretching.

Comparative Example 5 The procedure of Example 3 was repeated, except that 100 parts of a 5% aqueous solution of “Silwet L-7602” was replaced with 5 parts of a polypropylene wax “VISCOL 550P” (manufactured by Sanyo Chemical Industries, Ltd.). Master batch was obtained. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Further, spinning was performed in the same manner as in Example 1, but yarn breakage occurred due to clogging. [Comparative Example 6] Four components having the same composition as in Example 3 were kneaded with a three-roll mill,
Pelletization was performed with an extruder having a screw diameter of 65 mm, but a shortage of strands and a pulsating flow occurred due to poor supply, and a master batch could not be obtained.

Example 4 A 15% solution of a perfluoroalkyl phosphate ester "Surflon S-112" (manufactured by Asahi Glass Co., Ltd.) 5% aqueous solution 100 parts Ethylene / propylene copolymer resin "Mitsui Hypol J740P" 40 parts (Mitsui Petrochemical Co., Ltd., MFR: 25) Ethylene-vinyl acetate copolymer resin "Ultracene 680" 10 parts (Tosoh Corporation, MFR: 160) Condensed azo yellow "Chromophthal Yellow GR" 40 parts Titanium oxide "Taipe CR -80 "5 parts A masterbatch was obtained in the same manner as in Example 1 using the above five components. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Furthermore, spinning was performed in the same manner as in Example 1 to obtain a polypropylene fiber. Good dispersibility was exhibited without any problem in spinnability, clogging and stretching.

Comparative Example 7 A master batch was obtained in the same manner as in Example 4 except that 100 parts of a 5% aqueous solution of “Surflon S-112” was replaced with 5 parts of sodium dodecylbenzenesulfonate. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Furthermore, spinning was performed in the same manner as in Example 1 to obtain a polypropylene fiber. Spinnability, clogging,
Good dispersibility was exhibited without any problem with stretchability. [Comparative Example 8] Five components having the same composition as in Example 4 were kneaded with a three-roll mill,
The mixture was pelletized by an extruder having a screw diameter of 65 mm to obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Furthermore, spinning was performed in the same manner as in Example 1, to obtain a polypropylene fiber. There was no problem in spinnability.

Example 5 Side chain modified methylpolysiloxane polyethylene oxide "KF351A" (manufactured by Shin-Etsu Chemical Co., Ltd.) 50% 10% aqueous dispersion Copolymerized polyester "Byron GM900" manufactured by Toyobo Co., Ltd., MFR: 2 15 parts Polyethylene terephthalate "Unipet RT543" 27 parts (Nihon Unipet, MFR: 0.5) Partially saponified montanic acid "Luwax OP" 3 parts (BASF, saponification value: 150 mgKOH / g) Titanium oxide "TYPAQUE CR-80" 45 parts Carbon black "Mitsubishi Carbon MA-100" (Mitsubishi Chemical Industries) 5 parts

The above six components were premixed with a Henschel mixer, and the mixture was ground using a twin-screw co-rotating screw extruder as in Example 2 at a set temperature of 230 ° C. and a rotation speed of 350 rpm.
After extrusion, it was cut with a pelletizer to obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of polyethylene terephthalate “UNIPET RT543” 3 parts of the masterbatch obtained were mixed, spun and stretched 4 times in the same manner as in Example 1, and then heat-treated at 140 ° C. to give a 3-denier polyester. Fiber was obtained. Spinnability,
Good dispersibility was exhibited without any problem in both clogging and stretching properties.
The intrinsic viscosity of the fiber obtained against the intrinsic viscosity of polyethylene terephthalate without masterbatch 0.893 dl / g is
0.879 dl / g, and the intrinsic viscosity retention was 98.4%.

Comparative Example 9 A master batch was obtained in the same manner as in Example 5 except that 50 parts of a 10% aqueous dispersion of “KF351A” was replaced with 5 parts of a copolymerized polyester “Vylon GM900”. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Furthermore, when spinning was performed in the same manner as in Example 5, yarn breakage due to clogging occurred. Intrinsic viscosity of polyethylene terephthalate without addition of master batch 0.
The intrinsic viscosity of the fiber obtained against 893 dl / g is 0.523 dl / g
And the intrinsic viscosity retention was 58.6%. [Comparative Example 10] Six components having the same composition as in Example 5 were kneaded with a three-roll mill,
When pelletization was performed with an extrusion molding machine with a screw diameter of 65 mm, strand breaks and pulsation occurred due to poor supply,
Master batch could not be obtained.

Example 6 A 10% aqueous solution of glycerol borate-palmitate "Emalbon S-40" (manufactured by Toho Chemical Industry Co., Ltd.) 50 parts Perfluoroalkylethylene oxide adduct "MegaFac F-144D" (Dainippon Ink. 100 parts of a 5% aqueous solution of Chemical Industry Co., Ltd. 100 parts Nylon 6 "Unitika Nylon A1020" (manufactured by Unitika, MFR: 20) 15 parts Nylon 6 "Unitika Nylon A1030BRL" (manufactured by Unitika, MFR: 1) 25 parts Phthalocyanine Green Lionol Green Y-102 ”40 parts (Toyo Ink Mfg. Co., Ltd.) Titanium oxide“ Taipek CR-80 ”10 parts The above 6 components were premixed with a Henschel mixer, and the same twin-screw co-rotating screw extrusion as in Example 2 was performed. The mixture was extruded and extruded at a set temperature of 220 ° C. and a rotation speed of 400 rpm using a machine, and then cut with a pelletizer to obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Nylon 6
"Unitika Nylon A1030BRL" 3 parts of the masterbatch obtained were mixed with 100 parts by weight, and the same procedure as in Example 5 was carried out.
A 3-denier nylon fiber was obtained. Good dispersibility was exhibited without any problem in spinnability, clogging and stretching.

[Comparative Example 11] Except that 50 parts of a 10% aqueous solution of “Emalbon S-40” and 100 parts of a 5% aqueous solution of “Megafaque F-144D” were replaced with 10 parts of nylon 6 “Unitika Nylon A1020”, A master batch was obtained in the same manner as in Example 6. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Further, when spinning was performed in the same manner as in Example 6, yarn breakage due to clogging occurred. [Comparative Example 12] The components having the same composition as in Example 6 were kneaded with a three-roll mill,
When pelletization was performed with an extrusion molding machine with a screw diameter of 65 mm, strand breaks and pulsation occurred due to poor supply,
Master batch could not be obtained.

In order to evaluate the clogging property of the undispersed pigment of the master batch, Examples 1 to 4 and Comparative Examples 1, 3,
10 parts of each of the masterbatches obtained in 5, 7, and 8 were each 100 parts of polypropylene “Mitsui Noblen J400”, and 10 parts of each of the masterbatches obtained in Example 5 and Comparative Example 9 were 100 parts of polyethylene terephthalate “Unipet RT543” 100. Parts, 10 parts of each of the master batches obtained in Example 6 and Comparative Example 11 were mixed with 100 parts of nylon 6 “Unitika Nylon A1030BRL”, respectively. Extrudes 3kg of the mixture with a machine,
The pressure rise at the tip was compared. Table 1 shows the results.

Further, in order to evaluate the dispersive color developing property of the pigment, each part of the master batch obtained in Examples 1 to 4 and Comparative Examples 1, 3, 5, 7, and 8 was made of polypropylene “Mitsui Noblen J400” 100 1 part of the master batch obtained in Example 5 and Comparative Example 9 was replaced with 100 parts of polyethylene terephthalate “Unipet RT543”, and 1 part of the master batch obtained in Example 6 and Comparative Example 11 was replaced with nylon 6
Mix 100 parts of "Unitika Nylon A1030BRL" with 5 parts of titanium oxide "Taipek CR-80" and knead with a two-roll mill.
Molded into thick plates. Color difference meter (Hunter, USA)
Table 1 shows the results of measuring the reflection intensity at 600 nm by using. The reflection intensity was set to 100% in the example, and compared with the corresponding comparative example.

[0042]

[Table 1]

Example 7 50% 10% aqueous solution of polyoxyethylene glycol ether phosphate ester "Plysurf A-219B" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Polyethylene "Novatech MH40" (manufactured by Mitsubishi Kasei Co., MFR: 50) 15 parts Ethylene / ethyl acrylate copolymer resin "EVAFLEX-EEA A-704" 20 parts (Mitsui DuPont Polychemical Industries, Ltd., MFR: 275) Titanium oxide "Taipek CR-80" 50 parts Carbon black "Mitsubishi Carbon" MA-100 "(manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 10 parts The above five components were minced and extruded at a rotation speed of 400 rpm and a set temperature of 150 ° C. using the same twin-screw co-rotating screw extruder as in Example 2. Then, it was cut with a pelletizer to obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow.
100 parts of polyethylene “HIZEX 2100J” (manufactured by Mitsui Petrochemical Co., Ltd., MFR: 6.5) was mixed with 3 parts of the obtained master batch, and molded into a plate with an injection molding machine at a back pressure of 0 kg / cm ² .

Comparative Example 13 50 parts of a 10% aqueous solution of "Plysurf A-219B" was acid-modified polyethylene wax "AC540" (manufactured by Allied Signal).
A masterbatch was obtained in the same manner as in Example 7, except that 5 parts were used. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch was formed into a plate in the same manner as in Example 7.

Example 8 Polyoxyethylene glycol ether phosphate ester "Phosphanol RL210" (manufactured by Toho Chemical Industry Co., Ltd.) 20% aqueous solution 20 parts Glycerol borate-hydroxystearate "Emalbon S-260" (Toho) 30 parts of 10% aqueous solution of Chemical Industry Co., Ltd. 30 parts Polypropylene "Chisso Polypro K7050" (manufactured by Chisso Corporation, MFR: 45) 35 parts Propylene / ethylene copolymer resin "APAORT2280" 10 parts (manufactured by Ube Lexen Corporation, MFR: 250) Condensed azo yellow “Chromophthal Yellow GR” 20 parts Quinacridone red “Fast Gen Super Magenta RE03” 20 parts Titanium oxide “Taipek CR-80” 5 parts Carbon black “Mitsubishi Carbon MA-100” 5 parts Implemented using the above 8 components A masterbatch was obtained in the same manner as in Example 7. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Polypropylene "Mitsui Noblen JH-G" (Mitsui Petrochemical, M
FR: 4) 3 parts of the obtained master batch was mixed with 100 parts, and molded into a plate with an injection molding machine at a back pressure of 0 kg / cm ² .

Comparative Example 14 20 parts of a 10% aqueous solution of “Phosphanol RL210” and 30 parts of a 10% aqueous solution of “Emalbon S-260” were replaced with 5 parts of sodium lauryl sulfate “Emal O” (manufactured by Kao Corporation). A master batch was obtained in the same manner as in Example 8 except for the above. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch was formed into a plate in the same manner as in Example 8.

Example 9 Perfluoroalkyl group and hydrophilic group-containing oligomer "EFTOP EF-122C" (manufactured by Mitsubishi Metal Corporation) 10% aqueous dispersion 50 parts ABS resin "JSR ABS35" (manufactured by Nippon Synthetic Rubber Co., Ltd.) , MFR: 60) 40 parts Phthalocyanine blue "Lionol Blue POBS" 5 parts (manufactured by Toyo Ink Mfg. Co., Ltd.) Titanium oxide "Taipek CR-80" 50 parts Using the above four components, a master batch was prepared in the same manner as in Example 7. Obtained. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. ABS
100 parts of resin “JSR ABS10” (manufactured by Nippon Synthetic Rubber Co., Ltd., MFR: 0.5) were mixed with 3 parts of the obtained master batch and molded into a plate with an injection molding machine at a back pressure of 0 kg / cm ² .

Comparative Example 15 The procedure of Example 9 was repeated except that 50 parts of a 10% aqueous dispersion of “EFTOP EF-122C” was replaced with 5 parts of a polystyrene wax “Hymer ST95” (manufactured by Sanyo Chemical Industries, Ltd.). To obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch was formed into a plate in the same manner as in Example 9.

Example 10 Phosphoric acid ester of polyoxyethylene glycol ether 30% aqueous solution of "Plysurf M-208B" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 10 parts Side chain-modified dimethylsiloxane methyl (polyoxyethylene) siloxane 10% aqueous solution of copolymer “SH3746” (manufactured by Toray Dow Corning Silicone Co., Ltd.) 20 parts Polystyrene resin “Stylon 683” (manufactured by Asahi Kasei Kogyo Co., MFR: 2.8) 30 parts Polystyrene resin “Stylon 666” (manufactured by Asahi Kasei Kogyo Co., Ltd. MFR: 7.5) 15 parts Condensed azo yellow “Chromophthal Yellow GR” 20 parts Quinacridone red “Fast Gen Super Magenta RE03” 25 parts Titanium oxide “Typek CR-80” 5 parts Same as Example 7 using the above seven components. To obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of polystyrene resin “Stylon 683” was mixed with 3 parts of the obtained master batch, and the back pressure was 0 kg / cm ² using an injection molding machine.
To form a plate.

Comparative Example 16 10 parts of a 30% aqueous solution of "Plysurf M-208B" and "SH37
A masterbatch was obtained in the same manner as in Example 10, except that 20 parts of a 10% aqueous solution of "46" was replaced with 5 parts of a polystyrene wax "Himer SB130" (manufactured by Sanyo Chemical Industries, Ltd.). At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch is
A plate was formed in the same manner as in Example 10.

Example 11 100% aqueous solution of glycerol borate-hydroxystearate "Emalbon S-60" (manufactured by Toho Chemical Industry Co., Ltd.) 100 parts Nitrile rubber "Hycar1411" (manufactured by Zeon Corporation, MFR: 10) 25 part nitrile rubber "NipolDN502" (Nippon Zeon Co. Ltd., MFR: 120) 5 parts condensation azo yellow "cHROMOPHTHAL yellow GR" 5 parts phthalocyanine blue "Riono Le Blue FG7330" 5 parts of titanium oxide "Tipaque CR-80" 45 parts carbon 5 parts of black "Mitsubishi Carbon MA-100" A masterbatch was obtained in the same manner as in Example 7 using the above seven components. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of nitrile rubber “Hycar1411” and 3 parts of the obtained master batch were mixed and molded into a plate with an injection molding machine at a back pressure of 0 kg / cm ² .

Comparative Example 17 A master batch was obtained in the same manner as in Example 11, except that 100 parts of a 10% aqueous solution of "Emalbon S-60" was replaced with 10 parts of a nitrile rubber "NipolDN502". At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch was formed into a plate in the same manner as in Example 11.

Example 12 A 20% aqueous solution of terminal-modified methylpolysiloxane polyethylene oxide "Silwet FZ-2161" (manufactured by Nippon Unicar) 25 parts Acrylic resin "Dianal BR-117" (manufactured by Mitsubishi Rayon Co., Ltd.) MFR: 95) 45 parts Condensed azo yellow "Chromophthal Yellow GR" 5 parts Quinacridone red "Fast Gen Super Magenta RE03" 45 parts A masterbatch was obtained in the same manner as in Example 1 using the above four components. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Acrylic resin "Dianal BR-73" (Mitsubishi Rayon, MF
R: 20) To 100 parts, 3 parts of the obtained master batch was mixed and molded into a plate with an injection molding machine at a back pressure of 0 kg / cm ² .

Comparative Example 18 A masterbatch was obtained in the same manner as in Example 12, except that 25 parts of a 20% aqueous solution of “Silwet FZ-2161” was replaced with 5 parts of an acrylic resin “Dianal BR-117”. Was. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch was formed into a plate in the same manner as in Example 12.

Example 13 Polyoxyethylene glycol ether phosphate ester "Nikkor TDP-10" (manufactured by Nikko Chemicals) 50% 10% aqueous solution Polyamide "Versamide DPX640" (manufactured by Henkel Hakusui, MFR: 120) 15 Part Special nylon resin "Macromelt 6900" (manufactured by Henkel Hakusui Co., Ltd., MFR: 10) 30 parts Titanium oxide "Taipek CR-80" 55 parts Carbon black "Mitsubishi Carbon MA-100" 5 parts Examples using the above five components A master batch was obtained in the same manner as in No. 6. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Special nylon resin “Macromelt 6902” (Henkel Hakusui, M
FR: 3) Mix 100 parts of the obtained master batch with 3 parts,
It was molded into a plate with an injection molding machine at a back pressure of 0 kg / cm ² .

Comparative Example 19 50 parts of a 10% aqueous solution of “Nikkor TDP-10” was mixed with a special nylon resin “Macromelt 6903” (manufactured by Henkel Hakusui, MFR: 10).
0) A master batch was obtained in the same manner as in Example 13, except that 5 parts were used. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch was formed into a plate in the same manner as in Example 13.

[Example 14] A 30% solution of perfluoroalkyl betaine "Surflon S-131" (manufactured by Asahi Glass Co., Ltd.) 5% aqueous solution 40 parts Polyoxyethylene glycol ether phosphate "Phosphanol GB520" (Toho Chemical Co., Ltd.) 10% aqueous solution of Industrial Co., Ltd. 20 parts Vinyl chloride resin "Daichi PVC101EP" (Zeon Kasei Co., MFR: 250) 6 parts Vinyl chloride resin "Vinica P-540" (Mitsubishi Kasei Vinyl Co., MFR: 1.5) 44 Part Plasticizer "dioctylate phthalate" (manufactured by Tokyo Chemical Industry Co., Ltd.) 1 part Phthalocyanine blue "Lionol Blue FG7330" 30 parts Titanium oxide "Taipek CR-80" 15 parts Using the above five components, in the same manner as in Example 7 Master batch was obtained. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of vinyl chloride resin “Vinika P-540” was mixed with 3 parts of the obtained master batch, and molded into a plate with an injection molding machine at a back pressure of 0 kg / cm ² .

Comparative Example 20 40 parts of a 5% aqueous solution of "Surflon S-131" and 20 parts of a 10% aqueous solution of "Phosphanol GB520" were mixed with a vinyl chloride resin "Vinika 75BX" (MFR: manufactured by Mitsubishi Kasei Vinyl Co., Ltd.). 20) A masterbatch was obtained in the same manner as in Example 14, except that 4 parts were used. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch was formed into a plate in the same manner as in Example 14.

Example 15 Polyoxyethylene Glycol Phosphate Ester "Nikkor DDP-8" (manufactured by Nikko Chemicals) 30% aqueous solution 30 parts Polyoxyethylene glycerol borate-isostearate "Emalbon S-260" 30 parts of 10% aqueous solution of Toho Chemical Industry Co., Ltd. 30 parts Polyurethane resin "Desmocoll 540" 45 parts (Sumitomo Bayer Urethane, MFR: 65) Polyurethane resin "Desmocoll U42" 5 parts (Sumitomo Bayer Urethane, MFR : 120) Condensed azo yellow “Chromophthal Yellow GR” 40 parts Titanium oxide “Taipek CR-80” 4 parts A masterbatch was obtained in the same manner as in Example 1 using the above six components. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of polyurethane resin "Desmocol 540" is mixed with 3 parts of the obtained master batch, and the back pressure is 0 kg / c with an injection molding machine.
It was molded into a plate at m ^2.

Comparative Example 21 The procedure was carried out except that 30 parts of a 10% aqueous solution of "Nikkor DDP-8" and 30 parts of a 10% aqueous solution of "Emalbon S-260" were replaced with 6 parts of a polyurethane resin "Desmocol U42". A masterbatch was obtained in the same manner as in Example 15. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch was formed into a plate in the same manner as in Example 15.

Table 2 summarizes the results of evaluating the mechanical properties, color unevenness of the surface and the degree of pigment dispersion of the molded plates obtained in Examples 7 to 15 and Comparative Examples 13 to 21, and the productivity of the master batch.

[0062]

[Table 2] * 1 Retention rate of mechanical properties of resin colored with master batch compared to mechanical properties <100%> of uncolored resin. ：: 96% or more Δ: 90 to 96% ×: 90% or less * 2 Color unevenness on the surface of the molded plate was visually evaluated. ：: no color unevenness Δ: slight color unevenness ×: remarkable color unevenness * 3 A part of the molding plate was pressed with a press at a temperature of 170 ° C. to obtain a 0.1 mm thick film. This was magnified two times with a microscope, and the size and number of the coarse particles of the pigment were measured with an image processor "Luzex 450" (manufactured by Toyo Ink Mfg. Co., Ltd.). 5: Number of particles of 50 μ or less 1.0 × 10 ³ particles / cm ² or less 4: Number of particles of 50 μ or less 1.0 × 10 ³ to 7.0 × 10 ³ particles / cm ² 3: Number of particles of 50 μ or less 7.0 × 10 ³ to 2.7 × 10 ⁴ particles / cm ² 2: Number of particles of 50 μ or less 2.7 × 10 ⁴ to 7.0 × 10 ⁴ particles / cm ² 1: Number of particles of 50 μ or less 7.0 × 10 ⁴ particles / cm ² or more * 4 Extruder with screw diameter of 30 mm By master batch productivity. ：: good ×: bad

[0063]

Industrial Applicability The resin composition for coloring a thermoplastic resin of the present invention has excellent pigment dispersibility despite its extremely high pigment content. Has a great effect on its coloring power and processability. In addition, the manufacturing method using the twin-screw extruder of the present invention facilitates the automation of the manufacturing process, labor saving, cost reduction, and high quality of the coloring resin composition . Furthermore, the resin composition for coloring a thermoplastic resin of the present invention can enhance inorganic fillers and fiber reinforced materials in which physical properties such as mechanical properties and heat resistance, which were conventionally difficult to uniformly color with a master batch, are particularly important. very valid and color evenly worn against colored polyolefin resin composition containing at a content
Color is possible.

────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08J 3/20-3/22

Claims (8)

(57) [Claims] 1. An aqueous compound (a) having a surface activity of 1 to 30.
Parts by weight, 1 to 90 parts by weight of a pigment (b), 1 to 90 parts by weight of a thermoplastic resin (c) and 1 to 360 parts by weight of water (d) are supplied to a twin-screw extruder,
A method for producing a resin composition for coloring a thermoplastic resin, comprising performing phase replacement and dehydration. 2. A method according to claim 1, wherein the hydrophobic compound having surfactant properties (a) is characterized in that boric acid ester compound
A method for producing a coloring resin composition. 3. A process according to claim 1, wherein the hydrophobic compound having surfactant properties (a) is characterized in that it is a phosphoric acid ester compound
A method for producing a coloring resin composition. 4. The method for producing a coloring resin composition according to claim 1, wherein the aqueous compound (a) having surface activity is an organic silicon compound having at least a hydrophilic group. 5. The method for producing a coloring resin composition according to claim 1, wherein the aqueous compound (a) having surface activity is an organic fluorine compound having at least a hydrophilic group. 6. An aqueous compound (a) having a surfactant activity ,
Claims 1, characterized in that used as an aqueous solution or aqueous dispersion in the range of concentrations from 1 to 80 wt% 5 either
The method for producing a coloring resin composition according to any one of the above . 7. The thermoplastic resin (c) has a melt flow rate of
Claim 1 characterized by being in the range of 0.1 to 400
7. The method for producing a coloring resin composition according to any one of the above items. 8. A coloring resin composition produced by the method according to any one of claims 1 to 7 .