JPH07233275A - Production of resin composition for coloring, and resin composition for coloring - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. which enables a homogeneous coloring of a thermoplastic resin with an excellent pigment dispersion without decreasing the mechanical strengths of the resin by 5% or more by subjecting a pigment, water, and a thermoplastic resin to phase replacement and dehydration in a twin-screw extruder. CONSTITUTION:A resin compsn. for coloring is obtd. by subjecting a pigment, water, and a thermoplastic resin to phase replacement and dehydration in a twin-screw extruder. The pigment may be a dry powder, a wet cake before drying, or their mixture. The amt. of water added is pref. 20-120wt.% of the dry pigment. Since the pigment contg. water hardly contains agglomerated particles and contains only particles almost like primary particles and since the pigment is dispersed by flushing from an aq. phase to a resin phase with the thermoplastic resin, the state of pigment being almost like primary particles is maintained and the compsn. excellent in pigment dispersion is obtd.

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.

For example, when a high degree of pigment dispersion is required, such as when a thermoplastic resin is spun at a diameter of a few dozen microns or formed into a film, the pigment dispersibility of a conventional masterbatch may not be satisfied. That is, problems such as yarn breakage during spinning due to poor pigment dispersion, clogging of the filter of the melt spinning machine, and defective molding of the film occur. In order to solve these problems and improve the dispersibility of the masterbatch, stearic acid, zinc stearate, magnesium stearate, aluminum stearate, calcium stearate, ethylene stearate, and ethylene bisamide have been conventionally used as dispersants for imparting dispersibility. Polyethylene wax, polypropylene wax, and derivatives thereof, for example, one or more waxes composed of an acid-modified product are generally used. Further, efforts have been made to improve the processing method of the masterbatch and to improve the pigment dispersibility by using a powerful kneader. However, sufficient pigment dispersibility to solve the above problems was not obtained.

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. On the other hand, in the case of an injection molding machine, the plasticizing, mixing, and kneading steps are performed in a cylinder in which the screw retreats, but the kneading force is not sufficient compared to the extruder, and the molding cycle is shortened and the molding resin has a low viscosity. The kneading power has become smaller with the increase in the number of components, and 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 more likely to occur. This problem is recognized in various thermoplastic resins, but it is particularly noticeable in polypropylene-based resins, which have been increasingly used in home appliances and automobile parts, and an urgent solution has been demanded. In order to solve this problem, of the three main components of the masterbatch (pigment, dispersant and base resin), increase the content of the dispersant, or use a base resin having a viscosity lower than that of the resin to be colored. Color unevenness has been eliminated by lowering the melt viscosity of the masterbatch.
However, polypropylene-based resins filled with an inorganic filler and those having a melt flow rate (hereinafter referred to as MFR) of more than 25 for the purpose of thin-wall molding are liable to cause color unevenness and flow marks, which solves this problem. Was waiting.

Further, in the conventional masterbatch, a mixture of a powdered dry pigment, a dispersant and a base resin is premixed with a Henschel mixer or the like, and the mixture is subjected to a non-continuous system such as a three-roll mill or a kneader. It is introduced into a kneader and melt-kneaded for a long time, and the obtained pigment dispersion is crushed into a size that can be fed to a single-screw extruder using a crushing machine, etc., and then pelletized using a single-screw extruder. It is manufactured by However, since this manufacturing method has a long process and is a batch system, automation of the process and labor saving are desired, and further improvement in the working environment such as scattering of the pigment due to the use of the dry powder pigment has been desired.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to improve the above-mentioned various drawbacks, and to improve the mechanical strength such as tensile strength, bending strength and impact strength of the thermoplastic resin by 5% or more. An object of the present invention is to provide a method for efficiently manufacturing a resin composition (masterbatch) for coloring a thermoplastic resin, which does not impair physical properties and is excellent in pigment dispersibility and can be uniformly colored without color unevenness, in a good working environment. .

[0008]

That is, the present invention provides a method for producing a coloring resin composition, which comprises subjecting a pigment, water and a thermoplastic resin to phase substitution and dehydration in a twin-screw extruder. To do.

As the pigment, both organic pigments and inorganic pigments can be applied. The type of pigment is not particularly limited, for example, azo type, condensed azo type, phthalocyanine type, quinacridone type, indigo type, quinophthalone type, dioxane type, anthraquinone type, isoindolinone type,
Examples include pigments such as titanium white. The pigment may be any of a powder dry pigment, a pigment wet cake containing water in advance, and a mixture thereof before drying.

When the dry powder pigment is used, a fixed amount of the dry powder pigment, water and thermoplastic resin are premixed by a kneader such as a kneader or a Henschel mixer,
The compound is kneaded by a twin-screw extruder at a temperature at which water evaporates and the thermoplastic resin melts. In this kneading process, the water that wets the powder dry pigment evaporates, the molten thermoplastic resin covers the powder dry pigment (phase substitution), and the pigment is made fine by shearing during kneading. By being covered with, the reaggregation of the pigment is prevented, and a resin composition having excellent pigment dispersibility can be obtained. According to this method, by adding water to the blend of the powder dry pigment and the thermoplastic resin, the bulk density of the blend is increased, that is, the distance between the blended powder dry pigment and the thermoplastic resin is reduced, and kneading is performed. At this time, the association of the two is efficiently performed, and the powdered dry pigment is more wetted with the thermoplastic resin, and few pigments are reaggregated. Therefore, it is considered that a resin composition having excellent pigment dispersibility can be obtained.

As the water, tap water, distilled water, ion-exchanged water, hard water, soft water and the like can be used without particular limitation, but coarse particles and dissolved particles which affect the use of the resin composition as a component in water. Those that do not contain substances, ions, etc. are preferable. Also, the amount of water added is 5 with respect to the dry powder pigment.
It is preferably in the range of 200 to 200% by weight, more preferably 20 to 120% by weight. When the amount of water added is less than 5% by weight, the bulk density of the blend of the dry powder pigment and the thermoplastic resin is almost the same as when no water is added, and the effect on dispersion is small. On the other hand, if the amount of water added exceeds 200% by weight, the dehydration process requires a lot of time and energy and is not efficient.

Next, when a pigment wet cake is used, the respective amounts of the pigment wet cake and the thermoplastic resin are premixed by a kneader such as a kneader or a Henschel mixer, and the mixture is mixed with water by a twin screw extruder. Evaporate and knead at a temperature at which the thermoplastic resin melts. In this kneading process, water in the pigment wet cake evaporates, the molten thermoplastic resin covers the pigment (phase substitution), the pigment is made fine by shearing during kneading, and the surface is further covered with the thermoplastic resin. As a result, reaggregation of the pigment is prevented, and a resin composition having excellent pigment dispersibility can be obtained. According to this method, the pigment wet cake before drying containing water is a pigment particle having few agglomerated particles and being close to primary particles, and a pigment dispersion is produced by flushing this with a thermoplastic resin from an aqueous phase to a resin phase. Therefore, it is considered that the pigment particles in a state close to the primary particles are maintained and a resin composition having excellent pigment dispersibility can be obtained.

The pigment wet cake contains 2 to 70% by weight of water while the primary particles of the pigment are kept substantially non-aggregated. The smaller the water content, the higher the proportion of primary pigment particles that aggregate, and the higher the water content, the more time and energy is required for the phase replacement step and the dehydration step. 30-60% by weight is preferred. As the non-aggregated state of the primary pigment particles,
It is not necessary for each particle to be completely independent, as long as it is in a state where local excessive dehydration and accompanying aggregation are small, and some primary particles also include aggregates. A powdered dry pigment may be mixed with the pigment wet cake. The water content of the mixture of the pigment wet cake and the dry powder pigment is preferably 2 to 70% by weight.

The thermoplastic resin is preferably one that is compatible with the resin to be colored and has an MFR of 0.1 to 400, more preferably 10
Those in the range of to 250 are preferably used. MFR is
When it 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, MFR
If it exceeds 400, the mechanical strength and heat resistance of the resin composition itself will be low, and it will be difficult to manufacture the resin composition, and the heat resistance of the thermoplastic resin to be colored, and various physical properties such as strength. Have an adverse effect. The MFR is JIS K 7
It is the MFR measured according to 210.

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

Other than polyolefin resins, polymethylpentene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polydiene polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-EPDM-
Examples thereof include styrene (AES) resins, other acrylic resins, thermoplastic resins such as polyamide, polycarbonate, polyacetal, polyurethane, and the like, and one or more of these may be used. The thermoplastic resin 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.

The screw extruder includes a single-screw extruder, a twin-screw extruder, a multi-screw extruder and the like. For the purpose of continuous production of the coloring resin composition, the single-screw extruder is used. The movement of the processing material in the machine is unstable, the kneading property in the phase substitution step is low, and it is difficult to effectively associate the pigment and the thermoplastic resin. Also, in the multi-screw extruder, the twin-screw extruder is used. In many cases, you can expect an effect equal to or more than
The twin screw extruder is applied to the present invention because the structure is too complicated and the effect cannot be expected to be improved although the cost of the apparatus is greatly increased. The screw rotation direction of the twin screw extruder is preferably the same rotation direction in which the kneading function is excellent, and the L / D value of the screw is preferably 25 or more, more preferably 30 or more. L /
If the D value is less than 25, problems may occur in terms of poor kneading and quality stability.

The shape of the screw 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 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, depending on the characteristics of the pigment used and the melting characteristics of the thermoplastic resin, cooling in each barrel unit,
It is important to perform heating. The twin-screw extruder can be provided with a vent port connected to a vacuum pump 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, a small amount of a stabilizer such as an antioxidant or an ultraviolet absorber may be added within a range that does not impair the effects of the present invention. The coloring resin composition of the present invention can color almost all thermoplastic resins, inorganic fillers and glass fibers for the purpose of improving physical properties,
Those containing reinforcing materials such as organic fibers can also be colored. 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 comprises a polyolefin resin, polymethylpentene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-EPDM-.
It can be blended with thermoplastic resins such as styrene (AES) resin, acrylic resin, polyamide, polycarbonate, polyacetal, polyurethane and the like. The coloring resin composition of the present invention can also be used for applications such as inks, paints and adhesives.

[0021]

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. [Example 1] Polyethylene "NUC G5391" (manufactured by Nippon Unicar, MFR: 50) 60 parts Phthalocyanine blue "Rionol Blue 7110V" 40 parts (manufactured by Toyo Ink Mfg. Co., Ltd.) Tap water 40 parts

The above three components were premixed with a Henschel mixer, and the number of revolutions was measured with a twin screw co-rotating screw extruder "PCM-30" (made by Ikegai Co., Ltd.) having a screw diameter of 30 mm and an L / D value of 42.
After kneading and extruding under a processing condition of 350 rpm and a set temperature 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. Furthermore, 100 parts of polypropylene "Mitsui Noblen J400" (MFR, 3 manufactured by Mitsui Petrochemical Industry Co., Ltd.) was mixed with 3 parts of the obtained masterbatch, and a vertical test spinning machine "Spinning Tester" (manufactured by Fuji Filter Co., Ltd. ), The temperature under the hopper is 230 ° C., the kneading part and the die part temperature are 230 ° C.
A denier polypropylene fiber was obtained. 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 tap water was removed. 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 at a temperature of 140 ° C, the kneaded product was cooled and then pulverized, and pelletized by a single screw extruder having a screw diameter of 30 mm. However, due to insufficient dehydration, supply failure occurred, strand breakage and pulsating flow occurred, and a masterbatch could not be obtained.

[Example 2] Polypropylene / polyethylene block copolymer 55 parts "Mitsui Noblen J740P" (Mitsui Petrochemical Co., Ltd., MFR: 25) Quinacridone Red "Fastgen Super Magenta RE03" 45 parts (Dainippon Ink and Chemicals Co., Ltd. Manufacture) 22.5 parts of tap water Using the above 3 components, a masterbatch was obtained in the same manner as in Example 1. 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 obtained in the same manner as in Example 2 except that tap water was removed. 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 4] An attempt was made to produce a masterbatch in the same manner as in Example 2 except that the three components after premixing were used in the same manner as in Comparative Example 2, but insufficient dehydration resulted in insufficient supply, strand breakage and pulsation. And a masterbatch could not be obtained.

[Example 3] Polyethylene "NUC G5391" (MFR: 50) 63 parts Phthalocyanine blue wet cake "Rionol Blue FG7334P" 79 parts (Toyo Ink Mfg. Co., Ltd., pigment concentration 47.0%) Using the above two components, A masterbatch was obtained in the same manner as in Example 1. 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 5] Instead of phthalocyanine blue wet cake "Rionol Blue FG7334P", powder-dried phthalocyanine blue "Rionol Blue"
Example 3 using 37 parts of "FG7330" (manufactured by Toyo Ink Mfg. Co., Ltd.)
A masterbatch was obtained in the same manner as. 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 6] An attempt was made to produce a masterbatch in the same manner as in Example 3, using the two components after premixing, in the same manner as in Comparative Example 2, but insufficient dehydration resulted in insufficient supply, strand breakage and pulsation. And a masterbatch could not be obtained.

[Example 4] Polyethylene "Mitsubishi Polyethylene MV-31" (manufactured by Mitsubishi Petrochemical Co., Ltd., MFR: 45) 50 parts Polyethylene wax "Sunwax 165P" (manufactured by Sanyo Kasei Co., Ltd.) 15 parts Phthalocyanine blue wet cake " Lionol Blue SM-P ”70 parts (manufactured by Toyo Ink Mfg. Co., Ltd., pigment concentration 50.0%) A masterbatch was obtained in the same manner as in Example 1 using the above-mentioned 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 7] Instead of phthalocyanine blue wet cake "Rionol Blue SM-P", powder-dried phthalocyanine blue "Rionol Blue POB" was used.
A masterbatch was obtained in the same manner as in Example 4 using 35 parts of "S" (manufactured by Toyo Ink Mfg. 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 8] An attempt was made to produce a masterbatch in the same manner as in Example 4, using the three components after premixing, in the same manner as in Comparative Example 2. However, insufficient dehydration resulted in insufficient supply and strand breakage or pulsation. And a masterbatch could not be obtained.

[Example 5] Polypropylene / polyethylene block copolymer 65 parts "Mitsui Noblene J740P" (MFR: 25) Quinacridone red wet cake (78 parts "Fastgen Super Magenta RE03" manufactured by Dainippon Ink and Chemicals, Inc., pigment concentration 45.0) %) Using the above two components, a masterbatch was obtained in the same manner as in Example 1. 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 9 In place of the quinacridone red wet cake, 35 parts of powder dried quinacridone red “Fastgen Super Magenta RE03” (manufactured by Dainippon Ink and Chemicals, Inc.) was used, and the same procedure as in Example 5 was performed. A masterbatch was obtained. 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 10] 2 after premixing with the same composition as in Example 5
Using the components, an attempt was made to produce a masterbatch in the same manner as in Comparative Example 2, but insufficient dehydration caused insufficient supply, resulting in strand breakage and pulsating flow, making it impossible to obtain a masterbatch.

[Example 6] Polypropylene / polyethylene block copolymer 65 parts "Mitsui Noblene J740P" (MFR: 25) Phthalocyanine blue "Lionol Blue FG7330" 15 parts Phthalocyanine blue wet cake "Lionol Blue FG7334P" 43 parts (Pigment concentration 47.0%) A masterbatch was obtained in the same manner as in Example 1 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 11 Phthalocyanine blue wet cake “Rionol Blue FG7334P” 43 of Example 6 43
Phthalocyanine blue "Rionol blue FG7330"
A masterbatch was obtained in the same manner as the above, except for 20 parts. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Spinning was performed in the same manner as in Example 1, but yarn breakage due to clogging occurred. [Comparative Example 12] 3 after premixing with the same composition as in Example 6
Using the components, an attempt was made to produce a masterbatch in the same manner as in Comparative Example 2, but insufficient dehydration caused insufficient supply, resulting in strand breakage and pulsating flow, making it impossible to obtain a masterbatch.

[Example 7] Polyethylene "Mitsubishi Polyethylene MV-31" (MFR: 45) 50 parts Polyethylene wax "Sunwax 165P" 17 parts Quinacridone red "Fastgen Super Magenta RE03" 20 parts Quinacridone red wet cake 29 parts " Fastgen Super Magenta RE03 "(pigment concentration 45.0%) A masterbatch was obtained in the same manner as in Example 1 using the above-mentioned four 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 13] Quinacridone red wet cake "Fastgen Super Magenta RE" of Example 7
29 parts of "03" were changed to 13 parts of Quinacridone Red "Fastgen Super Magenta RE03", and other master batches were obtained in the same manner. 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 14] 4 after premixing with the same composition as in Example 7
Using the components, an attempt was made to produce a masterbatch in the same manner as in Comparative Example 2, but insufficient dehydration caused insufficient supply, resulting in strand breakage and pulsating flow, making it impossible to obtain a masterbatch.

[Example 8] Polyethylene "NUC G5391" (MFR: 50) 55 parts Phthalocyanine blue "Lionol blue 7110V" 40 parts Dispersant "Solspers 17000" (manufactured by ICI Japan) 5 parts Soft water 40 parts The above 4 components Was used in the same manner as in Example 1 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 15 A masterbatch was obtained in the same manner as in Example 8 except that soft water was removed. 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 16] 4 after premixing with the same composition as in Example 8
Using the components, an attempt was made to produce a masterbatch in the same manner as in Comparative Example 2, but insufficient dehydration caused insufficient supply, resulting in strand breakage and pulsating flow, making it impossible to obtain a masterbatch.

Examples 1-8 and Comparative Examples 1, 3, 5,
The following evaluation was performed about the masterbatch obtained by 7, 9, 11, 13, and 15. In order to evaluate the clogging property of undispersed pigment in the masterbatch, 10 parts of the masterbatch were mixed with 100 parts of polypropylene "Mitsui Noblen J400" (MFR: 3) and a screw diameter of 30 mm with a 500 mesh wire mesh attached to the tip was used. 3kg of the mixture was extruded by the single-screw extruder, and the pressure rise 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. In addition, in order to evaluate the dispersion color development of the pigment, 1 part of masterbatch, polypropylene “Mitsui Noblen J4
00 "100 parts and 5 parts of titanium oxide were mixed and kneaded with a two-roll mill, formed into a plate with a thickness of 2 mm by a cooling press, and the reflection intensity at 600 nm was measured with a color difference meter (manufactured by Hunter, USA). The results are shown in Table 1. The reflection intensity was set to 100% in the example and compared with the corresponding comparative example.

[0039]

[Table 1]

Example 9 Polyethylene “NUC G5391” (MFR: 50) 40 parts Polyethylene wax “High Wax 420P” 20 parts (manufactured by Mitsui Petrochemical Co., Ltd.) Condensed azo yellow “Chlomophthal yellow GR” (manufactured by Ciba Geigy) ) 15 parts Quinacridone red "Fastgen Super Magenta RE03" 10 parts Titanium oxide "Taipec CR-80" (manufactured by Ishihara Sangyo) 10 parts Carbon black "Mitsubishi Carbon MA-100" (manufactured by Mitsubishi Kasei) 5 parts Tap water 20 parts Using the same twin screw co-rotating screw extruder as in Example 1, the above 7 components were kneaded and extruded at a rotation speed of 400 rpm and a set temperature of 160 ° C., and then cut with a pelletizer to obtain a masterbatch. Obtained. 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 17] A masterbatch was obtained in the same manner as in Example 9 except that half the amount (10 parts) of the polyethylene wax "High Wax 420P" was changed to calcium stearate and tap water was removed. 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] ABS resin "Styrac 191F" (Asahi Kasei Corp., MFR: 55) 60 parts Phthalocyanine blue "Rionol Bull-7110V" 30 parts Titanium oxide "Taipec CR-80" 10 parts Ion-exchanged water 80 parts A masterbatch was obtained in the same manner as in Example 9 using the above four components. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Furthermore, ABS resin "JSR ABS10" (MF made by Japan Synthetic Rubber Co., Ltd., MF
(R: 0.5) 100 parts was mixed with 3 parts of the obtained masterbatch, and plate molding was carried out in the same manner as in Example 9.

[Comparative Example 18] A masterbatch was obtained in the same manner as in Example 10 except that ion-exchanged water was removed. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was carried out in the same manner as in Example 10.

[Example 11] Acrylic resin "DIANAL BR-73" (manufactured by Mitsubishi Rayon, MFR: 20) 40 parts Acrylic resin "DIANAL BR-117" (manufactured by Mitsubishi Rayon, MFR: 95) 20 parts Condensed Azo Yellow Wet Cake "Chromophtal Yellow GR" 12 parts (Ciba Geigy Co., Pigment concentration 40.0%) Quinacridone Red Wet Cake 78 parts "Fastgen Super Magenta RE03" (Pigment concentration 45.0%) A masterbatch was obtained in the same manner as in 9. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Furthermore, 100 parts of the acrylic resin "Dynar BR-73" was mixed with 3 parts of the obtained masterbatch, and plate molding was carried out in the same manner as in Example 9.

[Comparative Example 19] 12 parts of the condensed azo yellow wet cake "Chromophtal yellow GR" of Example 11 was added to 5 parts of powder-dried "chromophtal yellow GR", and quinacridone red wet cake "Fastgen Super Magenta RE03". “78 parts” was changed to 35 parts of “Fastgen Super Magenta RE03” in a powder dry form, and the others were similarly obtained to obtain a masterbatch. 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] Vinyl chloride resin "Vinica P540" (manufactured by Mitsubishi Kasei Vinyl Co., MFR: 1.5) 59 parts Plasticizer "Dioctyl phthalate" (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 1 part Phthalocyanine blue wet cake "Rio" Nolblue FG7334P "64 parts (pigment concentration 47.0%) Titanium oxide" Taipaque CR-80 "10 parts A masterbatch was prepared in the same manner as in Example 9 using the above-mentioned 4 components. 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 9.

[Comparative Example 20] A masterbatch was obtained in the same manner as in Example 12, except that 64 parts of phthalocyanine blue wet cake "Lionol blue FG7334P" was replaced with 30 parts of powder-dried form "phthalocyanine blue FG7330". 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] Polystyrene resin "Styron 683" (manufactured by Asahi Kasei Corporation, MFR: 2.8) 40 parts Polystyrene resin "Styron 666" (manufactured by Asahi Kasei Corporation, MFR: 7.5) 20 parts Condensed azo yellow "chromophthalate" Yellow GR "20 parts Quinacridone red wet cake 30 parts" Fastgen Super Magenta RE03 "(pigment concentration 50.0%) Titanium oxide" Taipec CR-80 "5 parts Tap water 30 parts Using the above 6 ingredients, in the same manner as in Example 9 I got a masterbatch. 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 9.

[Comparative Example 21] Quinacridone red wet cake "Fastgen Super Magenta RE" of Example 13
A masterbatch was obtained in the same manner except that 30 parts of "03" was changed to 15 parts of "Fastgen Super Magenta RE03" in powder dry form, tap water was further removed, and the others were the same. Using the obtained masterbatch, plate molding was performed in the same manner as in Example 13.

[Example 14] Polyurethane resin "Desmocoll 540" 45 parts (Sumitomo Bayer Urethane Co., MFR: 65) Polyurethane resin "Desmocoll U42" 15 parts (Sumitomo Bayer Urethane Co., MFR: 120) Condensed azo Yellow "Chromophtal yellow GR" 35 parts Titanium oxide "Taipeque CR-80" 5 parts Tap water 40 parts A masterbatch was prepared in the same manner as in Example 9 using the above 5 components. 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 9.

[Comparative Example 22] A masterbatch was obtained in the same manner as in Example 14 except that tap water was removed. 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 Polypropylene “Mitsui Noblen J900P” 50 parts (Mitsui Chemicals, MFR: 40) Phthalocyanine green “Rionol Green Y-102” 40 parts (Toyo Ink Mfg. Co.) Titanium oxide “Taipeque” CR-80 "5 parts Calcium stearate 5 parts Ion-exchanged water 68 parts A masterbatch was obtained in the same manner as in Example 9 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 9.

[Comparative Example 23] A masterbatch was obtained in the same manner as in Example 15 except that ion-exchanged water was removed. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Using the obtained masterbatch, plate molding was carried out in the same manner as in Example 15.

Table 2 summarizes the results of evaluation of mechanical properties, surface color unevenness and pigment dispersity of the molded plates obtained in Examples 9 to 15 and Comparative Examples 17 to 23, and the masterbatch productivity.

[0055]

[Table 2] * 1 Retention rate of mechanical properties of resin colored with masterbatch against mechanical properties <100%> of uncolored resin. ◯: 96% or more Δ: 90 to 96% ×: 90% or less * 2 The color unevenness on the surface of the molding plate was visually evaluated. ◯: No color unevenness Δ: Slight color unevenness X: 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 enlarged 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

[0056]

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.

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Claims (11)

[Claims] 1. A method for producing a coloring resin composition, which comprises subjecting a pigment, water and a thermoplastic resin to phase substitution and dehydration in a twin-screw extruder. 2. The method for producing a coloring resin composition according to claim 1, wherein the pigment is in a powder dry form. 3. The amount of water added is 5 to 200% by weight based on the pigment.
The method for producing the coloring resin composition according to claim 1 or 2. 4. The method for producing a coloring resin composition according to claim 1, wherein the pigment is a pigment wet cake which contains water in advance and which has not been dried. 5. The water content of the pigment wet cake is 2 to 70.
The method for producing a coloring resin composition according to claim 4, wherein the amount is% by weight. 6. The method for producing a coloring resin composition according to claim 1, wherein the pigment is a mixture of a powder dry pigment and a pigment wet cake which contains water in advance and which has not been dried. 7. The method for producing a coloring resin composition according to claim 6, wherein the content of water in the mixture of the powder dry pigment and the pigment wet cake is 2 to 70% by weight. 8. The melt flow rate of the thermoplastic resin is 0.1.
The method for producing a coloring resin composition according to any one of claims 1 to 7, wherein the amount is in the range of 400 to 400. 9. The method for producing a coloring resin composition according to claim 1, wherein the content of the pigment in the solid content is 5 to 70% by weight. 10. The coloring resin composition according to claim 1, wherein the L / D value of the screw used in the twin-screw extruder is 25 or more and the rotation directions of the screw are the same. Production method. 11. A coloring resin composition produced by the method according to any one of claims 1 to 10.