JPH07188577A - Coloring agent for thermoplstic polymer - Google Patents

Abstract

PURPOSE:To obtain a coloring agent for thermoplastic polymer containing a coloring component such as pigment or dye and a specific component such as stigmasterol and excellent in dispersibility to thermoplastic polymers, uniform coloring property, uniform color developing property and heat stability to coloring. CONSTITUTION:This coloring agent contains (A) one or more kinds of substance selected from inorganic pigments, organic pigments, dyes and inorganic extender pigments, as a coloring component, (B) one or more kinds of compounds selected from at least 0.1wt.% of stigmasterol, campesterol, brassicasterol, beta-sitosterol and modifiers of these cyclic alcohols and as necessary, (C) one or more kinds of compounds selected from synthetic wax, natural wax, higher fatty acids (metal salts) and fatty acid amides. Furthermore, a thermoplastic resin is preferably blended as a carrier resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to colorants for thermoplastic polymers. More specifically, stigmasterol, campesterol, pluscasterol, phytosterols such as β-sitosterol or a coloring agent for a thermoplastic polymer containing one or more modified substances of these phytosterols, and components thereof. The present invention relates to a coloring agent for a thermoplastic polymer, which further comprises a thermoplastic resin as a carrier resin for a masterbatch.

[0002]

2. Description of the Related Art Coloring of thermoplastic polymers is carried out by previously mixing coloring components such as coloring pigments and dyes with fatty acid metal salts, polymer waxes such as amide wax and polyethylene wax, co-grinding or kneading, kneading meat, etc. It is generally used as a masterbatch by carrying out a dispersion treatment to give a dry color (powdered colorant) or kneading with a carrier resin (carrier resin).

In the case of conventional dry coloration,
A metal salt of a higher fatty acid such as zinc stearate or magnesium stearate is blended as a pigment dispersant, and this dry color is molded at a relatively low temperature of polyethylene resin, polypropylene resin, polystyrene resin, ABS resin or the like. For coloring such general-purpose resins, it can be used without any particular problem, but when used for engineering resins such as polyamide resins, polycarbonate resins, and polyethylene terephthalate resins that require high-temperature molding, these resins (or The thermoplastic polymer) cannot be used because it causes problems such as heat deterioration, thermal decomposition, and molecular weight reduction.

Further, a conventional dry color prepared by blending a coloring component and a polymer wax such as polyethylene wax, or a conventional masterbatch produced by further blending with a carrier resin is a polyethylene resin or polypropylene. For coloring polyolefin resin such as resin, it has very good dispersion performance and also has relatively excellent thermal stability, but on the other hand, it has thermoplasticity other than polyolefin resin. The compatibility and miscibility with the resin (thermoplastic polymer) is very poor, and problems such as poor dispersion of the coloring component, turbidity, and uneven coloring occur. Therefore, for example, it is suitable for coloring polystyrene resins such as polystyrene resins, AS resins and ABS resins, and engineering resins such as polyamide resins, polycarbonate resins, polymethylmethacrylate resins, polyethylene terephthalate resins and polymethylpentene resins ( It could not be used because of poor compatibility, poor color pigment dispersion, etc.).

Therefore, in coloring these engineering resins, it is strongly desired to develop a coloring agent for a thermoplastic polymer, which has excellent dispersibility of a coloring component, compatibility with these resins, and thermal stability. Was there.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a coloring agent for a thermoplastic polymer, in which a coloring component can be easily dispersed and uniformly colored without depending on the type of the thermoplastic polymer. That is. In particular, polystyrene resin, polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polymethylpentene resin,
When added to a transparent thermoplastic polymer such as polyethylene naphthalate resin or polyamiamide-based resin and colored and molded, the dispersibility of the coloring component in these thermoplastic polymers is excellent, and the face due to poor dispersion is obtained. It is an object of the present invention to provide a coloring agent for a thermoplastic polymer, which does not cause unevenness (aggregate of pigment) or uneven color due to poor compatibility.

Further, it is added to an engineering resin required to be molded at a high temperature such that the molding temperature exceeds 240 ° C., for example, a thermoplastic polymer such as polycarbonate resin, polyethylene terephthalate resin, polymethylmethacrylate resin or polyamide resin. Provided is a coloring agent for a thermoplastic polymer, which does not cause deterioration such as heat deterioration or thermal decomposition even when colored and molded, and does not cause deterioration of mechanical strength physical properties of these thermoplastic polymers or molecular weight. That is.

[0008]

[Means for Solving the Problems] When the inventors of the present invention have conducted extensive studies to solve the problems of the above-described conventional colorants, the wax-like substance extracted from a certain plant is used at the above-mentioned high temperature. When a test sample was prepared by adding it to a thermoplastic polymer (which has a high melting point) that requires molding, and mixing it, it was found that this waxy substance markedly improved the dispersibility of the coloring component. Furthermore, they have found that they have good compatibility and miscibility with these thermoplastic polymers, and have the characteristic of suppressing the deterioration such as thermal decomposition and thermal degradation of these thermoplastic polymers. And when I analyzed the components of this substance extracted from plants,
It was found that a relatively large amount of phytosterol and the ester component of phytosterol described later were contained.

Furthermore, the present inventors have noticed that the cholesterol control agent used for pharmaceutical use contains phytosterol extracted and purified from a plant as a main component, and a coloring component and the like are added to this control agent. Then, mixing and co-pulverizing to make a dry color, and further adding a carrier resin to make a masterbatch by an extruder, and applying these colorants to polycarbonate resin, polyethylene terephthalate resin, etc. It was found that the dispersibility of the coloring component is excellent and that it has an effect of preventing thermal decomposition and thermal deterioration even at high temperature molding.

The present inventors have further expanded their research into coloring various types of transparent thermoplastic polymers and coloring various types of thermoplastic polymers that require high temperature molding. Also obtained good results and completed the present invention. That is, the present invention is as shown below.

(1) One or two selected from an inorganic pigment, an organic pigment, a dye and an inorganic extender pigment as a coloring component.
At least 0.1% by weight of stigmasterol, campesterol, brassicasterol, β-
A colorant for a thermoplastic polymer comprising one or more selected from sitosterol and modified products of these cyclic alcohols.

(2) One or two selected from an inorganic pigment, an organic pigment, a dye and an inorganic extender pigment as a coloring component.
One or more selected from at least 0.1% by weight of stigmasterol, campesterol, brassicasterol, β-sitosterol and modified products of these cyclic alcohols, and synthetic wax, natural wax, higher fatty acid. A colorant for a thermoplastic polymer, containing one or more selected from metal salts of higher fatty acids and amides of fatty acids.

(3) The above (1), wherein a thermoplastic resin is further blended as a carrier resin.
Alternatively, the coloring agent for thermoplastic polymer according to the item (2). Hereinafter, the present invention will be described in more detail.

In the present invention, as a coloring component, an inorganic pigment,
At least one selected from organic pigments, dyes, and inorganic extender pigments is essential. Among the coloring components, inorganic pigments include, for example, titanium oxide, carbon black, cadmium sulfide (yellow), cadmium sulfate selenide (orange or red), chrome yellow (yellow lead), chrome orange,
Rouge (red iron oxide, yellow iron oxide), ultramarine blue, cobalt violet, chrome green, cobalt aluminate, titanium yellow, zinc sulfide, zinc oxide, barium sulfate,
An inorganic pigment such as a calcined pigment (composite metal oxide pigment) is used. Further, as the organic pigments or dyes, azo pigments, polyazo pigments, isoindolinone pigments, quinophthalone pigments, quinacridone pigments, perinone pigments, perylene pigments, anthraquinone pigments, copper phthalocyanine pigments, etc. (Including sex dyes) are used. As the inorganic extender pigment, inorganic extender pigments such as talc, clay, silica, calcium carbonate, synthetic and natural zeolite as light diffusion pigments, and mica foil titanium coated powder (pearl pigment), metal foils such as aluminum and copper. Powder pigments are used. The present invention is not limited to these examples.

In the present invention, one or two kinds selected from stigmasterol, campesterol, brassicasterol, cyclic alcohol of β-sitosterol (phytosterol), and modified products thereof, as a dispersion medium or a compounding medium of the coloring component. The above is essential.

The cyclic alcohol (phytosterol) or its ester (phytosterol ester) is contained in some plants in a relatively small amount, and can be obtained by extraction and purification from these plants. Also,
The phytosterol and phytosterol ester obtained by the extraction and purification can be further reacted to be an ester with an organic acid such as fatty acid and an inorganic acid such as sulfonic acid, or Na, K, Ca, Cu. , Mg,
A metal compound of phytosterol (metal addition reaction product) can be obtained by reacting with a metal such as Zn or Al.

The above-mentioned modified product of cyclic alcohol in the present invention is, for example, phytosterol ester, ester with organic acid such as fatty acid, ester with inorganic acid such as sulfonic acid, Na, K, Ca, Cu, Mg. , A metal addition reaction product with Zn, Al or the like, or a modified product of a cyclic alcohol alkoxylated with an alkyl such as methyl or ethyl. The modified products of these cyclic alcohols have many cyclic basic skeletons similar to phytosterols.

Stigmasterol, a component of phytosterol (melting point 170 ° C.), campesterol (melting point 1
57 ° C.), plus casterol (melting point 145 ° C.) and β-sitosterol (melting point 140 ° C.) are all 14
It is a cyclic alcohol having a high melting point of 0 ° C or higher.

The molecular formulas of these cyclic alcohols are C ₂₉ H ₄₈ O, C ₂₈ H ₄₈ O, C ₂₈ H ₄₆ O and C ₂₉ H ₅₀ O, respectively. These are as shown in Chemical formula 1, Chemical formula 2, Chemical formula 3, and Chemical formula 4.

[0020]

[Chemical 1]

[0021]

[Chemical 2]

[0022]

[Chemical 3]

[0023]

[Chemical 4]

Among these plants, these cyclic alcohols are contained in agricultural products such as soybeans, rapeseed, tall, red beans and sugar cane, and marine products such as kelp, although they are present in relatively small amounts. The cyclic alcohol is present as a mixture. For example, the cyclic alcohol (phytosterol) contained in soybeans is contained at a ratio of about 0.08% by weight, and three types of cyclic alcohols of β-sitosterol, campesterol, and stigmasterol and their esters are the main components. Has become. The cyclic alcohol contained in rapeseed is contained in a proportion of about 0.04% by weight, and β-sitosterol, stigmasterol,
The main component is four cyclic alcohols, campesterol and brassicasterol.

In order to obtain a large amount of these cyclic alcohols or esters thereof, for example, if soybean is used, scum distilled out in the soybean oil refining and deodorizing steps is extracted with a solvent such as hexane or methanol. Finally, the cyclic alcohol and its ester can be obtained by crystallization. Purity can be increased by further purification.

The cyclic alcohol (phytosterol) of the present invention thus obtained is mixed with a coloring component,
By mixing or kneading, it has a feature of greatly improving the dispersibility of the coloring component. That is, these cyclic alcohols (phytosterols) are excellent in miscibility and compatibility with the thermoplastic polymer without changing depending on the type of the thermoplastic polymer, and among them, in particular, polycarbonate resin, polyethylene terephthalate resin, methyl methacrylate. It has excellent miscibility and compatibility with thermoplastic polymers such as resins, polymethylpentene resins, polyethylene naphthalate resins, and polyamide resins that require high-temperature molding. Further, the thermoplastic polymer to which phytosterol is added and blended also has very excellent thermal stability without causing thermal deterioration and molecular weight reduction.

The other component extracted from the plant, the ester of a cyclic alcohol (phytosterol ester) is generally an ester of phytosterol and a higher fatty acid, and their melting points are around 90 ° C.
It tends to be slightly lower than the melting point of the original cyclic alcohol (phytosterol). However, the ester component of these cyclic alcohols is also excellent in miscibility and compatibility with the above-mentioned thermoplastic polymer, like the original cyclic alcohol, and is also mixed with the above-mentioned coloring component and mixed or kneaded. By performing surface treatment such as, the dispersibility of the coloring component is remarkably improved. Further, the thermoplastic polymer containing the phytosterol ester has excellent thermal stability.

In the present invention, one or more selected from cyclic alcohols (phytosterols) of stigmasterol, campesterol, brassicasterol, β-sitosterol and modified products thereof are a coloring component and a filler (filler). ), For other additives,
Generally, it is blended in a proportion of 0.1 to 99% by weight, preferably 2 to 80% by weight, and most preferably 5 to 60% by weight. If the blending ratio is less than 0.1% by weight, the effect characteristic of the present invention cannot be expected so much.

In the present invention, one or more coloring components and one or more selected from stigmasterol, campesterol, brassicasterol, β-sitosterol and modified products of these cyclic alcohols. Are blended to give a coloring agent for thermoplastic polymers (dry color). Further, a thermoplastic resin is blended as a carrier resin (carrier resin) of the masterbatch to obtain a coloring agent (masterbatch) for a thermoplastic polymer.

The thermoplastic polymer to which the colorant for a thermoplastic polymer (dry color and masterbatch) of the present invention is applied is, for example, a polyamide resin, a polycarbonate resin, a polymethylmethacrylate resin, a polyethylene terephthalate resin, or a polyethylene. Naphthalate resin,
Polymethylpentene resin, polyarylate resin, polybutylene terephthalate resin, polyoxymethylene resin,
Polyetheretherketone resin, polysulfone resin,
Thermoplastic polymers called engineering plastics such as polyphenylene ether resin and polyphenylene sulfide resin, and polyethylene and copolymers thereof, polypropylene and copolymers thereof, polystyrene and copolymers thereof, AS resin, ABS resin, vinyl chloride And its copolymers, vinylidene chloride and its copolymers, vinyl acetate and its copolymers, styrene-butadiene block copolymers, 1,2-polybutadiene-based thermoplastic elastomers, styrene-butadiene-based thermoplastic elastomers, polyamide-based elastomers, polyester-based Elastomers, polyurethane elastomers, ionomer resins, etc.

Of these thermoplastic polymers, particularly preferred are polyamide resins, polymethyl methacrylate resins, polycarbonate resins, polyethylene terephthalate resins, polyethylene naphthalate resins, polyarylate resins, polymethylpentene resins, AS resins, ABS
Thermoplastic polymers such as resins having high melting and softening temperatures and requiring high molding and processing temperatures, polystyrene resins, transparent ABS resins, polypropylene and their copolymers, vinyl acetate and its copolymers, vinyl chloride And a thermoplastic polymer having transparency such as a copolymer thereof, vinylitene chloride and a copolymer thereof, polyethylene and a copolymer thereof.

As the carrier resin (carrier resin) of the masterbatch of the present invention, the same resin as the above-mentioned thermoplastic polymer can be used. Particularly preferred resins include polyamide resins, polycarbonate resins, polyethylene terephthalate resins, polystyrene resins, polymethylpentene resins, polypropylene resins,
Other resins.

In the present invention, in addition to one or more coloring components and one or more selected from stigmasterol, campesterol, brassicasterol, β-sitosterol and modified products of these cyclic alcohols. Thus, waxes such as synthetic wax, natural wax, higher fatty acid, metal salt of higher fatty acid and amide of higher fatty acid can be blended as an auxiliary agent.

Examples of synthetic waxes include synthetic waxes such as polyethylene wax, polypropylene wax and paraffin wax. Natural waxes include mineral waxes such as montan wax and montan ester, candelilla wax, carnauba wax, sugarcane wax, plant wax such as rice wax (rice bran hardened oil), beeswax, animal fats such as beef tallow oil. There is wax. In addition, calcium stearate, magnesium stearate, zinc stearate, metal salts of higher fatty acids such as aluminum stearate, fatty acid amide lubricants such as ethylene bisamide and oleic acid amide, higher fatty acids, fatty alcohols, alcohol esters of fatty acids, etc. Includes commonly used additives and the like.

The thermoplastic polymer colorant (dry color and masterbatch) of the present invention further includes, if necessary, an antioxidant for preventing thermal deterioration during molding.
Additives such as a heat deterioration inhibitor and a metal deactivator, an ultraviolet absorber for improving the light resistance of a molded article of a thermoplastic polymer, and a light stabilizer can be blended.
Further, additives such as an antistatic agent for preventing the chargeability of the resin and an antifogging agent can be blended.

The thermoplastic polymer colorant of the present invention can be produced by mixing with a Henschel mixer, a blender or the like, co-milling with a fine pulverizer such as an atomizer, kneading with a kneader such as a roll mill or a kneader, or biaxial extrusion. Machine,
Any known method such as an extruder (screw type kneading extruder) such as a single-screw extruder can be used.

For example, in the case of producing the colorant for a thermoplastic polymer (dry color) of the present invention, the above-mentioned coloring component and the cyclic alcohol (phytosterol) or a modified product thereof are used in a Henschel mixer, a ribbon blender, a drum tumbler. Or a fine mill such as an atomizer or a pin mill to give a powdery dry color, or a roll mill such as a two-roll mill or a three-roll mill, or a heating kneader. A method is used in which a kneader such as a pressure heating kneader, a Banbury mixer or an intensive mixer is used for mixing and kneading, and then pelletized or granulated, or further pulverized into a dry color.

In the case of producing a masterbatch, a blend of a coloring component and a cyclic alcohol (phytosterol) or a modified product thereof, or a dry color, pellet-like or granule-like coloring agent prepared by the above-mentioned method. In addition, a thermoplastic resin as the above-mentioned carrier resin is further mixed, and then kneaded by an extruder (screw type kneading extruder) or the like, and then pelletized (granulated).
The method of making a master batch of is used.

The dry color type and masterbatch type colorants for thermoplastic polymers thus obtained are mixed with the above-mentioned thermoplastic polymer to give a colored thermoplastic resin composition. At this time, the colorant for a thermoplastic polymer of the present invention is 0.01 to 0.01 with respect to the thermoplastic polymer.
It is added at a rate of 30%.

The thermoplastic resin composition thus obtained is superior in dispersibility of the coloring component as compared with the conventional general colorant, and causes facial mottle (aggregate of pigment), uneven color and It is useful as a resin composition that does not cause poor dispersion of a coloring agent such as uneven coloring. Further, this thermoplastic resin composition is molded into various molded bodies including films, fibers and the like.

[0041]

【The invention's effect】

(1) Excellent Dispersibility of Coloring Component in Thermoplastic Polymer The colorant for a thermoplastic polymer of the present invention is excellent in dispersibility of the coloring component, and has a low concentration range of 0 relative to the thermoplastic polymer. ．
Even when it is added in the proportion of 01% to 30% in the high concentration range, no pigment aggregate is generated due to poor dispersion of the coloring component. (2) Excellent uniform coloring and uniform coloring to the thermoplastic polymer The thermoplastic polymer such as polycarbonate resin, polyethylene terephthalate resin, polyamide resin, polymethylmethacrylate resin, polybutylene terephthalate resin has uniform coloring or It is said that it is very difficult to uniformly color the polymer. However, the coloring agent for thermoplastic polymer of the present invention has a low concentration range of 0.01% to a high concentration range of 30%. Even when added in proportion,
Color unevenness such as uneven coloring or uneven coloring does not occur.

(3) Coloring Thermal Stability of Thermoplastic Polymer Requiring High-Temperature Molding is Excellent The coloring agent for thermoplastic polymers of the present invention is excellent in thermal stability when colored with a resin such as a polycarbonate resin, High-temperature molding of polyethylene terephthalate resin, polyamide resin, polymethylmethacrylate resin, polybutylene terephthalate resin, etc. is required, but the low concentration range of 0 for the thermoplastic polymer which is apt to cause thermal deterioration and thermal decomposition of the resin. .0
Even when added in a proportion of 1% to 30% in a high concentration range and colored and molded, thermal deterioration of these thermoplastic polymers,
Does not cause deterioration such as thermal decomposition. Further, physical properties such as mechanical strength of these thermoplastic polymers are not deteriorated and molecular weight is not decreased.

[0043]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples,% means% by weight.

[0044]

Examples 1 to 9 and Comparative Examples 1 to 5 Cyclic alcohol (containing 90% or more as a phytosterol component) was blended in the range of 0 to 100% with respect to the coloring components shown in Table 1 and mixed with a Henschel mixer. Further, it was co-pulverized by an atomizer (fine pulverization mixer) to obtain a dry color type coloring agent for a thermoplastic polymer (dry color) of the present invention. For comparison, a dry color containing no cyclic alcohol and a dry color containing a metal salt of a higher fatty acid were prepared. The compositions of these dry colors are shown in Table 2.

Further, these dry colors were subjected to a density of 1.03 g / cm ³ and a melt flow rate (MFR).
7.5g / 10min transparent polystyrene (GPP
S) (Styron 666, Asahi Kasei Corporation, trade name)
After adding and blending in the range of 0.01 to 30%,
Using an injection molding machine with a mold clamping pressure of 40 tons, a wall thickness of 1 mm,
A 3 mm flat plate-shaped mold of 2 mm and 3 mm was attached, and a colored molded product (plate) was prepared under molding conditions of a molding temperature of 240 ° C., an injection pressure of 40 kg / cm ² , and a molding cycle of 60 sec / cycle.

With respect to these colored molded articles (plates), compared with a dry color containing no cyclic alcohol and a dry color containing a metal salt of a higher fatty acid, the concentration of each compound when a cyclic alcohol was mixed In addition, the presence or absence of aggregates of the coloring component and the particle size of the aggregates were observed with an optical microscope to evaluate the dispersibility.

As a result, the dry color of the present invention showed very excellent dispersibility in which coarse aggregates of the coloring component were hardly seen. Further, the dry color of the present invention was able to obtain a high dispersibility effect for any pigment without being affected by the type of coloring component. Further, the dispersing effect of the cyclic alcohol (containing 90% or more as a phytosterol component) was improved almost in proportion to the blending concentration, and the appropriate blending concentration obtained from the experimental result was 20 to 80%.

In comparison with this, in the coloring pigment containing no cyclic alcohol shown in Table 2, a large number of coarse aggregates having a particle diameter of more than 100 μ were observed. Also,
The colorants containing the conventionally used metal salts of higher fatty acids, which are generally used in Table 2, also showed extremely excellent dispersibility. However, this higher fatty acid metal salt-based dispersant is added to an engineering resin such as a polycarbonate resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyacetal resin, or a polyamide resin, when blended, with respect to those resins. It tends to cause thermal deterioration, thermal decomposition, and a significant decrease in molecular weight, and as a result, the mechanical properties of the resin tend to be significantly reduced, and it cannot be actually used.

[0049]

Examples 10 to 20 and Comparative Examples 6 to 13 Cyclic alcohol (containing 90% or more as a phytosterol component) was blended in the range of 0 to 100% with respect to the coloring components shown in Table 1 and heated to a temperature of 140 ° C. After kneading with a three-roll mill, it is further mixed with Panlite L-1225 (Teijin Kasei Co., Ltd., trade name), kneaded with a 35 mmφ twin-screw extruder, pelletized, and colored master pellets of the present invention. To obtain a colorant for thermoplastic polymer (masterbatch). As a comparative example, a master batch containing a metal salt of higher fatty acid and a general colored master batch containing polyethylene wax were prepared. The compositions of these colored masterbatches are shown in Table 3.

Furthermore, these colored masterbatches are
After adding in the range of 1 to 30% by weight to Panlite L-1225, using an injection molding machine with a mold clamping pressure of 40 tons, a two-step flat plate-shaped mold with a molded product wall thickness of 2 mm and 3 mm is used. Installation, molding temperature 290 ℃, injection pressure 60kg / cm
^{2. A} colored molded product (plate) was prepared under a molding condition of a molding cycle of 60 sec / cycle.

With respect to these colored molded articles (plates), as compared with a masterbatch in which no cyclic alcohol was blended and a general masterbatch in which polyethylene wax was blended, for each blending concentration of the masterbatch of the present invention, The pigment dispersibility and the uniform coloring property of the surface of the colored molded product were tested. As for the pigment dispersibility, the presence or absence of coarse pigment aggregates of 100 μm or more present in the colored molded article and the size of the coarse aggregates (aggregates) were measured using an optical microscope in the same manner as in Examples 1 to 9. Particle size) of each. Regarding the coloring uniformity of the colored molded product, a colorimetric spectrophotometer (color difference meter) is used to measure the occurrence of coloring unevenness and color unevenness on the surface of the molded product, and the central part of the colored molded product is used as the standard coloring. Color differences (ΔE) were measured at four points near the peripheral corners. Table 4 shows the results of the color uniformity (color difference (ΔE)) test results on the surface of the molded product when the polycarbonate resin was colored.

As a result, as shown in Table 4, in the colored masterbatch of the present invention, when the polycarbonate resin was colored, the addition concentration of the masterbatch was in the low concentration range of 1% to the high concentration range of 30%. The color difference value is 0.5
The following numerical values are shown, there is no uneven coloring on the molded product,
It showed very stable color uniformity.

On the other hand, in the general masterbatch shown in the comparative example, the color difference (ΔE) has a relatively high numerical value of 1.5 to 2.0 or more even in the low concentration range of 1%. In addition, the value of the color difference (ΔE) showed a large variation depending on the measurement point of the molded product. In addition, in the high concentration range where the added concentration of the masterbatch is 5% or more, the color difference (ΔE) shows a very large value of 3 to 5 or more, and also shows a very large variation depending on the measurement location of the colored molded product. It was
This indicates that in a conventional masterbatch containing a polyethylene wax or a metal salt of a higher fatty acid as a pigment dispersant, color unevenness is severely generated when the thermoplastic polymer is colored.

[0054]

Examples 21 to 31 and Comparative Examples 14 to 21 Generally, thermoplastic polymers are added with coloring components, lubricants, dispersants, fillers, etc. to cause resin deterioration phenomena such as heat deterioration, oxidative deterioration or thermal decomposition. And the deterioration of the resin causes a decrease in mechanical strength. In particular, in engineering resins that require high-temperature molding, the colorants and additives used therefor greatly affect the mechanical properties of the resin. Below, the comparative test of the thermal stability which compared the coloring agent for thermoplastic polymers of this invention and other general coloring agents was performed.

Cyclic alcohol (containing 90% or more as a phytosterol component) is not added to the coloring components shown in Table 1.
About 100% by weight of the coloring agent for a thermoplastic polymer (dry color and masterbatch) of the present invention, which is prepared by blending, is added to an engineering resin that requires high temperature molding, and heat when coloring is added. Stability tests (mechanical resin physical strength test and measurement of resin molecular weight reduction) were performed.

In addition, as a comparative example, a comparative test was carried out between a dry color containing polyethylene wax, which is a general colorant used conventionally, and a dry color containing a metal salt of a higher fatty acid.

As a thermal stability evaluation test, for polycarbonate resins and polyethylene terephthalate resins, the molecular weight of the resin (intrinsic viscosity method) was measured, and the thermal stability was evaluated from the degree of decrease in the molecular weight. The test results are shown in FIGS. In addition, the Izod impact strength of the colored molded article was measured as a comparison of the degree of deterioration of mechanical resin properties due to thermal deterioration or thermal decomposition. The results are shown in Table 5.
Shown in.

As a result, as shown in FIGS. 1 to 4, the colored dry color and the colored masterbatch of the present invention prepared by blending cyclic alcohol (containing 90% or more as a phytosterol component) were prepared by using polycarbonate resin. Even when added and colored, the polycarbonate resin could be colored with almost no decrease in the molecular weight. Table 5 also shows the actual colored molded products.
As shown in, the decrease in Izod impact strength was hardly seen.

On the other hand, the colorant containing the metal salt of higher fatty acid, which has been generally used in the past, tends to drastically reduce the molecular weight of the polycarbonate resin, and at a general addition concentration. The original molecular weight (2
70% to 5000) 15,000 to 18,000
Was falling to. Also, regarding the Izod impact strength of the colored molded product, the Izod impact strength was remarkably decreased in proportion to the addition concentration.

[0060]

Example 32 As an inorganic pigment, a density of 4.2 g / c
m ³ and rutile type titanium oxide having an average particle diameter of 0.21 μm (Taipaque CR-60, trade name of Ishihara Sangyo Co., Ltd.) were used, and a cyclic alcohol (containing 90% or more as a phytosterol component) was added to this titanium oxide. %, Mixed with a Henschel mixer, and further co-pulverized with an atomizer (fine pulverization mixer) to obtain a dry color type colorant for a thermoplastic polymer (dry color) of the present invention.

Further, this dry color is applied with a density of 1.4.
0, a melting point of 260 ° C, and polyethylene terephthalate (Mitsui PET J125, Mitsui Pet Resin Co., Ltd., trade name) were added to a concentration of 0.01 to 10%, and then an injection molding machine with a clamping pressure of 40 tons was used. Then, the molding temperature is 270 ° C,
Injection pressure 50kg / cm ² , molding cycle 60sec /
A colored molded product (plate) was prepared under the cycle molding conditions.

With respect to this colored molded article (plate), the molecular weight of the polyethylene terephthalate resin was measured by the solution viscosity method, and the thermal stability of the colorant was evaluated from the degree of decrease in the molecular weight. The result is shown in FIG.

As a result, in the coloring agent for thermoplastic polymer of the present invention, almost no decrease in the molecular weight of the polyethylene terephthalate resin was observed from a low concentration of 0.01% to a relatively high concentration of 5%. . However, when the high concentration of 10% was added, a slight decrease in the molecular weight was observed.

[0064]

[Comparative Example 22] In comparison with Example 32, a metal salt of a higher fatty acid was added instead of the cyclic alcohol (containing 90% or more as a phytosterol component), and a general dry color was prepared in the same manner as in Example 32. A type of colorant was prepared, and a colored molded product plate was prepared using the same resin, molding apparatus and molding conditions as in Example 32, and the molecular weight of the polyethylene terephthalate resin was measured for this colored molded product. The result is shown in FIG.

In the case of a general colorant containing a metal salt of higher fatty acid, the addition concentration is 0 to 0.01%, which is an extremely small amount.
No remarkable decrease in molecular weight is observed at concentrations up to,
At a relatively low concentration of 0.025% or higher, a remarkable decrease in molecular weight was observed, and at a concentration of 0.5%, the molecular weight decreased to about 60%.

[0066]

Example 33 As an organic color pigment, α-type copper phthalocyanine blue (CI, Pigment Blue)
15: 4), the density is 1.6 g / cm ³ , and the average particle size is 0.1.
First Gen Blue 5050 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) having a size of 10 μm was used, 50% of a cyclic alcohol (containing 90% or more as a phytosterol component) was mixed, and mixed with a Henschel mixer, and then further atomized (fine). Co-milling with a pulverizer / mixer) to give a dry color type coloring agent for thermoplastic polymers of the present invention (dry color)
Got

Further, this dry color was made to have a density of 1.4.
0, polyethylene terephthalate having a melting point of 260 ° C. (Mitsui PET J125, Mitsui Pet Resin Co., Ltd., trade name) was added at a concentration of 0.01 to 10%, and then an injection molding machine having a mold clamping pressure of 40 tons was added. Using the molding temperature 270
℃, injection pressure 50kg / cm ² , molding cycle 60se
Colored molded product (plate) under molding conditions of c / cycle
It was created.

In the same manner as in Example 32, the molecular weight of the polyethylene terephthalate resin of this colored molded article was measured by the solution viscosity method, and the thermal stability of the colorant was evaluated from the degree of decrease in the molecular weight. The result is shown in FIG.

As a result, in the coloring agent for thermoplastic polymers of the present invention, almost no decrease in the molecular weight of the polyethylene terephthalate resin was observed from a low concentration of 0.01% to a relatively high concentration of 5%. It was However, when the high concentration of 10% was added, a slight decrease in the molecular weight was observed.

[0070]

Comparative Example 23 A metal salt of a higher fatty acid was added to Example 33 in place of the cyclic alcohol (containing 90% or more as a phytosterol component), and a general dry color was prepared in the same manner as in Example 33. A type of colorant was prepared, and a colored molded product (plate) was prepared using the same resin, molding apparatus and molding conditions as in Example 33, and the molecular weight of the polyethylene terephthalate resin was measured for this colored molded product. . The result is shown in FIG.

As a result, a general colorant containing a metal salt of a higher fatty acid has an added concentration of 0 to 0.0.
No significant decrease in the molecular weight was observed at concentrations up to 1%, but a marked decrease in the molecular weight was observed at a relatively low concentration of 0.02% or higher, and at a concentration of 0.3%. The molecular weight had dropped to about 50%.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the concentration of a colorant for a thermoplastic polymer (dry color) of the present invention (dry color) added and the molecular weight of the polycarbonate resin.

FIG. 2 is a graph showing the relationship between the addition concentration and the molecular weight of the polycarbonate resin when the coloring agent for a thermoplastic polymer (dry color) of the present invention is added to the polycarbonate resin.

FIG. 3 is a graph showing the relationship between the concentration of a coloring agent for a thermoplastic polymer (masterbatch) of the present invention added to a polycarbonate resin and the molecular weight of the polycarbonate resin.

FIG. 4 is a graph showing the relationship between the addition concentration and the molecular weight of the polycarbonate resin when the coloring agent for a thermoplastic polymer (masterbatch) of the present invention is added to the polycarbonate resin.

FIG. 5 is a graph showing the relationship between the addition concentration and the molecular weight of the polyethylene terephthalate resin when the coloring agent for a thermoplastic polymer (dry color) of the present invention is added to the polyethylene terephthalate resin.

FIG. 6 is a graph showing the relationship between the addition concentration of a coloring agent for a thermoplastic polymer (dry color) of the present invention (dry color) and the molecular weight of the polyethylene terephthalate resin.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuhiko Naito 36 36 Saitobuncho, Kanagawa-ku, Yokohama-shi, Kanagawa (72) Inventor Yoshio Takamura 3-45-7, Nanaidai, Shirai-cho, Inba-gun, Chiba

Claims (3)

[Claims] 1. A coloring component comprising one or more selected from inorganic pigments, organic pigments, dyes and inorganic extender pigments, and at least 0.1% by weight of stigmasterol, campesterol, brassicasterol and β-. A colorant for a thermoplastic polymer comprising one or more selected from sitosterol and modified products of these cyclic alcohols. 2. One or more selected from inorganic pigments, organic pigments, dyes and inorganic extender pigments as a coloring component, and at least 0.1% by weight of stigmasterol, campesterol, brassicasterol, β-sitosterol. And one or more selected from modified products of these cyclic alcohols, and one or more selected from synthetic wax, natural wax, higher fatty acid, metal salt of higher fatty acid, amide of fatty acid, etc. A coloring agent for a thermoplastic polymer, characterized by comprising: 3. The colorant for a thermoplastic polymer according to claim 1 or 2, further comprising a thermoplastic resin as a carrier resin.