JPH11148020A - Colorant composition for thermoplastic resin - Google Patents

Abstract

(57) [Summary] [PROBLEMS] Among resin molded products used for automobiles, interior parts may be heated by heat rays such as sunlight, and lamp parts may generate volatile substances by receiving heat from lamps.
Contamination (fogging) of window glass and lamp glass occurs. SOLUTION: In a colorant composition for a thermoplastic resin mainly containing a pigment, a pigment dispersant, and a basic inorganic compound, the pigment dispersant is a fatty acid metal salt, and the basic inorganic compound is an oxidation of an alkaline earth metal. By forming the product and / or hydroxide of alkaline earth metal, the resin molded product can be colored at low cost in a vehicle such as an automobile, and even if the colored resin molded product is exposed to a heated environment, the vehicle can be colored. Window glass and lamp glass contamination (fogging).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a colorant composition for a thermoplastic resin. More specifically, the present invention relates to a colorant composition for a thermoplastic resin having an excellent effect of preventing fogging of glass, and to a colorant composition for a resin suitable for interior parts such as automobiles and vehicles.

The colorant composition of the present invention is used for coloring a molded article, and can be used in any molding method such as injection, extrusion, and hollow.

[0003]

2. Description of the Related Art In general, plastics are colored for the purpose of imparting various properties such as decorativeness to molded articles, and various forms of colorants are used in injection molding and extrusion molding. The coloring agent is a coloring component obtained by adding a dispersing aid to a pigment or dye, or is obtained by simply adding a resin and mixing or melt-kneading, but the coloring component varies depending on the use purpose and type of the plastic. Change.

Conventionally, as a colorant for a thermoplastic resin, a so-called dry color as a powdery colorant, a so-called liquid color as a liquid colorant, or a so-called master batch color as a granular colorant has been used. Each colorant is obtained by concentrating pigments and dyes required by a resin molded product to a concentration higher than the concentration in the molded product. For example, the master batch color is up to about 60% by weight, and a carrier similar to the resin to be colored is used. It is kneaded into resin. Accordingly, in the molding step, the pigment is used after being diluted according to the concentration ratio of the pigment.

In general, both organic pigments and inorganic pigments are used as pigments for coloring and molding thermoplastic resins. However, simply melting and kneading the pigment with the resin causes agglomeration in the resin, resulting in a poor appearance of the molded product and a decrease in coloring power, thereby causing a problem of impairing the commercial value of the molded product. Therefore, a method of dispersing the pigment inexpensively and easily is proposed. Generally, a method of mixing a fatty acid, a fatty acid metal salt, a fatty acid ester, a fatty acid amide or a known surfactant with a pigment as a pigment dispersant is cited. The purpose is achieved by adding these mixtures to the resin and melt-kneading.

In recent years, resin molded products have been widely used for automobiles and other vehicles from the viewpoints of weight reduction, cost reduction, and ease of processing. Especially in automobiles, it is used for interior parts such as instrument panels, console boxes, pillars, etc., or exterior parts such as bumpers and lamp supports. From the viewpoint of recycling, the resin contains olefin resin, mainly polypropylene, or inorganic filler. Composite polypropylene and the like have been used. Due to the inherent properties of these resins, stabilizers are often added for the purpose of improving heat resistance and light weather resistance, and the above coloring agents are used for coloring, and colorful and richly designed automobiles have been designed.

[0007]

However, among resin molded products used in automobiles, interior parts are heated by heat rays such as sunlight, and lamp parts receive heat from lamps, which generate volatile substances. May contaminate window glass or lamp glass. This contamination causes fogging, i.e., fogging or haze, and poses a safety problem that impairs the driver's external view and external visibility. For this reason, Japanese Patent Application Laid-Open No. 8-2692
As shown in No. 32, a method has been proposed to reduce fogging by devising the use of a stabilizer, which is one of the substances causing fogging. The only solution was to limit the amount of the agent used. However, in that case, pigment dispersion cannot be performed easily and favorably at low cost, and colorful colors cannot be designed in many cases.

[0008]

Means for Solving the Problems In view of such conventional problems, the present inventors have conducted intensive studies on the relationship between fogging and coloring. As a result, fatty acids and metal salts thereof as pigment dispersants are closely related to fogging. And found that it is better to use a basic inorganic compound in combination to prevent this. As a result of further investigation, it has been found that alkaline earth oxides and hydroxides are particularly excellent in preventing fogging. And it was found that when the colorant composition according to the present invention described below is used, a colorful resin molded product can be easily obtained.

That is, according to the present invention, first, a pigment, a pigment dispersant, and a basic inorganic compound are the main components, and the basic inorganic compound is an oxide and / or an alkali earth metal. A colorant composition for a thermoplastic resin having an effect of preventing fogging which is an earth metal hydroxide.

According to a second aspect of the present invention, there is provided a colorant composition for a thermoplastic resin, wherein the pigment dispersant according to the first aspect is a fatty acid metal salt.

According to a third aspect of the present invention, the alkaline earth metal oxide and / or the alkaline earth metal hydroxide according to the first aspect is used in an amount of 5 to 5 parts by weight per 100 parts by weight of the pigment dispersant according to the second aspect. A colorant composition for a thermoplastic resin comprising 200 parts by weight.

According to a fourth aspect of the present invention, there is provided the colorant composition for a thermoplastic resin according to any one of the first to third aspects, wherein the colorant composition contains a thermoplastic material as a carrier component.

And so on. Such compositions can take various forms, as usual, dry colours, liquid colours, or masterbatch colours.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The typical embodiment and the best state of the embodiment of the present invention will be specifically shown in the following examples. This will be described in detail below.

The colorant composition for a resin of the present invention contains a pigment, a pigment dispersant, and an oxide and / or hydroxide of an alkaline earth which is a basic inorganic compound. The pigment used in the present invention can be any pigment that can be used for coloring a thermoplastic resin. For example, organic pigments such as quinacridone, anthraquinone, perylene, isoindolinone, diketopyrrolopyrrole, quinophthalone, sulene or copper phthalocyanine, or red iron oxide, black iron oxide, titanium oxide, zinc oxide And inorganic pigments such as titanium black, titanium yellow, ultramarine blue, and cobalt blue, and extender pigments such as talc, calcium carbonate, and barium sulfate.

In the present invention, a fatty acid or a fatty acid metal salt is used as a pigment dispersing agent. Any of these is known, and is preferably in the form of a powder. Fatty acids have 12 to 30 carbon atoms, for example, lauric acid, myristic acid, palmitic acid, stearic acid, araginic acid, heptadecylic acid, behenic acid, oleic acid, elaidic acid, erucic acid, linoleic acid, linoleic acid , Ricinoleic acid, montanic acid, hydroxystearic acid and the like. The fatty acid metal salts are salts of these fatty acids such as alkaline earth metals, lithium and aluminum. Usually, these pigment dispersants are used in an amount of 10 to 200 parts by weight based on 100 parts by weight of the pigment.

The basic inorganic compound used in the present invention, that is, an oxide of an alkaline earth metal, is magnesium oxide,
Calcium oxide, strontium oxide, barium oxide and the like can be mentioned, preferably magnesium oxide,
It is calcium oxide, and examples of hydroxides of alkaline earth metals include magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. Preferred are magnesium hydroxide and calcium hydroxide. The amount of these basic inorganic compounds is not essentially limited, but if the amount is small, the effect of preventing fogging is poor, and if the amount is large, the effect of preventing the fogging is sufficient. Instead, it is used in an amount of 5 to 200 parts by weight based on 100 parts by weight of the pigment dispersant.
It is preferably from 10 to 100 parts by weight. These basic inorganic compounds are desirably in powder form, and the powder has an average particle diameter of 0.1.
-10 μm is preferred.

In the present invention, in addition to these components, dispersants and lubricants such as fatty acid esters, fatty acid amides, low molecular weight polyolefins and styrene oligomers, plasticizers such as phthalic acid esters, epoxy esters and polyesters, and further ultraviolet absorbing Additives such as agents, light stabilizers and heat stabilizers can be added to the formulation as appropriate.

The colorant composition of the present invention is a mixture of a pigment, a pigment dispersant, a basic inorganic compound and, if necessary, the above-mentioned other components. These mixtures are in the form of powder or liquid, and the colorant composition of the present invention further contains a thermoplastic material such as a thermoplastic resin as a carrier component, and is mixed with a high-speed rotary mixer, a tumbling granulator, or a tumble mixer. After mixing with a mixer such as a mixer, a granular colorant (master batch color) obtained by melting and kneading with a kneader of a Banbury mixer, a kneader, or a single-screw or twin-screw extruder may be used.

The object of using the colorant composition of the present invention, that is, the thermoplastic resin to be colored is an olefin resin containing a polymer such as ethylene, propylene, butene, octene or the like, or a copolymer such as EVA or EEA; Polymers of styrene and acrylate, copolymers thereof, styrene resins including copolymers such as styrene acrylonitrile, styrene acrylonitrile butadiene, engineering resins such as polycarbonate, polyoxymethylene, polyamide 6 and 66. These resins may be modified and compounded with talc, calcium carbonate, mica, glass fiber or the like.

It is preferable to use polypropylene for automobile interior parts and lamp parts, which is composited with various modifiers and fillers, and to use the present colorant composition. Further, fogging caused by a fatty acid metal salt previously contained as a catalyst deactivator or a lubricant in these resins can be simultaneously solved by using the present colorant composition.

The colorant composition of the present invention is added to these resins so as to have a desired pigment concentration, but is usually added in an amount of 10 parts by weight or less based on 100 parts by weight of the resin to be colored.

[0023]

Next, the present invention will be described specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples but has a wide range of application. All parts and percentages in Examples and Comparative Examples are based on weight.

The values of the glass haze shown in the examples and comparative examples are measured by the following procedure. In fogging, the colored resin molded article is heated, and the degree of fogging can be determined by the magnitude of the obtained glass haze.

(1) Preparation of Test Resin Molded Product Powdery colorant: dry color or granular colorant: masterbatch color is added to the resin to be colored so as to obtain a desired pigment concentration, and mixed, and 100 mm by an injection molding machine. × 25mm
It is molded into a test molded product (test piece) of × 2 mm.

With respect to the above test pieces, the effect of preventing fogging on glass was measured by the following method. (2) Heating test The tester shown in FIG. 1 is used. That is, the tester comprises a glass container (capacity: about 500 ml, inner diameter 70 mm, diameter 40 mm, height 170 mm) and an oil bath for heating the glass container. Place the mouth of the glass container with the test piece inside on a glass plate (47 mm x 47 mm x 3 mm, glass haze 0.4%
The glass container is immersed in a 100 ° C. oil bath at 110 mm below the liquid level and heated for 20 hours.

(3) Measurement of glass haze After heating, the glass plate is taken out, and the incident light amount T ₁ , the total light transmission amount T ₂ , and the scattered light amount T of the glass plate are measured using an integrating sphere type light transmittance measuring device. _3. Measure the amount of light T ₄ scattered by the apparatus and the test piece, and calculate the glass haze (%) according to the following “Equation 1”.

[0028]

(Equation 1)

Examples 1 to 4 and Comparative Examples 1 and 2 Pigments and low molecular weight polyethylene, zinc stearate, magnesium stearate, ethylene resin, magnesium oxide and calcium oxide were added in the mixing ratio (parts) shown in Table 1. After mixing with a high-speed mixer, the twin-screw extruder (L
/ D = 33), heat-melt and knead and extrude into strands Water temperature 2
After cooling in a water bath at 0 ° C., the mixture was processed into 100 parts of cylindrical brown masterbatch color pellets having a length of 2 to 3 mm using a rotary blade cutting type pelletizer. The obtained master batch color (4 parts) was mixed with a propylene-ethylene block copolymer [MFR (230 ° C., load 2.16 kg) = 60 gr / 10.
min.] and mixed with 96 parts, and the mixture was injected with a sub-flight screw using an injection molding machine with a mold clamping pressure of 50 tons.
It was molded into a molded product for a fogging test at a molding temperature of 220 ° C., a mold temperature of 30 ° C., and a back pressure of 10 kg / cm ² .

Although all the molded products showed a brown color with good pigment dispersion, the glass haze was measured by a fogging test. The glass haze was better when colored with a master batch color containing magnesium oxide or calcium oxide. Was small, indicating that there was little fogging.

[0031]

[Table 1]

The details of the raw materials in Table 1 are as follows. Red iron oxide: CI Pigment Red 101 Black iron oxide: CI Pigment Black 11 Titanium Yellow: Sb-Ni-Tioxide, CI Pigment Yellow
53 Titanium oxide: rutile type, CI Pigment White 6 Low molecular weight polyethylene: molecular weight (Mn) = 5000, viscosity (CPS: 14)
0 ° C) = 3000, softening point = 111 ° C Zinc stearate: mixture of stearate (55%), palmitate and myristate, melting point (differential thermal analysis) = 12
7 ° C Magnesium stearate: Mixture of stearate (55%), palmitate, and myristate, melting point (differential thermal analysis) = 118 ° C Ethylene resin: Low-density polyethylene MFR (190 ° C, load 2.16 Kg) = 60 gr / 10 min. Magnesium oxide: average particle size 0.7 μm, purity 99.5% Calcium oxide: average particle size 1.0 μm, purity 99%

Examples 5 and 6 and Comparative Examples 3 to 6 The pigment, low molecular weight polyethylene, aluminum stearate, calcium behenate, polypropylene resin, magnesium hydroxide, and zinc oxide were mixed at the mixing ratios (parts) shown in Table 2. After mixing with a high-speed mixer, the twin-screw extruder (L / D
= 33), melted and kneaded, extruded into strands, water temperature 2
After cooling in a water bath at 0 ° C., the mixture was processed into 100 parts of a gray cylindrical masterbatch color pellet having a length of 2 to 3 mm using a rotary blade cutting type pelletizer. The obtained master batch color (3 parts) was mixed with a propylene ethylene block copolymer [MFR (230 ° C., load 2.16 kg) = 30 gr / 10 mi.
n.] 97 parts, and after mixing, the mixture was fogged with an injection molding machine equipped with a subflight screw with a mold clamping pressure of 50 tons at a molding temperature of 220 ° C., a mold temperature of 30 ° C., and a back pressure of 10 kg / cm ² . It was molded into a molded article for testing.

All the molded products showed a gray color with a good pigment dispersion, but when the haze was measured by a fogging test, the value of the glass haze was higher when the glass was colored with a masterbatch color to which magnesium hydroxide was added. However, when the coloring was carried out with a masterbatch color to which zinc oxide was added, no effect was observed and fogging could not be reduced.

[0035]

[Table 2]

The details of the raw materials in Table 2 are as follows. Black iron oxide: the same as that used in Examples 1 to 4 and Comparative Examples 1 and 2 Furnace carbon black: average particle size 19 mμm, pH =
9, CI Pigment Black 9 Titanium oxide: the same as that used in Examples 1-4 and Comparative Examples 1 and 2 Low molecular weight polyethylene: the same as that used in Examples 1-4 and Comparative Examples 1 and 2 Aluminum stearate: Mixture of stearate (55%), palmitate and myristate, melting point (differential thermal analysis) = 131 ° C Calcium behenate: mixture of behenate (55%), palmitate and stearate, melting point (Differential thermal analysis) = 138
℃ Polypropylene-A: MFR homopolymer (230 ℃, load
2.16 kg) = 90 gr / 10 min. Magnesium hydroxide: average particle size 0.5 μm, purity 98% Zinc oxide: average particle size 0.3 μm, purity 99.8%

Examples 7 and 8 and Comparative Examples 7 to 10 The pigment, precipitated barium sulfate, lithium stearate, and magnesium oxide were mixed by a high-speed mixer in the proportions (parts) shown in Table 3 respectively. A polypropylene composition containing 10 parts (%) of talc by one part of the obtained dry color [MFR (230 ° C., load 2.16 kg) = 20 gr / 10 mi
n.] 99 parts, and after mixing, the mixture was fogged with an injection molding machine equipped with a subflight screw with a mold clamping pressure of 50 tons at a molding temperature of 220 ° C., a mold temperature of 30 ° C., and a back pressure of 10 kg / cm ² . It was molded into a molded article for testing.

Although all the molded products showed a dark blue color with good pigment dispersion, the glass haze was measured by a fogging test. The glass haze was smaller when the glass was colored with dry color to which magnesium oxide was added. , Indicating that there was little fogging.

[0039]

[Table 3]

The details of the compounding raw materials in Table 3 are as follows. Furnace carbon black: Examples 5 and 6 and Comparative Example 3
Copper phthalocyanine: CI Pigment Blue 15: 3 Titanium oxide: same as that used in Examples 1-4 and Comparative Examples 1 and 2 Lithium stearate: stearic acid salt (55%), palmitic acid Salt, mixture of myristate, melting point (differential thermal analysis) = 215 ° C Zinc behenate: mixture of behenate (55%), palmitate, stearate, melting point (differential thermal analysis) = 126 ° C Precipitation Barium sulfate: average particle size 0.3 μm Magnesium oxide: the same as that used in Examples 1-4 and Comparative Examples 1 and 2

[0041]

According to the present invention, a colorant composition for a thermoplastic resin, which comprises a fatty acid metal salt as a pigment and a pigment dispersant and further contains an oxide or hydroxide of an alkaline earth metal, is used for a vehicle such as an automobile. The resin molded product can be colored inexpensively, and even if the colored resin molded product is exposed to a heated environment, contamination (fogging) of the window glass or lamp glass surface of the vehicle does not occur.

[Brief description of the drawings]

FIG. 1 is a conceptual view of a heating tester for testing the effect of the present invention, and is a vertical sectional view of the apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Test piece 2 ... Glass container 3 ... Glass plate 4 ... Rubbing 5 ... Clamp 6 ... Support base 7 ... Silicon oil 8 ... Stirring motor with temperature control heater 9 ... liquid level

Claims (4)

[Claims] 1. An anti-fogging effect comprising a pigment, a pigment dispersant, and a basic inorganic compound as main components, wherein the basic inorganic compound is an oxide of an alkaline earth metal and / or a hydroxide of an alkaline earth metal. A colorant composition for a thermoplastic resin having: 2. The thermoplastic resin colorant composition according to claim 1, wherein the pigment dispersant according to claim 1 is a fatty acid metal salt. 3. The oxide of an alkaline earth metal and / or the hydroxide of an alkaline earth metal according to claim 1.
A colorant composition for a thermoplastic resin, comprising 5 to 200 parts by weight based on 100 parts by weight of the pigment dispersant described above. 4. The colorant composition for a thermoplastic resin according to claim 1, which contains a thermoplastic material as a carrier component.