JPH03269052A - Polybutylene terephthalate resin colored composition - Google Patents

Abstract

PURPOSE:To provide a polybutylene terephthalate resin colored composition not staining molds and having excellent color transfer resistance and thermal stability by compounding polybutylene terephthalate resin with a specific blue coloring agent as an essential coloring component. CONSTITUTION:A colored composition comprises (A) polybutylene terephthalate having a relative viscosity (0.5% ortho-chlorophenol solution, 25 deg.C) of 1.3-2, especially 1.35-1.7, (B) at least one green coloring agent of CI. pigment blue 15:3, CI. pigment blue 15:1 and CI. solvent blue 132 in an amount of 0.001-5 pts.wt., more preferably 0.01-2 pts.wt., per 100 pts.wt. of the component A, if necessary, any other coloring agent and (C) a dispersing agent (preferably N,N'-ethylenebisstearic acid amide) in an amount of 0.1-2 pts.wt., preferably 0.1-1.5 pts.wt., per 1 pt.wt. of the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a coloring composition of polybutylene terephthalate resin, which is used as a material for various electric/electronic parts, automobile parts, etc.

[Conventional technology]

Polybutylene terephthalate resin, which represents linear aromatic polyester, has low water absorption, low friction coefficient, and good elongation and moldability, as well as excellent crystallization properties, rigidity, heat resistance, Especially long-term heat resistance, creep resistance, electrical properties, stable dimensional stability, chemical resistance,
It has attracted attention as an extremely well-balanced engineering plastic with various properties such as oxidation resistance and weather resistance, and is used for various electrical and electronic parts, automobile parts, power tool parts,
It is widely used in other industrial fields.

In these application fields, colors are increasingly being colored in various hues to improve distinguishability or to provide design and decorative features, but recently, particularly vivid hues have been used. There is a strong need for colored compositions of colored polybutylene terephthalate resins.

Among the above-mentioned hues, for blue-based coloring, inorganic pigments such as ultramarine blue and cobalt blue, and dyes such as oil-soluble anthraquinone dyes have been mainly used as colorants.

[Problem to be solved by the invention]

As described above, inorganic pigments such as ultramarine blue and cobalt blue, anthraquinone dyes, and the like have conventionally been used as blue colorants for polybutylene terephthalate resins.

However, when the above-mentioned blue inorganic pigment is used as a coloring agent, it has a drawback that it has low tinting power and low chroma, so that it is not possible to color with a clear hue.

On the other hand, polybutylene terephthalate resin coloring compositions using the dye-based blue coloring agent described above tend to cause mold contamination as an adverse effect during injection molding.

This is a problem that causes major problems during molding, and the coloring agent may ooze out onto the surface of the molded product and the color may transfer to other substances, depending on the usage temperature and atmosphere. However, it has the major drawback of contaminating other substances, which can significantly reduce the commercial value.

The cause of the mold contamination is that the conventional blue colorant used is dissolved in the molten polymer.
It is thought that when it is cooled and solidified in the mold, it oozes out onto the surface of the molded product and contaminates the mold. In addition, especially when a dye-based material is used, the dye itself tends to sublimate, and the color often adheres to areas of the mold where gas venting is poor.

Therefore, as a result of intensive research in order to eliminate the various drawbacks associated with the conventional polybutylene terephthalate resin coloring compositions described above, the present inventors have found that a specific coloring agent among the many blue coloring agents is used as an essential coloring component. The present invention was achieved by discovering that a polybutylene terephthalate resin coloring composition free from mold contamination and having excellent color transfer and heat resistance stability can be obtained by doing so.

Therefore, the present invention has been developed to produce a polybutylene terephthalate resin that does not significantly deteriorate its excellent physical properties, has no problems with mold staining or color migration, and is colored in a vivid blue color with excellent heat resistance stability. The object of the present invention is to provide a polybutylene terephthalate resin coloring composition suitable for obtaining molded articles.

[Means to solve the problem]

In detail, the structure of the present invention for achieving the above object is as follows:
In a polybutylene terephthalate resin coloring composition in which a blue colorant is blended with a polybutylene terephthalate resin, CI. pigment blue 15 =
3. CI. Pigment Blue 15:1, CI. This is a polybutylene terephthalate resin coloring composition characterized by containing at least one type of Solvent Blue 132 as an essential coloring component.

The polybutylene terephthalate resin used in the present invention is
It means a polymer obtained by condensation reaction of terephthalic acid or its ester-forming derivative as the acid component and 1,4-butanediol or its ester-forming derivative as the diol component.

In addition, if the acid component is 20 mol% or less, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid,
, 5-naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4.4
'-diphenyl dicarboxylic acid, 4,4°-diphenyl ether dicarboxylic acid, 1,2-bisphenoxyethane-
44=Dicarboxylic acids other than terephthalic acid, such as dicarboxylic acids or ester-forming derivatives thereof, may be used.

In addition, if the diol component is 20 mol% or less, ethylene glycol, 1,2-propanediol, 1,3
-propanediol, 1,5-bentanediol, l,
6-hexanediol,]]10-decanediol I,
Diols other than 1,4-butanediol such as 4-cyclohexane dimetatool, neopentyl glycol, 2-methyl-1,3-propanediol, polytetramethylene glycol, polyethylene glycol, and polypropylene glycol may be used. .

In addition, the polybutylene terephthalate resin preferably has a relative viscosity of 130 or more when measuring a 0.5% orthochlorophenol solution at 25°C from the viewpoint of mechanical strength, and a relative viscosity of 2°C from the viewpoint of fluidity during molding. 00 or less is preferable.

In particular, those in the range of 1.35 to 1.70 can be preferably used.

As a result of research by the present inventors, the specific blue colorant used in the present invention for these polybutylene terephthalate resins was selected from among the various blue colorants listed in the Color Index. blue 1
5:3, CI. Pigment Blue 15:1, CI. It turned out to be Solvent Blue 132.

The amount of the blue colorant used in the present invention is preferably in the range of 0.001 parts by weight to 5.0 parts by weight, more preferably 0.01 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin. % to 2.0 parts by weight.

In addition, known inorganic pigments can be used as other colorants that can be used in combination for practical applications in a wide range of hues.

Next, examples of dispersants that are added to improve the dispersibility of pigments include higher fatty acid metal salts such as magnesium stearate, calcium stearate, and lithium stearate, fatty acid esters, N, N'- Although there are many alkylene bis fatty acid amides, etc., the dispersant that can be used in the polybutylene terephthalate resin coloring composition of the present invention is N,N'-alkylene bis fatty acid amide, preferably N, N'-ethylene bismyristic acid amide, N,N'-ethylene bisstearic acid amide, N,N'-ethylenebisoleic acid amide, N,N"-methylene bismyristic acid amide, N,N'-methylene bisstearic acid amide Among these, N,N'-ethylenebisstearamide is particularly preferred.

The blending ratio of the pigment and dispersant used in the present invention is not particularly limited, but is preferably within the range of 0.1 to 2.0 parts by weight of the dispersant to 1.0 part of the pigment. is 0.4
~1.5 parts.

The method for obtaining the polybutylene terephthalate resin coloring composition of the present invention is to mix a polybutylene terephthalate resin, a desired concentration of the above-mentioned blue organic pigment, and a predetermined amount of a dispersant in a mixer such as a tumbler mixer, and then extrude the resin. A colored pellet is created by melt-kneading in a machine to obtain a colored polybutylene terephthalate resin composition, or a high-concentration pigment, a dispersant, and a polybutylene terephthalate resin are mixed in a similar manner, and after melt-kneading, a polybutylene terephthalate resin coloring composition is obtained. There is a method of preparing a concentration master pellet and then mixing and diluting it with uncolored polybutylene terephthalate resin to a desired concentration to obtain the composition.

In addition, in each of the above working steps, it is necessary to avoid the presence of water as much as possible so as not to cause deterioration of the polybutylene terephthalate resin.

In addition, other additives may be added to the composition of the present invention as long as the purpose of the present invention is not impaired. That is, antistatic agents, ultraviolet absorbers, antioxidants,
As lubricants and mold release agents, nonflammable agents, flame retardant aids, and inorganic fillers, glass fibers, carbon fibers, metal fibers, asbestos, wollastenite, potassium titanate whiskers,
One or more conventional additives such as clay, mica, bentonite, glass peas, titanium oxide, calcium carbonate, barium sulfate, gypsum, aluminum oxide, talc, etc. can be added to the compositions of the present invention.

In addition, other thermoplastic resins (e.g. polyethylene, polypropylene, polyamide, polyacetal, polycarbonate, ethylene/ethyl acrylate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/glycidyl methacrylate/vinyl acetate copolymer, ethylene /
Propylene copolymer, ethylene/propylene/non-conjugated diene copolymer, ethylene/butene-1 copolymer, acrylic rubber, polyether ester elastomer, etc.
Among them, polyether ester elastomer ethylene/glycidyl methacrylate copolymer and ethylene/glycidyl methacrylate/vinyl acetate copolymer are preferred) and thermosetting resins can also be added.
You may use not only seeds but also two or more kinds in combination.

In addition, as long as the colorant formulation is based on the specific blue colorant according to the present invention, it is practically possible to apply it in any range of blue hues, and other pigments can be used as concomitant pigments and/or complementary color pigments. Of course, specific organic pigments that do not have color migration properties may be used in combination, and known inorganic pigments may also be used.

〔Example〕

EXAMPLES Below, the effects of the present invention will be explained in further detail with reference to Examples.

Examples (1, 1 to (6)), Comparative Examples (1) to (6) Polybutylene terephthalate resin (relative viscosity of 0.5% orthochlorophenol solution measured at 25°C is 1.
54) and 100 parts by weight of the colorant and dispersant of the type and amount shown in Table 1 in a tumbler at room temperature.
After mixing for 5 minutes, the resin temperature was set to 260° C. in an extruder with a diameter of 50 mm, and after melting and mixing, the mixture was granulated with a pelletizer to produce colored pellets.

Furthermore, using each of these colored pellets, a screw in-line type injection molding machine was used at a cylinder temperature of 250°C to test the color migration property, etc., so that the thickness was 1.5 ms+.
, rectangular test pieces each measuring 3an x 5cm were prepared.

(1) Prepare a white soft vinyl chloride sheet (vinyl chloride resin/plasticizer = 100150) with a thickness of 1 mm, bring it into close contact with the test piece, and apply a load of 300 g/a in an atmosphere at a temperature of 150°C for 3 hours. ! An experiment was conducted to determine whether the color would bleed into the white sheet under these conditions.

(2) A transparent vinyl chloride sheet with a thickness of 1 B and a size of 5 cn x 6 an (vinyl chloride resin/plasticizer = 1001
50), placed the prepared test piece on top of it, and left it for 30 hours in an atmosphere at a temperature of 120°C without any load, to conduct an experiment to see if the color would transfer to the transparent vinyl chloride sheet. went.

(3) Prepare a white board made of polybutylene terephthalate resin with a thickness of 1.5 mm and the size of 5 stamps x 6 countries, and place it on it.
Place the prepared test piece in an atmosphere with a temperature of 150°C and a load of 100g/c! The sample was left for 5 hours, and an experiment was conducted to see if the color would transfer to the white plate.

(4) Using the colored pellets prepared above, a screw in-line injection molding machine was used to mold the cylinder at a temperature of 26°C.
A residence test was conducted at 0° C. for 0 minutes, 5 minutes, and 10 minutes to confirm heat discoloration resistance.

(5) Using the colored pellets, using a 3 ounce screw in-line injection molding machine set at 250°C,
ASTMI Danher and 1/8 inch wide notched Izot impact test specimens were prepared at a mold temperature of 60°C. For these test pieces, tensile properties were measured according to ASTM D638, and impact strength was measured according to ASTM D256.

Also, 250°C according to ASTM DI238
Melt flow rate (MFR) was measured at a load of 325 g.

(6) Polybutylene terephthalate resin 1 similar to the above
00 parts by weight, 20 times the types and quantities shown in Example (5) and Comparative Example (5) in Table 1 were mixed in a tumbler for 15 minutes at room temperature, and then mixed in an extruder with a diameter of 50M. The resin was melt-kneaded at a temperature of 260° C. and then granulated using a pelletizer to produce colored masterbatches.

In order to investigate the contamination of the mold, a continuous molding test was conducted using this masterbatch in a screw in-line injection molding machine at a cylinder temperature of 250°C and a cycle of 1 minute (injection 10 seconds, cooling 20 seconds). After molding a number of shots, the mold (the embossed portion for the embossed color plate) was wiped off with a white cloth soaked in alcohol, and the degree of coloring on the white cloth was examined. Furthermore, the degree of coloring of the wiped white cloth portion was visually evaluated, and ΔE (color difference) was measured using a spectrophotometer.

Of the above test items, the results of (1) to (4) are shown in Table 2, the results of (5) are shown in Table 3, and the results of (6) are shown in Table 4. The compositions are shown below.

The blending amount in the table is polybutylene terephthalate resin 100
Indicates the number of parts by weight.

EBS in the table indicates ethylene bisstearamide.

Table-2 Experimental results of color migration and heat discoloration resistance table Endurance opposition Attack sex Na degree of fruit experience Conclusion Fruit All judgments were made by visual inspection.

Table 4 Mold staining test results x mark: Contamination [Effects of the invention] As is clear from Table 2, the polybutylene terephthalate resin coloring of the present invention using the blue colorant specified by the present invention The composition has very good color fastness.

Therefore, if the molded product is used in a high-temperature environment, the color material may ooze out onto the surface of the molded product, causing the color to migrate to other substances and contaminating them. However, according to the present invention, such problems can be solved.

Furthermore, as is clear from Table 4, in the case of Comparative Example (5), contamination of the mold was already recognized after 100 shots, but in the case of Example (5), contamination of the mold was detected even after 300 shots. I was not able to admit.

Therefore, when the coloring composition of the present invention is used, mold contamination during molding, which has been a problem in the past, can be solved.

Furthermore, as is clear from Table 3, when using the polybutylene terephthalate resin coloring composition of the present invention,
No remarkable deterioration phenomenon in the physical performance of the molded article was observed.

As described above, when using the polybutylene terephthalate resin coloring composition of the present invention, it is possible to provide colored molded products with good color migration resistance, heat discoloration resistance, and mold non-contamination. Colored molded products are expected to be widely used in various electrical and electronic parts, automobile parts, power tool parts, and other industrial applications that take advantage of the inherent properties of resin.

Claims (1)

[Scope of Claims] A polybutylene terephthalate resin coloring composition comprising a polybutylene terephthalate resin mixed with a blue colorant, wherein the blue colorant is CI. Pigment Blue 15:3, CI. Pigment Blue 15:1, CI. A polybutylene terephthalate resin coloring composition characterized in that at least one type of Solvent Blue 132 is blended as an essential coloring component.