JP3016210B2 - Polybutylene terephthalate resin coloring composition - Google Patents

Description

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

[Conventional technology]

Polybutylene terephthalate resin, which represents a linear aromatic polyester, has low water absorption, a low coefficient of friction, and good elongation and moldability, as well as excellent crystallization properties, rigidity, heat resistance, Especially, it has various properties such as long-term heat resistance, creep resistance, electrical characteristics, stable dimensional stability, chemical resistance, oxidation deterioration resistance, weather resistance, etc. It is widely used in electric and electronic parts, automobile parts, power tool parts and other various industrial fields.

In these fields of use, they are often colored in various hues for the purpose of improving discriminating power or for imparting designability and decorativeness. There is a strong demand for a colored composition of a colored polybutylene terephthalate resin.

Conventionally, ultramarine, cobalt blue and the like have been used as inorganic pigments and oil-soluble anthraquinone-based dyes have been mainly used as dyes because of the blue hue among the above hues.

[Problems to be solved by the invention]

As described above, conventionally, inorganic pigments such as ultramarine blue and cobalt blue, anthraquinone-based dyes, and the like have been used as a blue-based colorant for polybutylene terephthalate resin.

However, when the above-mentioned blue-based inorganic pigment is used as a coloring agent, there is a disadvantage that coloring of a clear hue cannot be performed due to low coloring power and low saturation.

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

This is a major problem during molding,
The molded product has a major drawback in that the colorant oozes out on the surface of the molded product due to the effect of the use temperature atmosphere, transfers color to other substances, and contaminates other substances. Can be significantly reduced.

As for the cause of the mold contamination, the conventional blue colorant used is dissolved in the polymer in a molten state, so that it oozes out on the surface of the molded product when cooled and solidified in the mold, It is considered to contaminate the mold. In particular, when a dye system is used, the dye itself tends to sublimate, and the color often adheres to a portion of the mold where gas is not easily vented.

Therefore, the present inventors have conducted intensive studies to eliminate the above-mentioned various drawbacks associated with the conventional polybutylene terephthalate resin coloring composition, and as a result, using a specific coloring agent as an essential coloring component among a large number of blue coloring agents. As a result, the present inventors have found that a polybutylene terephthalate resin colored composition having no mold contamination and excellent in color transfer resistance and heat stability can be obtained, and the present invention has been achieved.

Therefore, the present invention provides a clear blue color without significantly deteriorating the excellent physical properties of the polybutylene terephthalate resin itself, and having no problem in mold contamination and color transferability, and also having excellent heat stability. It is an object of the present invention to provide a polybutylene terephthalate resin coloring composition suitable for obtaining a molded article.

[Means for solving the problem]

If the configuration of the present invention for achieving the above object is described in detail, in a polybutylene terephthalate resin coloring composition obtained by mixing a blue colorant with polybutylene terephthalate resin, as the blue colorant, color CI in the index: Pigment Blue 15: 3, CI.
Pigment Blue 15: 1 and CI. Solvent Blue 132 are blended as an essential coloring component, and are a polybutylene terephthalate resin coloring composition.

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

If the acid component is 20 mol% or less, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-
Naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 1,2-bisphenoxyethane-4,4'-dicarboxylic acid Alternatively, a dicarboxylic acid other than terephthalic acid, such as an ester-forming derivative thereof, may be used.

If the diol component is 20 mol% or less, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol Diols other than 1,4-butanediol such as 1,4-cyclohexanedimethanol, neopentyl glycol, 2-methyl-1,3-propanediol, polytetramethylene glycol, polyethylene glycol, and polypropylene glycol may be used. .

The polybutylene terephthalate resin preferably has a relative viscosity of 1.30 or more in terms of mechanical strength when a 0.5% orthochlorophenol solution is measured at 25 ° C., and 2.00 or less in terms of fluidity during molding. Are preferred.

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

The specific blue colorant used in the present invention with respect to these polybutylene terephthalate resins is, among the various blue colorants described in the color index as a result of research by the present inventors, CI. Pigment Blue 15:
3, CI Pigment Blue 15: 1, CI Solvent Blue 132
It turned out to be.

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

Known inorganic pigments are used as other colorants to be used in combination for practically all hue ranges.

Next, as a dispersant that is generally blended to improve the dispersibility of the pigment, magnesium stearate, calcium stearate, higher fatty acid metal salts such as lithium stearate, fatty acid esters, N, N'-alkylene Although there are a large number of bis fatty acid amides and the like, the dispersant which 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 as a result of various experiments by the present inventors. '-Ethylenebismyristic amide, N, N'-ethylenebisstearic acid amide, N, N'-ethylenebisoleic amide, N, N'-
Methylenebismyristate amide, N, N'-methylenebisstearic acid amide, N, N'-methylenebisoleic acid amide and the like were found to be particularly preferable among them, N, N'-ethylebis Stearamide.

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

As a method for obtaining the polybutylene terephthalate resin colored composition of the present invention, a predetermined amount of the polybutylene terephthalate resin and the desired concentration of the above-mentioned blue-based organic pigment and dispersant are mixed by a mixer such as a tumbler and a mixer, and then extruded. Melting and kneading in a machine to produce colored pellets, a method for obtaining a polybutylene terephthalate resin colored composition, mixing with a high concentration pigment, a dispersant and a method similar to polybutylene terephthalate resin, and after melt-kneading, There is a method of obtaining the composition by mixing and diluting a non-colored polybutylene terephthalate resin to a desired concentration after preparing a concentration master pellet.

In each of the above-described working steps, it is necessary to minimize the presence of water so as not to deteriorate the polybutylene terephthalate resin.

Further, the composition of the present invention may contain other additives as long as the object of the present invention is not impaired. That is, as an antistatic agent, an ultraviolet absorber, an antioxidant, a lubricant and a release agent, other flame retardants, flame retardant aids, and inorganic fillers, glass fiber, carbon fiber, metal fiber, asbestos, wollastenite, titanium Acid whisker, clay, mica, bentonite, glass beads,
One or more conventional additives such as titanium oxide, calcium carbonate, barium sulfate, gypsum, aluminum oxide, and talc can be added to the composition of the present invention.

Further, other thermoplastic resins (for example, 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, polyetherester elastomer, etc., among which polyetherester elastomer, ethylene / glycidyl methacrylate copolymer Coalescence and ethylene /
A glycidyl methacrylate / vinyl acetate copolymer is preferred) or a thermosetting resin can be added, and these resins may be used alone or in combination of two or more.

In addition, as long as the specific colorant according to the present invention is used as a base, the colorant can be applied and developed in a practically any blue color hue range.
Alternatively, other specific organic pigments having no color transfer property may be used in combination as a complementary color pigment, or a known inorganic pigment may be used.

〔Example〕

Hereinafter, the effects of the present invention will be described in more detail with reference to examples.

Examples (1) to (6) and Comparative Examples (1) to (6) Polybutylene terephthalate resin (relative viscosity when a 0.5% orthochlorophenol solution was measured at 25 ° C.)
1.54) 100 parts by weight of a colorant and a dispersant of the type and amount shown in Table 1 were mixed in a tumbler at room temperature for 15 minutes, and then the resin temperature was adjusted to 260 ° C with a 50 mm diameter extruder. After melt-kneading, the mixture was granulated with a pelletizer to produce colored pellets.

Note that CI. Solvent Blue 132 shown in the examples is a product of Filamide Blue R / Ciba Geigy, and CI. Pigment Blue 15: 3 is a product of Lionol Blue SM / Toyo Ink. CI. Pigment Blue 15: 1 is a trade name of cyanine blue SR5020 / Dainichi Seika Co., Ltd., and CI. Pigment Blue 29 is a trade name of group blue # 8000 / Daiichi Kasei Kogyo Co., Ltd. Pigment Blue 28 is a trade name of Cobalt Blue 1024 / Azahi Kasei Kogyo Co., Ltd., CI.Pigment Green 50 is a trade name of 42-633A / Nippon Fellow Co., Ltd., and CI. Those manufactured by CR-60-2 / Ishihara Sangyo Co., Ltd. were used. Also, CI.Sol in the comparative example
Vent Blue 94 is a product of Dia Resin Blue N / Mitsubishi Chemical Co., Ltd., CI.Solvent Blue 35 is a product of Kaya Set Blue N / Nippon Kayaku Co., Ltd., CI.Solvent
Blue 78 is a product of Dia Resin Blue K / Mitsubishi Chemical Co., Ltd., CI. Pigment Black 7 is a product of MA100 / Mitsubishi Kasei Co., Ltd., CI.
6 is the product name 42-203A / manufactured by Nippon Fellow,
As CI. Pigment Yellow 147, Chromophtal Yellow AGR / Ciba Geigy Co., Ltd. was used.

Furthermore, using each of the colored pellets, using a screw in-line type injection molding machine, at a cylinder temperature of 250 ° C., for use in tests such as color migration, a thickness of 1.5 mm and 3 cm
Each of rectangular test pieces having a size of 5 cm was prepared.

Then, (1) A white soft vinyl chloride sheet (vinyl chloride resin / plasticizer = 100/50) having a thickness of 1 mm is prepared and brought into close contact with the test piece.
An experiment was performed to determine whether or not the color bleeds into the white sheet under the condition of cm ² .

(2) Prepare a transparent vinyl chloride sheet (vinyl chloride resin / plasticizer = 100/50) with a thickness of 1 mm and a size of 5 cm x 6 cm.
The prepared test piece is placed thereon, and the temperature is set to 120.
An experiment was performed to determine whether or not the color was transferred to the transparent vinyl chloride sheet after leaving it for 30 hours in an atmosphere of ° C. and no load.

(3) A white plate made of polybutylene terephthalate resin having a thickness of 1.5 mm and a size of 5 cm × 6 cm is prepared, and the prepared test piece is placed on the white plate under an atmosphere at a temperature of 150 ° C. under a load of 100 g / cm ² . It was left for 5 hours, and an experiment was performed to determine whether the color was transferred to the white plate.

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

(5) Using the colored pellets, set at 250 ° C.
ASTM No. 1 dumbbells and 1/8 inch wide notched Izod impact test specimens were prepared at a mold temperature of 60 ° C. using an ounce screw-in-line injection molding machine. The tensile properties of these test specimens were determined according to ASTM D638 according to ASTM D256.
The impact strength was measured according to the following.

Further, the melt flow rate (MFR) was measured at 325 g under a load of 250 ° C. according to ASTM D1238.

(6) Polybutylene terephthalate resin as described above
20 parts by weight of the types and amounts shown in Example (5) and Comparative Example (5) in Table 1 were mixed in a tumbler at room temperature for 15 minutes with respect to 100 parts by weight, and then the resin was extruded with a 50 mm diameter extruder. Temperature 260
° C, and the mixture was melt-kneaded and then granulated with a pelletizer to produce colored masterbatches.

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

Table 2 shows the results of (1) to (4) among the above test items.
Table 3 shows the result of (5), and Table 4 shows the result of (6).

[Effects of the Invention] As is clear from Table 2, the polybutylene terephthalate resin coloring composition of the present invention using the blue colorant specified by the present invention has very good color transfer resistance.

Therefore, when used in a state where the temperature atmosphere is high in the past, the coloring material oozes out on the surface of the molded product, and the color shifts to another substance, thereby contaminating the other substance. However, according to the present invention, such a problem can be solved.

In addition, as apparent from Table-4, Comparative Example (5)
In the case of (1), the mold was already contaminated by 100 shots, but in the case of Example (5), the mold was not contaminated by 300 shots.

Therefore, in the case of using the coloring composition of the present invention, it is possible to eliminate mold contamination at the time of molding, which has conventionally been a problem.

Furthermore, as is apparent from Table 3, in the case of using the polybutylene terephthalate resin coloring composition of the present invention, no remarkable decrease in the physical performance of the molded article was observed.

As described above, in the case of using the polybutylene terephthalate resin coloring composition of the present invention, it is possible to provide a colored molded article having good color transfer resistance, heat discoloration resistance, and mold non-staining property, so that the obtained clear Colored molded products of hue are expected to be widely used in various electric and electronic parts, automobile parts, electric tool parts, and other industrial fields utilizing the inherent properties of resins.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kiichi Yoneya 9-1, Oecho, Minato-ku, Nagoya-shi, Aichi Pref. Toray Industries, Inc. Nagoya Works (1) Toray Industries, Inc. Nagoya Office (56) References JP-A-49-120948 (JP, A) JP-A-56-49750 (JP, A) “Coloring Material Engineering Handbook” edited by the Coloring Material Association First edition, 1989 (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 67/00-67/08 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. 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 described in the Color Index. 3. A polybutylene terephthalate resin coloring composition comprising at least one of CI. Pigment Blue 15: 1 and CI. Solvent Blue 132 as an essential coloring component. 2. The polybutylene terephthalate resin colored composition according to claim 1, which is used for injection molding.