JP3016207B2 - 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, titanium yellow, yellow iron oxide and the like as inorganic pigments, and anthraquinone pigments and isoindolinone pigments having relatively good heat resistance at the time of molding as organic pigments for yellowish coloring among the above hues. Pigments, quinophthalone pigments and the like, and as dyes, anthraquinone dyes and quinophthalone dyes have been mainly used as coloring agents.

[Problems to be solved by the invention]

As described above, conventionally, as a yellow colorant for polybutylene terephthalate resin, inorganic pigments such as titanium yellow and yellow iron oxide, organic pigments such as anthraquinone pigments, isoindolinone pigments, and quinophthalone pigments, Quinone dyes, quinophthalone dyes and the like have been used.

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

On the other hand, with the polybutylene terephthalate resin coloring composition using the above-mentioned organic and dye-based yellow coloring agents, the problem of mold contamination is likely to occur 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.

Regarding the cause of the mold contamination, since the conventional organic pigments and dyes used are dissolved in the polymer in the molten state, they ooze 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 remove the various disadvantages associated with the conventional polybutylene terephthalate resin coloring composition described above, as a specific organic yellow pigment as an essential coloring component among a large number of yellow coloring agents. The present inventors have found that a polybutylene terephthalate resin colored composition which is free from mold contamination and has excellent color transfer resistance and heat stability can be obtained by using the same, and has reached the present invention.

Therefore, the present invention is a vivid yellowish color which is excellent in heat stability, without remarkably deteriorating the excellent physical properties of the polybutylene terephthalate resin itself, and has no problem in mold contamination and color transferability. It is an object of the present invention to provide a polybutylene terephthalate resin colored 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 blending a yellow colorant with polybutylene terephthalate resin, as the yellow colorant, color CI. Pigment Yellow 190, C listed in the index
A polybutylene terephthalate resin coloring composition comprising at least one of I. Pigment Yellow 150 as an essential coloring component.

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 yellow colorant used in the present invention for these polybutylene terephthalate resins is a variety of yellow colorants described in the color index as a result of various studies by the present inventors. Pigment Yellow 190 and CI Pigment Yellow 150.

The addition amount of the yellow 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, and among them, particularly preferred is N, N'-ethylenebisamide. 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 yellow organic pigment and dispersant are mixed by a mixer such as a tumbler and a mixer, and then extruded. Melt kneading in a machine to produce colored pellets, a method of obtaining a polybutylene terephthalate resin colored composition, or mixing a high concentration of pigment, dispersant and polybutylene terephthalate resin in the same manner, 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 far as the colorant is blended, as long as it is based on the specific yellow colorant according to the present invention, practically any yellow color hue can be applied and developed.
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 (5), Comparative Examples (1) to (5) Polybutylene terephthalate resin (relative viscosity when a 0.5% orthochlorophenol solution was measured at 25 ° C.)
1.54) 100 parts by weight of the pigments and dispersants of the types and amounts shown in Table 1 were mixed in a tumbler at room temperature for 15 minutes, and the resin temperature was adjusted to 260 ° C with a 50 mm diameter extruder. After setting and melt-kneading, the mixture was granulated with a pelletizer to produce colored pellets.

In the examples, CI.Pigment Yellow 190 was manufactured by Palio Tol Yellow K1570 / BASF, and CI.Pigment Yellow 150 was manufactured by Bayplast Yellow 5GN / Bayer. .Pigment Yellow 183 is the trade name Palio Thor Yellow K22
70 / BASF, CI. Pigment Yellow 53, trade name 42-420A / Nihon Fellow Co., Ltd., CI. Pigment White 6, CR-60-60 / Ishihara Sangyo And CI. Pigment Brown 24 as trade name 42
-118S / manufactured by Nippon Fellow Co. was used.

In addition, CI.Pigment Yellow 138 in Comparative Examples was manufactured by Palio Tole Yellow K0961 / BASF,
CI.Solvent Yellow 105 is a product of Diamond Resin Yellow HL / Mitsubishi Chemical Corporation, CI.Disperse Yellow
54 is the product name of Macrolex Yellow G / Bayer, CI.Solvent Yellow 116 is the product name of Kayaset Flavin FG / Nippon Kayaku, and CI.Pigment Yellow 181 is the product name of PV. First Yellow H
3R / Hoechst, CI. Pigment Yellow 147
Chromophtal Yellow AGR / Ciba Geigy Co., Ltd., and CI. Pigment Yellow 119 were trade name Talox T-10A / Titanium Kogyo Co., Ltd., respectively.

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. For these test pieces, tensile properties were measured according to ASTM D638, and impact strength was measured according to ASTM D256.

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 (4) and Comparative Example (4) in Table 1 were mixed in a tumbler at room temperature for 15 minutes with respect to 100 parts by weight, and 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 measured by ΔE (color difference) using 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 yellow coloring composition of the present invention using the organic pigment 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 (4)
In the case of (1), the mold was already contaminated by 100 shots, but in the case of Example (4), 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 Office (72) Inventor Noriyoshi 9-Oecho, Minato-ku, Nagoya-shi, Aichi (1) Toray Industries, Inc. Nagoya Office (56) References JP-A-49-120948 (JP, A) JP-A-47-13634 (JP, A) JP-A-3-259951 (JP, A) Material Materials Association Handbook, 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 obtained by mixing a yellow colorant with a polybutylene terephthalate resin, wherein the yellow colorant is CI. Pigment Yellow 190 described in the Color Index. A polybutylene terephthalate resin coloring composition comprising at least one of CI. Pigment Yellow 150 as an essential coloring component. 2. The polybutylene terephthalate resin colored composition according to claim 1, which is used for injection molding.