JP2003073534A - Black polytrimethylene terephthalate resin composition having excellent weather resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black polytrimethylene terephthalate resin composition which retains excellent mechanical characteristics, hardly causes fading of the black color, and gives excellent appearances to molded articles, even when used outdoors, especially exposed to rains. SOLUTION: This black polytrimethylene terephthalate resin composition comprises 100 pts.wt. of polytrimethylene terephthalate resin and 0.01 to 10 pts.wt. of carbon black.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a black-colored poly (trimethylene terephthalate) capable of retaining a high mechanical property and obtaining a molded product with little black fading even under conditions of use exposed outdoors, particularly to rainfall. The present invention relates to a resin composition.

[0002]

2. Description of the Related Art Thermoplastic polyesters typified by polyethylene terephthalate and polybutylene terephthalate are excellent in mechanical properties, heat resistance, chemical resistance, weather resistance and electrical properties and are widely used in automobile materials, electric / electronic parts and the like. Used in. Especially when it is used for outdoor use, it is used in the form of a black colored molded product. Among them, carbon black is generally added for the purpose of improving weather resistance or preventing discoloration during use in a high temperature atmosphere. For example, blending carbon black with a polybutylene terephthalate resin is disclosed in JP-A-9-2.
Although disclosed in Japanese Patent Application Laid-Open No. 91204 and Japanese Patent Application Laid-Open No. 11-140284, in these methods, the weather resistance under the conditions of use exposed outdoors, particularly to rainfall, is not at a level that satisfies high market demand. It was

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and has excellent mechanical properties and excellent appearance of molded articles with little black fading even under outdoor conditions, especially when used under exposure to rainfall. Another object is to provide a black colored polytrimethylene terephthalate resin composition.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present invention is: Polytrimethylene terephthalate resin (A) 100
Carbon black (B) 0.01 to 1 with respect to parts by mass
A black colored polytrimethylene terephthalate resin composition containing 0 part by mass.

2. The polytrimethylene terephthalate resin (A) has a number average molecular weight of 5,000 to 100,000.
1, a polytrimethylene terephthalate resin having a molecular weight distribution (Mw / Mn) of 1.2 to 4.5 and containing 1 to 20 mass% of molecules having a molecular weight of 100,000 or more. The black-colored polytrimethylene terephthalate resin composition as described in 1. 3. As the resin composition component, the organic dye (C) is further added in an amount of 0.001 to 5 parts by mass based on 100 parts by mass of the polytrimethylene terephthalate resin. It is a trimethylene terephthalate resin composition.

The present invention will be specifically described below.
First, the polytrimethylene terephthalate resin of the present invention will be described. The polytrimethylene terephthalate resin of the present invention also includes a composition in which various additives and fillers usually used in polytrimethylene terephthalate are blended. For example, additives include antioxidants, light stabilizers, ultraviolet absorbers, moldability improvers, nucleating agents, flame retardants, foaming agents, and the like, and fillers include inorganic fillers such as glass fibers. And thermoplastic resins other than polytrimethylene terephthalate.

Further, polytrimethylene terephthalate (hereinafter sometimes abbreviated as "PTT") represents a polyester polymer using terephthalic acid as an acid component and trimethylene glycol as a glycol component. In the present invention, trimethylene glycol is selected from 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, or a mixture thereof.
From the viewpoint of stability, 1,3-propanediol is particularly preferable.

In addition to the above, aromatic dicarboxylic acids other than terephthalic acid, such as phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid and diphenyl ether, are used as acid components within the range that does not impair the object of the present invention. Dicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylmethanedicarboxylic acid, diphenylketone dicarboxylic acid, diphenylsulfonedicarboxylic acid, etc .; aliphatic dicarboxylic acid such as succinic acid, adipic acid, sebacic acid; alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; Oxydicarboxylic acids such as ε-oxycaproic acid, hydroxybenzoic acid, and hydroxyethoxybenzoic acid are used as glycol components, and ethylene glycol, tetramethylene glycol, pentamethylene glycol,
Hexamethylene glycol, octamethylene glycol, neopentyl glycol, cyclohexanedimethanol, xylylene glycol, diethylene glycol,
A part of polyoxyalkylene glycol, hydroquinone or the like can be used for copolymerization.

The amount of the copolymerization in the case of copolymerization is not particularly limited as long as the object of the present invention is not impaired, but it is usually 20 mol% or less of the acid component or 2 of the glycol component.
It is preferably 0 mol% or less. Further, a branched component in the above polyester component, for example, tricarballylic acid, trimesic acid, trimellitic acid, etc., an acid having a trifunctional or tetrafunctional ester forming ability or a trifunctional such as glycerin, trimethylolpropane, pentaerythritol, etc. Alternatively, tetrafunctional ester-forming alcohols may be copolymerized, in which case they are 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0 mol% or less of the total dicarboxylic acid components. It is 0.3 mol% or less. Furthermore, PT
T may be a combination of two or more of these copolymerization components.

The method for producing PTT used in the present invention is as follows:
Although not particularly limited, for example, JP-A-51-1
40992, JP-A-5-262862, JP-A-8-311177, and the like, and terephthalic acid or its ester-forming derivative (for example, lower alkyl ester such as dimethyl ester, monomethyl ester) Trimethylene glycol or an ester-forming derivative thereof is heated and reacted in the presence of a catalyst at a suitable temperature / time, and the resulting glycol ester of terephthalic acid is subjected to a desired polymerization at a suitable temperature / time in the presence of a catalyst. A method in which the polycondensation reaction is performed up to a certain degree is included.

The PTT of the present invention preferably has a number average molecular weight of 5,000 to 100,000 and Mw / Mn showing a molecular weight distribution of 1.5 to 4.5. Furthermore, it is preferable that 1 to 20 mass% of molecules having a molecular weight of 100,000 or more are contained. A number average molecular weight of 5,000 or more is necessary from the viewpoint of mechanical strength, and 100,000 or less is preferable from the viewpoint of fluidity. Further, it is preferable that Mw / Mn falls within the range of 1.2 to 4.5 from the viewpoint of balance between moldability and mechanical properties. Particularly important is the content of molecules having a molecular weight of 100,000 or more, which is required to be 1% by mass or more for the mechanical strength under high temperature and high humidity, and 20% for the molding time not to be too long. % Or less is preferable.

Regarding the method for measuring the number average molecular weight and the molecular weight distribution, for example, the molecular weight can be measured by an osmotic pressure method, a terminal quantification method or a GPC method (gel permeation chromatography). For example,
Tosoh Co., Ltd. HLC-8120 and Showa Denko KK HFIP804-803 (30 cm column 2)
Hexafluoroisopropanol (hereinafter referred to as HFIP) as a carrier and PMMA manufactured by Polymer Laboratory as a standard sample can be used at a temperature of 40 ° C. and a flow rate of 0.5 ml / min.

The carbon black used in the present invention includes channel black type, furnace black type, lamp black type, thermal black type, Ketjen black type, naphthalene black type, etc. It is also possible to appropriately select and use the carbon black contained therein. Further, in order to control the specific surface area or impart other characteristics, the surface of carbon black can be treated with an acid or an alkali before use.

The carbon black used in the present invention preferably has an adsorption amount of dibutyl phthalate of 10 to 200 ml / 100 g, particularly preferably 30 to 150.
For the oil absorption of carbon black, 10 g of carbon black was charged into Brabender, dibutyl phthalate was dropped little by little, and the amount of dibutyl phthalate when the Brabender torque became constant was measured.
It is determined by converting it to the amount of dibutyl phthalate (ml) per 00 g.

PH of carbon black used in the present invention
Is the mechanical properties of the resulting composition, retention stability during molding,
3-11, preferably 4-1 in terms of appearance of molded products
0, particularly preferably 5 to 9.5. The above-mentioned PH is a value obtained by preparing an aqueous suspension in which 1 g of carbon black is dispersed in 20 ml of distilled water and measuring the pH of the suspension. The carbon black used in the present invention has a particle size of 10 to 10.
It is preferably 70 nm, particularly 15 to 60 nm, and more preferably 20 to 50 nm from the viewpoint of colorability and handleability. The method for measuring the particle size of carbon black was carried out by ultrasonically dispersing it in chloroform and measuring it with an electron microscope.

[0016] In addition, the specific surface area by BET equation low-temperature nitrogen adsorption method is in the range of 50 to 300 m ² / g, especially 200 meters ² / g
Hereafter, it is preferably 150 m ² / g or less.
The specific surface area is calculated by the BET method, that is, the multi-point method using a low temperature nitrogen adsorption device Soaptomatic-1800 (manufactured by Carlo Erba Co.). The amount of carbon black used in the present invention is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0.1 to 100 parts by mass of the polytrimethylene terephthalate resin.
3 parts by mass are used. For coloring, the amount of carbon black added is required to be 0.01 part by mass or more, while
From the viewpoint of sufficient jetness, cost and mechanical properties, the amount is preferably 10 parts by mass or less.

Further, as the resin composition component of the present invention,
When the organic dye (C) is used in combination, the appearance characteristics are further improved,
A resin composition having an excellent balance with weather resistance can be obtained. Examples of the organic dye (C) include azine dyes such as indulin, nigrosine, and aniline black, (alkyl) phthalimidomethyl copper phthalocyanine, dialkylaminomethyl copper phthalocyanine, (alkyl) anilinosulfamoyl copper phthalocyanine, and dialkylaminopropyl. Examples include copper phthalocyanine dyes such as sulfonamide copper phthalocyanine.

The addition amount of the organic dye used in the present invention is 100 parts by mass of the polytrimethylene terephthalate resin.
The amount is 0.001 to 5 parts by mass, preferably 0.005 to 1 part by mass, and more preferably 0.01 to 0.5 parts by mass. The resin composition of the present invention may further contain various additives that are commonly used, within the range that does not impair the object of the present invention. Types of additives include antioxidants such as hindered phenol compounds, phosphite compounds, hindered amine compounds, benzotriazole compounds, light stabilizers such as benzophenone compounds, ultraviolet absorbers, higher fatty acid metal salts. Moldability improving agents such as and higher fatty acid esters, nucleating agents, flame retardants, and coloring agents.

In particular, when the resin composition of the present invention is blended with 0.001 to 5 parts by mass of an inorganic crystal nucleating agent, a resin composition more suitable for the purpose of the present invention can be obtained. As the inorganic crystal nucleating agent, inorganic crystal nucleating agents include, for example, barium sulfate, sodium phosphate, talc, mica, kaolin, silica, clay, inorganic carboxylate, inorganic sulfonate, metal oxide, carbonate, organic. Examples thereof include carboxylates, organic sulfonates, molybdenum disulfide, boron nitride, and the like, or a mixture thereof.

The inorganic crystal nucleating agent of the present invention preferably has a particle size of 10 μm or less, more preferably 8 μm or less, and further 5 μm.
It is preferably m or less, and more preferably surface-treated with a silane-based or titanate-based coupling agent or the like in order to improve adhesion / adhesion with PTT. As the utilization of the present invention, the PTT resin composition of the present invention can be used by blending one or more fillers or other thermoplastic resins, if desired.

As the kind of the filler, especially glass fiber,
Inorganic fillers such as carbon fiber, silica, talc, glass beads and wollastonite are preferable, and other thermoplastic resins include polyester resins other than PTT such as polyethylene terephthalate and polybutylene terephthalate,
Polycarbonate resin, polyamide resin, ABS resin,
Examples of the polystyrene resin include polyethylene terephthalate resin, polybutylene terephthalate resin, and polycarbonate resin. The compounding amount of these fillers or other thermoplastic resins is preferably 5 to 300 parts by mass with respect to 100 parts by mass of the PTT resin composition of the present invention.

The PTT resin composition of the present invention is molded by a conventional molding method such as an injection molding method and put into practical use.
Further, a method of preparing a master pellet in which the carbon black used in the present invention is blended at a high concentration, and mixing the master pellet with a non-colored pellet at the time of molding and then molding, can be preferably used.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The polytrimethylene terephthalate resin used in the examples, main evaluation methods, and measured values were measured by the following methods. (1) Polytrimethylene terephthalate resin (A) A-1: Polytrimethylene terephthalate resin. The number average molecular weight was 9,800, Mw / Mn = 2.5, and the ratio occupied by molecules having 100,000 or more was 5.8%. A-2: PBT resin. (Duranex 2002 manufactured by Polyplastics Co., Ltd.)

(2) Measurement of molecular weight and molecular weight distribution The molecular weight and molecular weight distribution of the polytrimethylene terephthalate resin were measured by GPC (gel permeation chromatography). The measurement conditions are HLC-8120 manufactured by Tosoh Corporation and HFIP804-803 (30 cm column 2 manufactured by Showa Denko KK) as a column.
), Using HFIP as a carrier, at a temperature of 40 ° C. and a flow rate of 0.5 ml / min. A calibration curve was created and measured using PMMA manufactured by Polymer Laboratory as a standard sample. The molecular weight of standard PMMA is 620, 1680, 3
805, 7611, 13934, 24280, 6259
1, 186000 was used.

(3) Carbon black (B) B-1: Carbon black (manufactured by Degussa: PRINTE
XV) B-2: Carbon black (Mitsubishi Chemical Co., Ltd .: # 5)
0) (4) Azine dye (C) Nigrosine: (Orient Chemical Co., Ltd .: Spirit Black SB)

[Surface gloss] manufactured by Toshiba Machine Co., Ltd .; IS
Cylinder temperature 260 using 150E injection molding machine
100 × 90 ×, the injection pressure and speed are adjusted appropriately so that the filling time is about 2.5 seconds at a temperature of 90 ° C. and a mold temperature of 90 ° C.
A 3 mm injection molded plate was obtained. JIS-K7 using this flat plate and gloss meter (HORIBA; IG320)
60 degree gloss was measured according to 150. [Mechanical Properties] Toshiba Machine Co., Ltd .; IS-50EP injection molding machine was used to mold ASTM type 1 with a thickness of 3 mm under the molding conditions of screw rotation speed 200 rpm and resin temperature 260 ° C. Tensile breaking strength was measured according to D638.

[Weather Resistance] An injection-molded article obtained in the same manner as used for the evaluation of the surface glossiness and mechanical properties was used as a xenon arc type accelerated weathering tester (manufactured by Atlas; XEN).
OTEST 1200 CPS) and black panel temperature 65 ° C. for 6 hours under a water spray condition of 12 minutes per hour.
It was exposed for 00 hours and evaluated. The surface glossiness and the tensile breaking strength before and after the exposure were measured, and the gloss retention rate and the tensile strength retention rate were obtained, respectively. The measuring method is as described above. The gloss retention rate and the tensile strength retention rate are expressed by the percentage of the gloss degree and the tensile breaking strength after the exposure to the gloss degree before the exposure and the tensile breaking strength, and the higher the retention rate, the better the weather resistance is judged to be. it can.

[0028]

Examples 1 to 6 and Comparative Examples 1 to 3 The components shown in Table 1 were mixed in the amounts shown in the table, and a twin-screw extruder having a screw diameter of 25 mm (ZSK-manufactured by Warner & Freidler Co., Ltd.) was mixed.
In 25), the mixture was melt-kneaded at 260 ° C. and pelletized. The pellets were dried at 120 ° C. for 5 hours and then evaluated. The results are shown in Table 1.

[0029]

[Table 1]

From the results shown in Table 1, by using carbon black in the polytrimethylene terephthalate resin,
It is possible to obtain a material that has excellent mechanical properties, has little black fading, and has an excellent appearance of a molded product even under use conditions in which it is exposed outdoors, particularly to rainfall.

[0031]

EFFECT OF THE INVENTION The polytrimethylene terephthalate resin composition of the present invention has excellent mechanical properties even under use conditions of being exposed to rainfall, especially rain, and has a black color fading less and a molded article appearance. It is suitable for various other applications such as electric / electronic related equipment, precision machinery related equipment, office equipment, automobile / vehicle related parts, etc.

Claims (3)

[Claims] 1. A carbon black (B) based on 100 parts by mass of a polytrimethylene terephthalate resin (A).
A black colored polytrimethylene terephthalate resin composition containing 0.01 to 10 parts by mass. 2. The polytrimethylene terephthalate resin (A) has a number average molecular weight of 5,000 to 100,000.
0, a molecular weight distribution (Mw / Mn) of 1.2 to 4.5, and a polytrimethylene terephthalate resin containing 1 to 20 mass% of molecules having a molecular weight of 100,000 or more. 1. The black colored polytrimethylene terephthalate resin composition according to 1. 3. A polytrimethylene terephthalate resin 100 further containing an organic dye (C) as a resin composition component.
The black colored polytrimethylene terephthalate resin composition according to claim 1 or 2, which is added in an amount of 0.001 to 5 parts by mass with respect to parts by mass.