JPH10245492A - Thermoplastic resin composition, and extrusion molded articles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition little in generation of plate-out in a long term continuous molding, excellent in molding stability, and capable of obtaining a molded article excellent in appearance and physical properties, by making a coloring agent contain a specified dispersant and pigment. SOLUTION: This composition consists of (A) 100 pts.wt. of a thermoplastic resin and (B) 0.01-2 pts.wt. of a coloring agent, and the coloring agent consists of (i) as the dispersant, 10-80wt.% of a mixture comprising (a) hexachloroethylene and/or triglycerol hydroxystearate and (b) an acrylic resin, and (ii) 90-20% of the pigment. The component A is a vinyl chloride-based resin containing 56.8-71% of chlorine, and preferably the ratio of component a and component b is set to 90:10-10:90 (weight ratio).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin composition and an extruded product.

[0002]

2. Description of the Related Art A thermoplastic resin composition is usually formed by extrusion molding, injection molding or the like. At this time, a lubricant, a stabilizer, an antioxidant, a colorant, etc. are added as required. . Particularly in the case of molding a vinyl chloride resin composition which is difficult to mold, a long-term molding stability is maintained by adding a stabilizer, a lubricant, a processing aid, and the like. However, there is a problem that the physical properties are deteriorated by adding a large amount of the above additives. Such a problem becomes more prominent in the case of chlorinated vinyl chloride resin which requires heat resistance, since molding at a higher temperature is required, and it is necessary to balance both physical properties and long-term molding stability. Is often difficult.

[0003] Even if the above problems are solved, in a long-term continuous molding process, components such as pigments and inorganic substances having low compatibility with a vinyl chloride resin are deposited on the surface of a mold. (Hereinafter referred to as “plate-out”), and accompanying this, streaks and the like are generated in the molded body, which may cause poor appearance.

[0004] In order to prevent the above-mentioned pigment-based plate-out, for example, JP-A-4-366152 discloses a method of adding a dispersing agent such as an acryl-styrene copolymer system or a polyester resin system to improve lubricity. Colorant compositions for vinyl chloride resins with good and good color stability have been proposed, but for resin compositions that are difficult to mold or resin compositions that require high-temperature molding, they can be used in long-term continuous molding. The molding stability has not been satisfied.

[0005] For example, see Japanese Patent Application Laid-Open No. 60-139742.
Japanese Patent Application Laid-Open Publication No. H11-216, proposes a colorant composition for a vinyl chloride resin in which the dispersibility of a colorant is improved using a dispersant comprising a lubricant and an acrylic resin, but requires molding at a high temperature. The resin composition has not been able to satisfy molding stability in long-term continuous molding.

Therefore, in the prior art, when a resin composition, such as a chlorinated vinyl chloride resin, which is difficult to mold, is subjected to continuous molding for a long period of time, a good colorant that does not generate plate-out has not been found. It is the current situation.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin which can provide a molded product having a small plate-out, excellent molding stability, and excellent appearance and physical properties even after long-term continuous molding. An object of the present invention is to provide a composition and an extruded product using the thermoplastic resin composition.

[0008]

Means for Solving the Problems The thermoplastic resin composition of the present invention comprises 100 parts by weight of a thermoplastic resin and 0.01% of a coloring agent.
1 to 2 parts by weight, wherein the colorant is 10 to 80% by weight of a mixture of hexachloroethylene and / or hydroxystearic acid triglyceride and an acrylic resin as a dispersant, and a pigment 9
It is characterized by comprising 0 to 20% by weight.

Hereinafter, the present invention will be described in detail. The thermoplastic resin composition of the present invention comprises a thermoplastic resin and a coloring agent.

Examples of the thermoplastic resin include vinyl chloride resins; polyolefin resins such as polyethylene and polypropylene; aromatic resins such as polystyrene, poly-α-methylstyrene and polyester; acrylonitrile-butadiene-styrene copolymer. (ABS resin) and copolymers such as acrylonitrile-styrene copolymer (AS resin).

As the vinyl chloride resin, for example,
A homopolymer of vinyl chloride, a copolymer of vinyl chloride with a polymerizable monomer having an unsaturated bond other than vinyl chloride, a graft copolymer obtained by grafting vinyl chloride on a polymer other than vinyl chloride; ) A chlorinated vinyl chloride resin obtained by post-chlorination of a polymer by a conventionally known method; a mixture of the (co) polymer and a mixture of the (co) polymer and the chlorinated vinyl chloride resin; Can be

The polymerizable monomer other than the above-mentioned vinyl chloride has a radical-reactive double bond and can be copolymerized with vinyl chloride by a radical polymerization initiator.
There is no particular limitation, for example, α-olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl acetate and vinyl propionate; butyl vinyl ether;
Vinyl ethers such as cetyl vinyl ether; methyl (meth) acrylate, ethyl (meth) acrylate,
(Meth) acrylates such as butyl acrylate and phenyl methacrylate; aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; N-phenylmaleimide;
Examples include N-substituted maleimides such as N-cyclohexylmaleimide, which may be used alone or in combination of two or more.

The polymer other than vinyl chloride used in the above graft copolymer is not particularly limited as long as it is capable of subjecting vinyl chloride to the graft polymerization. For example, ethylene-vinyl acetate copolymer, ethylene-acetic acid Vinyl-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, acrylonitrile-butadiene copolymer , Polyurethane, chlorinated polyethylene, chlorinated polypropylene, etc., and these may be used alone or in combination of two or more.

When the chlorine content of the vinyl chloride resin becomes small, the performance as a vinyl chloride resin does not appear,
When it is increased, the chlorination rate is sharply reduced and a long time is required for chlorination, which is industrially disadvantageous. Therefore, the chlorine content is preferably 56.8 to 71% by weight.

When the average degree of polymerization of the vinyl chloride resin is small, the mechanical properties of the obtained molded product are reduced. When the average polymerization degree is large, the melt viscosity at the time of molding becomes high and molding becomes difficult. 400 is preferable, and 700 to 1,100 is more preferable.

The chlorine content of the chlorinated vinyl chloride resin is determined according to the heat resistance required in the above range, but may be adjusted at the reaction stage. It may be adjusted by blending a chlorinated vinyl chloride resin with a low chlorination degree or a normal vinyl chloride resin.

The chlorinated vinyl chloride resin is obtained by post-chlorination of the vinyl chloride resin, and various chlorination methods such as a water suspension method and a solution chlorination method which are conventionally known are used. However, industrially, a water suspension method is particularly preferred.

The colorant comprises a dispersant and a pigment,
A mixture of hexachloroethylene and / or triglyceride hydroxystearate and an acrylic resin is used as a dispersant.

Examples of the acrylic resin include alkyl (meth) acrylate resins such as methyl (meth) acrylate resin, ethyl (meth) acrylate resin, and butyl (meth) acrylate resin, and in particular, methyl methacrylate resin. preferable.

The mixing ratio of hexachloroethylene and / or triglyceride hydroxystearate to the acrylic resin in the above dispersant is 90:10 to 1: 1.
0:90 (weight ratio) is preferred, and more preferably 70:90.
30 to 30:70 (weight ratio). Outside the above range,
The effect of improving long-term moldability is reduced.

The ratio of the dispersant to the pigment in the colorant is 10 to 80% by weight of the dispersant and 90 to 2% of the pigment.
0% by weight, more preferably 40 to 7 dispersants.
The pigment is 60 to 30% by weight based on 0% by weight. When the proportion of the dispersant is less than 10% by weight, the effect of improving the long-term moldability decreases, and the effect of dispersing the pigment decreases.
If the content is more than 10% by weight, the hiding power and the color forming property of the colorant itself are reduced, and a color unique to a light yellow vinyl chloride resin is likely to appear.

The above-mentioned pigments are selected according to the required coloring, but known pigments conventionally used for vinyl chloride resins can be used. For example, in addition to titanium oxide and carbon black, azo resins, Organic pigments such as benzimidazolones, diallylides, quinacridones, isoindolinones, bats, phthalocyanines, and dioxanes;
Examples include inorganic pigments such as ultramarine blue, cobalt blue, red iron oxide, titanium yellow, and graphite.

The amount of the coloring agent to be added depends on the amount of the thermoplastic resin 10
The amount is limited to 0.01 to 2 parts by weight, preferably 0.1 to 0.6 parts by weight, based on 0 parts by weight. When the amount added is 0.
If the amount is less than 01 parts by weight, the desired color cannot be obtained. If the amount is more than 2 parts by weight, the pigment tends to adhere to the mold and to cause poor appearance of the molded article.

As the method for producing the colorant, a conventionally known method is employed, and examples thereof include a method for producing a master batch type, a dry blend type, a paste type, and a wet color type. Among these, a dry blend type production method is particularly preferable from the viewpoint of dispersibility of the colorant and the like. This production method is a method in which aluminum silicate, a pigment and the like are mixed with a Henschel mixer or the like, and then mixed into flakes or powder.

The thermoplastic resin composition of the present invention may contain, if necessary, di-2-ethylhexyl phthalate (DOP),
Plasticizers such as di-2-ethylhexyl adipate (DOA); heat stabilizers; lubricants such as polyethylene wax, ester wax, stearic acid, monoglyceride, montanic acid wax, calcium carbonate; glass fiber, carbon fiber, etc. In addition to the filler, an antistatic agent, a flame retardant, a processing aid, an ultraviolet absorber, and the like may be added.

The above-mentioned thermoplastic resin composition can be obtained by mixing the above-mentioned thermoplastic resin, coloring agent, and other additives such as a stabilizer and a lubricant with a usual mixing device such as a Henschel mixer.

The extruded product of the present invention can be obtained by extruding the thermoplastic resin composition using a conventional extruder and a mold. When the vinyl chloride resin is used as the thermoplastic resin, if the molding temperature is lower than 190 ° C., various physical properties of the molded article, particularly the impact resistance, are reduced.
If the temperature exceeds 300 ° C., problems such as occurrence of decomposition lines in the molded article and poor long-term moldability occur.

As the mold used for molding, any mold that can mold a rod-shaped body, a tubular body, a deformed cross-section such as a rain gutter, a plate-shaped body, a sheet, a film, and the like can be used.

[0029]

Embodiments of the present invention will be described below. [Preparation of Colorant] Each dispersant and pigment (10% by weight of carbon black and condensed azo red 9) in the amounts shown in Tables 1 and 2
0% by weight) with a Henschel mixer at 60 ° C.
Dry blending, 14 kinds of powdered colorants A to N
I got

[0030]

[Table 1]

[0031]

[Table 2]

(Examples 1 to 12, Comparative Examples 1 to 8) Tables 3 to
100 parts by weight of a chlorinated vinyl chloride resin having an average degree of polymerization and a chlorine content shown in 5, 5 parts by weight of an organic tin mercapto (“JF-10B” manufactured by Sankyoki Gosei Co., Ltd.), and 0.5 part of stearic acid
Parts by weight, ester lubricant ("SG-2" manufactured by Riken Vitamin Co., Ltd.)
2 ") 1 part by weight, polyethylene oxide-based lubricant (" Hiwax220MP "manufactured by Mitsui Petrochemical Co., Ltd.) 1.5 parts by weight, MB
8 parts by weight of an S modifier ("BTA-751" manufactured by Kureha Chemical Co., Ltd.) and a coloring agent having the compounding amount shown in Tables 3 to 5 were mixed at 120 ° C. with a Henschel mixer, then cooled to 40 ° C., and chlorided. A vinyl resin composition was obtained.

The above-mentioned vinyl chloride resin composition was added to a 50 mm
Extrusion molding was performed using a bidirectional twin screw extruder to obtain a plate-like molded product. As the mold, a slit die (slit interval: 2 mm, width: 20 mm) having a compression portion and a pressure release portion in consideration of long-term moldability and capable of performing an accelerated evaluation was used. When the resin temperature is 2
The temperature was set at 10 to 215 ° C. Then, the mold is caliber 20m
m, a tubular molded article was molded under the same conditions as above, except that a tubular article having a thickness of 3 mm could be molded.

The plate-like and tubular molded products obtained in the above Examples and Comparative Examples were evaluated as follows, and the results are shown in Tables 3 to 5. (1) Evaluation of Moldability (Evaluation by Tubular Molded Product) The external appearance and inner surface of the tubular molded product were visually observed,
(A) When the inner and outer surfaces are glossy and have no irregularities,
(B) Those with slightly unevenness, low gloss or slightly pale yellow color were evaluated as Δ, and (c) Poor gloss, those with unevenness or large yellow color were evaluated as x.

(2) Long-term moldability (evaluation by plate-like molded product) Immediately after continuous extrusion for 5 hours, the mold was disassembled, and the adhered matter on the mold surface was visually observed.が was determined when there was no 全 く, and △ was determined when (2) a slight amount of adhered substance was observed in the easily adhered portion such as a corner portion, and (C) × when the amount of adhered substance was large.

(3) Evaluation of Drop Weight Impact (Evaluation by Tubular Molded Product) After adjusting the state of the tubular molded product sample at 0 ° C. for 2 hours, JIS
A falling weight impact test was performed with a weight of 3 kg in accordance with -7211.

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

The thermoplastic resin composition of the present invention has the above-mentioned structure, and can be molded by a usual molding machine.
Even when molded continuously for a long time, there is little deposit on the mold, and it shows excellent stability in long-term molding. When the above-mentioned thermoplastic resin is a vinyl chloride resin, the above-mentioned effect is further exhibited. The extruded product obtained by extruding the resin composition of the present invention has a good appearance and excellent physical properties.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3:00 5: 103 5:02 9:04)

Claims (4)

[Claims] 1. A thermoplastic resin composition comprising 100 parts by weight of a thermoplastic resin and 0.01 to 2 parts by weight of a coloring agent, wherein the coloring agent comprises hexachloroethylene and / or hydroxystearic acid triglyceride as a dispersant. A thermoplastic resin composition comprising 10 to 80% by weight of a mixture with an acrylic resin and 90 to 20% by weight of a pigment. 2. The thermoplastic resin has a chlorine content of 56.8 or more.
2. The thermoplastic resin composition according to claim 1, which is 71% by weight of a vinyl chloride resin. 3. In a mixture of hexachloroethylene and / or hydroxystearic acid triglyceride and an acrylic resin, the ratio of hexachloroethylene and / or hydroxystearic acid triglyceride to the acrylic resin is 90:10 to 10:90 (weight). (Ratio). 4. An extruded product obtained by extruding the thermoplastic resin composition according to claim 1.