JPH10120912A - Thermoplastic resin composition and extrusion-molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in molding stability with reduced adhesion to the mold even when the molding operation is continued for many hours and can give molded products having excellent appearance and physical properties and a extrusion-molded product using the thermoplastic resin composition. SOLUTION: This thermoplastic resin composition comprises (A) 100 pts.wt. of a thermoplastic resin (for example, a vinyl chloride resin or a chlorinated vinyl chloride resin whose chlorine content id over 56.8wt.% to lower than 71wt.%), (B) 0.01-2 pts.wt of a coloring agent. In this case, the coloring agent comprises (a) 1-10wt.% of silicone oil, 9-70wt.% of zeolite as dispersants and 90-20wt.% of a pigment component or 10-80wt.% of phthalic anhydride as a dispersant and 90-20wt.% of a pigment component. The extrusion molded product is produced by extruding this composition.

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 Usually, a lubricant, a stabilizer, an antioxidant, a coloring agent, and the like are added to a molding process of a thermoplastic resin composition, if necessary. 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 requiring 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. Further, even if the above problem is solved, in a long-term continuous molding process, a component such as a pigment or an inorganic substance having low compatibility with a vinyl chloride resin is deposited on the mold surface, a phenomenon called build-up or plate-out. (Hereinafter, referred to as plate-out), and accompanying this, streaks and the like were formed on the molded body, which sometimes caused poor appearance.

[0003] In order to prevent plate-out of the pigment system and the like, for example, Japanese Patent Application Laid-Open No. 4-366152 discloses that
A colorant composition for a vinyl chloride resin having good lubricity and good color stability by adding a dispersant such as an acrylic-styrene copolymer or a polyester resin has been proposed. For a resin composition that is difficult to perform or a resin composition that requires high-temperature molding, the molding stability has not been satisfied in long-term continuous molding.

[0004] 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.

[0005] Therefore, in the prior art, for a resin composition such as chlorinated vinyl chloride resin which is difficult to mold, a good colorant which does not cause plate-out in long-term continuous molding has not been found at present. .

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to reduce the amount of deposits on a mold even after a long-term continuous molding process, and to improve the molding stability. An object of the present invention is to provide a thermoplastic resin composition from which a molded article excellent in appearance and physical properties can be obtained, and an extruded article using the thermoplastic resin composition.

[0007]

The present inventors have achieved the above object by using (a) a combination of a silicon-based oil and zeolite or (b) phthalic anhydride as a dispersant in a colorant. Have been achieved, and the present invention has been completed.

That is, the thermoplastic resin composition of the present invention comprises 100 parts by weight of a thermoplastic resin and 0.01 to 2 colorants.
1 part by weight of a silicone resin as a dispersant, 9 to 70% by weight of zeolite, and 90% by weight of a pigment component.
Or (b) 10 to 80% by weight of phthalic anhydride as a dispersant and 90 to 2% of a pigment component.
0% by weight.

In a preferred embodiment of the present invention, the thermoplastic resin is a vinyl chloride resin or a resin having a chlorine content of 5%.
More than 6.8% by weight and less than 71% by weight of the chlorinated vinyl chloride resin.

Further, an extruded product of the present invention is characterized in that the thermoplastic resin composition is extruded.

The thermoplastic resin used in the present invention includes, for example, vinyl chloride resins or chlorinated vinyl chloride resins; polyolefin resins such as polyethylene and polypropylene; and aromatic resins such as polystyrene, poly α-methylstyrene and polyester. Resin; poly (acrylonitrile-
Copolymer resins such as butadiene-styrene) (ABS resin) and poly (acrylonitrile-styrene) (AS resin).

Among them, a resin which is particularly effective is a resin such as a vinyl chloride resin or a chlorinated vinyl chloride resin which is difficult to mold and requires high temperature molding.

As the vinyl chloride resin, for example,
A homopolymer of vinyl chloride; a copolymer of vinyl chloride and a polymerizable monomer other than vinyl chloride; a graft copolymer obtained by grafting a vinyl chloride monomer on a polymer other than vinyl chloride; Examples thereof include a mixture of polymers.

The polymerizable monomer other than vinyl chloride is not particularly limited as long as it has a radical-reactive double bond and can be copolymerized with vinyl chloride by a radical polymerization initiator. Α-olefins such as ethylene, propylene and butylene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; methyl (meth) acrylate, ethyl (meth) acrylate, butyl acrylate and phenyl (Meth) such as methacrylate
Acrylic esters; 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 cyclohexylmaleimide, and these may be used alone or in combination of two or more.

The polymer other than vinyl chloride used for the above graft copolymer is not particularly limited.
Ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer,
Examples thereof include ethylene-propylene copolymer, acrylonitrile-butadiene copolymer, polyurethane, chlorinated polyethylene, and chlorinated polypropylene, and these may be used alone or in combination of two or more.

When the average degree of polymerization of the vinyl chloride resin is small, the mechanical properties, particularly impact resistance, of the obtained molded article are reduced. When the average polymerization degree is large, the melt viscosity at the time of molding becomes high and molding becomes difficult. 500 to 1,400 are preferred,
More preferably, it is 700 to 1,100.

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, the water suspension method is industrially preferable.

The degree of chlorination of the chlorinated vinyl chloride resin is determined according to the required heat resistance, but may be adjusted at the reaction stage. Alternatively, it may be adjusted by blending with a chlorinated vinyl chloride resin having a low degree of chlorination or an ordinary vinyl chloride resin.

In the chlorinated vinyl chloride resin, when the chlorine content is 71% by weight or more, the chlorination speed is sharply reduced, and a long time is required for chlorination, which is industrially disadvantageous. The chlorine content is preferably less than 71% by weight.

The silicone oil used as a dispersant for the colorant used in the thermoplastic resin composition of the present invention includes, for example, dimethyl silicone oil, diphenyl silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, and polyether-modified silicone oil. Examples include silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, phenol-modified silicone oil, carboxy-modified silicone oil, and mercapto-modified silicone oil.

As the zeolite as a colorant dispersant used in the present invention, natural products and synthetic products can be used.
Natural products are known as minerals having a tectosilicate structure. Synthetic products include A-type, X-type, Y-type, etc., each having a different composition ratio of silicon and aluminum. In the present invention, in particular, when a vinyl chloride resin or a chlorinated vinyl chloride resin is used as the thermoplastic resin, a synthetic product is preferable from the viewpoint of the effect of suppressing thermal decomposition of the resin, and more preferably, A-type zeolite is used. is there.

The pigment component used in the present invention is selected according to the required coloring, and known pigments conventionally used for thermoplastic resins can be used. Examples of the pigment include titanium oxide and carbon black. , Azo-, benzimidazolone-, diarylide-, quinacridone-, isoindolinone-, bat-, phthalocyanine-, dioxane-based organic pigments; Is mentioned.

When the weight ratio of the silicone oil, zeolite and pigment component in the colorant of the present invention is less than 1% by weight, the long-term moldability is poor, and when it exceeds 10% by weight, the zeolite is coalesced. Since the effect of improving long-term moldability is not further exhibited, if the content of zeolite is less than 10% by weight, the effect of improving long-term moldability is not exhibited, the effect of dispersing pigment is not exhibited, and the amount exceeds 70% by weight. When the pigment component exceeds 90% by weight, plate-out tends to occur, and when the pigment component is less than 20% by weight, a desired color tone is not exhibited. % By weight, zeolite 9 ~
70% by weight and 90 to 20% by weight of the pigment component.

The weight ratio of phthalic anhydride as a dispersant in the colorant of the thermoplastic resin composition of the present invention to the pigment component is as follows:
When the amount of phthalic anhydride is less than 10% by weight, the effect of improving long-term moldability is not exhibited, and the effect of dispersing pigment is not exhibited.
If the ratio exceeds 1, the concealing power and coloring of the colorant decrease, and when a vinyl chloride resin is used as the thermoplastic resin, the light yellow characteristic of the vinyl chloride resin tends to appear, so
It is limited to 0 to 80% by weight and 90 to 20% by weight.

The weight ratio of phthalic anhydride as a dispersant in the colorant to the pigment component is from 40 to 40%.
When the content is 70% by weight and the pigment component is 60 to 30% by weight, good results can be obtained due to long-term molding stability and physical properties and color tone of the obtained molded product.

The amount of the coloring agent to be added depends on the amount of the thermoplastic resin 10
If the amount is less than 0.01 part by weight, the desired color is hardly developed if the amount is less than 0.01 part by weight, and if the amount is more than 2 parts by weight, the pigment adheres to the mold or the molded article tends to cause poor appearance. It is limited to 0.01 to 2 parts by weight. Price, appearance,
From the viewpoint of adhesion to a mold, a preferable range is 0.1 to
0.6 parts by weight.

As the method for producing the coloring agent, a conventionally known method is employed, and examples thereof include a production method of a master batch type, a dry blend type, a paste type, a wet color type and the like. 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 a dispersant, 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 thermoplastic resin composition contains the thermoplastic resin, a colorant, and other additives such as a stabilizer and a lubricant.
It can be obtained by mixing with a usual mixing device, for example, a Henschel mixer.

The extruded product of the present invention is characterized in that:
By subjecting the thermoplastic resin composition described in (1) to extrusion molding using an ordinary extrusion molding machine and a mold. When a vinyl chloride resin or a chlorinated vinyl chloride resin is used as the thermoplastic resin, if the molding temperature is less than 190 ° C., various physical properties, particularly impact resistance, of the molded body are reduced. The temperature is preferably from 190 to 220 ° C. since problems such as decomposition lines and poor long-term moldability occur.

As the mold used for molding, any of rod-shaped bodies, tubular bodies, irregular cross-sections such as rain gutters, plate-shaped bodies, sheets, films and the like can be used.

[0032]

Embodiments of the present invention will be described below. [Preparation of Colorant] Each dispersant and pigment (composed of 10% by weight of carbon black and 90% by weight of condensed azo red) in the amounts shown in Table 1 were dry-blended at 60 ° C. with a Henschel mixer to form a powder. Agents AP were obtained.

[0033]

[Table 1]

(Examples 1 to 12, Comparative Examples 1 to 12) Table 2
100 parts by weight of a chlorinated vinyl chloride resin having an average degree of polymerization and a chlorine content shown in Table 2, 2 parts by weight of organotin mercapto ("JF-10B" manufactured by Sankyoki Gosei Co., Ltd.), 0.5 parts by weight of stearic acid, 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 Table 2 were mixed at 120 ° C. with a Henschel mixer, cooled to 40 ° C., and chlorinated. A vinyl resin composition was obtained.

The above chlorinated vinyl chloride resin composition was treated with 50
It was extruded using a mm-direction biaxial extruder to obtain a plate-like molded body. The die has a slit die (slit interval 2 mm, width 20 mm) having a compression part and a pressure release part so that the stability (plate-out property) of long-term molding processing can be promoted and evaluated.
Was used. Further, the resin temperature was set at 210 to 215 ° C.

Next, the mold was set to a diameter of 20 mm and a thickness of 3.0.
The tubular body was molded under the same conditions as described above, instead of those capable of molding a tubular body of mm.

The following evaluation was performed on the plate-like and tubular molded products obtained in the above Examples and Comparative Examples, and the results are shown in Tables 2 and 3. (1) Long-term moldability (evaluation by plate-like molded body) Immediately after 5 hours of continuous extrusion molding, the mold was dismantled and the adhered matter on the mold surface was visually observed. A sample having no deposit was evaluated as な い, a sample (b) slightly adhering to an easily adhering portion such as a corner portion was evaluated as Δ, and a sample (C) having a large amount of adhering substance was evaluated as ×.

(2) Moldability (Evaluation by Tubular Molded Body) The appearance of the outer and inner surfaces of the tubular molded body was 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.

(3) Evaluation of Impact on Falling Weight (Evaluation Using Tubular Molded Body) According to JIS-7221, a sample was conditioned at 0 ° C. for 2 hours, and then tested with a weight of 3 kg.

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

The thermoplastic resin composition according to claim 1 is
With the above-described configuration, molding by a normal molding machine is possible, and there is little adherence to the mold even when molding continuously for a long time,
The composition exhibits excellent stability in long-term molding, and a molded article obtained from the composition has a good appearance and excellent physical properties.

When the thermoplastic resin according to the first aspect is a vinyl chloride resin or a chlorinated vinyl chloride resin, the above effects are further exhibited.

An extruded product obtained by extruding the composition of the present invention has a good appearance and excellent physical properties.

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Claims (3)

[Claims] (1) 100 parts by weight of a thermoplastic resin and 0.1 parts of a coloring agent.
A thermoplastic resin composition comprising from 01 to 2 parts by weight,
The colorant is (a) a silicone oil 1 as a dispersant.
10 to 10% by weight, 9 to 70% by weight of zeolite and 90 to 20% by weight of a pigment component, or (b) 10 to 80% by weight of phthalic anhydride as a dispersant and 90 to 20% by weight of a pigment component % Of a thermoplastic resin composition. 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is a vinyl chloride resin or a chlorinated vinyl chloride resin having a chlorine content of more than 56.8% by weight and less than 71% by weight. . 3. An extruded product obtained by extruding the thermoplastic resin composition according to claim 1 or 2.