JP2013133376A - Thermoplastic resin and molded product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in cold resistance, low-temperature flexibility, moldability and the like, and suitably usable for an automobile window molding or the like, and an automobile window molding including the same.SOLUTION: The thermoplastic resin composition contains, based on 100 pts.wt. of a chlorine-based resin component (A) including 35-90 wt.% of chlorinated polyethylene resin (A-1) and 10-65 wt.% of vinyl chloride resin (A-2), 25-75 pts.wt. of a polyester elastomer (B), and 45-110 pts.wt. of a plasticizer (C).

Description

  The present invention relates to a thermoplastic resin composition, a molded product thereof, and an automobile wind molding using the thermoplastic resin composition. More specifically, the present invention is a relatively low hardness material used for automobile wind moldings, etc., which has excellent cold resistance and low temperature flexibility, and the gloss of the surface of the molded product without impairing the inherent moldability of the chlorinated resin. The present invention relates to a thermoplastic resin composition capable of setting a wide range (from glossy to non-glossy), a molded article thereof, and an automobile wind molding using the thermoplastic resin composition.

  Conventionally, various materials have been studied as a molding material installed around a window glass for a vehicle. Among them, vinyl chloride resin has been widely used for the same purpose because of its ease of molding, adhesion to other resins, high degree of freedom in setting hardness, and ease of design control such as surface gloss. It was.

  However, with the conventional vinyl chloride resin composition, when used as a molding material installed on a window glass that cannot be opened and closed, such as an automobile, especially when the automobile is running, especially when the automobile is running at low temperatures such as in winter. In addition, abnormal noises such as wind noises and squeak noises are often generated from this part, which hinders comfort in the vehicle. In other words, the vinyl chloride resin has the excellent performance as described above, but it is easy to cure in a low temperature region, and the flexibility and impact strength are reduced. was there.

  As a method for improving the cold resistance of a vinyl chloride resin, it is generally known that fatty acid esters are used as plasticizers. However, this method may reduce heat resistance and bleed resistance in terms of performance, Although the low temperature impact resistance is improved, the low temperature flexibility is not greatly improved, and there are problems such as high cost in terms of economy.

  As a method for solving such a problem, a polymer composition using a chlorinated ethylene cross-linked alloy is used from the viewpoint that it is excellent in rubber elasticity and low-temperature flexibility and can be coextruded with soft polyvinyl chloride. These are proposed in Patent Document 1 and Patent Document 2. However, these compositions are inferior in molding processability compared to conventional vinyl chloride resins, and there is a problem that the cost is high in terms of economy.

  On the other hand, for the purpose of improving the cold resistance and low temperature flexibility of vinyl chloride resins, attempts have been made to blend polyester elastomers having good compatibility with vinyl chloride resins. However, since polyester-based elastomers have a high affinity for metals at the time of melting, when mixing polyester-based elastomers with vinyl chloride resin, when using a conventional heating kneader, such as a mill roll, a pressure kneader, a Banbury mixer, etc. Since the melted polyester-based elastomer adheres to or adheres to these apparatuses, there is a problem that there is a limit to the amount to be kneaded at low temperature and the amount to be added during processing.

  As an improvement, Patent Document 3 proposes a method of using a chlorinated polyethylene having good low-temperature characteristics and good compatibility with a vinyl chloride resin in the same manner as a polyester elastomer.

Japanese Patent Laid-Open No. 07-109390 JP 09-176409 A Japanese Patent Laid-Open No. 08-104788

  However, as a result of detailed examination by the present inventor, when an attempt is made as it is with the blending ratio described in Patent Document 3, in a blending composition region having a low hardness such as that used in a vehicle wind molding, chlorine is formed during molding. The difference in melting characteristics (melting start temperature and melt viscosity) between the polyester resin and the polyester elastomer is large, so sufficient kneadability cannot be obtained, the moldability is lowered, and the ratio of the polyester elastomer is small enough Problems such as inability to obtain excellent low-temperature characteristics have been found.

  The object of the present invention is to solve the above-mentioned problems in the prior art, and to balance the low temperature characteristics such as cold resistance and low temperature flexibility and molding processability even in a relatively low blending composition region used for automobile wind molding and the like. An object of the present invention is to provide an excellent thermoplastic resin composition, and a molded article and an automobile wind molding comprising the same.

As a result of intensive studies in view of the above problems, the present inventors have found that a thermoplastic resin composition containing a chlorine-based resin component, a polyester-based elastomer and a plasticizer composed of a vinyl chloride resin and a chlorinated polyethylene resin in a specific blending ratio is as described above. I found out that the problem was solved.
That is, the gist of the present invention resides in the following [1] to [6].

[1] Polyester elastomer with respect to 100 parts by weight of chlorinated resin component (A) comprising 35 to 90% by weight of chlorinated polyethylene resin (A-1) and 10 to 65% by weight of vinyl chloride resin (A-2) (B) A thermoplastic resin composition containing 25 to 75 parts by weight and a plasticizer (C) 45 to 110 parts by weight.

[2] The thermoplastic resin composition according to [1], wherein the polyester elastomer (B) has a hard segment made of polybutylene terephthalate and a soft segment made of polyoxytetramethylene glycol.

[3] The plasticizer (C) is a group consisting of a phthalate ester plasticizer, an aliphatic dibasic ester plasticizer, a trimellitic ester plasticizer, an epoxy plasticizer, and a polyester polymer plasticizer. The thermoplastic resin composition according to [1] or [2], which is at least one selected from the above.

[4] A molded product obtained by molding the thermoplastic resin composition according to any one of [1] to [3].

[5] A molded product obtained by extrusion molding the thermoplastic resin composition according to any one of [1] to [4].

[6]
An automobile wind molding comprising the thermoplastic resin composition according to any one of [1] to [4].

According to the present invention, it is possible to provide a thermoplastic resin composition which is excellent in cold resistance and has low-temperature flexibility and molding processability even with a material having a low hardness.
Since the thermoplastic resin composition of the present invention is excellent in the above-mentioned properties, it is particularly suitable for automobile wind moldings, and can be suitably used for extruded products in the field of electric wires and building materials.

Hereinafter, the present invention will be described in detail. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description unless it exceeds the gist.
In the present specification, when the expression “to” is used, it is used as an expression including numerical values or physical property values before and after the expression.

1. Thermoplastic Resin Composition The thermoplastic resin composition of the present invention is a chlorinated resin component comprising 35 to 90% by weight of chlorinated polyethylene resin (A-1) and 10 to 65% by weight of vinyl chloride resin (A-2). (A) It is characterized by including 25-75 weight part of polyester-type elastomer (B) and 45-110 weight part of plasticizers (C) with respect to 100 weight part.

  The hardness of the thermoplastic resin composition of the present invention is preferably 30 to 90, more preferably 50 to 80 in terms of hardness measurement (Duro-A) based on JIS K6253.

  The thermoplastic resin composition of the present invention is excellent in cold resistance. In the present invention, the cold resistance can be evaluated based on JIS K7261, based on a 50% impact embrittlement temperature at a low temperature using a low temperature embrittlement tester. The 50% impact embrittlement temperature based on JIS K7261 is evaluated as being excellent in cold resistance as the value is lower, and is preferably −50 ° C. or lower, more preferably −55 ° C. or lower.

2. Chlorine-based resin component (A)
1-1. Chlorinated polyethylene resin (A-1)
The chlorinated polyethylene resin (A-1) contained in the thermoplastic resin composition of the present invention includes high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), and branched low-density polyethylene (LDPE) as raw polyethylene. It can be obtained by chlorinating ethylene homopolymers such as ethylene copolymers obtained by copolymerizing one or more monomers copolymerizable with ethylene. In addition, the method of this chlorination is not limited, A conventionally well-known method can be used.

  Among the raw material polyethylene, as the ethylene copolymer, for example, a copolymer of ethylene and an α-olefin other than ethylene (hereinafter, ethylene-α-olefin copolymer); an ethylene-vinyl acetate copolymer; an ethylene- Examples thereof include ethylene- (meth) acrylic acid ester copolymers such as ethyl acrylate copolymer and ethylene-butyl acrylate copolymer (here, (meth) acrylic acid means acrylic acid and / or methacrylic acid). Means acid). The α-olefin used in the ethylene-α-olefin copolymer is preferably an α-olefin having 3 to 20 carbon atoms. Specific examples include propylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-butene, 1-pentene and the like.

  In these ethylene copolymers, the proportion of monomers other than ethylene is preferably 15% by weight or less, particularly preferably 5% by weight or less in the constituent components of the ethylene copolymer.

  When the weight average molecular weight of the raw material polyethylene of the chlorinated polyethylene resin (A-1) is less than 100,000, not only the mechanical properties of the resulting thermoplastic resin composition are lowered, but also a polyester elastomer metal roll, etc. On the other hand, when it exceeds 500,000, the dispersibility in the vinyl chloride resin (A-2) decreases during blending, and the surface of the resulting molded product has a poor appearance. Tend to be. For this reason, as a weight average molecular weight of raw material polyethylene, 100-500,000, especially 150,000-400,000 are suitable.

  The chlorine content of the chlorinated polyethylene resin (A-1) is preferably 20 to 50% by weight, particularly preferably 25 to 40% by weight. When the chlorine content of the chlorinated polyethylene resin (A-1) is at least the above lower limit, the affinity with the plasticizer (C) is improved, and plasticizer bleeding tends to be difficult to occur. On the other hand, it is preferable that the chlorine content is not more than the above upper limit value because the low temperature characteristics are improved and the embrittlement temperature tends to be high.

  The chlorinated polyethylene resin (A-1) preferably has a heat of crystal fusion measured by a DSC (Differential Scanning Calorimeter) method of 20 cal / g or less, more preferably 15 cal / g or less. It is preferable for the heat of crystal fusion to be not more than the above upper limit value because the dispersibility of the vinyl chloride resin (A-2) tends to be improved.

  The chlorinated polyethylene resin (A-1) used in the present invention also suppresses the plasticizer bleed by improving the affinity with the plasticizer (C), and further enhances the effect of improving the low temperature characteristics. The oil absorption of di-2-ethylhexyl phthalate (DOP) measured according to K5101 is preferably 25 ml or more. The DOP oil absorption amount is agitated while adding DOP little by little to 100 g of chlorinated polyethylene resin (A-1) powder under a temperature condition of 23 ° C., and the chlorinated polyethylene resin (A-1) powder is formed into a dumpling lump. The amount of DOP oil absorption is 25 ml or more, which means that even if DOP 25 ml is added, it does not become a lump even if it is added or is in the form of a powder, or appears to be solid. It means something that is dispersed by force and impact.

1-2. Vinyl chloride resin (A-2)
As the vinyl chloride resin (A-2) contained in the thermoplastic resin composition of the present invention, a suspension polymerization method, a bulk polymerization method, or a mixture of vinyl chloride or a mixture of vinyl chloride and a monomer copolymerizable therewith is used. In addition, a polymer or copolymer produced by a usual method such as a fine suspension polymerization method or an emulsion polymerization method may be arbitrarily selected and used.

  Examples of the monomer include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate; acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylic acid esters such as methyl methacrylate and ethyl methacrylate. Maleic acid esters such as dibutyl maleate and diethyl maleate; fumaric acid esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; acrylonitrile, methacrylonitrile Vinyl cyanides such as ethylene; propylene, styrene and other α-olefins; vinylidene halides and vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide; Diallyl phthalate, although polyfunctional monomers such as ethylene glycol dimethacrylate, a monomer used is not limited to those described above. These monomers may be used individually by 1 type, and may use 2 or more types together. When the above monomer is used for the production of the vinyl chloride resin (A-2), the monomer is used in a constituent component of the vinyl chloride resin (A-2) in a range of 30% by weight or less. It is preferable to use it in a range of 20% by weight or less. The vinyl chloride resin (A-2) includes chlorinated polyvinyl chloride after post-chlorination of the product produced by the above-described method, and is crosslinked by adding a cross-linking agent during polymerization (hereinafter referred to as THF). And a crosslinked vinyl chloride resin containing an insoluble crosslinked gel component.

  The average degree of polymerization of the vinyl chloride resin (A-2) is preferably in the range of 700 to 3800, more preferably 1300, based on JIS K6721 from the workability, moldability and physical properties. It is in the range of 3000. When the average degree of polymerization is not less than the above lower limit, the physical properties of the obtained chlorinated thermoplastic resin composition tend to be better, and when it is less than the above upper limit, workability and moldability tend to be better. Because it is.

  In the present invention, for the purpose of controlling the design surface of the molded product, as the vinyl chloride resin (A-2), a crosslinked vinyl chloride resin containing the aforementioned crosslinked gel component can be used. When the crosslinked vinyl chloride resin contains a THF-insoluble crosslinked gel content, the crosslinked gel content is desirably 60% by weight or less, preferably 50% by weight or less, and the average degree of polymerization of the portion dissolved in THF is as described above. It is desirable to be in range. In addition, the cross-linked vinyl chloride resin may be used as it is for the cross-linked gel, or a product exceeding the above-mentioned gel content is produced, and this is appropriately blended with a vinyl chloride resin to contain the cross-linked gel content. May be adjusted. If the cross-linked gel content exceeds the upper limit, mechanical properties such as tensile strength tend to decrease. In the present invention, the THF-insoluble crosslinked gel component is charged with 2 g of vinyl chloride resin in 30 ml of THF while stirring and left at a temperature of 25 ° C. for 24 hours. Thereafter, the mixture is filtered using Teflon (registered trademark) filter paper (mesh size: 1 μm), and this operation is repeated three times.

  In addition, when an uncrosslinked vinyl chloride resin is used as the vinyl chloride resin (A-2), a molded article having a glossy appearance can be obtained. Further, when a cross-linked vinyl chloride resin is used as the vinyl chloride resin (A-2), a molded article having a dull appearance can be obtained. These may be appropriately selected and used according to the application to which the thermoplastic resin composition of the present invention is applied.

1-3. Mixing ratio of chlorinated polyethylene resin (A-1) and vinyl chloride resin (A-2) In the thermoplastic resin composition of the present invention, the chlorinated resin component (A) is chlorinated polyethylene resin (A-1) 35. And 90% by weight and 10 to 65% by weight of vinyl chloride resin (A-2) (100% by weight in total of chlorinated polyethylene resin (A-1) and vinyl chloride resin (A-2)).

  When the chlorine-based resin component (A) contains the vinyl chloride resin (A-2), the moldability and scratchability are not impaired, and the design is easily controlled. However, when there is too much vinyl chloride resin (A-2), the melt viscosity increase effect by containing chlorinated polyethylene resin (A-1) is not acquired, and the sufficient dispersion and kneading | mixing effect tends to worsen at the time of kneading | mixing. It is in. For this reason, from the viewpoint of workability, the chlorinated polyethylene resin (A-1) is preferably 60 to 90% by weight and the vinyl chloride resin (A-2) is 10 to 40% by weight.

2. Polyester elastomer (B)
The thermoplastic polyester elastomer used in the thermoplastic resin composition of the present invention has a high melting point polyester segment (hereinafter sometimes referred to as a hard segment) and a low melting point polymer segment (hereinafter sometimes referred to as a soft segment). Is a block copolymer having a crystalline melting point of usually 80 ° C. or higher. The polyester elastomer (B) can be polymerized by a known method using the following hard segment constituents and soft segment constituents as raw materials.

  The hard segment preferably has a melting point of 150 ° C. or higher when a high polymer is formed with only its constituent components. Polyesters constituting such a hard segment are, for example, terephthalic acid, isophthalic acid, 1,5 -Aromatic dicarboxylic acid residues such as naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, 4,4-sulfonyldibenzoic acid And polyesters comprising ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, 2,2-dimethyltrimethylene glycol, hexamethylene glycol, decamethylene glycol, p-xylene glycol, cyclohexanedimethanol, A copolyester obtained by reacting two or more of each of these dicarboxylic acids and diols, a polyester derived from oxyacids such as p- (β-hydroxyethoxy) benzoic acid and p-oxybenzoic acid, and residues thereof, Polyester such as polylactone such as polypivalolactone, a residue of an aromatic ether dicarboxylic acid such as 1,4-bis (4,4′-dicarboxydiphenoxy) ethane and the aforementioned diol residue, and more Examples thereof include copolymer polyesters containing the aforementioned dicarboxylic acid, oxyacid, diol and the like in an arbitrary composition ratio. In the present invention, a polyester comprising an aromatic dicarboxylic acid and an aliphatic diol is desirable as the hard segment, and polybutylene terephthalate is particularly preferable.

  One component constituting the polyester elastomer, the soft segment, shows a substantially amorphous state at normal temperature in the polyester elastomer, and the melting point or softening point when measured only with the segment constituent component is usually The number average molecular weight is suitably in the range of 400 to 6000. Typical soft segment constituents include, for example, polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, or mixtures thereof; and further copolymerization of two or more of alkylene oxides. Copolymerized polyoxyalkylene glycols comprising an aliphatic or alicyclic glycol having 2 to 10 carbon atoms and an aliphatic or alicyclic dicarboxylic acid having 2 to 12 carbon atoms, such as polyethylene adipate and polytetramethylene Polyester glycols such as adipate, polyethylene sebacate, polyneopentyl sebacate, polytetramethylene dodecanate, polytetramethylene azelate, polyhexamethylene azelate; ring-opening polymerization of poly-ε-caprolactone, etc. Aliphatic polyester glycol terminated with a hydroxyl group; Polyester glycol consisting of the above polyoxyalkylene glycols and dibasic acid; Two or more of aliphatic or alicyclic dicarboxylic acids and aliphatic or alicyclic glycol or polyoxyalkylene Examples thereof include copolymer polyester glycols obtained by using two or more kinds of glycols. Among these soft segments, in the present invention, polyoxytetramethylene glycol and poly-ε-caprolactone are preferable, and polyoxytetramethylene glycol is particularly preferable.

The polyester elastomer (B) preferably has a crystal melting point of 200 ° C. or lower, more preferably in the range of 120 ° C. to 190 ° C.
If the crystalline melting point of the polyester elastomer (B) is excessively low, the polyester elastomer (B) tends to be softened by heat. On the other hand, if it exceeds 200 ° C., it is necessary to increase the kneading temperature during production of the composition. It becomes easy to disassemble. Further, when a polyester elastomer having a high crystalline melting point is kneaded at a low temperature, the physical properties as a thermoplastic resin are not sufficiently exhibited, and an unmelted product appears as a foreign substance on the surface of the molded product at the time of molding, which causes a problem in appearance. The crystal melting point is a temperature showing the highest peak among all the crystal peaks of the DSC chart measured by DSC at a heating rate of 10 ° C./min.

The apparent melt viscosity (hereinafter simply referred to as “melt viscosity”) at a shear rate of 1200 sec ⁻¹ at a temperature of 200 ° C. is preferably 50 to 500 Pa · s, more preferably 100 to 400 Pa · s. When the melt viscosity is equal to or higher than the lower limit, workability is improved because it is difficult to adhere to the metal surface of the processing machine during kneading. On the other hand, when the melt viscosity is equal to or lower than the upper limit, the chlorine-based resin component (A ) And the viscosity difference tends to be small, and thus tends to facilitate uniform dispersion.

  The content of the polyester elastomer (B) in the thermoplastic resin composition of the present invention is 25 to 75 parts by weight, preferably 30 to 70 parts by weight, more preferably 100 parts by weight of the chlorine resin component (A). 40 to 60 parts by weight. When the content of the polyester elastomer (B) is not less than the above lower limit, the effect of improving cold resistance and low temperature flexibility due to the blending of the polyester elastomer can be obtained. When the content of the polyester elastomer (B) is not more than the above upper limit, the difference in melt viscosity from the chlorine resin component (A) is reduced during processing, so that the polyester elastomer can be sufficiently kneaded and the polyester elastomer remains undissolved. Since it becomes difficult, a foreign material etc. become difficult to produce at the time of shaping | molding.

3. Plasticizer (C)
The plasticizer (C) is a component that imparts flexibility to the thermoplastic resin composition. As the plasticizer (C), one or two or more plasticizers may be arbitrarily selected from the known plasticizers exemplified below and used.

  For example, the plasticizer (C) that can be used is di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), or Phthalate plasticizers such as phthalates of higher alcohols or mixed alcohols having about 10 to 13 carbon atoms; di-2-ethylhexyl adipate, di-n-octyl adipate, di-n-decyl adipate, diisodecyl adipate, Aliphatic dibasic acid ester plasticizers such as di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate; tri-2-ethylhexyl trimellitate (TOTM), tri-n-octyl trimellitate Tate, Tridecyl Trimelli , Triisodecyl trimellitate, di-n-octyl-n-decyl trimellrate and other trimellitic acid ester plasticizers; tributyl phosphate, tricresyl phosphate (TCP), triphenyl phosphate, trixylyl phosphate , Trioctyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2,3-dibromo Propyl) phosphate, tris (bromochloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, bis (chloropropyl) monooctyl Phosphate ester plasticizers such as phosphate; Biphenyltetracarboxylic acid tetraalkyl ester plasticizers such as 2,3,3 ′, 4′-biphenyltetracarboxylic acid tetraheptyl ester; Polyester polymer plasticizers; Large epoxidation There may be mentioned epoxy plasticizers such as bean oil, epoxidized linseed oil, epoxidized cottonseed oil and liquid epoxy resin; chlorinated paraffins; chlorinated fatty acid esters such as pentachlorostearic acid alkyl ester and the like.

  From the viewpoint of good compatibility with the vinyl chloride resin, it is preferable to use a plasticizer having a polar group, more preferably a phthalate ester plasticizer, an aliphatic dibasic ester plasticizer, or trimellitic acid ester. Plasticizers, epoxy plasticizers, and polyester polymer plasticizers are preferable because they have good plasticization efficiency and bleed resistance.

  The content of the plasticizer (C) in the thermoplastic resin composition of the present invention is in the range of 45 to 110 parts by weight with respect to 100 parts by weight of the chlorine-based resin component (A). When the content of the plasticizer (C) is 45 parts by weight or more, when the obtained molded body is used in an automobile molding or the like, a sufficient sealing effect as a sealing material can be obtained, and 110 parts by weight If it is below, the difference in melting characteristics between the softened chlorine-based resin component (A) and the polyester-based elastomer (B) becomes small, and it becomes easy to knead. In order to further enhance these effects, the content of the plasticizer (C) is desirably 50 to 90 parts by weight, more preferably 60 to 80 parts by weight with respect to 100 parts by weight of the chlorine-based resin component (A). It is.

4). Other additives The thermoplastic resin composition of the present invention includes, in addition to the essential components described above, a stabilizer, a lubricant, an antioxidant, an ultraviolet absorber, a flame retardant, an antistatic agent, a colorant, a foaming agent, and an impact. Various additives such as an improving agent, thermoplastic resins other than the chlorine-based resin component (A) and the polyester-based elastomer (B) can be blended as necessary as long as the effects of the present invention are not significantly impaired.

Stabilizers include inorganic salts such as tribasic lead sulfate, lead silicate, and basic lead carbonate, metal soaps mainly composed of organic acid salts of metals such as lead, cadmium, barium calcium, and zinc, and at least 2 metals. Including seeds, for example, Ba-Zn, Ca-Zn, Cd-Ba and other fatty acid complexes, fatty acid (phosphite) -based, carboxylate (phosphite) -based composite metal soap or composite liquid metal soap, organotin-based Although 1 type, or 2 or more types, such as a compound, is mentioned, it is not limited to these.
When a stabilizer is blended in the thermoplastic resin composition of the present invention, the blending amount of the stabilizer is 0.1 to 30 parts by weight, particularly 1 to 15 parts by weight, based on 100 parts by weight of the chlorine-based resin component (A). It is preferable that

As the flame retardant, one or more of antimony trioxide, barium borate, zinc borate, zinc oxide, chlorinated polyethylene, and other halogen flame retardants are used.
When mix | blending a flame retardant with the thermoplastic resin composition of this invention, the compounding quantity of a flame retardant shall be 1-30 weight part with respect to 100 weight part of chlorinated resin components (A), especially 1-15 weight part. It is preferable.

  Furthermore, a filler can be added to the chlorinated thermoplastic resin composition of the present invention. In addition to ensuring the rigidity of the resin member, the addition of a filler contributes to the capture of volatile components generated from the material and the cost reduction of the material itself. Examples of the filler include, but are not limited to, carbon black, calcium carbonate, titanium oxide, talc, aluminum hydroxide, magnesium hydroxide, hydrotalcite, clay, silica, and white carbon. These fillers may be used alone or in combination of two or more.

  When a filler is blended in the thermoplastic resin composition of the present invention, the blending amount of the filler is 1 to 100 parts by weight, particularly 5 to 50 parts by weight, per 100 parts by weight of the chlorine-based resin component (A). It is preferable. When the blending amount of the filler is too small, the above-described addition effect tends to be unable to be obtained, and when it is too large, mechanical properties and moldability tend to be impaired.

5. Method for Producing Thermoplastic Resin Composition The chlorine-based thermoplastic resin composition of the present invention comprises a chlorine-based resin component (A) comprising a chlorinated polyethylene resin (A-1) and a vinyl chloride-based resin (A-2), A polyester elastomer (B), a plasticizer (C), and other various additives are charged into a predetermined kneader or mixer, and a temperature range in which the vinyl chloride resin (A-1) does not deteriorate, for example, 100 to It can be easily prepared by mixing or kneading uniformly while heating to a temperature of 230 ° C., preferably 130 to 200 ° C. The chlorine-based resin component (A) is prepared by mixing a chlorinated polyethylene resin (A-1) and a vinyl chloride-based resin (A-2) in advance to obtain a polyester-based elastomer (B) and a plasticizer (C ) And other various additives, or all the components may be mixed at one time. The mixer or kneader used for mixing or kneading the above-described blending components is not particularly limited as long as it is a device capable of substantially uniformly blending and kneading the blend. Examples of the mixer include a Henschel mixer, a ribbon blender, and a planetary mixer. Examples of the kneader include a single screw extruder, a twin screw extruder, a mill roll, a Banbury mixer, a kneader, and an intensive mixer. And those that can be kneaded under shear force.

6). Applications The thermoplastic resin composition of the present invention can be molded by various typical molding methods such as extrusion molding and injection molding, and can be particularly preferably formed into a thermoplastic resin molded body by extrusion molding. There are no particular restrictions on the extrusion molding conditions, but a molding temperature of 130 to 220 ° C. is appropriate. If the temperature is lower than the above lower limit value, the resin cannot be sufficiently melted and the design and moldability are poor. Tend to be. On the other hand, when it is higher than the above upper limit value, the chlorine-based resin component tends to be easily decomposed.

  Since this molded body is excellent in cold resistance, low temperature flexibility, etc. even in a relatively low blending composition region, it can be suitably used in various industrial fields. It can be suitably used as automotive exterior materials such as side moldings, automotive interior materials such as knobs and grips, building materials such as packings, sealing materials and gaskets, and wire covering materials, and is particularly suitable for automotive wind moldings. As described above in “1-2. Vinyl chloride resin (A-2)”, when vinyl chloride resin is used as vinyl chloride resin (A-2), a molded article having a glossy appearance is obtained. And is particularly suitable for use in automobile exterior materials that need to be in harmony with the glossy metal coating surface, and when a cross-linked vinyl chloride resin is used as the vinyl chloride resin (A-2), the matte appearance This is particularly suitable for use in automobile interior materials that require a high-class feeling.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example at all. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

  In the following Examples and Comparative Examples, the raw materials used for the production of the thermoplastic resin composition and the evaluation methods of the obtained thermoplastic resin composition are as follows.

[Raw materials]
<Chlorine-based resin component (A)>
Chlorinated polyethylene resin (A-1)
(A-1): Chlorine produced by Showa Denko Co., Ltd., chlorinated raw material polyethylene having a weight average molecular weight of 350,000
Polyethylene,
Chlorine content: 30% by weight
Heat of crystal melting: 7 cal / g
DOP oil absorption: 28ml
Vinyl chloride resin (A-2)
(A-2a): Shin-Etsu Chemical Co., Ltd., vinyl chloride resin,
Average degree of polymerization: 2500
(A-2b): Shin-Etsu Chemical Co., Ltd., crosslinked vinyl chloride resin containing a crosslinked gel component,
Average degree of polymerization: 2400
Gel content: 20 (% by weight)

<Polyester elastomer (B)>
(B): Polyester elastomer (manufactured by LG CHEM) obtained by copolycondensation of polybutylene terephthalate prepolymer (hard segment) and polytetramethylene glycol (soft segment)
Crystal melting point: 165 ° C
Melt viscosity: 200 Pa · s (apparent melt viscosity at a shear rate of 1200 sec ⁻¹ at 200 ° C.)

<Plasticizer (C)>
(C): Diisononyl phthalate (DINP manufactured by Jay Plus)

[Evaluation method]
1) Hardness Hardness measurement (Duro-A) was carried out based on JIS K6253, and the value 10 seconds after contact was measured.

2) Workability The compounding ingredients were put into a Banbury mixer as a kneading machine, and after reaching the discharge temperature (168 ° C.), the discharge state was observed and evaluated according to the following criteria.
○: Drained well without adhesion to the Banbury mixer △: Slightly adhered to the inner wall and rotor of the Banbury mixer, but most could be discharged well ×: Large amount adhered to the inner wall and rotor of the Banbury mixer The discharge is extremely difficult

3) Cold resistance Based on JIS K7261, the 50% impact embrittlement temperature at low temperature was measured using a low temperature embrittlement tester.

4) Low temperature flexibility Based on JIS K6261, the low temperature torsion test was implemented, the change of the torsion modulus in -55 degreeC-25 degreeC was measured, and the following reference | standard evaluated.
○: Torsional modulus hardly changes in the range of −30 ° C. to 25 ° C. Δ: Torsional modulus slightly changes in the range of −30 ° C. to 25 ° C. ×: Torsional modulus changes remarkably in the entire measurement region.

5) Extrusion appearance After the pellets are dried by heating (90 ° C x 1 hour), they are formed into a 2.5cm x 1mm belt at a die temperature of 160 ° C using a 40φ extruder (a full flight screw is used as the screw). did. After molding, the belt appearance was observed and evaluated according to the following criteria.
○: Smooth with no foreign matter, etc. Δ: No foreign matter, but wavy and poor in appearance x: Innumerable foreign matter derived from polyester elastomer

[Examples 1-8, Comparative Examples 1-9]
Among the blending raw materials shown in Table-1 and Table-2, components other than the polyester-based elastomer (B) were charged into a Henschel mixer at the blending amounts described in Table-1, stirred and discharged until 110 ° C. Polyester elastomer (B) was added to the discharged mixture in the blending amounts described in Tables 1 and 2, kneaded with a Banbury mixer, and discharged when it reached 168 ° C. The state of discharge was evaluated and processability was evaluated.
For test samples of hardness, cold resistance and low temperature flexibility, this composition was formed into a sheet with a mill roll at 150 ° C., and this sheet was molded with a press molding machine at a molding temperature of 180 ° C. and a molding pressure of 200 kg / cm ² . An evaluation sheet was prepared.
Moreover, about the pellet used for an extrusion external appearance test, after Banbury mixer kneading | mixing, the strand extruded using the twin-screw extruder was pelletized with the cutter, and was prepared.
Each evaluation result is shown in Table-1 and Table-2.

[Discussion]
As shown in Table-1 and Table-2, the thermoplastic resin compositions of Examples 1-8 are excellent in cold resistance and low temperature flexibility in a low hardness region (hardness 55-75) applicable to automobile wind molding materials. The thermoplastic resin composition was excellent in the balance between processability and extrusion appearance of the chlorine-based resin.

  In Comparative Examples 1 to 3, the compounding amounts described in Patent Document 3 are studied. In any case, the amount of the plasticizer is small, so that the hardness is high, and the amount of the polyester-based elastomer (B) is small. There was a problem that the flexibility was not sufficient, and if the amount added was too large, there was a problem in workability.

  In Comparative Example 4, only chlorinated polyethylene (A-1) was used as the chlorinated resin component (A), but because of its high viscosity, there was a problem that the extrusion appearance was poor and the scratchability was reduced.

In Comparative Example 5, the chlorinated polyethylene resin (A-1) and the polyester elastomer (B) were excluded from the formulation of Example 1, but sufficient low temperature characteristics were not obtained.

  In Comparative Example 6, only the vinyl chloride resin (A-2) is used as the chlorine resin component (A), but since the difference in melt viscosity from the polyester elastomer (B) during processing is large, sufficient kneading dispersion The extrusion appearance was inferior.

  In Comparative Example 7, since the amount of the chlorinated polyethylene resin (A-1) was not sufficient, the processability and moldability were inferior as in Comparative Example 5.

  In Comparative Example 8, since the amount of the polyester-based elastomer (B) was not sufficient, the workability was good, but the low-temperature flexibility was slightly reduced.

  In Comparative Example 9, since the amount of the plasticizer (C) was not sufficient, the hardness was higher than that used for wind molding.

  In addition, since the molded body of Examples 1 to 5, 7 and 8 uses a vinyl chloride resin as the vinyl chloride resin (A-2), it is necessary to harmonize with a metallic coating surface having a glossy appearance and high gloss. It can be seen that it is suitable for use in certain automotive exterior materials. On the other hand, the molded article of Example 6 uses a cross-linked vinyl chloride resin as the vinyl chloride resin (A-2), so that the gloss of the appearance disappears and it is used for automobile interior materials that require a high-class feeling. It turns out that it is suitable.

  The chlorine-based thermoplastic resin of the present invention is excellent in cold resistance, low-temperature flexibility, molding processability, and the like, and therefore can be suitably used in various industrial fields. It can be suitably used as automotive interior materials, automotive interior materials such as knobs and grips, packing materials such as packings, sealing materials and gaskets, and wire covering materials, and is particularly suitable for automotive wind moldings.

Claims (6)

  Polyester elastomer (B) with respect to 100 parts by weight of chlorine resin component (A) consisting of 35 to 90% by weight of chlorinated polyethylene resin (A-1) and 10 to 65% by weight of vinyl chloride resin (A-2) A thermoplastic resin composition containing 25 to 75 parts by weight and 45 to 110 parts by weight of a plasticizer (C).   The thermoplastic resin composition according to claim 1, wherein the polyester-based elastomer (B) has a hard segment made of polybutylene terephthalate and a soft segment made of polyoxytetramethylene glycol.   The plasticizer (C) is selected from the group consisting of phthalate ester plasticizers, aliphatic dibasic ester plasticizers, trimellitic ester plasticizers, epoxy plasticizers, and polyester polymer plasticizers. The thermoplastic resin composition according to claim 1 or 2, wherein there is at least one.   The molded object formed by shape | molding the thermoplastic resin composition of any one of Claims 1 thru | or 3.   The molded object formed by extrusion molding the thermoplastic resin composition of any one of Claims 1 thru | or 4.   An automobile wind molding comprising the thermoplastic resin composition according to any one of claims 1 to 4.