JP2011001540A - Chlorine-containing hydrocarbon resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chlorine-containing hydrocarbon resin composition and a molded article having improved flame retardancy by sufficiently exhibiting excellent properties of materials.SOLUTION: The chlorine-containing hydrocarbon resin composition contains at least one kind of graphite selected from flaky graphite, expanded and crushed graphite and artificial graphite, a chlorine-containing hydrocarbon resin and a (meth)acrylate polymer, wherein the content of the graphite is ≥10 wt.% and ≤80 wt.% based on total weight of the chlorine-containing hydrocarbon resin composition. There is further provided the molded article produced by molding the composition.

Description

  The present invention relates to a chlorine-containing hydrocarbon resin composition and a molded body.

Conventionally, thermoplastic resins including chlorine-containing hydrocarbon resins such as vinyl chloride resins have excellent physical properties such as impact resistance and heat resistance and chemical properties such as solvent resistance and acid resistance. As a material, it is used in many applications such as plant plates, pipes, pipe joints, sheets and films.
However, when it burns, toxic gas and a large amount of black smoke are generated, and in the use of vehicles such as trains, the safety of passengers is impaired in the event of a fire.
As a method for improving the flame retardancy of a thermoplastic resin such as a vinyl chloride resin, for example, a method of adding a flame retardant such as aluminum hydroxide or magnesium hydroxide to a vinyl chloride resin has been proposed (for example, Patent Document 1).
A method of adding graphite to a vinyl chloride resin has been proposed (for example, Patent Document 2).

However, such a chlorine-containing hydrocarbon resin has a low flame-retardant effect, and a material having higher flame retardancy and non-flammability is required.
In particular, Section 5 “Combustion Tests Performed in accordance with Article 83 of the Vehicle Fire Countermeasures, etc. of the Ministerial Ordinance Establishing Technical Standards on Railways (December 25, 2001, Ministry of Land, Infrastructure, Transport and Tourism Ordinance No. 151)” (Hereinafter referred to as vehicle combustion test) In order to exhibit a combustion suppression effect, a large amount of filling is required, so that the physical properties such as impact resistance and secondary workability such as vacuum formability are significantly reduced. Therefore, there is a demand for a resin composition excellent not only in flame retardancy but also in secondary processability.

Japanese Patent Laid-Open No. 5-25347 JP-A-9-227747

  This invention is made | formed in view of the subject of the said prior art, and aims at providing the chlorine containing hydrocarbon resin and the molded object which were excellent in the flame retardance and secondary workability.

The chlorine-containing hydrocarbon resin composition of the present invention is a chlorine-containing hydrocarbon containing at least one graphite selected from scale-like graphite, post-expanded pulverized graphite, and artificial graphite, a chlorine-containing hydrocarbon resin, and a (meth) acrylate polymer. It is a resin composition, Comprising: The said graphite of 10 to 80 weight% is contained with respect to the total weight of this chlorine containing hydrocarbon resin composition, It is characterized by the above-mentioned.
Further, the molded article of the present invention has a thermal conductivity of 0.5 W / m · K or more, and at least one graphite selected from scale-like graphite, expanded and crushed graphite, and artificial graphite, a chlorine-containing hydrocarbon resin, and It is formed from a chlorine-containing hydrocarbon resin composition containing a (meth) acrylate polymer.

  According to the present invention, it is possible to provide a chlorine-containing hydrocarbon resin and a molded article excellent in flame retardancy and secondary processability.

The chlorine-containing hydrocarbon resin composition of the present invention contains at least one graphite selected from scale-like graphite, post-expanded pulverized graphite, and artificial graphite, a chlorine-containing hydrocarbon resin, and a (meth) acrylate polymer. Thus, by combining specific materials, the excellent characteristics of the materials themselves can be sufficiently exhibited, and for example, flame retardancy can be improved as an interior material for a railway vehicle.
In addition, in the case of interior material use, printing processing is performed on the surface layer surface or a decorative layer may be provided, but the chlorine-containing hydrocarbon resin composition is also subjected to these treatments, Excellent processing characteristics can be exhibited.

(graphite)
The graphite in the present invention preferably contains at least one of at least scale-like graphite, post-expanded pulverized graphite, and artificial graphite, and may contain two or all in combination. Moreover, not only these graphites but conventionally well-known graphite may be contained. As such graphite, both natural and artificial graphite (natural graphite, quiche graphite, etc.) can be used. For example, scaly graphite, scaly graphite, scaly (lumpy) graphite, earthy graphite, expanded graphite And expanded graphite, expanded graphite, pyrolytic graphite, and the like. Any of these graphites that have been refined, dried, fired, pulverized and / or classified can be used.

(Scale graphite)
Scaly graphite is a kind of naturally produced graphite and is conventionally known, and is not particularly limited, and any graphite can be used. Scalar graphite is preferable because the aspect ratio of the particles is large, heat is easily released in the plane direction rather than the thickness direction, and the flame retardancy of the interior material is improved. The scaly graphite includes scaly graphite and exfoliated graphite having a larger aspect ratio. Generally, the aspect ratio of flake graphite is about 30, and the aspect ratio of exfoliated graphite is about 100.

(Pulverized graphite after expansion)
Expanded graphite is a conventionally known one and is not particularly limited, and is usually produced by chemically treating graphite. For example, natural scale-like graphite, pyrolytic graphite, quiche graphite and other powders such as concentrated sulfuric acid, nitric acid, selenic acid and other inorganic acids and concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, Examples include crystalline compounds that maintain a carbon layer structure obtained by inserting an inorganic acid between graphite layers using a strong oxidizing agent such as hydrogen peroxide and performing acid treatment.
The expanded graphite is obtained by expanding the expanded graphite. The method for expanding is not particularly limited, and examples thereof include a method in which a heat treatment is performed for several minutes to several hours in a furnace at a temperature of several hundred degrees to several thousand degrees, and the like.
The expanded graphite after pulverization is obtained by pulverizing the expanded graphite, and the pulverization treatment is not particularly limited, and can be performed using a conventionally known apparatus such as a rod mill, a ball mill, a jet mill, or the like.

(Artificial graphite)
Artificial graphite is artificially produced by heating a carbon source as a raw material at a high temperature, and any graphite can be used as long as it is conventionally known. For example, it includes those prepared by pulverizing an artificial graphite electrode produced by heat-treating a binder such as coke and coal tar at a high temperature of 2000 ° C. or higher.

  Regardless of the type, the average particle size of graphite used in the present invention is preferably about 500 μm or less, more preferably about 300 μm, in consideration of dispersibility and / or physical properties with chlorine-containing hydrocarbon resins. The following is preferable. In addition, considering the thermal conductivity, the larger the particle size of graphite, the higher the probability of contact between graphite (the probability of contact with a material such as a thermoplastic resin with low thermal conductivity decreases), and the thermal conductivity increases. Therefore, it is preferable. In order to ensure a certain degree of thermal conductivity, it is preferably about 15 μm or more. Further, in order to keep the dispersibility and moldability in the molded article satisfactorily, about 25 μm to 200 μm is more preferable, and about 30 to 100 μm is particularly preferable. If the average particle size is too small, the bulk specific gravity increases, which may cause inconvenience in handling.

  In order to obtain a suitable particle size of graphite, it is preferable to use a conventionally known apparatus such as a rod mill, a ball mill, or a jet mill.

Graphite is preferably added in an amount of 10% by weight or more, and more preferably 20% by weight or more based on the total weight of the chlorine-containing hydrocarbon resin composition. More preferably, it is 40% by weight or more. When the composition is layered and used in a form in which the surface layer is decorated with a laminate such as a polyvinyl chloride laminate, the content is preferably 65% by weight or more. If too much is added, the moldability may be deteriorated, so that it is preferably 80% by weight or less. More preferably, it is 70 weight% or less. Therefore, it is suitable to contain in 10 to 80 weight%, and also 20 to 80 weight%, Preferably, it is 40 to 70 weight%. By setting it as this range, while being able to acquire a suitable thermal conductivity and a flame-retardant effect, the fall of a moldability can be prevented.
In particular, the addition amount of graphite dominates the magnitude of thermal conductivity as will be described later, but it is also affected by the shape as described later, the manufacturing method of a molded body made of a chlorine-containing hydrocarbon resin composition, etc. It is preferable to adjust appropriately within the range of the added amount. Or it is preferable to adjust so that the thermal conductivity mentioned later may be shown. Furthermore, it is more preferable to adjust so that the addition amount mentioned above and the thermal conductivity mentioned later may be shown.

  For example, when the thermal conductivity of the chlorine-containing hydrocarbon resin composition of the present invention is measured by the method described later, graphite is contained in the chlorine-containing hydrocarbon resin composition in a range of 0.5 W / m · K or more. Is suitable. In order to impart higher flame retardancy, such as when used as an interior material for railway vehicles, 1.4 W / m · K or more is preferable, and 3.0 W / m · K or more is more preferable.

  The shape of the graphite is not particularly limited, but when a chlorine-containing hydrocarbon resin composition is used as an interior material for a railway vehicle, by quickly releasing heat from a flame at the time of a fire, from the viewpoint of delaying ignition, A thin plate shape, that is, a large aspect ratio is preferable to a spherical shape. This is because, when the aspect ratio is large, heat is more easily released in the surface direction than in the thickness direction, and the flame retardancy of the interior material is improved. Therefore, when the chlorine-containing hydrocarbon resin composition is used as an interior material for a railway vehicle, it is preferable to align graphite having a long diameter (for example, pyrolytic graphite) along the surface direction of the interior material.

Further, the graphitization degree of the graphite is more preferably higher from the viewpoint of further increasing the thermal conductivity and improving the flame retardancy. For the same purpose, graphite having less impurities is more preferable.
The relative degree of graphitization can be measured, for example, by the following method.
The full width at half maximum (FWHM) of the largest peak appearing in the vicinity of 52 ° to 57 ° by 2θ is measured by X-ray diffraction. The smaller this value, the higher the graphitization degree.
For example, when this half-value width is measured using an X-ray diffractometer manufactured by Bulgar AXS, earth graphite has a large value of 0.47 and artificial graphite has a value of 0.53, and graphitization has not progressed. Scaly graphite is preferable because it has a low degree of graphitization of about 0.23 and a high degree of graphitization, so that the thermal conductivity is increased. In the present invention, the degree of graphitization is not limited, but the above-described half width value is suitably 0.4 or less, preferably 0.35 or less and 0.3 or less.

(Chlorine-containing hydrocarbon resin)
The chlorine-containing hydrocarbon resin is not particularly limited as long as it contains chlorine, that is, a hydrocarbon-based resin in which chlorine atoms are substituted. One or more carbon-carbon double bonds and / or triple bonds The thing including is included. Examples of the hydrocarbon resin include resins that do not contain elements other than chlorine atoms, and preferably linear or branched hydrocarbons. Specific examples include vinyl chloride resins and chlorinated polyolefin resins. Examples of the polyolefin resin include polyethylene and polypropylene, and among them, polyethylene is preferable. You may use these individually or in combination of 2 or more types. That is, a vinyl chloride resin and a chlorinated polyolefin resin may be used in combination.

The above vinyl chloride resin is a vinyl chloride homopolymer, a copolymer of a monomer having an unsaturated bond copolymerizable with a vinyl chloride monomer and a vinyl chloride monomer, and a graft copolymer of a vinyl chloride monomer to a (co) polymer. The graft copolymer etc. which were made are mentioned.
The vinyl chloride resin preferably contains 50% by weight or more of vinyl chloride.
In the present invention, these (co) polymers may be used alone or in combination of two or more. Further, the vinyl chloride resin may be chlorinated as necessary.

  Examples of the monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer include α-olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl acetate and vinyl propionate; butyl vinyl ether, cetyl vinyl ether, and the like. Vinyl ethers of (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and phenyl methacrylate; aromatic vinyls such as styrene and α-methylstyrene; vinylidene chloride, Examples thereof include vinyl halides such as vinylidene fluoride; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. These may be used alone or in combination of two or more.

  The polymer for graft copolymerization of vinyl chloride is not particularly limited as long as it is a (co) polymer capable of graft polymerization of vinyl chloride. For example, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-monooxide Carbon copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, acrylonitrile-butadiene copolymer, polyurethane, chlorine Examples thereof include chlorinated polyethylene and chlorinated polypropylene. These may be used alone or in combination of two or more.

The polymerization method of the vinyl chloride resin is not particularly limited, and any conventionally known polymerization method can be used. Examples thereof include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method.
The method for chlorinating the vinyl chloride resin is not particularly limited, and a conventionally known chlorination method can be used. Examples thereof include a thermal chlorination method and a photochlorination method.

  When the degree of polymerization of the vinyl chloride resin decreases, mechanical properties tend to decrease, and when it increases, moldability tends to deteriorate. Therefore, it is preferably about 400 to 2500, and more preferably about 600 to 1600. .

Chlorinated polyolefins, such as chlorinated polyethylene, are chlorinated parts of polyethylene, and are generally used alone as elastomers with excellent flexibility, weather resistance, heat aging resistance, flame resistance, and chemical resistance. . Further, it is used as a physical property improver for general purpose resins such as vinyl chloride resin, olefin resin, ABS, or rubbers such as EPDM, chlorosulfonated polyethylene, chloroprene, SBR.
Chlorinated polyethylene can be obtained using a conventionally known chlorination method.

  When graphite is added to the resin component, the elastic modulus is remarkably increased and the entire composition becomes rigid, so that the elongation at high temperature required for impact resistance and secondary workability may be lowered. In particular, by using chlorinated polyethylene, flexibility can be imparted to the entire composition, and it is considered that an effect of improving impact resistance and an effect of improving elongation at high temperatures are exhibited.

A weight average molecular weight of about 50,000 to 400,000 is suitable for chlorinated polyolefin, particularly chlorinated polyethylene. This molecular weight measurement method is a value measured by the GPC method. The degree of chlorination is suitably about 20% to 40%, preferably a molecular weight of about 150,000 to 350,000 and a degree of chlorination of 25% to 36%.
By setting the weight average molecular weight within this range, entanglement at the molecular chain level with the (meth) acrylate polymer described later can be expressed and compatibility can be improved. In particular, it is considered that, by relatively increasing the degree of chlorination of chlorinated polyethylene (for example, about 34% or more), a polarity close to that of a (meth) acrylate polymer can be imparted and compatibility can be improved.
Moreover, it is thought that by making the molecular weight relatively high (for example, about 320,000 or more), the entanglement at the molecular chain level with the (meth) acrylate polymer can be imparted and the compatibility can be further improved.

The addition amount of the chlorine-containing hydrocarbon resin is not particularly limited, and is preferably adjusted appropriately in consideration of secondary processability such as vacuum forming, moldability, and combustibility. For example, it is 1% by weight or more, preferably 5% by weight, more preferably 8% by weight or more, and particularly preferably 15% by weight or more with respect to the total chlorine-containing hydrocarbon resin composition. Moreover, as an upper limit, it is 85 weight% or less, Preferably it is 60 weight% or less, More preferably, it is 40 weight% or less, Most preferably, it is 30 weight% or less. If the amount added is too small, the amount (ratio) of vinyl chloride resin, chlorinated polyethylene, etc. decreases, and the combustibility becomes worse. Moreover, when there is too much addition amount, since the quantity of graphite and (meth) acrylate reduces, it exists in the tendency for combustibility and secondary workability to fall.
In particular, the addition amount of the vinyl chloride resin is preferably about 5 to 30% by weight with respect to the chlorine-containing hydrocarbon resin.
The addition amount of the chlorinated polyolefin is preferably about 5 to 30% by weight with respect to the chlorine-containing hydrocarbon resin. In particular, if the amount of chlorinated polyolefin added is too small, the impact resistance tends to decrease, and if it is too large, the rigidity tends to decrease.

((Meth) acrylate polymer)
The (meth) acrylate polymer is a general term for polymers mainly composed of acrylate monomers or methacrylate monomers, and can serve as a processing aid.
For example, homopolymers or copolymers of (meth) acrylate monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate; the above (meth) acrylate monomers and styrene, vinyltoluene, acrylonitrile And copolymers with other monomers. You may use these individually or in combination of 2 or more types.

The addition amount of the (meth) acrylate polymer can be appropriately adjusted in consideration of secondary processability such as vacuum forming, moldability and combustibility, which have been reduced by the addition of graphite.
In the chlorine-containing hydrocarbon resin composition, when the graphite content is increased, it is necessary to increase the addition amount of the (meth) acrylate polymer for the purpose of preventing deterioration of moldability. On the other hand, in the case where decoration such as a laminate of polyvinyl chloride is applied to the surface layer, or in order to determine that there is no ignition (non-combustion) in the vehicle flammability test, the amount of graphite added (ratio to the composition) ) Must be increased, which limits the amount of (meth) acrylate polymer that can be added. Thus, although affected by the addition amount of graphite, the addition amount of the (meth) acrylate polymer is 6% by weight or more, preferably 12% by weight, based on the total weight of the chlorine-containing hydrocarbon resin composition. More preferably, it is 18 weight% or more. The upper limit is 50% by weight or less, preferably 30% by weight or less, and more preferably 25% by weight or less.
By setting to the said range, the improvement of the combustion resistance by adding graphite and secondary workability can be made compatible.
In particular, when chlorinated polyethylene is used, the addition amount of (meth) acrylate polymer is 30 to 80% by weight when the total of (meth) acrylate polymer and chlorinated polyethylene is 100% by weight. It is preferable that it is 50 to 75% by weight. If the amount added is too small, the secondary processability such as vacuum forming tends to be reduced, and if too large, the formability tends to deteriorate.

  The (meth) acrylate polymer is added to improve secondary processability, particularly vacuum formability. Vacuum forming of the chlorine-containing hydrocarbon resin composition is generally performed by heating to a surface temperature of about 180 ° C to 220 ° C. In such a high temperature state, the tension of a chlorine-containing hydrocarbon resin, for example, a polyvinyl chloride resin is lowered and easily breaks. Therefore, a (meth) acrylate polymer having a higher tension in a high temperature region is preferably used. The addition of a (meth) acrylate polymer is indispensable because the addition of an inorganic substance, particularly a non-spherical type inorganic substance such as graphite, tends to break at high temperatures. Excellent compatibility with chlorine-containing hydrocarbon resins. NBR, thermoplastic elastomers such as ethylene-vinyl acetate-carbon monoxide copolymer (EVACO), and plasticizers such as DOP can be used as compounds that improve elongation at high temperatures. From the viewpoints of the above, a (meth) acrylate polymer is particularly preferable.

The weight average molecular weight of the (meth) acrylate polymer is not particularly limited. However, higher molecular weight is preferable from the viewpoint of higher tension at high temperature. For example, it is preferably 1 million or more, more preferably 3 million or more. Moreover, since it will have a bad influence on a moldability and a physical property when molecular weight becomes high too much, 6 million or less is preferable. More preferably, it is 5 million or less.
The weight average molecular weight is a polystyrene equivalent weight average molecular weight measured by GPC (gel permeation chromatography) of a styrene elastomer. In particular,
Apparatus: HLC-8120 (manufactured by Tosoh Corporation),
Using a solvent: THF, a calibration curve is prepared based on the molecular weight of polystyrene having a known molecular weight.
The column is appropriately selected depending on each molecular weight. For example, in the case of 3 million or more,
Column used: GMHHR-H (30) × 2 Solvent: THF, sample concentration: 0.05%, injection amount: 50 μl, flow rate: 0.5 ml / min, the sample concentration is also adjusted depending on the molecular weight.

(Additive)
A flame retardant may be further added to the chlorine-containing hydrocarbon resin composition of the present invention for the purpose of assisting the combustion suppression effect. In addition, one or more of various additives such as a heat stabilizer, a heat stabilization aid, a lubricant, an impact modifier, an antioxidant, a light stabilizer, and a pigment are added as necessary. Also good. Each of these additives may be used alone or in combination of two or more.

  Examples of the flame retardant include antimony oxide such as antimony dioxide, antimony trioxide, and antimony pentoxide, molybdenum compounds such as molybdenum trioxide, molybdenum disulfide, and ammonium molybdate, and bromine such as tetrabromobisphenol A and tetrabromoethane. And phosphorus compounds such as triphenyl phosphate and ammonium polyphosphate.

  The heat stabilizer is not particularly limited as long as it is a stabilizer used in molding a chlorine-containing hydrocarbon resin composition. For example, dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin Organotin stabilizers such as malate, dibutyltin malate polymer, dioctyltin malate, dioctyltin malate polymer, dioctyltin laurate, dibutyltin laurate, dibutyltin laurate polymer, lead white, lead stearate, dibasic stearin Lead stabilizers such as lead oxide, dibasic lead phosphite, basic lead sulfite, dibasic lead sulfite, tribasic lead sulfate, silica gel co-precipitated lead oxalate, lead benzoate, lead naphthenate, stear Metal soap stabilizers such as calcium phosphate, barium stearate, zinc stearate, calcium-zinc stabilizers, Potassium - zinc stabilizer, barium - cadmium stabilizer, hydrotalcite, and inorganic-based stabilizers such as zeolites.

  The heat stabilization aid is not particularly limited, and examples thereof include epoxidized soybean oil, epoxidized linseed bean oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphate ester.

  The lubricant is not particularly limited, and examples thereof include montanic acid wax, paraffin wax, polyethylene wax, stearic acid, stearyl alcohol, and butyl stearate.

  The impact modifier is not particularly limited as long as it is used as an impact modifier for a chlorine-containing hydrocarbon resin composition. For example, methyl methacrylate-butadiene-styrene graft copolymer (MBS resin) , Acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylic modifier and the like. Here, the acrylic modifier is at least one acrylic copolymer selected from the group consisting of one of acrylic acid ester or methacrylic acid ester, in particular an acrylic component as a main component, and is crosslinked and spherical. The one that became. Among them, chlorinated polyethylene that can efficiently compensate for the impact resistance reduced by graphite is preferably used by adopting a network structure in a matrix that has become hard and brittle by the addition of graphite and imparting flexibility. .

  The light stabilizer is not particularly limited, and examples thereof include ultraviolet absorbers such as salicylic acid esters, benzophenones, benzotriazoles, and cyanoacrylates, or hindered amine light stabilizers.

  The pigment is not particularly limited, and examples thereof include organic pigments such as azo, phthalocyanine, selenium, and dye lakes, oxides, molybdenum chromate, sulfide / selenide, ferrocyanide, and the like. An inorganic pigment etc. are mentioned.

  The addition method and order of addition of the additive are not particularly limited, and can be any method and order. For example, the addition method is not particularly limited, and it can be added to the chlorine-containing hydrocarbon resin by a hot blend method, a cold blend method, or the like.

(Molded body)
The chlorine-containing hydrocarbon resin composition of the present invention has a predetermined shape by any method known in the art such as, for example, an inflation method using a mold, extrusion molding, coating, etc., for example, a sheet shape or a plate shape Or the like. Further, by combining with other materials and co-extrusion by a known method such as an inflation method or a T-die method, a molded body laminated and integrated with other materials can be formed.

  In addition, it is suitable for such a molded body of the present invention that graphite is added in a range where the thermal conductivity is 0.5 W / m · K or more. 1.4 W / m · K or more is preferable, 3.0 W / m · K or more is more preferable in order to impart higher flame retardancy, such as when used as an interior material for railway vehicles, and polyvinyl chloride. In particular, when decorating with a laminate such as 4.6 W / m · K or more is preferable. In addition, the amount of addition for obtaining the above-described thermal conductivity may vary depending on the type or state of graphite, and when the amount of addition increases, the thermal conductivity is increased. It is preferable to adjust appropriately in consideration of the amount added.

  When a molded body made of a chlorine-containing hydrocarbon resin composition is used as an interior material for a railway vehicle or the like, a sheet-like or plate-like molding having a thickness of about 0.01 to 10 mm, and further a thickness of about 0.3 to 6 mm. The body is preferable. Moreover, when combining with other materials, in order to express a combustion-resistant effect efficiently, it is preferable to arrange | position other materials to the back surface side. Although it is possible to provide a coating layer, printing, or a decorative layer on the surface, it is preferable to have a minimum thickness within a range that does not impair combustion resistance. Here, when used for interior materials such as railway vehicles, the surface exposed to the passenger side is referred to as the surface.

(Thermal conductivity)
In the present invention, the thermal conductivity means a value measured as follows.
As an example of a method for producing a test piece, there is a method in which a resin composition is supplied to a twin screw extruder and melt kneaded to obtain a predetermined thickness sheet. As another example, the composition is supplied to a kneader and melt-kneaded at a temperature of 185 ° C. to obtain a sheet having a thickness of 1 mm. Next, this is a method of supplying to a hot press molding machine and pressurizing at a temperature of 190 ° C. and 200 kgf to obtain a 3.2 mm B5 press plate. A test piece is produced from the sheet | seat obtained by these methods. That is, the chlorine-containing hydrocarbon resin composition is used as a sheet-like test piece having a thickness of 3.2 mm and 150 × 100 mm.
Then, at room temperature, using a thermal conductivity meter, stack the test piece on a standard plate (silicon, quartz, zircon brick) with known thermal conductivity, and apply the probe to the surface of the test piece. Measure the thermal conductivity. Here, as the thermal conductivity meter, Chemtherm. QTM-D3 (trade name) (manufactured by Kyoto Electronics Industry Co., Ltd.) is used.
Subsequently, the thermal conductivity of the standard plate and the deviation of the measured thermal conductivity are plotted, and the thermal conductivity can be obtained from the intersection of the obtained straight line and the deviation = 0.

  Examples of the chlorine-containing hydrocarbon resin composition of the present invention will be described below, but are not limited to the following examples.

Examples 1-13 and Comparative Examples 1-2
A predetermined amount of vinyl chloride resin, graphite, flame retardant, heat stabilizer and lubricant shown in Table 1 were supplied to a 20 L super mixer (manufactured by Kawata) and mixed by stirring to obtain a chlorine-containing hydrocarbon resin composition. .

The materials used are as follows.
(1) Vinyl chloride resin:
Made by Tokuyama Sekisui Industry Co., Ltd., trade name “TS-800E”, polymerization degree 800
(2) Thermal stabilizer:
TVS # 1380 (trade name “TVS # 1380”, manufactured by Nitto Kasei Kogyo Co., Ltd.)
(3) Lubricant:
HW220MP (trade name “Hiwax220MP”, manufactured by Mitsui Chemicals)
G70S (trade name “LOXIOL G70S”, manufactured by Emery Oleo Chemicals Japan)
(4) Graphite:
Scale graphite (trade name “CFW18AK”, manufactured by Chuetsu Graphite Co., Ltd., average particle size: 18 μm)
Scale graphite (trade name “CFW100”, manufactured by Chuetsu Graphite Co., Ltd., average particle size: 100 μm)
Scale graphite (trade name “CFW300”, manufactured by Chuetsu Graphite Co., Ltd., average particle size: 300 μm)
Pulverized graphite after expansion (trade name “CS-F400”, manufactured by Maruho Casting Co., Ltd., average particle size 200 μm)
Artificial graphite (trade name “4443”, manufactured by ASBURY, average particle size 300 μm)
(5) Impact resistance modifier:
Tyrin 3615P (trade name “Tyrin 3615P”, manufactured by Dow Chemical Co., Ltd.)
(6) (Meth) acrylate polymer:
P-530A (trade name “METABBRENE P-530A”, manufactured by Mitsubishi Rayon Co., Ltd., molecular weight 3.1 million)

The obtained vinyl chloride resin composition was supplied to an SLM50 twin screw extruder (manufactured by Nagata Seisakusho) and melt kneaded at a resin temperature of 185 ° C. to obtain a sheet having a thickness of 3.2 mm.
Next, impact resistance (notched Izod), tensile elongation at break, and vehicle combustion test were evaluated by the following methods.

<Impact resistance (Izod with notch)>
The obtained sheet | seat was cut | disconnected and the test piece was created and it measured at 23 degreeC based on ASTMD-256.

<Tensile fracture elongation>
(Dumbell production)
The obtained sheet was cut to produce a dumbbell having the same size as that of a tensile dumbbell cut out from a pipe having a nominal diameter of 25 or less described in FIG. 1 of JIS K6741 (2004).
(Measurement)
A tensile test was performed at 130 ° C. in accordance with JIS K7113. The tester used was Autograph AGS-J manufactured by Shimadzu Corporation, the test speed was 500 mm / min, and the state adjustment was 2 h.
(Calculation of tensile fracture elongation)
The distance between marked lines a (mm) was measured at 23 ° C. A tensile test was conducted until the dumbbell broke, the chuck moving distance before and after the tensile test was defined as b (mm), and b ÷ a × 100 (%) was defined as the tensile fracture elongation.
Since the tensile fracture elongation at high temperature reflects secondary workability such as vacuum forming, this evaluation was used as a substitute evaluation method for vacuum forming.
(Criteria)
◎: 130 ° C. tensile elongation at break of 400% or more ◎: 130 ° C. tensile elongation at break of 200% or more and less than 400% ○: 130 ° C. tensile elongation at break of 100% or more but less than 200% Δ: 130 ° C. tensile elongation at break 30% or more and less than 100% ×: 130 ° C. tensile fracture elongation is less than 30%

<Vehicle combustion test>
Ignition: Evaluated in accordance with Article 83 of Section 5 of the Fire Countermeasures for Vehicles in “Ministerial Ordinance Establishing Technical Standards on Railways (December 25, 2001, Ministry of Land, Infrastructure, Transport and Tourism Ordinance No. 151)”. Evaluation was made according to the following evaluation.
In addition, all the surfaces which contact the flame of alcohol in Examples 1-3 are from the combustion-resistant layer side.
Judgment criteria:
A: No ignition (equivalent to nonflammability)
○: Ignition time is 70 seconds or more and the fire after ignition is weak (equivalent to extremely flame retardant)
Δ: Ignition over 30 seconds and less than 70 seconds (equivalent to flame retardant)
X: Ignition within 30 seconds

(Thermal conductivity)
A sheet having a thickness of 3 mm and 140 × 100 mm obtained by hot press molding was used as a test piece. At room temperature, using a thermal conductivity meter (trade name Chemtherm. QTM-D3 (trade name) manufactured by Kyoto Electronics Industry Co., Ltd.) on a standard plate (silicon, quartz, zircon brick) whose thermal conductivity is known. The test pieces were brought into close contact with each other, and the conductivity was measured by applying a probe to the surface of the test piece. Specifically, when the thermal conductivity was 1.4 or more, the sample was brought into close contact with a quartz standard plate, and a probe was placed on the sample and allowed to stand for 2 minutes, followed by measurement. After the measurement, the probe was allowed to stand on an aluminum cooling plate for 2 minutes, and then the sample was brought into close contact with the zircon brick standard plate, and the probe was placed on the plate for 2 minutes to perform measurement. Subsequently, when measuring another sample, the probe was allowed to stand on an aluminum cooling plate for 15 minutes, and then the above operation was performed. The thermal conductivity of the standard plate and the deviation of the measured thermal conductivity were plotted, and the thermal conductivity was determined from the intersection of the obtained straight line and deviation = 0. QTM-D3 (manufactured by Kyoto Electronics Industry) software was used for calculation of thermal conductivity.

Claims (2)

A chlorine-containing hydrocarbon resin composition comprising at least one graphite selected from scale-like graphite, expanded and pulverized graphite, and artificial graphite, a chlorine-containing hydrocarbon resin, and a (meth) acrylate polymer,
A chlorine-containing hydrocarbon resin composition comprising 10% by weight or more and 80% by weight or less of the graphite based on the total weight of the chlorine-containing hydrocarbon resin composition.   Chlorine having a thermal conductivity of 0.5 W / m · K or more and containing at least one graphite selected from scale-like graphite, post-expanded pulverized graphite, and artificial graphite, a chlorine-containing hydrocarbon resin, and a (meth) acrylate polymer A molded article characterized by being molded from the containing hydrocarbon resin composition.