JP2020070327A - Method for producing chlorine-containing resin, chlorine-containing resin and chlorine-containing resin molding - Google Patents

Abstract

To provide a method for producing a chlorine-containing resin that can improve moldability and can improve thermal fusion properties of the molding.SOLUTION: A method for producing a chlorine-containing resin has a soft segment polymer polymerization step of polymerizing a soft segment monomer to obtain a soft segment polymer, and a graft copolymerization step of graft copolymerizing a polymerization component containing the soft segment polymer and a vinyl chloride monomer to obtain a chlorine-containing resin.SELECTED DRAWING: None

Description

  The present invention relates to a chlorine-containing resin obtained by polymerizing a polymerization component containing a vinyl chloride monomer. The present invention also relates to a method for producing the above chlorine-containing resin and a molded product using the above chlorine-containing resin.

  BACKGROUND ART Thermoplastic elastomers have been proposed as useful materials for various molded products such as automobiles, electronic materials, and packaging materials. In recent years, it has been desired to maintain flexibility in a wide temperature range (0 ° C. to 50 ° C.) from a low temperature environment to room temperature or higher, as represented by a food package, from the viewpoint of improving the handleability. .. For this reason, blending a thermoplastic resin such as vinyl chloride resin with a thermoplastic resin (polymer) or rubber has been studied.

  It is known that when a thermoplastic resin (polymer) is blended with a thermoplastic resin such as a vinyl chloride resin, the physical properties and moldability after blending are strongly influenced by the compatibility of the blended polymers. For example, regarding the flexibility, in a system in which the polymers to be blended are completely compatible with each other, the polymers are compatible with each other, so that the flexibility changes greatly with temperature changes. On the other hand, in a system in which the polymers to be blended have low compatibility with each other, the polymers are not compatible with each other and are phase-separated, so that flexibility and strength can be maintained in a wide temperature range.

  In addition, Patent Documents 1 and 2 below describe blending rubber with a thermoplastic resin such as a vinyl chloride resin.

  In Patent Document 1, 80 wt% to 99.9 wt% of a polyalkyl (meth) acrylate composite rubber (A) is graft-polymerized with 20 wt% to 0.1 wt% of a vinyl monomer (B). An impact strength modifier composed of an acrylic rubber-based graft copolymer is disclosed. The polyalkyl (meth) acrylate-based composite rubber (A) contains two or more types of acrylic rubber components having different glass transition temperatures. The acrylic rubber component contains a monomer having two or more unsaturated bonds in the molecule in an amount of 20% by weight or less. The polyalkyl (meth) acrylate-based composite rubber (A) has a particle size number distribution in a polydisperse distribution having at least two peaks at 0.05 μm to 0.4 μm. 70% by weight or more of the polyalkyl (meth) acrylate-based composite rubber (A) is particles having a particle diameter of 0.05 μm to 0.4 μm.

  Patent Document 2 discloses an acrylic rubber-based graft copolymer in which a vinyl-based monomer (B) is graft-polymerized on a polyalkyl (meth) acrylate-based composite rubber (A). The acrylic rubber-based graft copolymer contains an acid group. The polyalkyl (meth) acrylate-based composite rubber (A) contains two or more types of acrylic rubber components having different glass transition temperatures (Tg).

JP 2000-319482 A JP 2002-348335 A

  From the viewpoint of maintaining flexibility in a wide temperature range, when a thermoplastic resin (polymer) is blended with a thermoplastic resin such as a vinyl chloride resin, a thermoplastic elastomer obtained by blending polymers having relatively low compatibility Are considered useful. However, if the polymers having relatively low compatibility are blended and molded, the polymer having relatively high flexibility may stick to the metal surface of the molding machine, and molding may be difficult. If the compatibility of the polymers to be blended is too low, the polymers may be separated from each other.

  Further, when a rubber is blended with a thermoplastic resin such as a vinyl chloride resin, for example, in the case of the acrylic rubber graft copolymer described in Patent Documents 1 and 2, it is possible to maintain flexibility in a wide temperature range. However, since the rubber to be blended is cross-linked, when the content of the rubber becomes high, the heat-sealing property of the molded product may be lowered. When the heat-sealing property of the molded body is lowered, peeling may occur during molding of the multilayer sheet. Further, as a building application, when producing a wide range of sheets such as a rooftop waterproof sheet, it is necessary to heat the molded products to fuse them together, but if the thermal fusion property of the molded products is low, peeling defects will occur. May occur. In the conventional thermoplastic elastomer, it is difficult to achieve both moldability and heat fusion property of the molded body.

  An object of the present invention is to provide a chlorine-containing resin that can improve moldability and can also improve the heat-sealing property of a molded product using a chlorine-containing resin. Moreover, the objective of this invention is providing the manufacturing method of the said chlorine containing resin, and the molded object using the said chlorine containing resin.

  According to a broad aspect of the present invention, by polymerizing a soft segment monomer to obtain a soft segment polymer, a soft segment polymer polymerization step, and graft-copolymerizing a polymerization component containing the soft segment polymer and a vinyl chloride monomer. Then, a method for producing a chlorine-containing resin is provided, which comprises a graft copolymerization step of obtaining a chlorine-containing resin.

  In a specific aspect of the method for producing a chlorine-containing resin according to the present invention, water is used as a medium in the graft copolymerization step.

  In a specific aspect of the method for producing a chlorine-containing resin according to the present invention, the soft segment polymer does not contain a crosslinking agent.

  In one specific aspect of the method for producing a chlorine-containing resin according to the present invention, the glass transition temperature of the soft segment polymer is −40 ° C. or lower, and the glass transition temperature of the chlorine-containing resin is 50 ° C. or higher.

  In a specific aspect of the method for producing a chlorine-containing resin according to the present invention, the SP value of the soft segment polymer is smaller than the SP value of the vinyl chloride monomer, and the SP value of the soft segment polymer is 7.3 or more. It is 8.9 or less.

  In one specific aspect of the method for producing a chlorine-containing resin according to the present invention, the content of oxygen atoms is 10% by weight or more in 100% by weight of the soft segment monomer.

  In a particular aspect of the method for producing a chlorine-containing resin according to the present invention, in 100% by weight of the chlorine-containing resin, the content of the component derived from the soft segment polymer is 5% by weight or more and less than 80% by weight, The soft segment monomer contains a (meth) acrylic acid ester compound or a silicone compound.

  According to a broad aspect of the present invention, a soft segment polymer that is a polymer of a soft segment monomer, and a chlorine-containing resin that is a graft copolymer of a polymerization component that contains a vinyl chloride monomer, and a glass transition of the chlorine-containing resin. A chlorine-containing resin having a temperature of 50 ° C. or higher is provided.

  In a specific aspect of the chlorine-containing resin according to the present invention, the content of the component derived from the soft segment polymer is 5 wt% or more and less than 80 wt% in 100 wt% of the chlorine-containing resin, and the soft segment is The monomer includes a (meth) acrylic acid ester compound or a silicone compound.

  According to a broad aspect of the present invention, there is provided a chlorine-containing resin molded body that is a molded body of the above-mentioned chlorine-containing resin.

  The method for producing a chloride-containing resin according to the present invention is a soft segment polymer polymerization step of polymerizing a soft segment monomer to obtain a soft segment polymer, the soft segment polymer, and a graft component containing a polymerization component containing a vinyl chloride monomer. A graft copolymerization step of obtaining a chlorine-containing resin by polymerizing. In the method for producing a chlorine-containing resin according to the present invention, since the above-mentioned configuration is provided, the moldability can be enhanced, and the heat-sealing property of the molded body using the chlorine-containing resin can be enhanced. ..

  The chlorine-containing resin according to the present invention is a graft copolymer of a polymerization component containing a soft segment polymer, which is a polymer of a soft segment monomer, and a vinyl chloride monomer. In the chlorine-containing resin according to the present invention, the glass transition temperature of the chlorine-containing resin is 50 ° C or higher. Since the chlorine-containing resin according to the present invention is provided with the above configuration, the moldability can be enhanced, and the heat-sealing property of the molded product using the chlorine-containing resin can be enhanced.

  Hereinafter, the present invention will be described in detail.

(Chlorine-containing resin and method for producing chlorine-containing resin)
The chlorine-containing resin according to the present invention is a graft copolymer of a polymerization component containing a soft segment polymer, which is a polymer of a soft segment monomer, and a vinyl chloride monomer. The chlorine-containing resin according to the present invention can be obtained by graft-copolymerizing a soft segment polymer, which is a polymer of a soft segment monomer, and a polymerization component containing a vinyl chloride monomer. The chlorine-containing resin according to the present invention has a component derived from a soft segment polymer (a structural unit derived from a soft segment polymer) and a component derived from a vinyl chloride monomer (a structural unit derived from a vinyl chloride monomer).

  The method for producing a chlorine-containing resin according to the present invention is a soft segment polymer polymerization step of polymerizing a soft segment monomer to obtain a soft segment polymer, the above soft segment polymer, and a graft component containing a polymerization component containing a vinyl chloride monomer. A graft copolymerization step of obtaining a chlorine-containing resin by polymerizing. In the method for producing a chlorine-containing resin according to the present invention, it is preferable that water is used as a medium in the graft copolymerization step. By using water as a medium in the graft copolymerization step, the vinyl chloride monomer gathers at the interface of water, and the vinyl chloride monomer polymer has a structure in which the soft segment polymer is incorporated. Therefore, at the time of molding, it is possible to prevent the polymer of the vinyl chloride monomer from first contacting the metal surface of the molding machine and sticking the soft segment polymer to the metal surface of the molding machine, and it is possible to improve the moldability.

  The chlorine-containing resin according to the present invention and the method for producing a chlorine-containing resin according to the present invention are provided with the above-mentioned structure, so that the moldability can be improved, and the heat of the molded body using the chlorine-containing resin can be improved. Fusing property can be improved. Here, "improving the moldability" means that a peeling defect caused by a polymer having a relatively high flexibility (soft segment polymer) sticking to the metal surface of the molding machine does not occur. Moreover, since the chlorine-containing resin according to the present invention and the method for producing a chlorine-containing resin according to the present invention have the above-described configuration, the storage elastic modulus is maintained in a wide temperature range (0 ° C. to 50 ° C.). It is possible to maintain flexibility.

  In the present invention, since the soft segment polymer having a relatively flexible property and the polymerization component containing the vinyl chloride monomer are graft-copolymerized, it is obtained as compared with the case where the above-mentioned polymerization component is randomly copolymerized. The chlorine-containing resin exhibits the characteristics of the soft segment polymer and the characteristics of the vinyl chloride polymer, respectively. As a result, in a wide temperature range (0 ° C. to 50 ° C.), not only the flexibility can be maintained, but also the moldability and the heat fusion property of the molded body can be made compatible.

  In the present invention, the soft segment polymer contributes to the flexibility, and the polymer of the vinyl chloride monomer has a wide melting point so that it does not melt on the metal surface of the molding machine, so that peeling defects can be suppressed.

  The chlorine-containing resin can be obtained by graft-copolymerizing the polymerization component. The grafting ratio in the graft copolymerization is not particularly limited. From the viewpoint of further reducing the amount of substances eluted from the chlorine-containing resin, the grafting ratio is preferably 0.1% or more, more preferably 1% or more.

  The grafting rate can be measured as follows.

  The grafting ratio can be calculated by preparing a sample of a predetermined size, dissolving and filtering the sample, and then measuring the weight of the solid content in the filtrate.

  In 100% by weight of the chlorine-containing resin, the chlorine content is preferably 15% by weight or more, more preferably 30% by weight or more, preferably 95% by weight or less, more preferably 70% by weight or less. When the chlorine content is not less than the lower limit and not more than the upper limit, the moldability can be more effectively enhanced.

  The chlorine content can be measured by a potentiometric titration method according to JIS K7229.

  From the viewpoint of further maintaining flexibility in a wide temperature range, the glass transition temperature (Tg-R) of the chlorine-containing resin is preferably 50 ° C or higher, more preferably 60 ° C or higher. The upper limit of Tg-R is not particularly limited. The Tg-R may be 150 ° C or lower.

  The Tg-R can be measured as follows.

  The chlorine-containing resin is preheated, heated and pressed to prepare a test piece. The obtained test piece is used to measure with a dynamic viscoelastic device under the measurement conditions of a temperature range of −120 ° C. to 100 ° C., a heating rate of 5 ° C./min, and 2 Hz. From the obtained measurement result, the inflection point in the curve of storage elastic modulus is read in the temperature range of 0 ° C to 100 ° C and used as the glass transition temperature (Tg-R) of the chlorine-containing resin. In addition, when there are a plurality of inflection points in the curve of the storage modulus of the chlorine-containing resin, the inflection point existing on the highest temperature side is read as the Tg-R.

(Soft segment polymer)
The soft segment polymer is preferably a polymer having a glass transition temperature lower than that of polyvinyl chloride which is a polymer of vinyl chloride monomer. The soft segment polymer is preferably a polymer that is softer than polyvinyl chloride, which is a polymer of vinyl chloride monomer, at 0 ° C.

  With respect to polyvinyl chloride, which is a polymer of the above vinyl chloride monomer, it means a polymer obtained in the same manner as the chlorine-containing resin of the present invention, except that the soft segment monomer is not used. By using the soft segment polymer, the chlorine-containing resin obtained, which is derived from the soft segment polymer, can include a structural portion having a relatively low glass transition temperature. The structure of the soft segment polymer is not particularly limited. The soft segment polymer can be obtained by polymerizing a soft segment monomer. The soft segment polymer is a polymer of soft segment monomers.

  From the viewpoint of more effectively improving the heat fusion property of the molded product using the chlorine-containing resin, the soft segment polymer preferably does not contain a crosslinking agent. If the soft segment polymer contains a cross-linking agent, the heat-sealing property of the molded product using the chlorine-containing resin may be impaired.

  The glass transition temperature (Tg-S) of the soft segment polymer is preferably −40 ° C. or lower, more preferably −50 ° C. or lower from the viewpoint of further maintaining flexibility in a wide temperature range. The lower limit of Tg-S is not particularly limited. The Tg-S may be -80 ° C or higher.

  The Tg-S can be measured as follows.

  After drying the soft segment polymer emulsion, measurement is performed with a differential scanning calorimeter under the measurement conditions of a temperature range of −120 ° C. to 100 ° C. and a heating rate of 5 ° C./min. From the obtained measurement results, the inflection point of the heat flow (Heat-flow) is read in the temperature range of −120 ° C. to 0 ° C., and is set as the glass transition temperature (Tg-S) of the soft segment polymer.

  The degree of polymerization of the soft segment polymer is preferably 400 or more and 5000 or less, more preferably 500 or more and 3000 or less, and further preferably 600 or more and 2500 or less. When the degree of polymerization of the soft segment polymer satisfies the above preferable range, moldability and long-term durability can be more effectively enhanced.

  The molecular weight distribution (Mw / Mn) of the soft segment polymer is preferably 1 or more and 5 or less, more preferably 1 or more and 4.5 or less, and further preferably 1 or more and 4 or less. When the molecular weight distribution (Mw / Mn) of the soft segment polymer satisfies the above-mentioned preferable range, it is possible to more effectively suppress the variation in moldability.

  The SP value of the soft segment polymer is preferably smaller than the SP value of the vinyl chloride monomer. The SP value of the soft segment polymer is preferably 7.3 or more, more preferably 7.4 or more, preferably 8.9 or less, more preferably 8.8 or less. When the SP value of the soft segment polymer satisfies the above-mentioned preferred embodiment, the soft segment polymer can be collected inside the vinyl chloride monomer during the graft copolymerization to obtain the chlorine-containing resin, and the molding apparatus can be used. It is possible to further suppress the adhesion of the soft segment polymer to the metal part of the. As a result, the moldability of the chlorine-containing resin can be improved more effectively. Further, when the SP value of the soft segment polymer satisfies the above-mentioned preferred embodiment, the obtained chlorine-containing resin has a hydrophobic compound disposed inside and is hydrophilic so as to cover the outer surface of the hydrophobic compound. It has a core-shell structure in which the functional compound is arranged.

  The SP value of the soft segment polymer can be obtained by the Hansen or Hoy calculation method, the Fedors estimation method, or the like. The SP value of the soft segment polymer is preferably obtained by the Fedors estimation method.

  From the viewpoint of further maintaining flexibility in a wide temperature range, the content of oxygen atoms in 100% by weight of the soft segment monomer is preferably 10% by weight or more, more preferably 12% by weight or more. The upper limit of the content of oxygen atoms is not particularly limited. The oxygen atom content may be 30% by weight or less. When the oxygen atom content is not less than the above lower limit and not more than the above upper limit, the polymerization components containing the soft segment polymer and the vinyl chloride monomer are compatible with each other, and it is even more effective that the polymerization components are separated during molding. Can be prevented.

  The oxygen atom content can be measured as follows.

  The content of oxygen atoms can be measured by performing elemental analysis of the chlorine-containing resin. The oxygen atom content can be calculated based on the following formula.

  Oxygen atom content (wt%) = 100 wt%-(Chlorine atom content (wt%))-(Carbon atom content (wt%))-(Hydrogen atom content (wt%))- (Content of other atoms (% by weight))

  The carbon atom content and the hydrogen atom content can be calculated, for example, from a weight change due to combustion. The chlorine atom content can be calculated, for example, according to JIS K7229. The content of the above other atoms can be calculated by, for example, known elemental analysis.

  The content of the component derived from the soft segment polymer in 100% by weight of the chlorine-containing resin is preferably 5% by weight or more, more preferably 10% by weight or more, further preferably 20% by weight or more, and preferably 80% by weight or more. It is less than wt%, more preferably less than 75 wt%, even more preferably less than 70 wt%. When the content of the component derived from the soft segment polymer is at least the above lower limit, the flexibility can be further maintained in a wide temperature range. When the content of the component derived from the soft segment polymer is less than the above upper limit, the moldability of the chlorine-containing resin can be more effectively enhanced.

  The soft segment polymer material (soft segment monomer) is not particularly limited. Examples of the soft segment polymer material (soft segment monomer) include vinyl ester compounds, vinyl ether compounds, (meth) acrylic acid ester compounds, α-olefin compounds, and silicone compounds.

  From the viewpoint of further maintaining flexibility in a wide temperature range, the soft segment polymer material (soft segment monomer) preferably contains a (meth) acrylic acid ester compound or a silicone compound, and (meth) acrylic acid It is more preferable to include an ester compound.

  Examples of the vinyl ester compound include vinyl acetate and vinyl propionate. Examples of the vinyl ether compound include butyl vinyl ether and 2-ethylhexyl vinyl ether. Examples of the (meth) acrylic acid ester compound include butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.

(Soft segment polymer polymerization process)
A soft segment polymer polymerization step of obtaining the soft segment polymer by polymerizing the soft segment monomer will be described. The polymerization method in the above soft segment polymer polymerization step is not particularly limited. Examples of the above-mentioned polymerization method include water suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization. In the graft copolymerization step of obtaining a chlorine-containing resin, from the viewpoint of more easily dissolving the soft segment polymer in a vinyl chloride monomer, and from the viewpoint of further facilitating waste liquid treatment, the polymerization method is emulsion polymerization. Alternatively, solution polymerization is preferable, and emulsion polymerization is more preferable.

(Emulsion polymerization)
Examples of the emulsion polymerization include a batch polymerization method, a monomer dropping polymerization method and an emulsion dropping polymerization method. From the viewpoint that the soft segment polymer can be polymerized more easily, the emulsion polymerization is preferably an emulsion dropping polymerization method.

(Batch polymerization method)
In the batch polymerization method, ion exchanged water, a surfactant and a polymerization initiator are placed in a jacketed polymerization reactor, and the material of the soft segment polymer (soft segment monomer) is added under a nitrogen stream pressure to emulsify. After that, a heating medium is supplied to the jacket to raise the temperature in the reactor to start the polymerization.

(Monomer dropping polymerization method)
In the above monomer dropping polymerization method, ion-exchanged water, a surfactant and a polymerization initiator are put in a jacketed polymerization reactor, a heating medium is supplied to the jacket to heat the inside of the reactor, and a nitrogen stream is applied under pressure. A method of initiating the polymerization by dropping the soft segment polymer material (soft segment monomer).

(Emulsion drop polymerization method)
In the emulsion dropping polymerization method, ion-exchanged water and a polymerization initiator are put in a jacketed polymerization reactor, a heating medium is supplied to the jacket to heat the inside of the reactor, and the soft segment polymer material (soft segment) is added. This is a method of initiating polymerization by dropping an emulsion obtained by emulsifying a (monomer) and a surfactant at high speed under a nitrogen stream pressure.

  In the batch polymerization method and the monomer dropping polymerization method, the surfactant may be added all at once at the initial stage of polymerization, or may be appropriately divided and added from before initiation of polymerization to after completion of polymerization.

(Surfactant)
The surfactant is added for the purpose of improving the dispersion stability of the soft segment polymer material (soft segment monomer) and efficiently performing emulsion polymerization. The surfactant is not particularly limited. Examples of the surfactant include anionic surfactants, nonionic surfactants, and cationic surfactants. As for the said surfactant, only 1 type may be used and 2 or more types may be used together.

  The anionic surfactant is preferably an aliphatic monocarboxylic acid salt such as sodium dodecylcarboxylate, or a sulfonate such as ammonium paraffin sulfonate, ammonium polyoxyethylene styrenated phenyl ether sulfate, and a sulfonate. Is more preferable.

  Examples of the nonionic surfactants include polyoxyethylene alkylphenol ether, partially saponified polyvinyl acetate, sucrose fatty acid ester, and acyl polyethylene glycol.

  Examples of the cationic surfactant include dodecylamine hydrochloride, alkyltrimethylammonium salt and the like. From the viewpoint of more efficiently performing emulsion polymerization, the cationic surfactant is preferably a surfactant containing an amine.

  The content of the surfactant with respect to 100 parts by weight of the soft segment polymer material (soft segment monomer) is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, and preferably 5 parts by weight. It is below, more preferably 3 parts by weight or less. When the content of the surfactant is not less than the lower limit and not more than the upper limit, it is possible to further improve the dispersion stability of the material of the soft segment polymer (soft segment monomer) during emulsion polymerization, and further, The content of the impure part in the obtained soft segment polymer can be further reduced.

(Polymerization initiator)
The above-mentioned polymerization initiator is not particularly limited, and a polymerization initiator generally used in emulsion polymerization can be appropriately used. Examples of the above-mentioned polymerization initiator include a water-soluble polymerization initiator and the like. Specific examples of the polymerization initiator include potassium persulfate, ammonium persulfate, hydrogen peroxide solution, tartaric acid and the like. As for the said polymerization initiator, only 1 type may be used and 2 or more types may be used together.

  The content of the polymerization initiator is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, and preferably 3 parts by weight, based on 100 parts by weight of the soft segment polymer material (soft segment monomer). It is below, more preferably 2 parts by weight or less. When the content of the polymerization initiator is not less than the above lower limit and not more than the above upper limit, heat removal during emulsion polymerization can be performed more effectively, and further emulsion polymerization can be performed more efficiently. it can.

  In the above soft segment polymer polymerization step, it is preferable not to use a crosslinking agent. The soft segment polymer obtained by the above soft segment polymer polymerization step preferably contains no crosslinking agent. The cross-linking agent means a monomer for cross-linking the soft segment polymer such as a polyfunctional monomer or a graft crossing agent.

  No cross-linking agent in the soft segment polymer polymerization step, the soft segment polymer obtained by the soft segment polymer polymerization step does not contain a cross-linking agent, further heat fusion of the molded article using a chlorine-containing resin Can be effectively increased. Further, in a process involving heat fusion using a chlorine-containing resin (multilayer sheet molding, fusion bonding between molded products, etc.), occurrence of defects such as peeling can be further suppressed. On the other hand, a crosslinking agent is used in the soft segment polymer polymerization step, and when the soft segment polymer obtained by the soft segment polymer polymerization step contains a crosslinking agent, the heat-sealing property of the molded article using the chlorine-containing resin is improved. It tends to be difficult to raise it sufficiently. Further, in a process involving heat fusion using a chlorine-containing resin (multilayer sheet molding, fusion of moldings, etc.), defects such as peeling tend to occur.

(Graft copolymerization process)
A graft copolymerization step of obtaining a chlorine-containing resin by graft-polymerizing the above-mentioned soft segment polymer and a polymerization component containing a vinyl chloride monomer will be described. The polymerization method in the graft copolymerization step is not particularly limited. From the viewpoint of more effectively improving the moldability and the heat fusion property of the molded body, it is preferable to use water as a medium in the graft copolymerization step. From the viewpoint of more effectively enhancing the moldability and the heat fusion property of the molded body, the polymerization method in the graft copolymerization step is preferably a polymerization method using water as a medium. By using water as a medium, when the vinyl chloride monomer incorporates the soft segment polymer, the soft segment polymer easily separates from the interface between the vinyl chloride monomer oil droplets and the water. As a result, it is considered that the soft segment polymer is arranged inside the polymer of vinyl chloride monomer and the moldability can be improved. Examples of the polymerization method include water suspension polymerization and emulsion polymerization. From the viewpoint of controlling the particle size of the obtained chlorine-containing resin and further improving the handling property, the above-mentioned polymerization method is preferably water suspension polymerization.

  In the water suspension polymerization, a reaction vessel equipped with a temperature controller and a stirrer is charged with ion-exchanged water, a soft segment polymer, a vinyl chloride monomer, a surfactant and an oil-soluble polymerization initiator. In this method, a property increasing agent, a polymerization degree adjusting agent, a coagulant, etc. are added, and after the air in the reactor is discharged by a vacuum pump, the reaction vessel is heated to carry out polymerization. At the time of the above water suspension polymerization, other monomers, pH adjusters, antioxidants and the like may be used, if necessary.

  The polymerization temperature in the above water suspension polymerization is preferably 30 ° C. or higher, and preferably 90 ° C. or lower. The polymerization time in the above water suspension polymerization is preferably 2 hours or more, and preferably 20 hours or less. After completion of the polymerization reaction, it may be made into a slurry and further dehydrated and dried.

  The above-mentioned surfactant is added for the purpose of improving the dispersion stability of the above-mentioned polymerization components and efficiently performing graft copolymerization. The surfactant is not particularly limited. Examples of the surfactant include anionic surfactants, nonionic surfactants, and cationic surfactants. In the case of water suspension polymerization, nonionic surfactants are particularly preferable. As for the said surfactant, only 1 type may be used and 2 or more types may be used together.

  Examples of the anionic surfactant, the nonionic surfactant, and the cationic surfactant include the surfactants used in the soft segment polymer polymerization step described above. Moreover, in the said water suspension polymerization, polyvinylpyrrolidone, modified cellulose, etc. can be used as said surfactant.

  The content of the surfactant with respect to 100 parts by weight of the vinyl chloride monomer is preferably 0.1 parts by weight or more, more preferably 0.11 parts by weight or more, preferably 2 parts by weight or less, and more preferably 1. It is 5 parts by weight or less. When the content of the surfactant is not less than the lower limit and not more than the upper limit, it is possible to more effectively suppress the incorporation of the surfactant into the chlorine-containing resin during the graft copolymerization. Further, when the content of the surfactant is not less than the lower limit and not more than the upper limit, the particle diameter of the obtained chlorine-containing resin can be controlled to 100 μm to 200 μm, and the handling property is further improved. You can

(Oil-soluble polymerization initiator)
The oil-soluble polymerization initiator is not particularly limited. As the oil-soluble polymerization initiator, an oil-soluble polymerization initiator used for water suspension polymerization can be used as appropriate. From the viewpoint of more efficient graft copolymerization, the oil-soluble polymerization initiator is preferably a radical polymerization initiator. As for the said oil-soluble polymerization initiator, only 1 type may be used and 2 or more types may be used together.

  Examples of the oil-soluble polymerization initiator include organic peroxides and azo compounds. Examples of the organic peroxide include lauroyl peroxide, t-butyl peroxypivalate, diisopropyl peroxy dicarbonate, dioctyl peroxy dicarbonate, t-butyl peroxy neodecanoate, α-cumyl peroxy neodecano. Examples thereof include ates and di-sec-butyl peroxydicarbonate. Examples of the azo compound include 2,2-azobisisobutyronitrile and 2,2-azobis-2,4-dimethylvaleronitrile.

  The content of the oil-soluble polymerization initiator relative to 100 parts by weight of the vinyl chloride monomer is preferably 0.01 parts by weight or more, more preferably 0.15 parts by weight or more, preferably 3 parts by weight or less, and more preferably It is 2 parts by weight or less. When the content of the oil-soluble polymerization initiator is not less than the above lower limit and not more than the above upper limit, heat removal during graft copolymerization can be performed more effectively, and further graft copolymerization can be performed more efficiently. Can be done.

(Water-soluble thickener)
The water-soluble thickener is not particularly limited. As the water-soluble thickener, a water-soluble thickener used in water suspension polymerization can be appropriately used. The water-soluble thickener can be used as necessary. In the graft copolymerization step, the water-soluble thickener may not be used. Examples of the water-soluble thickeners include poly (meth) acrylic acid, alkyl (meth) acrylate-acrylic acid copolymers, casein and metal salts thereof. As for the said water-soluble thickener, only 1 type may be used and 2 or more types may be used together.

  The content of the water-soluble thickener with respect to 100 parts by weight of the vinyl chloride monomer is preferably 0 part by weight or more, preferably 2 parts by weight or less, and more preferably 1 part by weight or less. When the content of the water-soluble thickener is not less than the lower limit and not more than the upper limit, the particle size of the obtained chlorine-containing resin can be controlled more effectively.

(Polymerization degree regulator)
The polymerization degree regulator is not particularly limited. As the above-mentioned polymerization degree controlling agent, a polymerization degree controlling agent used in water suspension polymerization can be appropriately used. The above-mentioned degree-of-polymerization regulator can be used if needed. In the graft copolymerization step, the degree of polymerization regulator may not be used. Examples of the polymerization degree controlling agent include a chain transfer agent and a crosslinking agent. Examples of the chain transfer agent include mercaptomethanol, mercaptoethanol and mercaptopropanol. Examples of the cross-linking agent include divinylbenzene and ethylene glycol dimethacrylate. As for the said polymerization degree regulator, only 1 type may be used and 2 or more types may be used together.

  The content of the polymerization degree control agent with respect to 100 parts by weight of the vinyl chloride monomer is preferably 0 parts by weight or more, preferably 3 parts by weight or less, and more preferably 2 parts by weight or less. When the content of the polymerization degree control agent is not less than the above lower limit and not more than the above upper limit, the degree of polymerization of the obtained chlorine-containing resin can be more suitably adjusted without changing the polymerization temperature.

(Flocculant)
The aggregating agent is not particularly limited. The aggregating agent can be used if necessary. In the graft copolymerization step, the coagulant may not be used. Examples of the aggregating agent include sodium chloride, calcium chloride, aluminum sulfate and the like.

  The content of the aggregating agent relative to 100 parts by weight of the soft segment polymer is preferably 0 parts by weight or more, more preferably 0.01 parts by weight or more, further preferably 0.05 parts by weight or more, preferably 1 part by weight. Hereafter, it is more preferably 0.9 parts by weight or less. When the content of the aggregating agent is not less than the above lower limit and not more than the above upper limit, the vinyl chloride monomer can incorporate the soft segment polymer, and the graft copolymerization can be performed more efficiently. Further, when the content of the aggregating agent is not less than the lower limit and not more than the upper limit, the soft segment polymer is taken into the vinyl chloride monomer without aggregating, so that the moldability can be more effectively enhanced. ..

(Other monomers)
In the graft copolymerization step, a chlorine-containing resin is obtained by graft-copolymerizing the soft segment polymer and a polymerization component containing a vinyl chloride monomer. The other monomer means a monomer other than the vinyl chloride monomer used for the graft copolymerization. The other monomer is a monomer other than the vinyl chloride monomer contained in the polymerization component. The above-mentioned other monomer is a monomer used in the above-mentioned graft copolymerization, if necessary, and the above-mentioned other monomer may not be used in the above-mentioned graft copolymerization.

  The above-mentioned other monomers are not particularly limited. Examples of the other monomer include vinyl ester compounds, vinyl ether compounds, (meth) acrylic acid ester compounds, α-olefin compounds, vinylidene chloride and maleimide compounds.

  Examples of the vinyl ester compound include vinyl acetate and vinyl propionate. Examples of the vinyl ether compound include methyl ether and butyl vinyl ether. Examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate. As for the above-mentioned other monomers, only one kind may be used, or two or more kinds may be used in combination.

  The content of the other monomer based on 100 parts by weight of the vinyl chloride monomer is preferably 0 part by weight or more, preferably 50 parts by weight or less, and more preferably 30 parts by weight or less. When the content of the other monomer is not less than the lower limit and not more than the upper limit, flexibility can be further maintained in a wide temperature range. Further, when the content of the other monomer is not less than the lower limit and not more than the upper limit, the other monomer can be more effectively made compatible with the vinyl chloride monomer.

  When the other monomer is a solid, the graft copolymerization may be performed in a state where the other monomer is dissolved in a solvent that is insoluble in water. At the time of the graft copolymerization, even if there is a solvent that does not dissolve in water, the soft segment polymer can be mixed, and the moldability can be more effectively enhanced. Examples of the solvent that is insoluble in water include ethyl acetate, THF, chloroform, dichloromethane, cyclohexanone, and toluene.

(Other details of chlorine-containing resin and chlorine-containing resin molded product)
The degree of polymerization of the chlorine-containing resin is preferably 500 or more, and preferably 2000 or less. When the degree of polymerization is at least the above lower limit, long-term performance such as fatigue properties is less likely to be impaired. When the above-mentioned degree of polymerization is below the above-mentioned upper limit, it becomes unnecessary to make it under high temperature at the time of molding, and the workability becomes better.

  The chlorine-containing resin before molding is preferably particles. The particle size of the chlorine-containing resin that is a particle is preferably 0.1 μm or more, and preferably 500 μm or less. When the particle diameter is equal to or more than the lower limit, it does not become a fine powder state when dried, and the handling property can be further improved. When the particle diameter is equal to or less than the upper limit, the reaction during polymerization when obtaining particles is less likely to be unstable.

  The chlorine-containing resin may be used in combination with other organic materials as long as the effects of the present invention are not impaired. For example, in order to further improve the mechanical strength, the chlorine-containing resin may be used in combination with a post-chlorinated vinyl chloride resin, an acrylic resin or the like.

  The chlorine-containing resin can be used alone to obtain a chlorine-containing resin molded product (molded product). The chlorine-containing resin can be used as a chlorine-containing resin material (chlorine-containing resin composition) by being mixed with other components as necessary. The chlorine-containing resin material preferably contains the chlorine-containing resin according to the present invention in an amount of 1% by weight or more, more preferably 10% by weight or more, and further preferably 50% by weight or more. The above-mentioned molded product is preferably obtained by molding using 1% by weight or more of a chlorine-containing resin, and preferably 1% by weight or more of the above-mentioned chlorine-containing resin.

  The molded body is a molded body of the chlorine-containing resin. The molded product is obtained by molding the chlorine-containing resin. A chlorine-containing resin material (chlorine-containing resin composition) containing the above chlorine-containing resin may be used when obtaining the above-mentioned molded body.

  Examples of the molded body include sheets, pipes, plates and containers. The molded body may be a molded body other than these.

  The method for molding the chlorine-containing resin and the chlorine-containing resin material is not particularly limited. Examples of the molding method of the chlorine-containing resin and the chlorine-containing resin material include an extrusion molding method, an injection molding method, a calender molding method and a press molding method.

  The molding machine used for molding is not particularly limited. Examples of the molding machine include a single-screw extruder, a twin-screw different-direction parallel extruder, a twin-screw different-direction conical extruder, and a double-screw same-direction extruder. When molding is performed using the above molding machine, the mold to be shaped, the resin temperature, etc. are not particularly limited.

  The chlorine-containing resin material may contain various additives as required. Examples of the additives include stabilizers, stabilizing aids, lubricants, processing aids, impact modifiers, heat resistance improvers, antioxidants, ultraviolet absorbers, light stabilizers, fillers, pigments and plasticizers. Can be mentioned. It is particularly preferable to use a stabilizer in the molded article according to the present invention. The above additives may be used alone or in combination of two or more.

  The stabilizer is not particularly limited. Examples of the stabilizer include a heat stabilizer and a heat stabilization aid. The heat stabilizer is not particularly limited. Examples of the heat stabilizer include organotin stabilizers, lead stabilizers, calcium-zinc stabilizers, barium-zinc stabilizers, and barium-cadmium stabilizers. Examples of the organic tin-based stabilizer include dibutyltin mercapto, dioctyltin mercapto, dimethyltin mercapto, dibutyltin mercapto, dibutyltin malate, dibutyltin malate polymer, dioctyltin malate, dioctyltin malate polymer, dibutyltin laurate, and Examples thereof include dibutyltin laurate polymer. As for the said stabilizer, only 1 type may be used and 2 or more types may be used together.

  The heat stabilization aid is not particularly limited. Examples of the heat stabilization aid include epoxidized soybean oil, phosphoric acid ester, polyol, hydrotalcite, and zeolite. As for the said heat stabilization aid, only 1 type may be used and 2 or more types may be used together.

  Examples of the lubricant include internal lubricants and external lubricants. The internal lubricant is used for the purpose of reducing the flow viscosity of the molten resin during molding and preventing frictional heat generation. The internal lubricant is not particularly limited. Examples of the internal lubricant include butyl stearate, lauryl alcohol, stearyl alcohol, epoxy soybean oil, glycerin monostearate, stearic acid, and bisamide. The external lubricant is used for the purpose of enhancing the sliding effect between the molten resin and the metal surface during molding. The external lubricant is not particularly limited. Examples of the external lubricant include paraffin wax, polyolefin wax, ester wax, montanic acid wax and the like. The above lubricants may be used alone or in combination of two or more.

  The processing aid is not particularly limited. Examples of the processing aid include acrylic processing aids and the like. Examples of the acrylic processing aid include alkyl acrylate-alkyl methacrylate copolymers having a weight average molecular weight of 100,000 to 2,000,000, and specifically, n-butyl acrylate-methyl methacrylate copolymer, and 2-ethylhexyl acrylate-methyl methacrylate-butyl methacrylate copolymer and the like can be mentioned. The above processing aids may be used alone or in combination of two or more.

  The impact modifier is not particularly limited. Examples of the impact modifier include methyl methacrylate-butadiene-styrene copolymer (MBS), chlorinated polyethylene, and acrylic rubber. The impact modifier may be used alone or in combination of two or more.

  The heat resistance improver is not particularly limited. Examples of the heat resistance improver include α-methylstyrene-based and N-phenylmaleimide-based resins. As for the said heat resistance improver, only 1 type may be used and 2 or more types may be used together.

  The antioxidant is not particularly limited. Examples of the antioxidant include phenolic antioxidants and the like. As for the said antioxidant, only 1 type may be used and 2 or more types may be used together.

  The ultraviolet absorber is not particularly limited. Examples of the UV absorber include salicylic acid ester-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, and cyanoacrylate-based UV absorbers. As for the said ultraviolet absorber, only 1 type may be used and 2 or more types may be used together.

  The light stabilizer is not particularly limited. Examples of the light stabilizer include hindered amine light stabilizers. As for the said light stabilizer, only 1 type may be used and 2 or more types may be used together.

  The filler is not particularly limited. Examples of the filler include calcium carbonate and talc. As for the said filler, only 1 type may be used and 2 or more types may be used together.

  The pigment is not particularly limited. Examples of the pigment include organic pigments and inorganic pigments. Examples of the organic pigment include azo organic pigments, phthalocyanine organic pigments, slene organic pigments, and dye lake organic pigments. Examples of the inorganic pigment include oxide inorganic pigments, molybdenum chromate inorganic pigments, sulfide-selenide inorganic pigments, and ferrocyanide inorganic pigments.

  The plasticizer may be added for the purpose of improving the processability during molding. Since the heat resistance of the molded article may be lowered by the addition of the plasticizer, it is preferable that the addition amount of the plasticizer is small. The plasticizer is not particularly limited. Examples of the plasticizer include dibutyl phthalate, di-2-ethylhexyl phthalate, and di-2-ethylhexyl adipate. As for the said plasticizer, only 1 type may be used and 2 or more types may be used together.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.

(Preparation of soft segment polymer)
Preparation of Soft Segment Polymer 1:
To form a seed by stirring and mixing 2-ethylhexyl acrylate, a surfactant (polyoxyethylene styrenated phenyl ether ammonium sulfate), sodium hydroxide, and ion-exchanged water in the amounts shown in Table 1 below. Was prepared. The emulsified monomer obtained was added to a glass reactor equipped with a stirrer and a condenser, and the inside of the reactor was replaced with nitrogen. Then, the temperature was raised to 70 ° C. with stirring, ammonium persulfate was added to the reactor, and emulsion polymerization was started. Thirty minutes after the initiation of the polymerization, the dropping monomers obtained by stirring and mixing in the amounts shown in Table 1 were added dropwise over 2 hours. One hour after the dropping of the dropped monomer was completed, the emulsion polymerization was completed to obtain a soft segment polymer 1 having a solid content of 30.1% by weight.

Preparation of Soft Segment Polymer 2:
Ethyl acrylate, surfactant (polyoxyethylene styrenated phenyl ether ammonium sulfate), sodium hydroxide, and ion-exchanged water were stirred and mixed in the amounts shown in Table 1 below to emulsify to form seeds. The monomer was prepared. The emulsified monomer obtained was added to a glass reactor equipped with a stirrer and a condenser, and the inside of the reactor was replaced with nitrogen. Then, the temperature was raised to 70 ° C. with stirring, ammonium persulfate was added to the reactor, and emulsion polymerization was started. Thirty minutes after the initiation of the polymerization, the dropping monomers obtained by stirring and mixing in the amounts shown in Table 1 were added dropwise over 2 hours. One hour after the dropping of the dropping monomer was finished, the emulsion polymerization was finished to obtain a soft segment polymer 2 having a solid content of 29.8% by weight.

Preparation of Soft Segment Polymer 3:
2-Ethylhexyl acrylate, trimethylolpropane triacrylate, a surfactant (polyoxyethylene styrenated phenyl ether ammonium sulfate), sodium hydroxide, and ion-exchanged water are mixed by stirring at the compounding amounts shown in Table 1 below. Then, an emulsifying monomer for forming a seed was prepared. The emulsified monomer obtained was added to a glass reactor equipped with a stirrer and a condenser, and the inside of the reactor was replaced with nitrogen. Then, the temperature was raised to 70 ° C. with stirring, ammonium persulfate was added to the reactor, and emulsion polymerization was started. Thirty minutes after the initiation of the polymerization, the dropping monomers obtained by stirring and mixing in the amounts shown in Table 1 were added dropwise over 2 hours. One hour after the dropping of the dropping monomer was finished, the emulsion polymerization was finished to obtain a soft segment polymer 3 having a solid content of 30.5% by weight.

(SP value)
The SP value of the obtained soft segment polymer was calculated by the Fedors estimation method. The SP values obtained are shown in Table 1.

(Volume average particle diameter)
The volume average particle diameter of the obtained soft segment polymer was measured using a particle size distribution measuring device (“SALD-2000” manufactured by Shimadzu Corporation). The obtained volume average particle diameter is shown in Table 1.

(Glass transition temperature (Tg-S))
The emulsion of the obtained soft segment polymer was dried at 60 ° C. for 48 hours. After that, measurement was performed with a differential scanning calorimeter (DSC) (“DSC-60A Plus” manufactured by Shimadzu Corp.) under the measurement conditions of a temperature range of −120 ° C. to 100 ° C. and a heating rate of 5 ° C./min. .. From the obtained measurement results, the inflection point of the heat flow (Heat-flow) was read in the temperature range of −120 ° C. to 0 ° C., and the glass transition temperature (Tg-S) of the soft segment polymer was determined. The glass transition temperature (Tg-S) of the obtained soft segment polymer is shown in Table 1.

(Example 1)
Production of chlorine-containing resin:
A reactor equipped with a stirrer and a jacket was charged with the blending components and blending amounts shown in Table 2 below except for vinyl chloride monomer. Thereafter, the air in the reactor was evacuated with a vacuum pump, and vinyl chloride monomer was added under the stirring conditions in the compounding amounts shown in Table 2 below. Then, the polymerization temperature was controlled to the temperature shown in Table 2 below by controlling the jacket temperature to initiate the graft copolymerization. When the pressure inside the reactor dropped to the pressure shown in Table 2 below, the completion of the reaction was confirmed. After adding a defoaming agent ("Toray Silicon SH5510" manufactured by Toray Industries, Inc.) under pressure, the reaction was stopped.

  After that, the chlorine-containing resin was obtained by dehydration by centrifugation and static drying at 60 ° C. for 12 hours.

(Example 2)
A chlorine-containing resin was obtained in the same manner as in Example 1 except that the soft segment polymer 2 was used instead of the soft segment polymer 1 in the graft copolymerization.

(Example 3)
A chlorine-containing resin was obtained in the same manner as in Example 1 except that 11 parts by weight of vinyl acetate was added during the graft copolymerization.

(Example 4)
A chlorine-containing resin was obtained in the same manner as in Example 1 except that the reaction termination pressure was changed from 0.37 MPa to 0.69 MPa during the graft copolymerization.

(Example 5)
In the same manner as in Example 1, except that the soft segment polymer 2 was used instead of the soft segment polymer 1 in the graft copolymerization, and the reaction end pressure was changed from 0.37 MPa to 0.69 MPa, A chlorine-containing resin was obtained.

(Comparative Example 1)
A chlorine-containing resin was obtained in the same manner as in Example 1 except that the soft segment polymer 3 was used instead of the soft segment polymer 1 in the graft copolymerization.

(Comparative Examples 2 to 4)
A chlorine-containing resin was obtained by mixing polyvinyl chloride (“TS1000R” manufactured by Tokuyama Sekisui Kogyo KK) and a soft segment polymer in the blending amounts shown in Table 3 below, and drying.

(Evaluation)
(1) Content of components derived from soft segment polymer (content of structural units derived from soft segment polymer)
The content of the component derived from the soft segment polymer (content of the structural unit derived from the soft segment polymer) was measured using NMR. Specifically, a small amount of the obtained chlorine-containing resin is dissolved in a heavy solvent (THF, etc.), the area ratio is calculated from the characteristic peak of the 1H spectrum of NMR, and the content of the component derived from the soft segment polymer (soft segment The content of structural units derived from the polymer) was calculated.

(2) Content of polymer of vinyl chloride monomer (content of structural unit derived from vinyl chloride monomer)
The chlorine content (Cl%) in the obtained chlorine-containing resin was measured by potentiometric titration according to JIS K7229.

  The content of the polymer of vinyl chloride monomer (content of structural units derived from vinyl chloride monomer) was calculated from the obtained chlorine content by weight (C = Cl% / 100) by the following formula (X).

  Content of polymer of vinyl chloride monomer (content of structural unit derived from vinyl chloride monomer) (% by weight) = (C / 56.7) x 100 ... Formula (X)

(3) Content of components derived from other monomers (content of structural units derived from other monomers)
The content of components derived from other monomers (content of structural units derived from other monomers) was measured using NMR. Specifically, a small amount of the obtained chlorine-containing resin is dissolved in a heavy solvent (THF, etc.), the area ratio is calculated from the difference between the characteristic peaks of the 1H spectrum of NMR, and the content of components derived from other monomers ( The content of structural units derived from other monomers) was calculated.

(4) Volume average particle diameter With respect to the obtained chlorine-containing resin, the volume average particle diameter was measured using a particle size distribution measuring device (“SALD-2000” manufactured by Shimadzu Corporation).

(5) Glass transition temperature (Tg-R) of chlorine-containing resin
The chlorine-containing resin was preheated under the conditions of 175 ° C. and 2 minutes, and heated and pressed under the conditions of 175 ° C., 3 minutes and 10 MPa to prepare a test piece (length 50 mm, width 10 mm, thickness 2 mm). Using the obtained test piece, a dynamic viscoelastic device (“MCR302” manufactured by Anton Paar) was used to measure temperature range −120 ° C. to 100 ° C., heating rate 5 ° C./min, and measurement conditions of 2 Hz. I went. From the obtained measurement results, the inflection point in the curve of storage elastic modulus was read in the temperature range of 0 ° C. to 100 ° C. and taken as the glass transition temperature (Tg-R) of the chlorine-containing resin. In addition, in the curve of the storage elastic modulus in the chlorine-containing resin, when there are a plurality of inflection points, the inflection point existing on the highest temperature side was defined as the Tg-R.

(6) Moldability For Examples 1 to 5 and Comparative Example 1, the components were compounded in the amounts and amounts shown in Table 2, kneaded at 170 ° C for 3 minutes, and then roll-molded. In addition, in Comparative Examples 2 to 4, the components and the amounts thereof shown in Table 3 were blended, kneaded at 170 ° C. for 3 minutes, and then roll-molded. The moldability was judged according to the following criteria.

[Moldability judgment criteria]
◯: The molded body does not adhere to the metal surface (roll surface) and the molded body can be collected. ×: The molded body adheres to the metal surface (roll surface) and the molded body cannot be collected.

(7) Heat fusion property The molded product obtained in (6) above is preheated under the conditions of 175 ° C. and 2 minutes, and heated and pressed under the conditions of 175 ° C., 2 minutes and 10 MPa to obtain a molded plate ( A length of 150 mm × width of 150 mm × thickness of 1.5 mm) was produced. The obtained molded plate was cut out to obtain a pressed plate (2 mm x 100 mm x 1.5 mm). Next, prepare two press plates, arrange the press plates so that they overlap only in a range of 2 cm × 2 cm, preheat at 120 ° C. for 30 seconds, and heat at 120 ° C. for 30 seconds and 1 MPa. By pressing, the press plates were heat-sealed to each other to obtain a measurement sample. Using the measurement sample obtained by heat-sealing the press plate, a tensile test was carried out under the condition of a tensile speed of 200 mm / min. The heat fusion property was judged according to the following criteria.

[Criteria for heat fusion]
◯: The base material is broken in the tensile test. ×: The base material is not broken in the tensile test and peeling occurs.

(8) Flexibility holding property The molded body obtained in (6) above is preheated under the conditions of 175 ° C. and 2 minutes, and heated and pressed under the conditions of 175 ° C., 2 minutes and 10 MPa to obtain a test piece. (Length 50 mm × width 10 mm × thickness 2 mm) was produced. Using the obtained test piece, a dynamic viscoelastic device (“MCR302” manufactured by Anton Paar) was used to measure temperature range −120 ° C. to 100 ° C., heating rate 5 ° C./min, and measurement conditions of 2 Hz. did. The storage elastic modulus at 0 ° C. and 50 ° C. was read from the obtained measurement result, and the ratio of the storage elastic modulus at 0 ° C. to the storage elastic modulus at 50 ° C. was calculated. In addition, the flexibility retention characteristics were evaluated according to the following criteria.

[Criteria for holding flexibility]
◯: Storage elastic modulus at 0 ° C. is less than 1 GPa, and ratio of storage elastic modulus at 0 ° C. to storage elastic modulus at 50 ° C. is 3 or less ○: Storage elastic modulus at 0 ° C. is less than 1 GPa, and , The ratio of the storage elastic modulus at 0 ° C to the storage elastic modulus at 50 ° C is more than 3 and 6 or less ×: The storage elastic modulus at 0 ° C is 1 GPa or more, or the storage elastic modulus at 0 ° C is stored at 50 ° C. Ratio to elastic modulus exceeds 6

  The composition and results are shown in Tables 1 to 3 below.

Claims (10)

By polymerizing the soft segment monomer, a soft segment polymer polymerization step of obtaining a soft segment polymer,
A method for producing a chlorine-containing resin, comprising a graft copolymerization step of obtaining a chlorine-containing resin by graft-copolymerizing a polymerization component containing the soft segment polymer and a vinyl chloride monomer.   The method for producing a chlorine-containing resin according to claim 1, wherein water is used as a medium in the graft copolymerization step.   The method for producing a chlorine-containing resin according to claim 1, wherein the soft segment polymer does not contain a crosslinking agent. The glass transition temperature of the soft segment polymer is −40 ° C. or lower,
The glass transition temperature of the said chlorine containing resin is 50 degreeC or more, The manufacturing method of the chlorine containing resin of any one of Claims 1-3. The SP value of the soft segment polymer is smaller than the SP value of the vinyl chloride monomer,
The method for producing a chlorine-containing resin according to claim 1, wherein the soft segment polymer has an SP value of 7.3 or more and 8.9 or less.   The method for producing a chlorine-containing resin according to any one of claims 1 to 5, wherein the content of oxygen atoms is 10% by weight or more based on 100% by weight of the soft segment monomer. In 100% by weight of the chlorine-containing resin, the content of the component derived from the soft segment polymer is 5% by weight or more and less than 80% by weight,
The method for producing a chlorine-containing resin according to claim 1, wherein the soft segment monomer contains a (meth) acrylic acid ester compound or a silicone compound. A soft segment polymer which is a polymer of a soft segment monomer, and a chlorine-containing resin which is a graft copolymer of a polymerization component containing a vinyl chloride monomer,
A chlorine-containing resin in which the glass transition temperature of the chlorine-containing resin is 50 ° C. or higher. In 100% by weight of the chlorine-containing resin, the content of the component derived from the soft segment polymer is 5% by weight or more and less than 80% by weight,
The chlorine-containing resin according to claim 8, wherein the soft segment monomer contains a (meth) acrylic acid ester compound or a silicone compound.   A chlorine-containing resin molded body which is the chlorine-containing resin molded body according to claim 8.