JP2017115043A - Soft vinyl chloride resin composition - Google Patents

Abstract

Provided is a soft vinyl chloride resin composition that has good processability, plasticizer bleeding, and mechanical properties of a molded product even when a non-phthalic acid plasticizer is used.
A soft polyvinyl chloride resin composition comprising a polyvinyl chloride resin, a non-phthalic acid plasticizer, and a (meth) acrylic acid ester copolymer. The soft polyvinyl chloride resin composition according to claim 1, wherein the non-phthalic acid plasticizer is diisononylcyclohexane-1,2-dicarboxylate and / or di-2-ethylhexyl terephthalate.
[Selection figure] None

Description

  The present invention relates to a soft vinyl chloride resin composition. More specifically, the present invention relates to a soft vinyl chloride resin composition that has less bleeding and volatilization of a plasticizer even when a non-phthalic acid plasticizer is used, and is excellent in flexibility and mechanical properties.

  Vinyl chloride resin is widely used as a general-purpose resin material with high utility value because it has excellent chemical and physical properties such as chemical resistance, weather resistance, flame resistance, and electrical insulation, and is inexpensive. It has been. Soft vinyl chloride compositions are widely used because they have excellent properties and can be easily given flexibility by the addition of plasticizers. Sheets and tapes such as coated electric wires, flooring materials, and waterproof sheets are also widely used.・ Various applications such as films for agriculture are used.

  In many cases, a phthalic acid plasticizer is used in the soft vinyl chloride composition. In recent years, it has been pointed out that environmental hormone substances (endocrine disrupting substances) contained in plastic additives have an adverse effect on the human body. For example, di-2-ethylhexyl phthalate (DOP), which is a phthalic acid plasticizer used in polyvinyl chloride resin, is a representative substance. Alternative non-phthalic acid plasticizers include diisononylcyclohexane-1,2-dicarboxylate or di-2-ethylhexyl terephthalate.

  Patent Document 1 discloses that diisononylcyclohexane-1,2-dicarboxylate is used as a plasticizer in a vinyl chloride resin. However, processability, plasticizer bleeding, and mechanical properties of a molded product are disclosed. There is a need for further improvement.

JP 2011-231226 A

  An object of the present invention is to provide a soft vinyl chloride resin composition that has good processability, plasticizer bleeding, and mechanical properties of a molded product even when a non-phthalic acid plasticizer is used.

The present invention has the following aspects.
[1] A soft polyvinyl chloride resin composition comprising a polyvinyl chloride resin, a non-phthalic acid plasticizer, and a (meth) acrylic acid ester copolymer.
[2] The soft polyvinyl chloride resin composition according to [1], wherein the non-phthalic acid plasticizer is diisononylcyclohexane-1,2-dicarboxylate and / or di-2-ethylhexyl terephthalate.
[3] A molded article obtained by molding the soft polyvinyl chloride composition according to [1] or [2].

  According to the soft vinyl chloride resin composition of the present invention, even if a non-phthalic acid plasticizer is used, the processability, the plasticizer bleeding property, and the mechanical properties of the molded product are improved.

Hereinafter, the present invention will be described in detail.
[Vinyl chloride resin]
The vinyl chloride resin used in the present invention refers to all polymers having a group represented by —CH ₂ —CHCl—, and is a vinyl chloride homopolymer; vinyl chloride / vinyl acetate copolymer, vinyl chloride / (meta ) Acrylic acid copolymer, vinyl chloride / (meth) acrylic acid methyl copolymer, vinyl chloride / (meth) ethyl acrylate copolymer, vinyl chloride / maleic acid ester copolymer, vinyl chloride / ethylene copolymer , Vinyl chloride / propylene copolymer, vinyl chloride / styrene copolymer, vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride terpolymer, vinyl chloride・ Styrene / acrylonitrile terpolymer, vinyl chloride / butadiene copolymer, vinyl chloride / isoprene copolymer, vinyl chloride / chlorine Other monomers that can be copolymerized with vinyl chloride and vinyl chloride, such as propylene copolymer, vinyl chloride / vinylidene chloride / vinyl acetate terpolymer, vinyl chloride / acrylonitrile copolymer, vinyl chloride / various vinyl ether copolymers, etc. Copolymers with vinyl chlorides; modified vinyl chloride homopolymers such as chlorinated vinyl copolymers and vinyl chloride copolymers; and chlorination similar in structure to vinyl chloride resins such as chlorinated polyethylene Includes polyolefins. These vinyl chloride resins may be used alone or in combination of two or more.

  The average degree of polymerization of the vinyl chloride resin (A) used in the present invention is preferably in the range of 300 to 5,000, more preferably 500 to 3,000, and even more preferably 700 to 1,300. . By setting the average degree of polymerization to 300 or more, the mechanical properties of the obtained molded article are improved. Moreover, a gelling characteristic becomes favorable because an average degree of polymerization shall be 5,000 or less.

  There is no restriction | limiting in particular in the manufacturing method of vinyl chloride resin (A) used for this invention, The thing manufactured by various polymerization methods, such as an emulsion polymerization method, suspension polymerization method, and block polymerization method, can be used.

[Non-phthalate plasticizer]
The plasticizer used in the present invention is not particularly limited as long as it is non-phthalic acid-based, but trimellitic acid compound, phosphoric acid compound, adipic acid compound, citric acid compound, ether compound, polyester compound , Soybean oil-based compound, cyclohexanedicarboxylate-based compound, and terephthalic acid-based compound, preferably trimellitic acid such as trimellitic acid tris (2-ethylhexyl), trimellitic acid triisononyl Esters; Phosphate esters such as tri (2-ethylhexyl) phosphate, tricresyl phosphate, and trixylenyl phosphate; Adipic esters such as adipic acid (2-ethylhexyl) and diisononyl adipate; Tributyl acetylcitrate, etc. Citrate ester; polypropylene Ether compounds such as coal; polyester compounds; soybean oil compounds such as epoxidized soybean oil; dimethylcyclohexane-1,2-dicarboxylate, diethylcyclohexane-1,2-dicarboxylate, di-n-butylcyclohexane- Cyclohexane dicarboxylates such as 1,2-dicarboxylate, di-2-ethylhexylcyclohexane-1,2-dicarboxylate, diisononylcyclohexane-1,2-dicarboxylate, diisodecylcyclohexane-1,2-dicarboxylate Terephthalic acid compounds such as di-2-ethylhexyl diterephthalate. Among these, diisononylcyclohexane-1,2-dicarboxylate and di-2-ethylhexyl terephthalate are preferable in terms of safety to the human body. These may be used alone or in combination of two or more.

  The added amount of the non-phthalic plasticizer is preferably 10 to 100 parts by mass, more preferably 20 to 95 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. When the amount of the non-phthalic plasticizer added is 10 parts by mass or more, flexibility is improved, and when it is 100 parts by mass or less, there is little stickiness and excellent moldability.

[(Meth) acrylic acid ester copolymer]
The (meth) acrylic acid ester copolymer mainly increases the frictional force between the particles of the vinyl chloride resin, and promotes the entanglement between the molecules of the vinyl chloride resin, in particular, the melt viscosity characteristics of the vinyl chloride resin composition. It works to improve. As a result, the processability of the vinyl chloride resin composition, the bleeding property of the plasticizer, and the mechanical properties of the molded product are improved. Further, by homogenizing the composition, the strength of the obtained molded product is made uniform.

  As the (meth) acrylic acid ester copolymer used in the present invention, methyl methacrylate units are 10 to 95% by mass, preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and other vinyl monomers. What contains 5-90 mass% of units, Preferably it is 10-80 mass%, More preferably, it contains 15-70 mass%. When the content of the methyl methacrylate unit in the (meth) acrylic acid ester copolymer is 10% by mass or more, the efficiency of melting and kneading can be increased, and a molded article having a good appearance can be obtained. Moreover, the collection | recovery property as a powder of a (meth) acrylic acid ester copolymer becomes easy by setting it as 95 mass% or less.

  Examples of other vinyl monomers that are raw materials for other vinyl monomer units include methacrylic acid alkyl esters other than methyl methacrylate, acrylic acid alkyl esters, aromatic vinyls, and vinyl cyanides. Among these, methacrylic acid alkyl esters and / or acrylic acid alkyl esters other than methyl methacrylate are preferable, and methacrylic acid alkyl esters having 2 to 6 carbon atoms and / or alkyl alkyl esters having 1 to 6 carbon atoms are more preferable. In addition, superposition | polymerization in the case of emulsion polymerization becomes easy by using a C2-C6 methacrylic acid alkylester and a C1-C6 acrylic acid alkylester.

  Various methods can be used as a method for producing the (meth) acrylic acid ester copolymer. Examples of the polymerization method include emulsion polymerization, suspension polymerization, and solution polymerization. is there. Furthermore, any method such as batch addition of monomers, dropwise addition, and divided addition of monomers may be used, and methods such as random copolymerization and block copolymerization may be used.

  The emulsifier that can be used in the emulsion polymerization is not particularly limited, and various emulsifiers can be used. For example, anionic surfactants such as fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl phosphate esters, dialkyl sulfosuccinates, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan acid fatty esters, Nonionic surfactants such as glycerin fatty acid esters, and cationic surfactants such as alkylamine salts can be used. These emulsifiers can be used alone or in combination.

  When the pH of the polymerization system is on the alkali side depending on the type of emulsifier used, an appropriate pH adjusting agent can be used to prevent hydrolysis of the alkyl methacrylate. Examples of pH regulators include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, potassium dihydrogen phosphate -Borax, disodium hydrogen phosphate-citric acid and the like can be used.

  The polymerization initiator may be a water-soluble or oil-soluble single type or redox type. For example, an ordinary inorganic initiator such as persulfate may be used alone, or sulfite, bisulfite, thiosulfuric acid may be used. It can also be used as a redox initiator in combination with a salt or the like. Furthermore, organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, azo compounds, etc. are used alone or in combination with sodium formaldehyde sulfoxylate as a redox initiator. Although it can be used, the present invention is not limited to these specific examples.

  The method for recovering the (meth) acrylic acid ester copolymer in a powder form is not particularly limited. For example, in the case of producing by an emulsion polymerization method, the obtained methacrylic acid alkyl ester polymer latex is cooled, Thereafter, the polymer is precipitated by acid coagulation or salting out with an acid such as sulfuric acid, hydrochloric acid, phosphoric acid or the like, or a salt such as aluminum chloride, calcium chloride, magnesium sulfate, aluminum sulfate, calcium acetate, etc. Further, it can be obtained by filtration, washing and drying. It can also be recovered as a powder by spray drying, freeze coagulation or the like. In the present invention, good powder recoverability means that the (meth) acrylic acid ester copolymer does not become coarse powder or ultrafine powder under general pulverization conditions, and powder recovery is easy.

  Although there is no restriction | limiting in particular in the molecular weight of a (meth) acrylic acid ester copolymer, The weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) is preferable 100,000-10 million, 150,000-7 million It is more preferable that it is 200,000-6 million. By setting the weight average molecular weight (Mw) to 100,000 or more, processability at the time of processing the soft vinyl chloride resin composition is improved. Moreover, by making it 10 million or less, the melting at the time of a process becomes quick, and the dispersibility of a (meth) acrylic acid ester copolymer improves.

  The molecular weight of the (meth) acrylic acid ester copolymer can be adjusted by a conventional method such as adjustment of the amount of chain transfer agent and initiator used during polymerization and adjustment of the polymerization temperature.

  Examples of the chain transfer agent include alkyl mercaptans such as n-octyl mercaptan and t-dodecyl mercaptan. The amount of the chain transfer agent is not particularly limited, but is preferably 0 to 2 parts by mass, for example, 0 to 1 part by mass with respect to 100 parts by mass of the total monomer of the (meth) acrylic acid ester copolymer. It is more preferable that it is 0-0.5 mass part.

  Moreover, the (meth) acrylic acid ester copolymer of this invention may contain an additive as needed. Examples of the additive include powder fluidity modifiers such as inorganic salts and Aerosil.

  The content of the (meth) acrylic acid ester copolymer in the soft vinyl chloride resin composition of the present invention is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. More preferably, it is 5-20 mass parts, More preferably, it is 0.5-15 mass parts. When the addition amount of the (meth) acrylic acid ester copolymer is 0.1 parts by mass or more, the gelling characteristics are sufficient, and the molded appearance improving effect is obtained, and the plasticizing efficiency improving effect is obtained. Moreover, by setting it as 20 mass parts or less, the remarkable increase in the melt viscosity in a molding machine can be prevented, a favorable shaping | molding external appearance can be obtained, and the overload to the motor of a processing machine can be prevented.

  In the soft vinyl chloride resin composition of the present invention, as long as the effects of the present invention are not impaired, conventional stabilizers, fillers, flame retardants, lubricants, impact modifiers, etc. Various additives can be added as needed.

  Examples of stabilizers include lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate, and metals such as potassium, magnesium, barium, zinc, cadmium, and lead. Metal soap stabilizers derived from fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid; alkyl Group, ester group, fatty acid group, maleic acid group, organotin-based stabilizer having a sulfide-containing group, etc .; Ba—Zn, Ca—Zn, Ba—Ca—Sn, Ca—Mg—Sn , Ca—Zn—Sn, Pb—Sn, Pb—Ba—Ca and other complex metal soap stabilizers; metal groups such as barium and zinc and 2-ethylhexanoic acid, isodeca Acids, branched fatty acids such as trialkylacetic acid, unsaturated fatty acids such as oleic acid, ricinoleic acid, linoleic acid, alicyclic acids such as naphthenic acid, aromatic acids such as carboxylic acid, benzoic acid, salicylic acid, substituted derivatives thereof, etc. Metal salt stabilizers derived from two or more kinds of organic acids; these stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols, glycerin derivatives, and further phosphites, epoxy compounds, color-preventing agents In addition to metal stabilizers such as transparency improvers, light stabilizers, antioxidants, bleed-out inhibitors, and metal salt liquid stabilizers that contain stabilizers such as lubricants, epoxy resins, epoxidized Non-metallic stabilizers such as epoxy compounds such as fatty acid alkyl esters and organic phosphites are used, and these are used alone or in combination of two or more.

  Although it does not restrict | limit especially about the addition amount of a stabilizer, 1-15 mass parts is preferable with respect to 100 mass parts of vinyl chloride-type resin, and 1-8 mass parts is more preferable. By setting it as 1 mass part or more, the thermal decomposition at the time of a process can be suppressed, and the fall of the mechanical physical property of a molded object can be prevented by setting it as 15 mass parts or less.

  As fillers, carbonates such as talc, heavy calcium carbonate, precipitated calcium carbonate, colloidal calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, clay, mica, wollastonite, zeolite, silica, zinc oxide In addition, inorganic fibers such as magnesium oxide, carbon black, graphite, glass beads, glass fibers, carbon fibers, and metal fibers, and organic fibers such as polyamide can be used, and these are used alone or in combination of two or more. be able to.

  Although there is no restriction | limiting in particular about the addition amount of a filler, 1-150 mass parts is preferable with respect to 100 mass parts of vinyl chloride-type resin, and 10-100 mass parts is more preferable. By setting it as 1 mass part or more, moderate rigidity can be provided to a molded object, and the fall of the softness | flexibility of a molded object can be prevented by setting it as 150 mass parts or less.

  Examples of flame retardants that can be used include metal hydroxides, bromine compounds, triazine ring-containing compounds, zinc compounds, phosphorus compounds, halogen flame retardants, silicon flame retardants, intomescent flame retardants, and antimony oxide. . These can be used alone or in combination of two or more.

  Although it does not restrict | limit in particular about the addition amount of a flame retardant, 1-150 mass parts is preferable with respect to 100 mass parts of vinyl chloride-type resin, and 10-100 mass parts is more preferable. The flame retardance of a molded object can be improved by setting it as 1 mass part or more, and the fall of the softness | flexibility of a molded object can be prevented by setting it as 150 mass parts or less.

  Examples of the lubricant include liquid hydrocarbon, natural paraffin, micro wax, synthetic paraffin, pure hydrocarbon lubricant such as low molecular weight polyethylene, halogenated hydrocarbon lubricant, fatty acid lubricant such as higher fatty acid and oxy fatty acid, fatty acid amide, bis Fatty acid amide lubricants such as fatty acid amides, lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids (ester waxes), and other metallic soaps , Fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, partial ester of fatty acid and polyhydric alcohol, fatty acid and polyglycol, partial ester of polyglycerol, etc., and these may be used alone or in combination of two or more. It is possible.

  Although it does not restrict | limit especially about the addition amount of a lubricant, 0.1-15 mass parts is preferable with respect to 100 mass parts of vinyl chloride-type resin, and 0.1-5 mass parts is more preferable. By setting it as 0.1 mass part or more, adhesion to the molding machine of a resin composition can be reduced, and the fall of workability can be prevented by setting it as 15 mass parts or less.

  When blending impact modifiers, for example, chlorinated polyethylene, polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, methyl methacrylate -Styrene-butadiene copolymer rubber, acrylic core-shell type rubber such as acrylic ester-methacrylic ester copolymer, silicone-acrylic ester-methacrylic ester copolymer, silicone-acrylic ester-acrylonitrile-styrene copolymer Silicone core-shell type rubber such as polymer, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-ethylene-butylene-styrene block copolymer rubber Ethylene - propylene copolymer rubber, ethylene - propylene - diene copolymer rubber (EPDM) and the like. As the diene of EPDM, 1,4-hexadiene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, propenyl norbornene and the like can be used. These impact modifiers can be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular about the addition amount of an impact modifier, 1-20 mass parts is preferable with respect to 100 mass parts of vinyl chloride resin, and 1-15 mass parts is more preferable. By setting it as 1 mass part or more, the impact strength of a molded object can be improved, and the fall of a molded external appearance can be prevented by setting it as 20 mass parts or less.

  In addition, a release agent, a fluidity improver, a colorant, an antistatic agent, a surfactant, an antifogging agent, an antibacterial agent, a foaming agent, and the like are arbitrarily selected depending on the purpose as long as the effects of the present invention are not impaired. Can be blended.

  The method for obtaining the soft vinyl chloride resin composition of the present invention is not particularly limited, and a generally known method can be used. For example, a predetermined amount of vinyl chloride resin and a non-phthalic acid plasticizer, (meth) It can be obtained by mixing an acrylic ester copolymer with a Henschel mixer, a Banbury mixer, a V-type mixer, a ribbon blender or the like.

  The obtained soft vinyl chloride-based resin composition can be used for ordinary molding methods such as injection molding, hollow molding, roll processing, etc., in addition to extrusion molding using a kneading extruder such as a single screw extruder or twin screw extruder. In addition, various desired molded articles can be obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to this Example. In each example and comparative example, “part” means “part by mass”, and evaluation was performed as follows.
(1) Hardness Surface hardness after holding for 4 seconds using a type A durometer (manufactured by Kobunshi Keiki Co., Ltd., “Digital Rubber Hardness Tester DD2-A”) based on JISK7215 for a molded sheet of a soft vinyl chloride resin composition Was measured. The lower the value, the better the flexibility. The evaluation sheets were stacked with four 1 mm thick sheets, and the hardness was measured.

(2) Tensile properties A molded sheet (1 mm thickness) of a soft vinyl chloride resin composition was measured by performing a tensile test at 200 mm / min by punching out a JIS No. 2 dumbbell based on JISK6723. The higher the tensile strength and the tensile elongation, the better the mechanical properties of the soft vinyl chloride resin composition.

(3) Bleed resistance A 1 mm thick molded product sheet of a soft vinyl chloride resin composition is cut into a 40 mm square, placed on a slide glass, and heated at 140 ° C. for 4 hours to determine the haze value of the slide glass with a haze meter ( Murakami Color Research Laboratory HR-100) was used for evaluation. The lower the Haze of the slide glass, the better the bleed resistance.

(4) Molecular weight of (meth) acrylic acid ester copolymer The (meth) acrylic acid ester copolymer was dissolved in tetrahydrofuran (THF) and measured using gel permeation chromatography (GPC). In the present invention, Mw and Mn were calculated based on a calibration curve using standard polystyrene.
Apparatus: HLC-8220GPC manufactured by Tosoh Corporation
Column: Tosoh Corporation TSKgel SuperHZM-M
(Inner diameter: 4.6 mm × length 15 cm, number: 4, exclusion limit: 4 × 10 ⁶ )
Eluent: THF
Flow rate: 0.35 ml / min Temperature: 40 ° C
Sample concentration: 0.1%
Sample injection volume: 10 μl
Detector: RI (UV)

[Production Example 1] Production of (meth) acrylic acid ester copolymer (C-1) 230 parts of ion-exchanged water was charged into a reaction vessel equipped with a stirrer and a reflux condenser, and dipotassium alkenyl succinate was used as an emulsifier. 1 part, 80 parts of methyl methacrylate and 20 parts of acrylic acid-n-butyl were added, and the inside of the container was replaced with nitrogen under stirring. Thereafter, the temperature of the reaction vessel was raised to 45 ° C., 0.15 part of potassium persulfate was added to start the polymerization reaction, and the polymerization was terminated by heating and stirring for 2 hours. After cooling the obtained emulsion, it is dropped into 600 parts of ion-exchanged water and 2 parts of a dilute sulfuric acid aqueous solution and coagulated. After maintaining the slurry temperature at 90 ° C. for 5 minutes, a washing step and a drying step are added, ) The acrylic ester copolymer (C-1) was recovered as a powder. The solid content of the emulsion was 30.3%, and the weight average molecular weight (Mw) was 3.1 million.

[Production Example 2] Production of (meth) acrylic acid ester copolymer (C-2) 300 parts of ion-exchanged water was charged into a reaction vessel equipped with a stirrer and a reflux condenser, and dipotassium alkenyl succinate was added to the reaction vessel as an emulsifier. 65 parts, 80 parts of methyl methacrylate and 20 parts of acrylic acid-n-butyl were added, and the inside of the container was replaced with nitrogen under stirring. Thereafter, the temperature of the reaction vessel was raised to 42 ° C., 0.15 part of potassium persulfate was added to start the polymerization reaction, and the polymerization was terminated by heating and stirring for 2 hours. After cooling the obtained emulsion, it is dropped into 600 parts of ion-exchanged water and 2 parts of a dilute sulfuric acid aqueous solution and coagulated. After maintaining the slurry temperature at 90 ° C. for 5 minutes, a washing step and a drying step are added, ) The acrylic ester copolymer (C-2) was recovered as a powder. The solid content of the emulsion was 25.1%, and the weight average molecular weight (Mw) was 4.5 million.

[Production Example 3] Production of (meth) acrylic acid ester copolymer (C-3) A reaction vessel equipped with a stirrer and a reflux condenser was charged with 180 parts of ion-exchanged water, in which 0.1 parts of anhydrous sodium carbonate and methacrylic acid were added. 68 parts of methyl, 3 parts of n-butyl acrylate, 29 parts of n-butyl methacrylate and 0.004 part of n-octyl mercaptan were added, and the inside of the container was replaced with nitrogen. Thereafter, 1.1 parts of sodium lauryl sulfate was added, the reaction vessel was heated to 45 ° C. with stirring, 0.15 part of potassium persulfate was added to start the polymerization reaction, and the mixture was heated and stirred for 2 hours for polymerization. finished. After cooling the obtained emulsion, spray drying was performed under conditions of an inlet temperature of 160 ° C. and an outlet temperature of 70 ° C. to obtain a powdered (meth) acrylic acid ester copolymer (C-3). The solid content of the emulsion was 35.5%, and the weight average molecular weight (Mw) was 2.2 million.

[Production Example 4] Production of (meth) acrylic acid ester copolymer (C-4) 151 parts of ion-exchanged water was charged into a reaction vessel equipped with a stirrer and a reflux condenser, and 30 parts of methyl methacrylate and n-butyl methacrylate were charged. 50 parts and 0.09 parts of n-octyl mercaptan were added, and the inside of the container was replaced with nitrogen. Thereafter, 1.2 parts of dipotassium alkenyl succinate was added, the reaction vessel was heated to 45 ° C. with stirring, and 0.15 part of potassium persulfate was added to initiate the polymerization reaction. When the internal temperature reached 70 ° C. after reaching the peak temperature due to polymerization exotherm, a monomer mixture consisting of 20 parts of methyl methacrylate and 0.05 part of n-octyl mercaptan was added dropwise over 40 minutes. Polymerization was completed by holding for a minute. After cooling the obtained emulsion, it is dropped into 600 parts of ion-exchanged water and 2 parts of a dilute sulfuric acid aqueous solution and coagulated. After maintaining the slurry temperature at 90 ° C. for 5 minutes, a washing step and a drying step are added, ) The acrylic ester copolymer (C-4) was recovered as a powder. The solid content of the emulsion was 40.2%, and the weight average molecular weight (Mw) was 260,000.

[Production Example 5] Production of (meth) acrylic acid ester copolymer (C-5) A reaction vessel equipped with a stirrer and a reflux condenser was charged with 260 parts of ion-exchanged water, 67 parts of methyl methacrylate, and n-butyl acrylate. 1 part and 0.017 part of n-octyl mercaptan were added, and the inside of the container was replaced with nitrogen. Thereafter, 1.5 parts of dipotassium alkenyl succinate was added, the reaction vessel was heated to 43 ° C. with stirring, and 0.15 part of potassium persulfate was added to initiate the polymerization reaction. When the internal temperature reached 68 ° C. after reaching the peak temperature due to the polymerization exotherm, a monomer mixture consisting of 11 parts of methyl methacrylate, 11 parts of acrylic acid-n-butyl and 0.2 part of n-octyl mercaptan was added. Dropped over a minute and held for 60 minutes after dropping. After the retention, a monomer mixture consisting of 10 parts of methyl methacrylate and 0.05 part of n-octyl mercaptan was added dropwise over 30 minutes, and the polymerization was completed with the retention of 90 minutes after the addition. After cooling the obtained emulsion, it is dropped into 600 parts of ion-exchanged water and 2 parts of a dilute sulfuric acid aqueous solution and coagulated. After maintaining the slurry temperature at 90 ° C. for 5 minutes, a washing step and a drying step are added, ) The acrylic ester copolymer (C-5) was recovered as a powder. The solid content of the emulsion was 28.1%, and the weight average molecular weight (Mw) was 950,000.

[Production Example 6] Production of (meth) acrylate copolymer (C-6) 150 parts of ion-exchanged water was charged into a reaction vessel equipped with a stirrer and a reflux condenser, and 40 parts of methyl methacrylate and n-butyl acrylate were charged. Two parts and 0.004 part of n-octyl mercaptan were added, and the inside of the container was replaced with nitrogen. Thereafter, 1.05 part of dipotassium alkenyl succinate was added, the reaction vessel was heated to 50 ° C. with stirring, and 0.12 part of potassium persulfate was added to initiate the polymerization reaction. When the internal temperature reached 70 ° C. after reaching the peak temperature due to polymerization exotherm, a monomer mixture consisting of 44 parts of methyl methacrylate and 14 parts of acrylic acid-n-butyl was added dropwise over 90 minutes. Polymerization was completed by holding for a minute. After cooling the obtained emulsion, it is dropped into 600 parts of ion-exchanged water and 2 parts of a dilute sulfuric acid aqueous solution and coagulated. After maintaining the slurry temperature at 90 ° C. for 5 minutes, a washing step and a drying step are added, ) The acrylic ester copolymer (C-6) was recovered as a powder. The solid content of the emulsion was 40.3%, and the weight average molecular weight (Mw) was 1.5 million.

[Reference Example 1]
100 parts of vinyl chloride resin (TK-800 average polymerization degree 800 manufactured by Shin-Etsu Chemical Co., Ltd.), 2 parts of barium-zinc stabilizer, diisononylcyclohexane-1,2-dicarboxylate (made by Hexamol DINCH BASF) 90 as a plasticizer The parts were mixed at 2000 rpm with an Henschel mixer until the internal temperature reached 110 ° C. The obtained soft vinyl chloride resin composition was kneaded with an 8-inch hot roll at 140 ° C. for 5 minutes to form a soft vinyl chloride resin composition sheet. The obtained soft vinyl chloride resin composition sheet was molded into a thickness of 1 mm by a hot press machine at 160 ° C. and subjected to various evaluations. The results are shown in Table 1.

[Example 1]
In Reference Example 1, after obtaining a soft vinyl chloride resin composition, 5 parts of the (meth) acrylic acid ester copolymer (C-1) prepared in Production Example 1 was blended, and 140 ° C., 5 ° C. with an 8 inch hot roll. The resulting mixture was kneaded to form a soft vinyl chloride resin composition sheet. The obtained soft vinyl chloride resin composition sheet was molded into a thickness of 1 mm by a hot press machine at 160 ° C. and subjected to various evaluations. The results are shown in Table 1.

[Examples 2 to 6]
Various evaluations were performed in the same manner as in Example 1 except that the type of the (meth) acrylic acid ester copolymer used was changed as shown in Table 1. The results are shown in Table 1.

Abbreviations in the table are as follows.
DINCH: Diisononylcyclohexane-1,2-dicarboxylate (Hexamol DINCH BASF)

[Reference Example 2]
Various evaluations were performed in the same manner as in Reference Example 1 except that the type of plasticizer used was changed to di-2-ethylhexyl terephthalate (manufactured by DOTP J-PLUS). The results are shown in Table 2.

[Examples 7 to 12]
Various evaluations were performed in the same manner as in Examples 1 to 6 except that the type of plasticizer used was changed to di-2-ethylhexyl terephthalate (DOTP manufactured by J-Plus). The results are shown in Table 2.

Abbreviations in the table are as follows.
DOTP: Di-2-ethylhexyl terephthalate (DOTP manufactured by J-Plus)

In contrast to Reference Example 1 in which no (meth) acrylic acid ester copolymer is blended, Examples 1 to 6 blended with a (meth) acrylic acid ester copolymer have improved tensile strength and tensile elongation, Bleed resistance was also good.
In contrast to Reference Example 2 in which no (meth) acrylic acid ester copolymer was blended, Examples 7 to 12 in which a (meth) acrylic acid ester copolymer was blended had improved tensile strength and tensile elongation. The bleed resistance was also good.

Claims (3)

  A soft polyvinyl chloride resin composition comprising a polyvinyl chloride resin, a non-phthalic acid plasticizer, and a (meth) acrylic acid ester copolymer.   The soft polyvinyl chloride resin composition according to claim 1, wherein the non-phthalic acid plasticizer is diisononylcyclohexane-1,2-dicarboxylate and / or di-2-ethylhexyl terephthalate.   The molded object formed by shape | molding the soft polyvinyl chloride composition of Claim 1 or 2.