WO2014084313A1 - Plasticizer for vinyl chloride resin, and vinyl chloride resin composition containing same - Google Patents

Plasticizer for vinyl chloride resin, and vinyl chloride resin composition containing same Download PDF

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Publication number
WO2014084313A1
WO2014084313A1 PCT/JP2013/082058 JP2013082058W WO2014084313A1 WO 2014084313 A1 WO2014084313 A1 WO 2014084313A1 JP 2013082058 W JP2013082058 W JP 2013082058W WO 2014084313 A1 WO2014084313 A1 WO 2014084313A1
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Prior art keywords
vinyl chloride
chloride resin
acid
plasticizer
resin composition
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PCT/JP2013/082058
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French (fr)
Japanese (ja)
Inventor
西村　拓也
中山　真吾
稲山　俊宏
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Ｋｈネオケム株式会社
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Publication of WO2014084313A1 publication Critical patent/WO2014084313A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols

Definitions

  • the present invention relates to a plasticizer for vinyl chloride resin and a vinyl chloride resin composition containing the same.
  • Vinyl chloride-based resin compositions are widely used in plastic products, etc. in every part of society and life.
  • a vinyl chloride resin composition is usually used by appropriately adding various additives such as a plasticizer, a stabilizer, a filler, and a pigment to the vinyl chloride resin.
  • the plasticizer imparts various performances including flexibility to the vinyl chloride resin, and lowers the processing temperature during the molding process of the vinyl chloride resin composition. It is an indispensable additive for facilitating (Non-Patent Document 1, Non-Patent Document 2).
  • the performance required for the plasticizer used in such a vinyl chloride resin composition includes flexibility, heat resistance, low smoke generation, electrical insulation, etc. when the composition is used as a molded product. is there.
  • Typical plasticizers used in such vinyl chloride resin compositions include higher alkyl esters of dibasic acids such as phthalic acid esters and adipic acid esters. Among them, di-2-ethylhexyl phthalate is widely used because it has a good balance of physical properties such as flexibility, but it is difficult to meet the demands for further heat resistance, low smoke generation and electrical insulation. is there.
  • phthalates are limited for toys and child-care items [for example, revision of standards for food, additives, etc. (2010 Ministry of Health, Labor and Welfare Notification No. 336), etc.] Is also expected to be limited. Therefore, it is necessary to develop a plasticizer whose basic skeleton does not contain a phthalate ester and has a performance equal to or higher than that of a phthalate ester.
  • Patent Document 1 describes that an ester of pentaerythritol and propionic anhydride can be used as a plasticizer.
  • a vinyl chloride resin composition containing a plasticizer the heat resistance, electrical insulation, low It does not describe effects such as smoke generation.
  • Plasticizers in Life Plasticizer Industry Association, 2004
  • Plasticizer 50 Year History Plasticizer Industry Association
  • Plasticizer Industry Association 2007 “Fireproofing of PVC and safety in the event of a fire”
  • PVC Industry and Environment Association PVC Environmental Committee
  • 2007 PVC and construction materials
  • PVC Industry and Environment Association PVC Environmental Committee, 2007
  • An object of the present invention is to provide a plasticizer for a vinyl chloride resin and a chloride containing the same, which imparts excellent performance such as flexibility, heat resistance, low smoke generation, and electrical insulation to a vinyl chloride resin.
  • the object is to provide a vinyl-based resin composition.
  • a plasticizer for a vinyl chloride resin comprising a mixed ester of pentaerythritol and a mixed carboxylic acid, wherein the mixed carboxylic acid is isobutyric acid and an aliphatic monocarboxylic acid having 8 or 9 carbon atoms.
  • a plasticizer for a vinyl chloride resin characterized in that the ratio of isobutyric acid contained in the mixed carboxylic acid is in the range of 35 to 65 mol%.
  • a vinyl chloride resin composition comprising a vinyl chloride resin and the vinyl chloride resin plasticizer according to [1] or [2], wherein the vinyl chloride resin composition is used in 100 parts by weight of the vinyl chloride resin.
  • a vinyl chloride resin composition comprising 10 to 100 parts by weight of the plasticizer for vinyl chloride resin according to [1] or [2].
  • a plasticizer for a vinyl chloride resin that imparts excellent performance such as flexibility, heat resistance, low smoke generation, and electrical insulation to a vinyl chloride resin in a well-balanced manner, and a vinyl chloride resin containing the same A resin composition can be provided.
  • the plasticizer for vinyl chloride resin of the present invention comprises a mixed ester of pentaerythritol and mixed carboxylic acid.
  • the mixed carboxylic acid is a mixed carboxylic acid composed of isobutyric acid and an aliphatic monocarboxylic acid having 8 or 9 carbon atoms, and the ratio of isobutyric acid to the mixed carboxylic acid is in the range of 35 to 65 mol%. It is.
  • the plasticizer for vinyl chloride resin of the present invention imparts excellent performance such as flexibility, heat resistance, low smoke generation, and electrical insulation to the vinyl chloride resin in a balanced manner. Moreover, it is excellent in compatibility with the vinyl chloride resin, and the vinyl chloride resin plasticizer of the present invention is not separated when preparing the vinyl chloride resin composition. Moreover, since it has sufficient molecular weight, it is excellent also in low volatility.
  • the plasticizer for vinyl chloride resin of the present invention is a mixture of the above-mentioned mixed carboxylic acids from the viewpoint of imparting excellent performance such as flexibility, heat resistance, low smoke generation and electrical insulation to the vinyl chloride resin in a particularly well-balanced manner.
  • the ratio of isobutyric acid to be converted to acid is preferably in the range of 38 to 65 mol%, more preferably in the range of 50 to 65 mol%.
  • the mixed ester which is a plasticizer for a vinyl chloride resin of the present invention
  • the mixed ester when the mixed ester is a mixed ester of pentaerythritol, isobutyric acid and an aliphatic monocarboxylic acid having 8 carbon atoms, the mixed ester includes: (I) to (iii): (I) Mixed ester in which constituent carboxylic acids in the same molecule are both isobutyric acid and C8 aliphatic monocarboxylic acid (ii) ester of pentaerythritol and isobutyric acid, and pentaerythritol and C8 aliphatic Mixtures of esters with monocarboxylic acids (iii) Embodiments of the mixtures of (i) and (ii) above are included.
  • the mixed ester which is a plasticizer for a vinyl chloride resin of the present invention
  • the mixed ester when the mixed ester is a mixed ester of pentaerythritol, isobutyric acid and an aliphatic monocarboxylic acid having 9 carbon atoms, the mixed ester includes: (Iv)-(vi): (Iv) Mixed ester in which the constituent carboxylic acids in the same molecule are both isobutyric acid and an aliphatic monocarboxylic acid having 9 carbon atoms (v) an ester of pentaerythritol and isobutyric acid, and pentaerythritol and aliphatic having 9 carbon atoms Mixtures of esters with monocarboxylic acids (vi) Embodiments of the mixtures of (iv) and (v) above are included.
  • the mixed ester which is a plasticizer for a vinyl chloride resin according to the present invention may contain, as an impurity, a partial ester in which a part of the hydroxyl group of pentaerythritol is not esterified and remains as a hydroxyl group.
  • the aliphatic monocarboxylic acid having 8 or 9 carbon atoms constituting the mixed ester which is the plasticizer for vinyl chloride resin of the present invention may be either a linear or branched aliphatic monocarboxylic acid.
  • the mixed ester which is a plasticizer for a vinyl chloride resin of the present invention includes, for example, pentaerythritol, isobutyric acid, and an aliphatic monocarboxylic acid having 8 or 9 carbon atoms at 120 to 250 ° C. and 5 to 5 It can be produced by reacting for 60 hours.
  • a catalyst may be used.
  • the catalyst include mineral acids, organic acids, Lewis acids, organic metals, solid acids and the like.
  • the mineral acid include hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid and the like.
  • the organic acid include p-toluenesulfonic acid, benzenesulfonic acid, butanesulfonic acid, propanesulfonic acid, ethanesulfonic acid, methanesulfonic acid and the like.
  • Specific examples of the Lewis acid include boron trifluoride, aluminum chloride, tin tetrachloride, titanium tetrachloride and the like.
  • Specific examples of the organic metal include tetrapropoxy titanium, tetrabutoxy titanium, tetrakis (2-ethylhexyloxy) titanium, and the like.
  • Specific examples of the solid acid include a cation exchange resin.
  • the sum of the amount of isobutyric acid used and the amount of aliphatic monocarboxylic acid having 8 or 9 carbon atoms is 1.1 to 1.4 times the mole of the hydroxyl group of pentaerythritol used. Is preferred.
  • a solvent may be used.
  • the solvent include hydrocarbon solvents such as benzene, toluene, xylene, hexane, heptane, isohexane, isooctane, isononane, decane, and the like.
  • isobutyric acid constituting the resulting mixed ester and having 8 or 9 carbon atoms are mixed.
  • the molar ratio with the aliphatic monocarboxylic acid may be different from that in the amount used to produce the mixed ester.
  • the mixed ester is purified by methods commonly used in organic synthetic chemistry (washing with water and / or alkaline aqueous solution, treatment with activated carbon, adsorbent, etc., various chromatography, distillation, etc.). May be.
  • the mixed ester can also be produced by using a corresponding acid anhydride instead of isobutyric acid or an aliphatic monocarboxylic acid having 8 or 9 carbon atoms as a raw material.
  • the vinyl chloride resin composition of the present invention is a vinyl chloride resin composition containing the vinyl chloride resin and the plasticizer for vinyl chloride resin of the present invention.
  • the vinyl chloride resin include a vinyl chloride homopolymer, a vinyl chloride copolymer with a monomer copolymerizable with vinyl chloride, and a graft copolymer of vinyl chloride with a polymer other than the vinyl chloride copolymer. Examples thereof include a polymerized vinyl chloride graft copolymer, a resin composition containing these as a main component, and a resin composition comprising a mixture thereof.
  • the vinyl chloride resin may be produced by any polymerization method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a bulk polymerization method.
  • the monomer copolymerizable with vinyl chloride may be any monomer having a polymerizable double bond in the molecule, for example, ⁇ -olefins such as ethylene, propylene, 1-butene; vinyl acetate, propion Vinyl esters such as vinyl acid; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl methacrylate, and phenyl methacrylate Aromatic vinyls such as styrene and ⁇ -methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. These monomers can be used alone or in combination of two or more.
  • ⁇ -olefins such as ethylene
  • the polymer other than the vinyl chloride copolymer may be any polymer that can be graft copolymerized with vinyl chloride, such as an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer. Examples thereof include a copolymer, an ethylene-propylene copolymer, an acrylonitrile-butadiene copolymer, polyurethane, chlorinated polyethylene, and chlorinated polypropylene. These copolymers can be used alone or in combination of two or more.
  • the content of the plasticizer for vinyl chloride resin is 10 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
  • the content of the plasticizer for vinyl chloride resin of the present invention can be appropriately adjusted depending on the use of the vinyl chloride resin composition.
  • the content of the plasticizer for vinyl chloride resin is less than 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, the flexibility or workability exhibited by the plasticizer cannot be sufficiently realized.
  • the content of the plasticizer for vinyl chloride resin is more than 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, it is difficult to ensure necessary mechanical properties, and molding processing This is a problem because the bleeding on the surface of the product tends to be intense.
  • the vinyl chloride resin composition of the present invention may contain additives other than the vinyl chloride resin plasticizer of the present invention, if necessary.
  • plasticizers other than the plasticizer for vinyl chloride resin of the present invention heat stabilizer, heat stabilization aid, antioxidant, light stabilizer, antistatic agent, antibacterial / antifungal agent, lubricant, colorant, Examples thereof include an antifogging agent, an antifogging agent, a processing aid, a filler, and a pigment.
  • heat stabilizer examples include tribasic lead sulfate, dibasic lead phosphite, lead (II) carbonate carbonate, zinc stearate (II), calcium stearate, barium stearate, dibutylbis (2-ethylhexyl).
  • examples thereof include oxycarbonylmethylthio) tin (IV), dibutylbis (isooctyloxycarbonylmethylthio) tin (IV), dibutyltin (IV) maleate, and di-n-octyltin (IV) maleate.
  • plasticizer other than the plasticizer for vinyl chloride resin of the present invention examples include dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, di-2-propylheptyl phthalate, and phthalic acid.
  • Phthalic acid esters such as diundecyl and di-2-ethylhexyl terephthalate; Adipic acid esters such as di-2-ethylhexyl adipate, diisononyl adipate and diisodecyl adipate; Tri-2-ethylhexyl trimellitic acid and trimellitic acid Trimellitic acid esters such as triisodecyl; phosphoric acid esters such as tri-2-ethylhexyl phosphate and tricresyl phosphate; 1,2-cyclohexanedicarboxylic acid diisononyl ester and the like.
  • the content of additives other than the plasticizer for vinyl chloride resin of the present invention impairs the excellent performance of the vinyl chloride resin composition of the present invention such as flexibility, heat resistance, low smoke generation, and electrical insulation. As long as there is no range.
  • the vinyl chloride resin composition of the present invention is obtained by superimposing additives other than the vinyl chloride resin, the plasticizer for vinyl chloride resin of the present invention, and, if necessary, the plasticizer for vinyl chloride resin of the present invention. It is obtained by putting in a commonly used mixing apparatus such as a mixer, and heating, stirring and cooling. The heating temperature and stirring time can be determined while looking at the mixing state from a monitoring window or the like.
  • the vinyl chloride resin composition of the present invention includes, for example, building materials such as wallpaper and flooring, members for transportation equipment such as vehicles, airplanes and ships, electric wire covering materials such as electric wires, cables and sheaths, furniture, office tools, and home appliances. It can be molded into food packaging wraps, toys, agricultural materials, synthetic leather, hoses, gaskets and the like.
  • Examples of the method for molding the vinyl chloride resin composition of the present invention include an extrusion molding method, an injection molding method, a calendar molding method, a blow molding method, an injection blow molding method, a compression molding method, and a rotational molding method.
  • a molding method can be appropriately selected according to the shape and size of the molded product.
  • the vinyl chloride resin composition of the present invention contains 10 to 100 parts by weight of the plasticizer for vinyl chloride resin of the present invention with respect to 100 parts by weight of the vinyl chloride resin. It has excellent performance such as low smoke generation and electrical insulation in a well-balanced manner.
  • the vinyl chloride resin composition is required to have excellent flexibility and heat resistance as basic mechanical properties.
  • the flexibility is measured by measuring the tensile strength and elongation of a vinyl chloride resin composition in accordance with a tensile test described in Japanese Industrial Standard (JIS) K6723-1995 (type of compound; type 2 No. 1). Can be evaluated.
  • the heat resistance is determined by, for example, the residual ratio of the tensile strength of the vinyl chloride resin composition according to the tensile test after heating described in Japanese Industrial Standard (JIS) K6723-1995 (Type of compound; Type 2 No. 1). It can be evaluated by measuring the residual elongation rate.
  • the tensile strength measured by the above test is preferably 20 MPa or more, and the elongation is preferably 300% or more.
  • the residual ratio of tensile strength measured by the above test is 90 to 110%, and the residual ratio of elongation is 60 to 110. % Is preferred. It can be said that the vinyl chloride resin composition is more excellent in moldability as the flexibility and heat resistance are higher.
  • Excellent low smoke generation is required for vinyl chloride resin compositions used as building materials, members for transportation equipment, wire covering materials, furniture, office tools, home appliances, and the like.
  • the low smoke generation can be evaluated by measuring the maximum smoke concentration of the vinyl chloride resin composition in accordance with, for example, the method described in American Industrial Standard (ASTM) E662-05.
  • the maximum smoke concentration measured in the above test is preferably as low as possible. If the maximum smoke concentration is high, the amount of smoke generated by the combustion of the vinyl chloride resin composition in the event of a fire increases, which may hinder the victims from finding evacuation routes and emergency exits, May be an obstacle. The amount of smoke generated is allowable depending on the application, but the maximum smoke concentration is preferably 500 or less depending on the type of interior material of the building.
  • the vinyl chloride resin composition used as a wire coating material is required to have excellent electrical insulation.
  • the electrical insulation is, for example, a volume resistance of a vinyl chloride resin composition at 30 ° C. according to a volume resistivity test described in Japanese Industrial Standard (JIS) K6723-1995 (type of compound; type 2 No. 1). It can be evaluated by measuring the value.
  • JIS Japanese Industrial Standard
  • the volume resistance value at 30 ° C. measured in the above test is preferably 1.0 ⁇ 10 14 ⁇ ⁇ cm or more from the viewpoint of preventing leakage.
  • the vinyl chloride resin composition of the present invention preferably satisfies all the preferred ranges from the viewpoint of balance in the various tests described above.
  • the plasticizer contained in the vinyl chloride resin composition volatilizes into the air, which may deteriorate the quality and work environment of the molded product.
  • the low volatility of the vinyl chloride resin composition is required.
  • the food packaging wrap may come into contact with the food, so the plasticizer contained in the food packaging wrap must have low migration to food. It is done.
  • the vinyl chloride resin composition of the present invention contains the plasticizer for vinyl chloride resin of the present invention as a plasticizer, it is excellent in low volatility and has low migration to foods and the like. .
  • Example 1 [Preparation of Vinyl Chloride Resin Composition 1 and Production of Evaluation Sheet 1] 100 parts by weight of a vinyl chloride resin (manufactured by Taiyo PVC Co., Ltd., product name: Taiyo PVC TH-1300), 3 parts by weight of tribasic lead sulfate (manufactured by NI Chemtech Co., Ltd., product name: BS-T) and 50 parts by weight of mixed ester Parts were mixed at room temperature, heated to 95 ° C., and allowed to stand at that temperature for 1 hour to obtain a vinyl chloride resin composition 1. The obtained vinyl chloride resin composition 1 is kneaded at 170 to 190 ° C.
  • Example 2 [Preparation of Vinyl Chloride Resin Composition 2 and Production of Evaluation Sheet 2] A vinyl chloride resin composition 2 was obtained in the same manner as in Example 1 except that the mixed ester 2 was used instead of the mixed ester 1. Also, an evaluation sheet 2 was obtained in the same manner as in Example 1 except that the vinyl chloride resin composition 2 was used instead of the vinyl chloride resin composition 1.
  • Example 1 [Preparation of vinyl chloride resin composition A and preparation of evaluation sheet A] A vinyl chloride resin composition A was obtained in the same manner as in Example 1 except that di-2-ethylhexyl phthalate (manufactured by J-Plus) was used in place of the mixed ester 1. Further, an evaluation sheet A was obtained in the same manner as in Example 1 except that the vinyl chloride resin composition A was used instead of the vinyl chloride resin composition 1.
  • Test Example 2 Evaluation of heat resistance (tensile test after heating) The tensile strength and elongation before and after heating of the evaluation sheet 1, the evaluation sheet 2 and the evaluation sheet A were measured in accordance with the post-heating tensile test described in JIS K6723-1995 (type of compound; type 2 No. 1). The residual ratio of tensile strength after heating and the residual ratio of elongation after heating were calculated. The results are shown in Table 1. It shows that it is excellent in heat resistance, so that the residual rate of the tensile strength after a heating and the residual rate of the elongation after a heating are near 100%.
  • the vinyl chloride resin compositions (Examples 1 and 2) containing the plasticizer for vinyl chloride resin of the present invention are chlorides containing di-2-ethylhexyl phthalate which has been conventionally used as a plasticizer. It turns out that it has the same outstanding softness
  • the residual ratio of tensile strength is 101% and the residual ratio of elongation is 96%.
  • Example 2 the residual ratio of tensile strength is 96%, and the residual ratio of elongation is 67%. It turns out that it has the outstanding heat resistance.
  • Example 1 has a maximum smoke concentration value of 466, and Example 2 has a maximum smoke concentration value of 427, indicating that it has excellent low smoke generation.
  • Example 1 has a volume resistance value of 3.0 ⁇ 10 14 ⁇ ⁇ cm, and Example 2 has a volume resistance value of 4.8 ⁇ 10 14 ⁇ ⁇ cm, and has excellent electrical insulation. I understand. It can be seen that Examples 1 and 2 are excellent in balance between flexibility, heat resistance, low smoke generation and electrical insulation.
  • Comparative Example 1 the residual rate of tensile strength is 181%, the residual rate of elongation is 4%, the maximum value of smoke concentration is 623, and the volume resistance value is 2.5 ⁇ 10 13 ⁇ ⁇ cm. The heat resistance, low smoke generation and electrical insulation are poor, and the physical properties are not balanced.
  • a plasticizer for a vinyl chloride resin that imparts excellent performance such as flexibility, heat resistance, low smoke generation, and electrical insulation to a vinyl chloride resin in a well-balanced manner, and a vinyl chloride resin containing the same A resin composition can be provided.

Abstract

Provided is a plasticizer for a vinyl chloride resin, which comprises an ester mixture of pentaerythritol and a carboxylic acid mixture, said plasticizer being characterized in that the carboxylic acid mixture is a carboxylic acid mixture composed of isobutyric acid and an aliphatic monocarboxylic acid having 8 or 9 carbon atoms and the content ratio of isobutyric acid in the carboxylic acid mixture ranges from 35 to 65 mol%. The plasticizer for a vinyl chloride resin can impart excellent properties including flexibility, heat resistance, a low smoke evolution property and an electrical insulation property to a vinyl chloride resin in a balanced manner.

Description

塩化ビニル系樹脂用可塑剤およびそれを含有する塩化ビニル系樹脂組成物Plasticizer for vinyl chloride resin and vinyl chloride resin composition containing the same
　本発明は、塩化ビニル系樹脂用可塑剤およびそれを含有する塩化ビニル系樹脂組成物に関する。 The present invention relates to a plasticizer for vinyl chloride resin and a vinyl chloride resin composition containing the same.
　塩化ビニル系樹脂組成物は、社会と暮らしのあらゆるところにあるプラスチック製品等に広く使用されている。このような塩化ビニル系樹脂組成物は、通常、塩化ビニル系樹脂に、可塑剤、安定剤、充填剤、顔料等の各種添加剤を適切に添加され用いられる。そのような添加剤の中でも、可塑剤は、塩化ビニル系樹脂に柔軟性をはじめとする種々の性能を付与するとともに、塩化ビニル系樹脂組成物の成形加工時の加工温度を低下させ、加工を容易にするために不可欠な添加剤である（非特許文献１、非特許文献２）。 Vinyl chloride-based resin compositions are widely used in plastic products, etc. in every part of society and life. Such a vinyl chloride resin composition is usually used by appropriately adding various additives such as a plasticizer, a stabilizer, a filler, and a pigment to the vinyl chloride resin. Among such additives, the plasticizer imparts various performances including flexibility to the vinyl chloride resin, and lowers the processing temperature during the molding process of the vinyl chloride resin composition. It is an indispensable additive for facilitating (Non-Patent Document 1, Non-Patent Document 2).
　このような塩化ビニル系樹脂組成物に用いられる可塑剤に求められる性能としては、該組成物を原料として成型加工品とした場合の、柔軟性、耐熱性、低発煙性、電気絶縁性等がある。 The performance required for the plasticizer used in such a vinyl chloride resin composition includes flexibility, heat resistance, low smoke generation, electrical insulation, etc. when the composition is used as a molded product. is there.
　特に、壁紙、床材等の建材、車両、航空機、船舶等の輸送機器用部材、家具、事務用具、家電等では、火炎時に大量の発煙が生じることで、避難や消火活動に支障をきたすだけでなく、二次災害の可能性も高まるため、低発煙性が求められる（非特許文献３）。 Especially in building materials such as wallpaper, flooring, vehicles, aircraft, ships and other transportation equipment, furniture, office equipment, home appliances, etc., a large amount of smoke is generated at the time of the flame, which hinders evacuation and fire fighting activities. Moreover, since the possibility of a secondary disaster increases, low smoke generation property is calculated | required (nonpatent literature 3).
　また、電線、ケーブル、シース等の電線被覆材では、漏電を防ぐために、電気絶縁性が求められる（非特許文献４）。 In addition, electric wire covering materials such as electric wires, cables, and sheaths are required to have electrical insulation in order to prevent electric leakage (Non-Patent Document 4).
　このような塩化ビニル系樹脂組成物に用いられる代表的な可塑剤としては、フタル酸エステルやアジピン酸エステル等の二塩基酸の高級アルキルエステルがある。中でも、フタル酸ジ－２－エチルヘキシルは、柔軟性など諸物性のバランスが良いことから、広く使用されているが、更なる耐熱性、低発煙性および電気絶縁性の要求には対応が困難である。 Typical plasticizers used in such vinyl chloride resin compositions include higher alkyl esters of dibasic acids such as phthalic acid esters and adipic acid esters. Among them, di-2-ethylhexyl phthalate is widely used because it has a good balance of physical properties such as flexibility, but it is difficult to meet the demands for further heat resistance, low smoke generation and electrical insulation. is there.
　一方、フタル酸エステルの使用は、玩具や育児用品等では制限され[例えば、食品、添加物等の規格基準の改正（平成２２年厚生労働省告示第３３６号）等]、将来は種々の用途においても制限されることが予想される。従って、基本骨格がフタル酸エステルを含まず、フタル酸エステルと同等以上の性能を有する、可塑剤の開発が必要とされている。 On the other hand, the use of phthalates is limited for toys and child-care items [for example, revision of standards for food, additives, etc. (2010 Ministry of Health, Labor and Welfare Notification No. 336), etc.] Is also expected to be limited. Therefore, it is necessary to develop a plasticizer whose basic skeleton does not contain a phthalate ester and has a performance equal to or higher than that of a phthalate ester.
　特許文献１には、ペンタエリスリトールと無水プロピオン酸とのエステルが可塑剤として使用できることが記載されているが、可塑剤が配合された塩化ビニル系樹脂組成物としての耐熱性、電気絶縁性、低発煙性などの効果については記載されていない。 Patent Document 1 describes that an ester of pentaerythritol and propionic anhydride can be used as a plasticizer. However, as a vinyl chloride resin composition containing a plasticizer, the heat resistance, electrical insulation, low It does not describe effects such as smoke generation.
特開２０１２－３１２２０号公報Japanese Patent Application Laid-Open No. 2012-3220
　本発明の目的は、塩化ビニル系樹脂に対して、柔軟性、耐熱性、低発煙性、電気絶縁性等の優れた性能をバランスよく付与する塩化ビニル系樹脂用可塑剤およびそれを含有する塩化ビニル系樹脂組成物を提供することにある。 An object of the present invention is to provide a plasticizer for a vinyl chloride resin and a chloride containing the same, which imparts excellent performance such as flexibility, heat resistance, low smoke generation, and electrical insulation to a vinyl chloride resin. The object is to provide a vinyl-based resin composition.
　本発明は、以下の［１］～［４］を提供する。
［１］ペンタエリスリトールと混合カルボン酸との混合エステルからなる塩化ビニル系樹脂用可塑剤であって、前記混合カルボン酸が、イソ酪酸と、炭素数８または炭素数９の脂肪族モノカルボン酸とからなる混合カルボン酸であり、前記混合カルボン酸にしめるイソ酪酸の割合が３５～６５モル％の範囲であることを特徴とする塩化ビニル系樹脂用可塑剤。
［２］炭素数８または炭素数９の脂肪族モノカルボン酸が、２－エチルヘキサン酸または３，５，５－トリメチルヘキサン酸である［１］に記載の塩化ビニル系樹脂用可塑剤。
［３］塩化ビニル系樹脂と、［１］または［２］に記載の塩化ビニル系樹脂用可塑剤とを含有する塩化ビニル系樹脂組成物であって、塩化ビニル系樹脂１００重量部に対して、［１］または［２］に記載の塩化ビニル系樹脂用可塑剤を１０～１００重量部含有することを特徴とする塩化ビニル系樹脂組成物。
［４］日本工業規格（ＪＩＳ）Ｋ６７２３－１９９５（コンパウンドの種類；２種１号）に準じて加熱後引張試験で測定される引張強さの残率が９０～１１０％の範囲である［３］に記載の塩化ビニル系樹脂組成物。 The present invention provides the following [1] to [4].
[1] A plasticizer for a vinyl chloride resin comprising a mixed ester of pentaerythritol and a mixed carboxylic acid, wherein the mixed carboxylic acid is isobutyric acid and an aliphatic monocarboxylic acid having 8 or 9 carbon atoms. A plasticizer for a vinyl chloride resin, characterized in that the ratio of isobutyric acid contained in the mixed carboxylic acid is in the range of 35 to 65 mol%.
[2] The plasticizer for vinyl chloride resin according to [1], wherein the aliphatic monocarboxylic acid having 8 or 9 carbon atoms is 2-ethylhexanoic acid or 3,5,5-trimethylhexanoic acid.
[3] A vinyl chloride resin composition comprising a vinyl chloride resin and the vinyl chloride resin plasticizer according to [1] or [2], wherein the vinyl chloride resin composition is used in 100 parts by weight of the vinyl chloride resin. A vinyl chloride resin composition comprising 10 to 100 parts by weight of the plasticizer for vinyl chloride resin according to [1] or [2].
[4] Residual ratio of tensile strength measured in a tensile test after heating according to Japanese Industrial Standard (JIS) K6723-1995 (type of compound; type 2 No. 1) is in the range of 90 to 110% [3 ] The vinyl chloride-type resin composition of description.
　本発明により、塩化ビニル系樹脂に対して、柔軟性、耐熱性、低発煙性、電気絶縁性等の優れた性能をバランスよく付与する塩化ビニル系樹脂用可塑剤およびそれを含有する塩化ビニル系樹脂組成物を提供できる。 INDUSTRIAL APPLICABILITY According to the present invention, a plasticizer for a vinyl chloride resin that imparts excellent performance such as flexibility, heat resistance, low smoke generation, and electrical insulation to a vinyl chloride resin in a well-balanced manner, and a vinyl chloride resin containing the same A resin composition can be provided.
＜塩化ビニル系樹脂用可塑剤＞
　本発明の塩化ビニル系樹脂用可塑剤は、ペンタエリスリトールと混合カルボン酸との混合エステルからなる。前記混合カルボン酸は、イソ酪酸と、炭素数８または炭素数９の脂肪族モノカルボン酸とからなる混合カルボン酸であり、前記混合カルボン酸にしめるイソ酪酸の割合は、３５～６５モル％の範囲である。本発明の塩化ビニル系樹脂用可塑剤は、塩化ビニル系樹脂に対して、柔軟性、耐熱性、低発煙性、電気絶縁性等の優れた性能をバランスよく付与する。また、塩化ビニル系樹脂との相溶性に優れ、塩化ビニル系樹脂組成物を調製する際に、本発明の塩化ビニル系樹脂用可塑剤が分離することはない。また、十分な分子量を有しているため、低揮発性にも優れる。 <Plasticizer for vinyl chloride resin>
The plasticizer for vinyl chloride resin of the present invention comprises a mixed ester of pentaerythritol and mixed carboxylic acid. The mixed carboxylic acid is a mixed carboxylic acid composed of isobutyric acid and an aliphatic monocarboxylic acid having 8 or 9 carbon atoms, and the ratio of isobutyric acid to the mixed carboxylic acid is in the range of 35 to 65 mol%. It is. The plasticizer for vinyl chloride resin of the present invention imparts excellent performance such as flexibility, heat resistance, low smoke generation, and electrical insulation to the vinyl chloride resin in a balanced manner. Moreover, it is excellent in compatibility with the vinyl chloride resin, and the vinyl chloride resin plasticizer of the present invention is not separated when preparing the vinyl chloride resin composition. Moreover, since it has sufficient molecular weight, it is excellent also in low volatility.
　本発明の塩化ビニル系樹脂用可塑剤は、塩化ビニル系樹脂に対して、柔軟性、耐熱性、低発煙性、電気絶縁性等の優れた性能を特にバランスよく付与する観点より、前記混合カルボン酸にしめるイソ酪酸の割合が、３８～６５モル％の範囲であるのが好ましく、５０～６５モル％の範囲であるのがより好ましい。 The plasticizer for vinyl chloride resin of the present invention is a mixture of the above-mentioned mixed carboxylic acids from the viewpoint of imparting excellent performance such as flexibility, heat resistance, low smoke generation and electrical insulation to the vinyl chloride resin in a particularly well-balanced manner. The ratio of isobutyric acid to be converted to acid is preferably in the range of 38 to 65 mol%, more preferably in the range of 50 to 65 mol%.
　本発明の塩化ビニル系樹脂用可塑剤である混合エステルにおいて、該混合エステルがペンタエリスリトールとイソ酪酸と炭素数８の脂肪族モノカルボン酸との混合エステルであるとき、該混合エステルには、下記（ｉ）～（iii）：
（ｉ）同一分子における構成カルボン酸がイソ酪酸および炭素数８の脂肪族モノカルボン酸の双方からなる混合エステル
（ii）ペンタエリスリトールとイソ酪酸とのエステル、およびペンタエリスリトールと炭素数８の脂肪族モノカルボン酸とのエステルの混合物
（iii）上記（ｉ）および（ii）の混合物
の各態様が包含される。 In the mixed ester which is a plasticizer for a vinyl chloride resin of the present invention, when the mixed ester is a mixed ester of pentaerythritol, isobutyric acid and an aliphatic monocarboxylic acid having 8 carbon atoms, the mixed ester includes: (I) to (iii):
(I) Mixed ester in which constituent carboxylic acids in the same molecule are both isobutyric acid and C8 aliphatic monocarboxylic acid (ii) ester of pentaerythritol and isobutyric acid, and pentaerythritol and C8 aliphatic Mixtures of esters with monocarboxylic acids (iii) Embodiments of the mixtures of (i) and (ii) above are included.
　本発明の塩化ビニル系樹脂用可塑剤である混合エステルにおいて、該混合エステルがペンタエリスリトールとイソ酪酸と炭素数９の脂肪族モノカルボン酸との混合エステルであるとき、該混合エステルには、下記（iv）～（vi）：
（iv）同一分子における構成カルボン酸がイソ酪酸および炭素数９の脂肪族モノカルボン酸の双方からなる混合エステル
（v）ペンタエリスリトールとイソ酪酸とのエステル、およびペンタエリスリトールと炭素数９の脂肪族モノカルボン酸とのエステルの混合物
（vi）上記（iv）および（v）の混合物
の各態様が包含される。 In the mixed ester which is a plasticizer for a vinyl chloride resin of the present invention, when the mixed ester is a mixed ester of pentaerythritol, isobutyric acid and an aliphatic monocarboxylic acid having 9 carbon atoms, the mixed ester includes: (Iv)-(vi):
(Iv) Mixed ester in which the constituent carboxylic acids in the same molecule are both isobutyric acid and an aliphatic monocarboxylic acid having 9 carbon atoms (v) an ester of pentaerythritol and isobutyric acid, and pentaerythritol and aliphatic having 9 carbon atoms Mixtures of esters with monocarboxylic acids (vi) Embodiments of the mixtures of (iv) and (v) above are included.
　本発明の塩化ビニル系樹脂用可塑剤である混合エステルには、ペンタエリスリトールの水酸基の一部がエステル化されずに水酸基のまま残っている部分エステルが不純物として含まれていても良い。 The mixed ester which is a plasticizer for a vinyl chloride resin according to the present invention may contain, as an impurity, a partial ester in which a part of the hydroxyl group of pentaerythritol is not esterified and remains as a hydroxyl group.
　本発明の塩化ビニル系樹脂用可塑剤である混合エステルを構成する炭素数８または炭素数９の脂肪族モノカルボン酸としては、直鎖または分岐脂肪族モノカルボン酸のいずれでもよい。例えば、オクタン酸、２－エチル－２－メチルペンタン酸、２－エチルヘキサン酸、３－エチルヘキサン酸、２－メチルヘプタン酸、６－メチルヘプタン酸、イソオクタン酸（炭素数８の脂肪族モノカルボン酸の異性体混合物）、ノナン酸、３，５，５－トリメチルヘキサン酸、２，２－ジメチルヘプタン酸、２－メチルオクタン酸、７－メチルオクタン酸、イソノナン酸（炭素数９の脂肪族モノカルボン酸の異性体混合物）等が挙げられ、中でも、２－エチルヘキサン酸または３，５，５－トリメチルヘキサン酸が好ましい。 The aliphatic monocarboxylic acid having 8 or 9 carbon atoms constituting the mixed ester which is the plasticizer for vinyl chloride resin of the present invention may be either a linear or branched aliphatic monocarboxylic acid. For example, octanoic acid, 2-ethyl-2-methylpentanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 2-methylheptanoic acid, 6-methylheptanoic acid, isooctanoic acid (aliphatic monocarboxylic acid having 8 carbon atoms) Isomer mixture of acids), nonanoic acid, 3,5,5-trimethylhexanoic acid, 2,2-dimethylheptanoic acid, 2-methyloctanoic acid, 7-methyloctanoic acid, isononanoic acid (aliphatic monocarboxylic acid having 9 carbon atoms) Isomer mixtures of carboxylic acids), among which 2-ethylhexanoic acid or 3,5,5-trimethylhexanoic acid is preferred.
　本発明の塩化ビニル系樹脂用可塑剤である混合エステルは、例えば、ペンタエリスリトールと、イソ酪酸と、炭素数８または炭素数９の脂肪族モノカルボン酸とを、１２０～２５０℃で、５～６０時間反応させることにより製造することができる。 The mixed ester which is a plasticizer for a vinyl chloride resin of the present invention includes, for example, pentaerythritol, isobutyric acid, and an aliphatic monocarboxylic acid having 8 or 9 carbon atoms at 120 to 250 ° C. and 5 to 5 It can be produced by reacting for 60 hours.
　前記反応において触媒を用いてもよく、触媒としては、例えば、鉱酸、有機酸、ルイス酸、有機金属、固体酸等が挙げられる。鉱酸の具体例としては、例えば、塩酸、フッ化水素酸、硫酸、リン酸、硝酸等が挙げられる。有機酸の具体例としては、例えば、ｐ－トルエンスルホン酸、ベンゼンスルホン酸、ブタンスルホン酸、プロパンスルホン酸、エタンスルホン酸、メタンスルホン酸等が挙げられる。ルイス酸の具体例としては、例えば、三フッ化ホウ素、塩化アルミニウム、四塩化スズ、四塩化チタン等が挙げられる。有機金属の具体例としては、例えば、テトラプロポキシチタン、テトラブトキシチタン、テトラキス(２－エチルヘキシルオキシ)チタン等が挙げられる。固体酸の具体例としては、例えば、陽イオン交換樹脂等が挙げられる。 In the above reaction, a catalyst may be used. Examples of the catalyst include mineral acids, organic acids, Lewis acids, organic metals, solid acids and the like. Specific examples of the mineral acid include hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid and the like. Specific examples of the organic acid include p-toluenesulfonic acid, benzenesulfonic acid, butanesulfonic acid, propanesulfonic acid, ethanesulfonic acid, methanesulfonic acid and the like. Specific examples of the Lewis acid include boron trifluoride, aluminum chloride, tin tetrachloride, titanium tetrachloride and the like. Specific examples of the organic metal include tetrapropoxy titanium, tetrabutoxy titanium, tetrakis (2-ethylhexyloxy) titanium, and the like. Specific examples of the solid acid include a cation exchange resin.
　イソ酪酸の使用量と、炭素数８または炭素数９の脂肪族モノカルボン酸の使用量との和が、使用するペンタエリスリトールの水酸基に対して、１．１～１．４倍モルであるのが好ましい。 The sum of the amount of isobutyric acid used and the amount of aliphatic monocarboxylic acid having 8 or 9 carbon atoms is 1.1 to 1.4 times the mole of the hydroxyl group of pentaerythritol used. Is preferred.
　前記反応において、反応により生成する水を反応混合物から取り除きながら反応を行うことが好ましい。反応により生成する水を反応混合物から取り除くとき、同時にイソ酪酸も反応混合物から取り除いてしまうことがある。 In the above reaction, it is preferable to carry out the reaction while removing water produced by the reaction from the reaction mixture. When water generated by the reaction is removed from the reaction mixture, isobutyric acid may be removed from the reaction mixture at the same time.
　前記反応において溶媒を用いてもよく、溶媒としては、例えば、ベンゼン、トルエン、キシレン、ヘキサン、ヘプタン、イソヘキサン、イソオクタン、イソノナン、デカン等の炭化水素系溶媒等が挙げられる。溶媒を用いることで、反応により生成する水を反応混合物から効率よく取り除くことができ、反応時間を短縮することができる。 In the above reaction, a solvent may be used. Examples of the solvent include hydrocarbon solvents such as benzene, toluene, xylene, hexane, heptane, isohexane, isooctane, isononane, decane, and the like. By using a solvent, water generated by the reaction can be efficiently removed from the reaction mixture, and the reaction time can be shortened.
　また、ペンタエリスリトールに対する、イソ酪酸と、炭素数８または炭素数９の脂肪族モノカルボン酸との反応性の差から、得られた混合エステルを構成するイソ酪酸と炭素数８または炭素数９の脂肪族モノカルボン酸とのモル比が、混合エステルの製造に使用した量におけるそれとは異なることがある。 Further, from the reactivity difference between isobutyric acid and aliphatic monocarboxylic acid having 8 or 9 carbon atoms with respect to pentaerythritol, isobutyric acid constituting the resulting mixed ester and having 8 or 9 carbon atoms are mixed. The molar ratio with the aliphatic monocarboxylic acid may be different from that in the amount used to produce the mixed ester.
　反応後、必要に応じて、該混合エステルを有機合成化学で通常用いられる方法（水および／またはアルカリ水溶液を用いた洗浄、活性炭、吸着剤等による処理、各種クロマトグラフィー、蒸留等）で精製してもよい。 After the reaction, if necessary, the mixed ester is purified by methods commonly used in organic synthetic chemistry (washing with water and / or alkaline aqueous solution, treatment with activated carbon, adsorbent, etc., various chromatography, distillation, etc.). May be.
　また、該混合エステルは、原料として、イソ酪酸や炭素数８または炭素数９の脂肪族モノカルボン酸を使用する代わりに、対応する酸無水物を使用しても、製造することができる。 The mixed ester can also be produced by using a corresponding acid anhydride instead of isobutyric acid or an aliphatic monocarboxylic acid having 8 or 9 carbon atoms as a raw material.
＜塩化ビニル系樹脂組成物＞
　本発明の塩化ビニル系樹脂組成物は、塩化ビニル系樹脂と本発明の塩化ビニル系樹脂用可塑剤を含有する塩化ビニル系樹脂組成物である。前記塩化ビニル系樹脂としては、例えば、塩化ビニル単独重合体、塩化ビニルと共重合可能な単量体との塩化ビニル共重合体、前記塩化ビニル共重合体以外の重合体に塩化ビニルをグラフト共重合させた塩化ビニルグラフト共重合体、これらを主成分とする樹脂組成物、及びこれらの混合物からなる樹脂組成物等が挙げられる。前記塩化ビニル系樹脂は、乳化重合法、懸濁重合法、溶液重合法、塊状重合法等いずれの重合方法で製造してもよい。 <Vinyl chloride resin composition>
The vinyl chloride resin composition of the present invention is a vinyl chloride resin composition containing the vinyl chloride resin and the plasticizer for vinyl chloride resin of the present invention. Examples of the vinyl chloride resin include a vinyl chloride homopolymer, a vinyl chloride copolymer with a monomer copolymerizable with vinyl chloride, and a graft copolymer of vinyl chloride with a polymer other than the vinyl chloride copolymer. Examples thereof include a polymerized vinyl chloride graft copolymer, a resin composition containing these as a main component, and a resin composition comprising a mixture thereof. The vinyl chloride resin may be produced by any polymerization method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a bulk polymerization method.
　前記塩化ビニルと共重合可能な単量体としては、分子中に重合性二重結合を有するものであればよく、例えば、エチレン、プロピレン、１－ブテン等のα－オレフィン類；酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；イソブチルビニルエーテル、セチルビニルエーテル等のビニルエーテル類；アクリル酸、メタクリル酸等の不飽和カルボン酸類；アクリル酸メチル、メタクリル酸エチル、メタクリル酸フェニル等のアクリル酸又はメタクリル酸のエステル類；スチレン、α－メチルスチレン等の芳香族ビニル類；塩化ビニリデン、フッ化ビニル等のハロゲン化ビニル類；Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等のＮ－置換マレイミド類等が挙げられる。これらの単量体は、１種類のみで用いることも２種以上併用することもできる。 The monomer copolymerizable with vinyl chloride may be any monomer having a polymerizable double bond in the molecule, for example, α-olefins such as ethylene, propylene, 1-butene; vinyl acetate, propion Vinyl esters such as vinyl acid; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl methacrylate, and phenyl methacrylate Aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. These monomers can be used alone or in combination of two or more.
　前記塩化ビニル共重合体以外の重合体としては、塩化ビニルをグラフト共重合できるものであればよく、例えば、エチレン－酢酸ビニル共重合体、エチレン－エチルアクリレート共重合体、エチレン－メチルメタクリレート共重合体、エチレン－プロピレン共重合体、アクリロニトリル－ブタジエン共重合体、ポリウレタン、塩素化ポリエチレン、塩素化ポリプロピレン等が挙げられる。これらの共重合体は、１種類のみで用いることも２種以上併用することもできる。 The polymer other than the vinyl chloride copolymer may be any polymer that can be graft copolymerized with vinyl chloride, such as an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer. Examples thereof include a copolymer, an ethylene-propylene copolymer, an acrylonitrile-butadiene copolymer, polyurethane, chlorinated polyethylene, and chlorinated polypropylene. These copolymers can be used alone or in combination of two or more.
　本発明の塩化ビニル系樹脂組成物において、塩化ビニル系樹脂用可塑剤の含有量は、塩化ビニル系樹脂１００重量部に対して、１０～１００重量部である。本発明の塩化ビニル系樹脂用可塑剤の含有量は、塩化ビニル系樹脂組成物の用途により適切に調整され得る。塩化ビニル系樹脂用可塑剤の含有量が、塩化ビニル系樹脂１００重量部に対して、１０重量部未満の場合には、該可塑剤によって示される柔軟性または加工性を十分に実現できない。また、塩化ビニル系樹脂用可塑剤の含有量が、塩化ビニル系樹脂１００重量部に対して、１００重量部より多い場合には、必要な機械的特性を確保することが難しく、また、成形加工品の表面へのブリードが激しくなる傾向にあるため問題となる。 In the vinyl chloride resin composition of the present invention, the content of the plasticizer for vinyl chloride resin is 10 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. The content of the plasticizer for vinyl chloride resin of the present invention can be appropriately adjusted depending on the use of the vinyl chloride resin composition. When the content of the plasticizer for vinyl chloride resin is less than 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, the flexibility or workability exhibited by the plasticizer cannot be sufficiently realized. Further, when the content of the plasticizer for vinyl chloride resin is more than 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, it is difficult to ensure necessary mechanical properties, and molding processing This is a problem because the bleeding on the surface of the product tends to be intense.
　本発明の塩化ビニル系樹脂組成物は、必要に応じて、本発明の塩化ビニル系樹脂用可塑剤以外の添加剤を含有してもよい。例えば、本発明の塩化ビニル系樹脂用可塑剤以外の可塑剤、熱安定剤、熱安定化助剤、酸化防止剤、光安定剤、帯電防止剤、抗菌・抗カビ剤、滑剤、着色剤、防曇剤、防霧剤、加工助剤、充填剤、顔料等が挙げられる。 The vinyl chloride resin composition of the present invention may contain additives other than the vinyl chloride resin plasticizer of the present invention, if necessary. For example, plasticizers other than the plasticizer for vinyl chloride resin of the present invention, heat stabilizer, heat stabilization aid, antioxidant, light stabilizer, antistatic agent, antibacterial / antifungal agent, lubricant, colorant, Examples thereof include an antifogging agent, an antifogging agent, a processing aid, a filler, and a pigment.
　前記熱安定剤としては、例えば、三塩基性硫酸鉛、二塩基性亜リン酸鉛、炭酸水酸化鉛（II）、ステアリン酸亜鉛（II）、ステアリン酸カルシウム、ステアリン酸バリウム、ジブチルビス（２－エチルヘキシルオキシカルボニルメチルチオ）スズ（IV）、ジブチルビス（イソオクチルオキシカルボニルメチルチオ）スズ（IV）、マレイン酸ジブチルスズ（IV）、マレイン酸ジ－ｎ－オクチルスズ（IV）等が挙げられる。 Examples of the heat stabilizer include tribasic lead sulfate, dibasic lead phosphite, lead (II) carbonate carbonate, zinc stearate (II), calcium stearate, barium stearate, dibutylbis (2-ethylhexyl). Examples thereof include oxycarbonylmethylthio) tin (IV), dibutylbis (isooctyloxycarbonylmethylthio) tin (IV), dibutyltin (IV) maleate, and di-n-octyltin (IV) maleate.
　本発明の塩化ビニル系樹脂用可塑剤以外の可塑剤としては、例えば、フタル酸ジブチル、フタル酸ジ－２－エチルヘキシル、フタル酸ジイソノニル、フタル酸ジイソデシル、フタル酸ジ－２－プロピルヘプチル、フタル酸ジウンデシル、テレフタル酸ジ－２－エチルヘキシル等のフタル酸エステル類；アジピン酸ジ－２－エチルヘキシル、アジピン酸ジイソノニル、アジピン酸ジイソデシル等のアジピン酸エステル類；トリメリット酸トリ－２－エチルヘキシル、トリメリット酸トリイソデシル等のトリメリット酸エステル類；リン酸トリ－２－エチルヘキシル、リン酸トリクレジル等のリン酸エステル類；１，２－シクロヘキサンジカルボン酸ジイソノニルエステル等が挙げられる。 Examples of the plasticizer other than the plasticizer for vinyl chloride resin of the present invention include dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, di-2-propylheptyl phthalate, and phthalic acid. Phthalic acid esters such as diundecyl and di-2-ethylhexyl terephthalate; Adipic acid esters such as di-2-ethylhexyl adipate, diisononyl adipate and diisodecyl adipate; Tri-2-ethylhexyl trimellitic acid and trimellitic acid Trimellitic acid esters such as triisodecyl; phosphoric acid esters such as tri-2-ethylhexyl phosphate and tricresyl phosphate; 1,2-cyclohexanedicarboxylic acid diisononyl ester and the like.
　本発明の塩化ビニル系樹脂用可塑剤以外の添加剤の含有量は、本発明の塩化ビニル系樹脂組成物の、柔軟性、耐熱性、低発煙性、電気絶縁性等の優れた性能を損なわない範囲であればよい。 The content of additives other than the plasticizer for vinyl chloride resin of the present invention impairs the excellent performance of the vinyl chloride resin composition of the present invention such as flexibility, heat resistance, low smoke generation, and electrical insulation. As long as there is no range.
　本発明の塩化ビニル系樹脂組成物は、前記塩化ビニル系樹脂、本発明の塩化ビニル系樹脂用可塑剤、及び必要に応じて本発明の塩化ビニル系樹脂用可塑剤以外の添加剤を、スーパーミキサー等の通常用いられる混合装置に投入し、加熱、撹拌、冷却することにより得られる。加熱温度や撹拌時間は、監視窓等から混合状態を見ながら決定することができる。 The vinyl chloride resin composition of the present invention is obtained by superimposing additives other than the vinyl chloride resin, the plasticizer for vinyl chloride resin of the present invention, and, if necessary, the plasticizer for vinyl chloride resin of the present invention. It is obtained by putting in a commonly used mixing apparatus such as a mixer, and heating, stirring and cooling. The heating temperature and stirring time can be determined while looking at the mixing state from a monitoring window or the like.
　本発明の塩化ビニル系樹脂組成物は、例えば、壁紙、床材等の建材、車両、航空機、船舶等の輸送機器用部材、電線、ケーブル、シース等の電線被覆材、家具、事務用具、家電、食品包装用ラップ、玩具、農業用資材、合成皮革、ホース、ガスケット等に成形して用いることができる。 The vinyl chloride resin composition of the present invention includes, for example, building materials such as wallpaper and flooring, members for transportation equipment such as vehicles, airplanes and ships, electric wire covering materials such as electric wires, cables and sheaths, furniture, office tools, and home appliances. It can be molded into food packaging wraps, toys, agricultural materials, synthetic leather, hoses, gaskets and the like.
　本発明の塩化ビニル系樹脂組成物を成形する方法としては、例えば、押出成形法、射出成形法、カレンダー成形法、ブロー成形法、射出ブロー成形法、圧縮成形法、回転成形法等があり、成形品の形状、大きさに応じて、成形方法を適宜選択することができる。 Examples of the method for molding the vinyl chloride resin composition of the present invention include an extrusion molding method, an injection molding method, a calendar molding method, a blow molding method, an injection blow molding method, a compression molding method, and a rotational molding method. A molding method can be appropriately selected according to the shape and size of the molded product.
　本発明の塩化ビニル系樹脂組成物は、本発明の塩化ビニル系樹脂用可塑剤を、塩化ビニル系樹脂１００重量部に対して、１０～１００重量部含有しているため、柔軟性、耐熱性、低発煙性、電気絶縁性等の優れた性能をバランスよく有している。 The vinyl chloride resin composition of the present invention contains 10 to 100 parts by weight of the plasticizer for vinyl chloride resin of the present invention with respect to 100 parts by weight of the vinyl chloride resin. It has excellent performance such as low smoke generation and electrical insulation in a well-balanced manner.
　塩化ビニル系樹脂組成物には、基本的な機械的特性として、優れた柔軟性と耐熱性が求められる。柔軟性は、例えば、日本工業規格（ＪＩＳ）Ｋ６７２３－１９９５（コンパウンドの種類；２種１号）に記載の引張試験に準じて、塩化ビニル系樹脂組成物の引張強さと伸びを測定することで評価できる。耐熱性は、例えば、日本工業規格（ＪＩＳ）Ｋ６７２３－１９９５（コンパウンドの種類；２種１号）に記載の加熱後引張試験に準じて、塩化ビニル系樹脂組成物の引張強さの残率と伸びの残率を測定することで評価できる。 The vinyl chloride resin composition is required to have excellent flexibility and heat resistance as basic mechanical properties. For example, the flexibility is measured by measuring the tensile strength and elongation of a vinyl chloride resin composition in accordance with a tensile test described in Japanese Industrial Standard (JIS) K6723-1995 (type of compound; type 2 No. 1). Can be evaluated. The heat resistance is determined by, for example, the residual ratio of the tensile strength of the vinyl chloride resin composition according to the tensile test after heating described in Japanese Industrial Standard (JIS) K6723-1995 (Type of compound; Type 2 No. 1). It can be evaluated by measuring the residual elongation rate.
　本発明の塩化ビニル系樹脂組成物において、柔軟性の観点から、上記試験で測定される引張強さは２０ＭＰａ以上であることが好ましく、伸びは３００％以上であることが好ましい。また、本発明の塩化ビニル系樹脂組成物において、耐熱性の観点から、上記試験で測定される引張強さの残率は９０～１１０％であることが好ましく、伸びの残率は６０～１１０％であることが好ましい。塩化ビニル系樹脂組成物は、柔軟性と耐熱性が優れている程、成型加工性に優れていると言える。 In the vinyl chloride resin composition of the present invention, from the viewpoint of flexibility, the tensile strength measured by the above test is preferably 20 MPa or more, and the elongation is preferably 300% or more. In the vinyl chloride resin composition of the present invention, from the viewpoint of heat resistance, it is preferable that the residual ratio of tensile strength measured by the above test is 90 to 110%, and the residual ratio of elongation is 60 to 110. % Is preferred. It can be said that the vinyl chloride resin composition is more excellent in moldability as the flexibility and heat resistance are higher.
　建材、輸送機器用部材、電線被覆材、家具、事務用具、家電等として用いられる塩化ビニル系樹脂組成物には、優れた低発煙性が求められる。低発煙性は、例えば、米国工業規格（ＡＳＴＭ）Ｅ６６２－０５に記載の方法に準じて、塩化ビニル系樹脂組成物の煙濃度の最大値を測定することで評価できる。 Excellent low smoke generation is required for vinyl chloride resin compositions used as building materials, members for transportation equipment, wire covering materials, furniture, office tools, home appliances, and the like. The low smoke generation can be evaluated by measuring the maximum smoke concentration of the vinyl chloride resin composition in accordance with, for example, the method described in American Industrial Standard (ASTM) E662-05.
　本発明の塩化ビニル系樹脂組成物において、上記試験で測定される煙濃度の最大値は低いほど好ましい。煙濃度の最大値が高いと、火災時に、塩化ビニル系樹脂組成物が燃焼することで発生する煙量が多くなり、被災者が避難経路や非常口を見つけるのに支障が生じたり、消火活動の障害となることがある。どの程度の発煙量が許容されるかはその用途によって異なるが、建築物の内装材の種類によっては、煙濃度の最大値が５００以下であることが好ましい。 In the vinyl chloride resin composition of the present invention, the maximum smoke concentration measured in the above test is preferably as low as possible. If the maximum smoke concentration is high, the amount of smoke generated by the combustion of the vinyl chloride resin composition in the event of a fire increases, which may hinder the victims from finding evacuation routes and emergency exits, May be an obstacle. The amount of smoke generated is allowable depending on the application, but the maximum smoke concentration is preferably 500 or less depending on the type of interior material of the building.
　電線被覆材として用いられる塩化ビニル系樹脂組成物には、優れた電気絶縁性が求められる。電気絶縁性は、例えば、日本工業規格（ＪＩＳ）Ｋ６７２３－１９９５（コンパウンドの種類；２種１号）に記載の体積抵抗率試験に準じて、塩化ビニル系樹脂組成物の３０℃での体積抵抗値を測定することで評価できる。 The vinyl chloride resin composition used as a wire coating material is required to have excellent electrical insulation. The electrical insulation is, for example, a volume resistance of a vinyl chloride resin composition at 30 ° C. according to a volume resistivity test described in Japanese Industrial Standard (JIS) K6723-1995 (type of compound; type 2 No. 1). It can be evaluated by measuring the value.
　本発明の塩化ビニル系樹脂組成物において、上記試験で測定される３０℃での体積抵抗値は、漏電防止の観点から、１．０×１０１４Ω・ｃｍ以上であることが好ましい。 In the vinyl chloride resin composition of the present invention, the volume resistance value at 30 ° C. measured in the above test is preferably 1.0 × 10 14 Ω · cm or more from the viewpoint of preventing leakage.
　本発明の塩化ビニル系樹脂組成物は、上記の各種試験において、バランスの観点から、好ましい範囲を全て満たすものがより好ましい。 The vinyl chloride resin composition of the present invention preferably satisfies all the preferred ranges from the viewpoint of balance in the various tests described above.
　一般に、塩化ビニル系樹脂組成物を高温で成形加工する場合は、塩化ビニル系樹脂組成物に含まれる可塑剤が空気中へ揮発し、成形品の品質や作業環境が悪化することがあるため、塩化ビニル系樹脂組成物の低揮発性が求められる。 In general, when a vinyl chloride resin composition is molded at a high temperature, the plasticizer contained in the vinyl chloride resin composition volatilizes into the air, which may deteriorate the quality and work environment of the molded product. The low volatility of the vinyl chloride resin composition is required.
　また、塩化ビニル系樹脂組成物を食品包装用ラップとして用いる場合は、食品包装用ラップが食品に接触することがあるため、食品包装用ラップに含まれる可塑剤の食品への低移行性が求められる。 In addition, when the vinyl chloride resin composition is used as a food packaging wrap, the food packaging wrap may come into contact with the food, so the plasticizer contained in the food packaging wrap must have low migration to food. It is done.
　本発明の塩化ビニル系樹脂組成物は、可塑剤として、本発明の塩化ビニル系樹脂用可塑剤を含有しているため、低揮発性に優れ、また食品等に対する低移行性も有している。 Since the vinyl chloride resin composition of the present invention contains the plasticizer for vinyl chloride resin of the present invention as a plasticizer, it is excellent in low volatility and has low migration to foods and the like. .
　以下、製造例、実施例、参考例および試験例により、本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to production examples, examples, reference examples, and test examples, but the present invention is not limited to the following examples.
　以下の製造例１～３で得られた混合エステルにおいて、以下の測定機器、測定条件により、核磁気共鳴スペクトルを測定し、該混合エステルを構成する混合カルボン酸のモル比を算出した。
　　測定機器；ＧＳＸ－４００（４００ＭＨｚ）（日本電子社製）
　　測定条件；
　・核種；1Ｈ
　・標準物；テトラメチルシラン
　・溶媒；ＣＤＣｌ3  In the mixed esters obtained in the following Production Examples 1 to 3, a nuclear magnetic resonance spectrum was measured using the following measuring equipment and measurement conditions, and the molar ratio of the mixed carboxylic acid constituting the mixed ester was calculated.
Measuring instrument: GSX-400 (400 MHz) (manufactured by JEOL Ltd.)
Measurement condition;
・ Nuclide: 1 H
Standard: Tetramethylsilane Solvent: CDCl 3
［製造例１]
［イソ酪酸と２－エチルヘキサン酸のモル比（イソ酪酸／２－エチルヘキサン酸比）が３８／６２であるペンタエリスリトールとイソ酪酸と２－エチルヘキサン酸との混合エステル（混合エステル１）の製造]
　ディーンスタークトラップの付いた反応器にペンタエリスリトール３４０．４ｇ（２．５モル、広栄パーストープ社製）、イソ酪酸３９６．８ｇ（４．５モル、東京化成社製）および２－エチルヘキサン酸１０８１．８ｇ（７．５モル、ＫＨネオケム社製）を仕込み、混合液を５２ｋＰａの減圧下、室温で１５分間窒素バブリングを行うことで脱気した。次いで、脱気後の混合液を常圧下、１６３～２１８℃で３８時間窒素バブリングを行いながら撹拌した。反応後、反応液を１．３ｋＰａの減圧下、１９５℃で１時間濃縮した。濃縮液を、濃縮液の酸価に対して２倍モルの水酸化ナトリウムを含むアルカリ水溶液５００ｍＬで１回、水５００ｍＬで４回洗浄した。有機層を１．３ｋＰａの減圧下、１０５℃で１時間、窒素バブリングを行いながら脱水した。次いで、吸着剤２６ｇ（協和化学工業社製、製品名；キョーワード５００）と活性炭５２ｇ（日本エンバイロケミカルズ社製、製品名；白鷺Ｐ）を加え、０．８ｋＰａの減圧下、１００℃で１時間撹拌した。次いで、濾過助剤（昭和化学工業社製、製品名；ラヂオライト＃５００）を用いて濾過することにより、混合エステル１を１１５９．５ｇ得た。 [Production Example 1]
[Mixed ester (mixed ester 1) of pentaerythritol, isobutyric acid and 2-ethylhexanoic acid in which the molar ratio of isobutyric acid to 2-ethylhexanoic acid (ratio of isobutyric acid / 2-ethylhexanoic acid) is 38/62 Manufacturing]
In a reactor equipped with a Dean-Stark trap, 340.4 g of pentaerythritol (2.5 mol, manufactured by Guangei Perstorp), 396.8 g of isobutyric acid (4.5 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-ethylhexanoic acid 1081. 8 g (7.5 mol, manufactured by KH Neochem) was charged, and the mixture was degassed by bubbling nitrogen at room temperature for 15 minutes under a reduced pressure of 52 kPa. Next, the degassed mixture was stirred at 163 to 218 ° C. for 38 hours with nitrogen bubbling under normal pressure. After the reaction, the reaction solution was concentrated at 195 ° C. for 1 hour under a reduced pressure of 1.3 kPa. The concentrate was washed once with 500 mL of an aqueous alkaline solution containing sodium hydroxide twice as much as the acid value of the concentrate and four times with 500 mL of water. The organic layer was dehydrated under nitrogen bubbling at 105 ° C. for 1 hour under a reduced pressure of 1.3 kPa. Next, 26 g of an adsorbent (Kyowa Chemical Industry Co., Ltd., product name: KYOWARD 500) and activated carbon 52 g (Nippon Enviro Chemicals Co., Ltd., product name: Shirasagi P) were added, and the pressure was reduced to 0.8 kPa at 100 ° C. for 1 hour. Stir. Subsequently, 1159.5 g of mixed ester 1 was obtained by filtering using a filter aid (Product name; Radiolite # 500, manufactured by Showa Chemical Industry Co., Ltd.).
［製造例２］
［イソ酪酸と３，５，５－トリメチルヘキサン酸のモル比（イソ酪酸／３，５，５－トリメチルヘキサン酸比）が６１／３９であるペンタエリスリトールとイソ酪酸と３，５，５－トリメチルヘキサン酸との混合エステル（混合エステル２）の製造］
　２－エチルヘキサン酸の代わりに３，５，５－トリメチルヘキサン酸（ＫＨネオケム社製）を用い、ペンタエリスリトール、イソ酪酸および３，５，５－トリメチルヘキサン酸の使用量のモル比（ペンタエリスリトール／イソ酪酸／３，５，５－トリメチルヘキサン酸比）を１．００／２．９５／１．８５にする以外は、製造例１と同様に操作して、混合エステル２を得た。 [Production Example 2]
[Pentaerythritol, isobutyric acid and 3,5,5-trimethyl having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) of 61/39 Production of mixed ester with hexanoic acid (mixed ester 2)]
Instead of 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid (manufactured by KH Neochem) was used, and the molar ratio of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol) The mixed ester 2 was obtained in the same manner as in Production Example 1 except that (isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) was changed to 1.00 / 2.95 / 1.85.
［製造例３］
［イソ酪酸と３，５，５－トリメチルヘキサン酸のモル比（イソ酪酸／３，５，５－トリメチルヘキサン酸比）が２４／７６であるペンタエリスリトールとイソ酪酸と３，５，５－トリメチルヘキサン酸との混合エステル（混合エステル３）の製造］
　イソ酪酸の代わりに無水イソ酪酸（東京化成社製）を用い、２－エチルヘキサン酸の代わりに３，５，５－トリメチルヘキサン酸（ＫＨネオケム社製）を用い、ペンタエリスリトール、無水イソ酪酸および３，５，５－トリメチルヘキサン酸の使用量のモル比（ペンタエリスリトール／無水イソ酪酸／３，５，５－トリメチルヘキサン酸比）を１．００／０．５０／３．００にする以外は、製造例１と同様に操作して、混合エステル３を得た。 [Production Example 3]
[Pentaerythritol, isobutyric acid and 3,5,5-trimethyl having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) of 24/76 Production of mixed ester with hexanoic acid (mixed ester 3)]
Instead of isobutyric acid, isobutyric anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) is used, and instead of 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid (manufactured by KH Neochem) is used, pentaerythritol, isobutyric anhydride and The molar ratio of the amount of 3,5,5-trimethylhexanoic acid used (pentaerythritol / isobutyric anhydride / 3,5,5-trimethylhexanoic acid ratio) was changed to 1.00 / 0.50 / 3.00. The mixed ester 3 was obtained in the same manner as in Production Example 1.
［実施例１］
［塩化ビニル系樹脂組成物１の調製および評価用シート１の作製］
　塩化ビニル樹脂（大洋塩ビ社製、製品名；大洋ＰＶＣ　ＴＨ－１３００）１００重量部、三塩基性硫酸鉛（ＮＩケミテック社製、製品名；ＢＳ－Ｔ）３重量部および混合エステル１の５０重量部を、室温で混合し、９５℃まで昇温後、その温度で１時間静置し、塩化ビニル系樹脂組成物１を得た。得られた塩化ビニル系樹脂組成物１を、混練・押出成形評価試験装置（イプロス社製、ロールサイズ；６×１６インチ）を用いて、１７０～１９０℃で５分間混練し、その後、押出成形（プレス温度；１８０℃、予熱時間；５分間、加圧時間；１分間、冷却時間；５分間）し、厚さ１ｍｍの評価用シート１を作製した。 [Example 1]
[Preparation of Vinyl Chloride Resin Composition 1 and Production of Evaluation Sheet 1]
100 parts by weight of a vinyl chloride resin (manufactured by Taiyo PVC Co., Ltd., product name: Taiyo PVC TH-1300), 3 parts by weight of tribasic lead sulfate (manufactured by NI Chemtech Co., Ltd., product name: BS-T) and 50 parts by weight of mixed ester Parts were mixed at room temperature, heated to 95 ° C., and allowed to stand at that temperature for 1 hour to obtain a vinyl chloride resin composition 1. The obtained vinyl chloride resin composition 1 is kneaded at 170 to 190 ° C. for 5 minutes using a kneading / extrusion molding evaluation test apparatus (manufactured by Ipros, roll size: 6 × 16 inches), and then extruded. (Pressing temperature: 180 ° C., preheating time: 5 minutes, pressurizing time: 1 minute, cooling time: 5 minutes) to produce a sheet 1 for evaluation having a thickness of 1 mm.
［実施例２］
［塩化ビニル系樹脂組成物２の調製および評価用シート２の作製］
　混合エステル１の代わりに混合エステル２を用いた以外は、実施例１と同様に操作して、塩化ビニル系樹脂組成物２を得た。また、塩化ビニル系樹脂組成物１の代わりに塩化ビニル系樹脂組成物２を用いた以外は、実施例１と同様に操作して、評価用シート２を得た。 [Example 2]
[Preparation of Vinyl Chloride Resin Composition 2 and Production of Evaluation Sheet 2]
A vinyl chloride resin composition 2 was obtained in the same manner as in Example 1 except that the mixed ester 2 was used instead of the mixed ester 1. Also, an evaluation sheet 2 was obtained in the same manner as in Example 1 except that the vinyl chloride resin composition 2 was used instead of the vinyl chloride resin composition 1.
［比較例１］
［塩化ビニル系樹脂組成物Ａの調製および評価用シートＡの作製］
　混合エステル１の代わりにフタル酸ジ－２－エチルヘキシル（ジェイプラス社製）を用いた以外は、実施例１と同様に操作して、塩化ビニル系樹脂組成物Ａを得た。また、塩化ビニル系樹脂組成物１の代わりに塩化ビニル系樹脂組成物Ａを用いた以外は、実施例１と同様に操作して、評価用シートＡを得た。 [Comparative Example 1]
[Preparation of vinyl chloride resin composition A and preparation of evaluation sheet A]
A vinyl chloride resin composition A was obtained in the same manner as in Example 1 except that di-2-ethylhexyl phthalate (manufactured by J-Plus) was used in place of the mixed ester 1. Further, an evaluation sheet A was obtained in the same manner as in Example 1 except that the vinyl chloride resin composition A was used instead of the vinyl chloride resin composition 1.
［参考例１］
［塩化ビニル系樹脂組成物Ｂの調製および評価用シートの作製］
　混合エステル１の代わりに混合エステル３を用いた以外は、実施例１と同様に操作して、塩化ビニル系樹脂組成物Ｂを得た。また、塩化ビニル系樹脂組成物１の代わりに塩化ビニル系樹脂組成物Ｂを用いた以外は、実施例１と同様に操作して評価用シートの作製を試みたが、混練時に混合エステル３が分離したため、評価用シートは得られなかった。 [Reference Example 1]
[Preparation of vinyl chloride resin composition B and preparation of evaluation sheet]
A vinyl chloride resin composition B was obtained in the same manner as in Example 1 except that the mixed ester 3 was used instead of the mixed ester 1. Further, except that the vinyl chloride resin composition B was used in place of the vinyl chloride resin composition 1, an attempt was made to produce an evaluation sheet by operating in the same manner as in Example 1. Since it separated, the evaluation sheet was not obtained.
（試験例１）柔軟性の評価（引張試験）
　ＪＩＳ Ｋ６７２３－１９９５（コンパウンドの種類；２種１号）に記載の引張試験に準じて、評価用シート１、評価用シート２および評価用シートＡの引張強さと伸びを測定した。結果を表１に示す。引張強さと伸びが大きい程、柔軟性に優れていることを示す。 (Test Example 1) Evaluation of flexibility (tensile test)
The tensile strength and elongation of the evaluation sheet 1, the evaluation sheet 2, and the evaluation sheet A were measured according to the tensile test described in JIS K6723-1995 (type of compound; type 2 No. 1). The results are shown in Table 1. The larger the tensile strength and elongation, the better the flexibility.
（試験例２）耐熱性の評価（加熱後引張試験）
　ＪＩＳ Ｋ６７２３－１９９５（コンパウンドの種類；２種１号）に記載の加熱後引張試験に準じて、評価用シート１、評価用シート２および評価用シートＡの加熱前後の引張強さと伸びを測定し、加熱後の引張強さの残率と加熱後の伸びの残率を算出した。結果を表１に示す。加熱後の引張強さの残率と加熱後の伸びの残率が１００％に近い程、耐熱性に優れていることを示す。 (Test Example 2) Evaluation of heat resistance (tensile test after heating)
The tensile strength and elongation before and after heating of the evaluation sheet 1, the evaluation sheet 2 and the evaluation sheet A were measured in accordance with the post-heating tensile test described in JIS K6723-1995 (type of compound; type 2 No. 1). The residual ratio of tensile strength after heating and the residual ratio of elongation after heating were calculated. The results are shown in Table 1. It shows that it is excellent in heat resistance, so that the residual rate of the tensile strength after a heating and the residual rate of the elongation after a heating are near 100%.
（試験例３）低発煙性の評価（発煙性試験）
　ＡＳＴＭ　Ｅ６６２－０５（有炎）の方法に準じて、評価用シート１、評価用シート２および評価用シートＡの煙濃度の最大値を測定した。結果を表１に示す。煙濃度の最大値が小さい程、低発煙性に優れていることを示す。 (Test Example 3) Evaluation of low smoke generation (smoke test)
According to the method of ASTM E662-05 (flamed), the maximum smoke density values of the evaluation sheet 1, the evaluation sheet 2, and the evaluation sheet A were measured. The results are shown in Table 1. It shows that it is excellent in low smoke generation property, so that the maximum value of smoke density is small.
（試験例４）電気絶縁性の評価（体積抵抗率試験）
　ＪＩＳ Ｋ６７２３－１９９５（コンパウンドの種類；２種１号）に記載の体積抵抗率試験に準じて、評価用シート１、評価用シート２および評価用シートＡの３０℃における体積抵抗値を測定した。結果を表１に示す。体積抵抗値が大きい程、電気絶縁性に優れていることを示す。 (Test Example 4) Evaluation of electrical insulation (volume resistivity test)
In accordance with the volume resistivity test described in JIS K6723-1995 (type of compound; type 2 No. 1), the volume resistance values at 30 ° C. of the evaluation sheet 1, the evaluation sheet 2 and the evaluation sheet A were measured. The results are shown in Table 1. It shows that it is excellent in electrical insulation, so that a volume resistance value is large.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１より、本発明の塩化ビニル系樹脂用可塑剤を含む塩化ビニル系樹脂組成物(実施例１および２)は、従来から可塑剤として用いられているフタル酸ジ－２－エチルヘキシルを含む塩化ビニル系樹脂組成物（比較例１）と比較して、同等の優れた柔軟性を有することが分かる。また、実施例１は引張強さの残率が１０１％、伸びの残率が９６％であり、実施例２は引張強さの残率が９６％、伸びの残率が６７％であり、優れた耐熱性を有することが分かる。また実施例１は煙濃度の最大値が４６６であり、実施例２は煙濃度の最大値が４２７であり、優れた低発煙性を有することが分かる。また、実施例１は体積抵抗値が３．０×１０14Ω・ｃｍであり、実施例２は体積抵抗値が４．８×１０14Ω・ｃｍであり、優れた電気絶縁性を有することが分かる。実施例１および２は、柔軟性、耐熱性、低発煙性および電気絶縁性がバランスよく優れていることが分かる。 From Table 1, the vinyl chloride resin compositions (Examples 1 and 2) containing the plasticizer for vinyl chloride resin of the present invention are chlorides containing di-2-ethylhexyl phthalate which has been conventionally used as a plasticizer. It turns out that it has the same outstanding softness | flexibility compared with a vinyl-type resin composition (comparative example 1). In Example 1, the residual ratio of tensile strength is 101% and the residual ratio of elongation is 96%. In Example 2, the residual ratio of tensile strength is 96%, and the residual ratio of elongation is 67%. It turns out that it has the outstanding heat resistance. In addition, Example 1 has a maximum smoke concentration value of 466, and Example 2 has a maximum smoke concentration value of 427, indicating that it has excellent low smoke generation. Moreover, Example 1 has a volume resistance value of 3.0 × 10 14 Ω · cm, and Example 2 has a volume resistance value of 4.8 × 10 14 Ω · cm, and has excellent electrical insulation. I understand. It can be seen that Examples 1 and 2 are excellent in balance between flexibility, heat resistance, low smoke generation and electrical insulation.
　これに対して、比較例１は引張強さの残率が１８１％、伸びの残率が４％、煙濃度の最大値が６２３、体積抵抗値が２．５×１０13Ω・ｃｍであり、耐熱性、低発煙性および電気絶縁性が悪く、物性値のバランスが取れていない。 On the other hand, in Comparative Example 1, the residual rate of tensile strength is 181%, the residual rate of elongation is 4%, the maximum value of smoke concentration is 623, and the volume resistance value is 2.5 × 10 13 Ω · cm. The heat resistance, low smoke generation and electrical insulation are poor, and the physical properties are not balanced.
　本発明により、塩化ビニル系樹脂に対して、柔軟性、耐熱性、低発煙性、電気絶縁性等の優れた性能をバランスよく付与する塩化ビニル系樹脂用可塑剤およびそれを含有する塩化ビニル系樹脂組成物を提供できる。 INDUSTRIAL APPLICABILITY According to the present invention, a plasticizer for a vinyl chloride resin that imparts excellent performance such as flexibility, heat resistance, low smoke generation, and electrical insulation to a vinyl chloride resin in a well-balanced manner, and a vinyl chloride resin containing the same A resin composition can be provided.

Claims (4)

  1. 　ペンタエリスリトールと混合カルボン酸との混合エステルからなる塩化ビニル系樹脂用可塑剤であって、前記混合カルボン酸が、イソ酪酸と、炭素数８または炭素数９の脂肪族モノカルボン酸とからなる混合カルボン酸であり、前記混合カルボン酸にしめるイソ酪酸の割合が３５～６５モル％の範囲であることを特徴とする塩化ビニル系樹脂用可塑剤。 A plasticizer for vinyl chloride resin comprising a mixed ester of pentaerythritol and a mixed carboxylic acid, wherein the mixed carboxylic acid comprises isobutyric acid and an aliphatic monocarboxylic acid having 8 or 9 carbon atoms. A plasticizer for a vinyl chloride resin, which is a carboxylic acid, and the ratio of isobutyric acid to be mixed with the mixed carboxylic acid is in the range of 35 to 65 mol%.
  2. 　炭素数８または炭素数９の脂肪族モノカルボン酸が、２－エチルヘキサン酸または３，５，５－トリメチルヘキサン酸である請求項１に記載の塩化ビニル系樹脂用可塑剤。 The plasticizer for vinyl chloride resin according to claim 1, wherein the aliphatic monocarboxylic acid having 8 or 9 carbon atoms is 2-ethylhexanoic acid or 3,5,5-trimethylhexanoic acid.
  3. 　塩化ビニル系樹脂と、請求項１または２に記載の塩化ビニル系樹脂用可塑剤とを含有する塩化ビニル系樹脂組成物であって、塩化ビニル系樹脂１００重量部に対して、請求項１または２に記載の塩化ビニル系樹脂用可塑剤を１０～１００重量部含有することを特徴とする塩化ビニル系樹脂組成物。 A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer for a vinyl chloride resin according to claim 1 or 2, wherein the vinyl chloride resin is based on 100 parts by weight of the vinyl chloride resin. A vinyl chloride resin composition comprising 10 to 100 parts by weight of the plasticizer for vinyl chloride resin according to 2.
  4. 　日本工業規格（ＪＩＳ）Ｋ６７２３－１９９５（コンパウンドの種類；２種１号）に準じて加熱後引張試験で測定される引張強さの残率が９０～１１０％の範囲である請求項３に記載の塩化ビニル系樹脂組成物。
     
          The residual ratio of tensile strength measured in a tensile test after heating according to Japanese Industrial Standard (JIS) K6723-1995 (type of compound; type 2 No. 1) is in the range of 90 to 110%. A vinyl chloride resin composition.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016043639A1 (en) * 2014-09-15 2016-03-24 Perstorp Ab A highly stabile plasticized polyvinyl halide composition
JP2018145380A (en) * 2017-03-09 2018-09-20 Ｍｃｐｐイノベーション合同会社 Vinyl chloride-based resin composition
US20220117844A1 (en) * 2014-02-20 2022-04-21 Fresenius Kabi Deutschland Gmbh Medical Containers And System Components With Non-Dehp Plasticizers For Storing Red Blood Cell Products, Plasma And Platelets

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210119209A (en) * 2020-03-24 2021-10-05 애경유화주식회사 Plasticizer and Polymer Resin Composition Using the Same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5430108A (en) * 1994-01-14 1995-07-04 Exxon Chemical Patents Inc. Polyol ester PVC plasticizers
JP2012031220A (en) * 2010-07-28 2012-02-16 Dic Corp Plasticizer for vinyl chloride resin, vinyl chloride resin composition using the same and molded product of the composition
WO2012026861A1 (en) * 2010-08-23 2012-03-01 Perstorp Ab Non-phthalic plasticiser

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5430108A (en) * 1994-01-14 1995-07-04 Exxon Chemical Patents Inc. Polyol ester PVC plasticizers
JP2012031220A (en) * 2010-07-28 2012-02-16 Dic Corp Plasticizer for vinyl chloride resin, vinyl chloride resin composition using the same and molded product of the composition
WO2012026861A1 (en) * 2010-08-23 2012-03-01 Perstorp Ab Non-phthalic plasticiser

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220117844A1 (en) * 2014-02-20 2022-04-21 Fresenius Kabi Deutschland Gmbh Medical Containers And System Components With Non-Dehp Plasticizers For Storing Red Blood Cell Products, Plasma And Platelets
WO2016043639A1 (en) * 2014-09-15 2016-03-24 Perstorp Ab A highly stabile plasticized polyvinyl halide composition
JP2018145380A (en) * 2017-03-09 2018-09-20 Ｍｃｐｐイノベーション合同会社 Vinyl chloride-based resin composition

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