Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08L27/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

• the present invention relates to plasticizers for vinyl chloride resins, vinyl chloride resin compositions, molded articles thereof, and laminates thereof.
• Vinyl chloride resin is one of the representative plastics, and it is usually added with a plasticizer for the purpose of imparting performance such as flexibility and low temperature properties and facilitating thermoforming processability. It is used after softening vinyl chloride resin.
• Plasticizers used in vinyl chloride resins are required to have various properties such as compatibility, cold resistance, and heat resistance. It has been known. Among them, phthalates were often used from the viewpoint of price and performance balance.
• trimellitic esters which have higher heat resistance than phthalates
• Patent Document 1 trimellitic esters, which have higher heat resistance than phthalates
• tri-2-ethylhexyl trimellitate, tri-normal octyl trimellitate, tri-normal decyl trimellitate, triisononyl trimellitate and triisodecyl trimellitate are plasticizers with very high heat resistance. Therefore, it is widely used for automobile dashboards and the like.
• Automobile dashboards include a laminate part of a vinyl chloride resin layer and a urethane resin layer (urethane foam layer). If the plasticizer contained in the vinyl chloride resin layer migrates to the urethane resin layer, There is a problem that the amount of plasticizer in is reduced and the flexibility is lost.
• the vinyl chloride resin layer in the automobile dashboard loses its flexibility, the vinyl chloride resin layer may turn into hard fragments and scatter when the airbag is deployed, making the interior of the vehicle dangerous.
• the above trimellitate ester plasticizer has not been able to satisfy the non-migratory property.
• the problem to be solved by the present invention is to provide a vinyl chloride resin plasticizer that is excellent in heat resistance and non-migration.
• the inventors of the present invention conducted intensive studies to solve the above problems, and found that a plasticizer for vinyl chloride resin, which is a polyester using a specific glycol, can exhibit excellent heat resistance and non-migratory properties. He found this and completed the present invention.
• the present invention comprises a glycol having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, a monoalcohol having 4 to 18 carbon atoms and/or a monocarboxylic acid having 2 to 21 carbon atoms.
• a plasticizer for vinyl chloride resin that is a polyester that uses an acid as a reaction raw material, wherein the glycol is an alkylene glycol having 5 to 18 carbon atoms, and the main chain is substituted with one or more methyl groups.
• the present invention relates to a vinyl chloride resin plasticizer containing 30 mol % or more of alkylene glycol.
• the present invention can provide a vinyl chloride resin plasticizer that is excellent in heat resistance and non-migratory properties.
• the vinyl chloride resin plasticizer of the present invention comprises a glycol having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, a monoalcohol having 4 to 18 carbon atoms and/or 2 carbon atoms.
• a vinyl chloride resin plasticizer which is a polyester obtained by reacting with a monocarboxylic acid of 1 to 21, wherein the glycol is an alkylene having 5 to 18 carbon atoms in which the number of carbon atoms between two hydroxyl groups is 5 or more. It contains 30 mol % or more of alkylene glycol which is a glycol and has one or more methyl groups substituted on its main chain.
• reaction raw material means a raw material that constitutes the polyester of the present invention, and does not contain a solvent or catalyst that does not constitute the polyester.
• polyester that is the plasticizer for vinyl chloride resins of the present invention may be hereinafter simply referred to as "the polyester of the present invention”.
• the above-mentioned glycol having 2 to 18 carbon atoms is preferably alkylene glycol having 2 to 18 carbon atoms or oxyalkylene glycol having 2 to 18 carbon atoms.
• alkylene glycol having 2 to 18 carbon atoms examples include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol and 1,2-propanediol.
• the alkylene glycol having 2 to 18 carbon atoms is preferably an alkylene glycol having 3 to 10 carbon atoms, more preferably an alkylene glycol having 3 to 6 carbon atoms, and still more preferably 1,2-propanediol. , 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1, 5-pentanediol and 1,6-hexanediol.
• the oxyalkylene glycol having 2 to 18 carbon atoms is, for example, the alkylene glycol having 2 to 18 carbon atoms in which one of the carbon atoms is replaced with an oxygen atom, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and the like.
• the oxyalkylene glycol having 2 to 18 carbon atoms is preferably oxyalkylene glycol having 3 to 10 carbon atoms, more preferably oxyalkylene glycol having 4 to 10 carbon atoms, still more preferably diethylene glycol or tri- Ethylene glycol.
• the glycol having 2 to 18 carbon atoms contains 30 mol % or more of alkylene glycol having 5 to 18 carbon atoms and having one or more methyl groups substituted on the main chain.
• the "main chain” refers to the longest alkylene chain among the alkylene chains between two hydroxyl groups.
• alkylene glycol having 5 to 18 carbon atoms and having one or more methyl groups substituted on the main chain examples include neopentyl glycol and 3-methyl-1,5-pentanediol. .
• the ratio of the alkylene glycol having 5 to 18 carbon atoms and having one or more methyl groups substituted on the main chain may be 30 mol% or more, preferably 35 mol% or more, It is more preferably 40 mol % or more, still more preferably 55 mol % or more.
• the upper limit of the ratio of the alkylene glycol having 5 to 18 carbon atoms and having one or more methyl groups substituted on the main chain is not particularly limited, for example, 100 mol% or less, 90 mol% or less, It is 80 mol % or less, or 70 mol % or less.
• glycols having 2 to 18 carbon atoms which are reaction raw materials for the polyester of the present invention, may be used singly or in combination of two or more.
• the aliphatic dicarboxylic acid having 4 to 14 carbon atoms is preferably an alkylenedicarboxylic acid having 4 to 14 carbon atoms, more preferably an alkylenedicarboxylic acid having 6 to 12 carbon atoms.
• alkylenedicarboxylic acids having 4 to 14 carbon atoms examples include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid (dodecanedioic acid), cyclohexanedicarboxylic acid, hexahydrophthalic acid, and the like. mentioned. Among these, adipic acid, azelaic acid, sebacic acid and dodecanedioic acid are more preferred, adipic acid and sebacic acid are more preferred, and adipic acid is particularly preferred.
• the alkylenedicarboxylic acids having 4 to 14 carbon atoms which are reaction raw materials for the polyester of the present invention, may be used singly or in combination of two or more.
• the monoalcohol having 4 to 18 carbon atoms is preferably an aliphatic monoalcohol having 4 to 18 carbon atoms.
• Examples of the aliphatic monoalcohol having 4 to 18 carbon atoms include butanol, heptanol, hexanol, cyclohexanol, heptanol, octanol, 2-ethylhexanol, isononyl alcohol, nonanol, decanol, undecanol and dodecanol.
• the monoalcohol having 4 to 18 carbon atoms which is the reaction raw material of the polyester of the present invention, may be used alone or in combination of two or more.
• the monocarboxylic acid having 2 to 21 carbon atoms is preferably an aliphatic monocarboxylic acid having 2 to 21 carbon atoms.
• Examples of the aliphatic monocarboxylic acids having 2 to 21 carbon atoms include acetic acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, and stearin. acid, arachidic acid, and the like.
• the monocarboxylic acid having 2 to 21 carbon atoms may be a hydrogenated vegetable oil fatty acid.
• the hydrogenated vegetable oil fatty acid include hydrogenated coconut oil fatty acid, hydrogenated palm kernel oil fatty acid, hydrogenated palm oil fatty acid, hydrogenated olive oil fatty acid, hydrogenated castor oil fatty acid, and hydrogenated rapeseed oil fatty acid. These are obtained by decomposing and hydrogenating oil agents obtained from palm, palm kernel, palm, olive, castor and rapeseed, respectively, and all contain aliphatic monocarboxylic acids having 8 to 21 carbon atoms 2 It is a mixture of more than one species of long-chain aliphatic monocarboxylic acids. It should be noted that the vegetable oil fatty acid that has not been hydrogenated may be used as long as the effects of the present invention are not impaired. Also, the vegetable oil fatty acid is not limited to the above.
• the polyester of the present invention comprises a glycol having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, a monoalcohol having 4 to 18 carbon atoms and/or a monocarboxylic acid having 2 to 21 carbon atoms.
• the glycol is an alkylene glycol having 5 to 18 carbon atoms, and may contain 30 mol% or more of an alkylene glycol having one or more methyl groups substituted on the main chain. Raw materials other than these may be used as long as the effects of the above are not impaired.
• the reaction raw materials for the polyester of the present invention are preferably a glycol having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, a monoalcohol having 4 to 18 carbon atoms and/or 2 carbon atoms.
• ⁇ 21 monocarboxylic acids more preferably glycols of 2 to 18 carbon atoms, aliphatic dicarboxylic acids of 4 to 14 carbon atoms, monoalcohols of 4 to 18 carbon atoms and/or Alternatively, it consists only of a monocarboxylic acid having 2 to 21 carbon atoms.
• the polyester of the present invention includes a mixture of compounds represented by the following formula (1) having different values of p, a mixture of compounds represented by the following formula (2) having different values of q, and a mixture of compounds represented by the following formula (2) having different values of p.
• G is a glycol residue of 2-18 carbon atoms.
• A is an aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms.
• S 11 and S 12 are each independently a monocarboxylic acid residue having 1 to 20 carbon atoms.
• S 21 and S 22 are each independently a monoalcohol residue having 4 to 18 carbon atoms.
• S 31 is a monocarboxylic acid residue having 1 to 20 carbon atoms.
• S 32 is a monoalcohol residue with 4 to 18 carbon atoms.
• p, q and r are each independently an integer.
• the term “carboxylic acid residue” refers to the remaining organic groups other than the carboxyl group of the carboxylic acid. Incidentally, the number of carbon atoms in the “carboxylic acid residue” does not include the carbon atoms in the carboxy group.
• the term “alcohol residue” refers to an organic group remaining after removing a hydroxyl group from an alcohol.
• glycol residue refers to the organic group remaining after removing the hydroxyl group from the glycol.
• the glycol residue having 2 to 18 carbon atoms of G is a group corresponding to the glycol having 2 to 18 carbon atoms which is the starting material for the polyester of the present invention.
• 30 mol % or more are alkylene glycol residues having 5 to 18 carbon atoms, and the main chain is substituted with one or more methyl groups.
• the aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms of A is a group corresponding to the aliphatic dicarboxylic acid having 4 to 14 carbon atoms which is the reaction raw material of the polyester of the present invention.
• the monocarboxylic acid residue having 1 to 20 carbon atoms of S 11 , S 12 and S 31 is a group corresponding to the monocarboxylic acid having 2 to 21 carbon atoms which is the starting material for the polyester of the present invention.
• the monoalcohol residues having 4 to 18 carbon atoms of S 21 , S 22 and S 32 are groups corresponding to monoalcohols having 4 to 18 carbon atoms which are reaction raw materials of the polyester of the present invention.
• each of p, q and r is not particularly limited, but is 30, for example.
• the average value of p is in the range of 3-20
• the average value of q is in the range of 3-20
• the average value of r is in the range of 3-20.
• the average values of p, q and r can be confirmed from the number average molecular weight of the polyester.
• the polyester of the present invention has a number average molecular weight (Mn) of 500 to 6,000, preferably 1,000 to 5,000, more preferably 2,000 to 4,000, still more preferably 2 ,000 to 3,700.
• Mn number average molecular weight
• the acid value of the polyester of the present invention is preferably 2.0 or less, more preferably 1.0 or less.
• the hydroxyl value of the polyester of the present invention is preferably 15 or less, more preferably 10 or less.
• the viscosity of the polyester of the present invention is preferably 7,000 mPa ⁇ s or less, more preferably 5,000 mPa ⁇ s or less. The acid value, hydroxyl value and viscosity of the polyester of the present invention are confirmed by the methods described in Examples.
• the plasticizer for vinyl chloride resin of the present invention is an alkylene glycol having 5 to 18 carbon atoms, and contains 30 mol% or more of alkylene glycol substituted with one or more methyl groups on the main chain, and has 2 to 2 carbon atoms. Synthesizing a polyester by reacting a glycol having 18 carbon atoms, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, and a monoalcohol having 4 to 18 carbon atoms and/or a monocarboxylic acid having 4 to 21 carbon atoms. and preferably the resulting polyester is further steam stripped.
• the polyester represented by the formula (1) can be obtained, for example, by the method shown below.
• Method 1 A method in which monocarboxylic acid, dicarboxylic acid and glycol constituting each residue of the polyester represented by formula (1) are charged all at once and reacted.
• Method 2 Dicarboxylic acid and glycol constituting each residue of the polyester represented by the formula (1) are reacted under conditions in which the equivalent weight of the hydroxyl group is greater than the equivalent weight of the carboxyl group to convert the hydroxyl group to the end of the main chain.
• the polyester represented by the formula (2) can be obtained, for example, by the method shown below.
• Method 3 A method in which the monoalcohol, dicarboxylic acid and glycol constituting each residue of the polyester represented by formula (2) are charged all at once and reacted.
• Method 4 The dicarboxylic acid and glycol constituting each residue of the polyester represented by the formula (2) are reacted under conditions where the equivalent weight of the carboxyl group is greater than the equivalent weight of the hydroxyl group to form a carboxyl group on the main chain.
• the polyester represented by the formula (3) can be obtained, for example, by the method shown below.
• Method 4 A method in which the monoalcohol, monocarboxylic acid, dicarboxylic acid and glycol constituting each residue of the polyester represented by formula (3) are charged all at once and reacted.
• Method 5 Dicarboxylic acid and glycol constituting each residue of the polyester represented by the formula (3) are reacted under conditions where the equivalent weight of the carboxyl group and the equivalent weight of the hydroxyl group are the same to convert the carboxyl group and the hydroxyl group, respectively.
• a method in which a polyester having a main chain terminal is obtained, and then the obtained polyester is reacted with a monoalcohol and a monocarboxylic acid constituting S31 and S32 .
• the above reaction may be carried out in the presence of an esterification catalyst, if necessary, at a temperature of 180 to 250° C. for 5 to 25 hours.
• Conditions such as the temperature and time of the esterification reaction are not particularly limited and may be set as appropriate.
• esterification catalyst examples include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin-based catalysts such as dibutyltin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid.
• the amount of the esterification catalyst to be used may be appropriately set, but it is usually preferably in the range of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials.
• the steam stripping treatment is a treatment in which the obtained polyester is brought into contact with steam to remove unreacted components, catalysts and low-molecular-weight components contained in the polyester.
• the residual amount of monoalcohol derived from the reaction raw material in the polyester of the present invention can be reduced to less than 1,000 mass ppm.
• the residual amount of monoalcohol is measured by the method described in Examples.
• the amount of residual monoalcohol derived from the reaction raw material in the polyester of the present invention has a correlation with the odor of the polyester itself, and the odor can be reduced by reducing the amount of residual monoalcohol.
• the residual amount of monoalcohol derived from the reaction raw material in the polyester of the present invention may be, for example, less than 1,000 mass ppm, preferably 900 mass ppm or less, more preferably 800 mass ppm or less, and still more preferably. is 700 mass ppm or less.
• the lower limit of the amount of residual monoalcohol derived from the reaction raw material in the polyester of the present invention is not particularly limited, it is, for example, 0 mass ppm.
• the steam stripping treatment is carried out, for example, by passing the obtained polyester through a stripping tower equipped with perforated plates from which steam is ejected, the stripping treatment temperature is, for example, in the range of 100 to 180° C., and the stripping
• the treatment pressure should be set in the range of 0.005 to 0.03 STMkg/hr/kg.
• the stripping time can be set, for example, in the range of 2-10 hours.
• the vinyl chloride resin composition of the present invention contains the plasticizer for vinyl chloride resin of the present invention and a vinyl chloride resin.
• vinyl chloride resins include vinyl chloride homopolymers, vinylidene chloride homopolymers, copolymers containing vinyl chloride as an essential component, copolymers containing vinylidene chloride as an essential component, and the like.
• the vinyl chloride resin is a copolymer containing vinyl chloride as an essential component or a copolymer containing vinylidene chloride as an essential component
• examples of comonomers that can be copolymerized include ethylene, propylene, ⁇ - Olefins; conjugated dienes such as butadiene and isoprene; vinyl alcohol, styrene, acrylonitrile, vinyl acetate, vinyl propionate, fumaric acid, fumaric acid ester, maleic acid, maleic acid ester, maleic anhydride, acrylic acid, acrylic acid ester, Methacrylic acid, methacrylic acid esters, isoprenol and the like can be mentioned.
• the degree of polymerization of vinyl chloride resin is usually 300 to 5,000, preferably 400 to 3,500, more preferably 700 to 3,000.
• the degree of polymerization of the vinyl chloride resin is in this range, it is possible to obtain a molded product with high heat resistance and to obtain a vinyl chloride resin composition having excellent workability.
• Vinyl chloride resins can be produced by known methods, such as suspension polymerization in the presence of an oil-soluble polymerization catalyst and emulsion polymerization in an aqueous medium in the presence of a water-soluble polymerization catalyst.
• a commercial item may be used for the vinyl chloride resin.
• Commercially available vinyl chloride resins include TH-640, TH-700, TH-800 (manufactured by Taiyo Vinyl Co., Ltd.); S-1004, S-1008, PSH-10 (manufactured by Kaneka Corporation). TK-700, TK-800. TK-1300 (manufactured by Shin-Etsu Polymer Co., Ltd.); ZEST800Z, ZEST1000Z, ZEST1300Z (manufactured by Shin-Daiichi PVC Co., Ltd.);
• the content of the vinyl chloride resin plasticizer of the present invention in the vinyl chloride resin composition of the present invention is preferably 10 to 150 mass parts per 100 mass parts of the vinyl chloride resin from the viewpoint of compatibility with the vinyl chloride resin. parts, more preferably 30 to 120 parts by mass, still more preferably 50 to 120 parts by mass, and particularly preferably 70 to 120 parts by mass.
• the vinyl chloride resin composition of the present invention may contain the vinyl chloride resin and the plasticizer for vinyl chloride resin of the present invention, and may include a plasticizer (other plasticizer) other than the plasticizer for vinyl chloride resin of the present invention, and other plasticizers. Additives and the like may be contained.
• plasticizers examples include benzoic acid esters such as diethylene glycol dibenzoate; dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), Phthalates such as diundecyl phthalate (DUP) and ditridecyl phthalate (DTDP); terephthalates such as bis(2-ethylhexyl) terephthalate (DOTP); isophthalates such as bis(2-ethylhexyl) isophthalate (DOIP) acid ester; pyromellitic acid ester such as tetra-2-ethylhexyl pyromellitic acid (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (D
• Alkyl esters of polyhydric alcohols such as pentaerythritol; Polyesters with a molecular weight of 800 to 4,000 synthesized by polyesterification of dibasic acids such as adipic acid and glycol; Epoxidized soybean oil, epoxidized linseed Epoxidized esters such as oils; alicyclic dibasic acids such as hexahydrophthalic acid diisononyl ester; fatty acid glycol esters such as 1,4-butanediol dicaprate; acetyl tributyl citrate (ATBC); paraffin wax and n-paraffin chlorinated paraffin obtained by chlorinating ; chlorinated fatty acid esters such as chlorinated stearate; and higher fatty acid esters such as butyl oleate.
• dibasic acids such as adipic acid and glycol
• Epoxidized soybean oil, epoxidized linseed Epoxidized esters such as oils
• plasticizers it is preferable to use one or more selected from trimellitic acid ester plasticizers and sebacic acid derivative plasticizers.
• trimellitate ester plasticizer examples include trimethyl trimellitate, triethyl trimellitate, tri-n-propyl trimellitate, tri-n-butyl trimellitate, tri-n-pentyl trimellitate, and trimellitic acid.
• sebacic acid derivative plasticizer examples include di-n-butyl sebacate, di-(2-ethylhexyl) sebacate, diisodecyl sebacate, di-(2-butyloctyl) sebacate, and the like.
• plasticizers may be used singly or in combination of two or more.
• trimellitic acid esters and sebacic acid derivatives are preferable from the viewpoint of obtaining good tensile elongation and cold resistance.
• the content of the other plasticizer is, for example, 10 to 300 parts by mass with respect to 100 parts by mass of the vinyl chloride resin plasticizer of the present invention. and preferably 20 to 200 parts by mass.
• additives examples include flame retardants, stabilizers, stabilizing aids, colorants, processing aids, fillers, antioxidants (antiaging agents), ultraviolet absorbers, light stabilizers, lubricants, and electrification agents.
• examples include inhibitors, cross-linking aids, and the like.
• the flame retardant examples include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, zinc borate; cresyldiphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, trisdichloropropyl phosphate Phosphorus compounds such as phate; halogen compounds such as chlorinated paraffin, and the like are exemplified.
• the flame retardant is added to the vinyl chloride resin composition, the amount thereof is usually in the range of 0.1 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.
• the stabilizer examples include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octylate, zinc laurate, and zinc ricinoleate. , zinc stearate and other metal soap compounds; dimethyltin bis-2-ethylhexyl thioglycolate, dibutyltin maleate, dibutyltin bisbutyl maleate, dibutyltin dilaurate and other organotin compounds; antimony mercaptide compounds; lanthanum oxide, water Examples include lanthanoid-containing compounds such as lanthanum oxide.
• the amount thereof is usually in the range of 0.1 to 20 parts by weight per 100 parts by weight of the vinyl chloride resin.
• the stabilizing aid examples include phosphite compounds such as triphenylphosphite, monooctyldiphenylphosphite and tridecylphosphite; beta-diketone compounds such as acetylacetone and benzoylacetone; glycerin, sorbitol, pentaerythritol and polyethylene. polyol compounds such as glycol; perchlorate compounds such as barium perchlorate and sodium perchlorate; hydrotalcite compounds; When the stabilizing aid is added to the vinyl chloride resin composition, the amount thereof is usually in the range of 0.1 to 20 parts by weight per 100 parts by weight of the vinyl chloride resin.
• coloring agent examples include carbon black, lead sulfide, white carbon, titanium white, lithopone, safflower, antimony sulfide, chrome yellow, chrome green, cobalt blue, and molybdenum orange.
• the coloring agent is added to the vinyl chloride resin composition, the amount thereof is usually in the range of 1 to 100 parts by weight per 100 parts by weight of the vinyl chloride resin.
• processing aid examples include liquid paraffin, polyethylene wax, stearic acid, stearamide, ethylene bis stearamide, butyl stearate, and calcium stearate.
• the processing aid is blended into the vinyl chloride resin composition, the blending amount is generally in the range of 0.1 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.
• the filler examples include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, and ferrite; fibers and powders such as glass, carbon, and metals; glass spheres, graphite, aluminum hydroxide, and barium sulfate. , magnesium oxide, magnesium carbonate, magnesium silicate, and calcium silicate.
• metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, and ferrite
• fibers and powders such as glass, carbon, and metals
• magnesium oxide, magnesium carbonate, magnesium silicate, and calcium silicate When the filler is added to the vinyl chloride resin composition, the amount thereof is usually in the range of 1 to 100 parts by mass per 100 parts by mass of the vinyl chloride resin.
• antioxidants examples include 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol)propionate]methane, 2-hydroxy-4-methoxy Phenolic compounds such as benzophenone; Sulfur compounds such as alkyl disulfide, thiodipropionate, benzothiazole; -butylphenyl)phosphite; and organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate.
• the antioxidant is added to the vinyl chloride resin composition, the amount thereof is usually in the range of 0.2 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.
• the ultraviolet absorber examples include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenones such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone; 5-methyl-1H-benzotriazole, 1-dioctylaminomethylbenzotriazole, and other benzotriazole compounds, as well as cyanoacrylate compounds.
• the ultraviolet absorber is blended into the vinyl chloride resin composition, the blending amount thereof is usually in the range of 0.1 to 10 parts by mass per 100 parts by mass of the vinyl chloride resin.
• a hindered amine light stabilizer can be exemplified.
• the lubricant examples include silicone, liquid paraffin, paraffin wax, fatty acid metal salts such as metal stearate and metal laurate; fatty acid amides, fatty acid waxes, and higher fatty acid waxes.
• the amount thereof is usually in the range of 0.1 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin.
• the antistatic agent examples include alkylsulfonate-type, alkylethercarboxylic acid-type, or dialkylsulfosuccinate-type anionic antistatic agents; nonionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, and diethanolamine derivatives; type, quaternary ammonium salts such as alkyldimethylbenzyl type, alkylpyridinium type organic acid salts or hydrochlorides; amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. .
• the amount thereof is generally in the range of 0.1 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin.
• cross-linking aid examples include polyfunctional monomers such as tetraethylene glycol dimethacrylate, divinylbenzene diallyl phthalate, triallyl isocyanurate, trimethylolpropane triarylate, tetramethylolmethane tetramethacrylate, and trimethoxyethoxyvinylsilane.
• the blending amount is usually in the range of 0.5 to 30 parts by mass per 100 parts by mass of the vinyl chloride resin.
• the vinyl chloride resin composition of the present invention can be produced by a known method.
• the vinyl chloride resin composition of the present invention can be prepared by mixing the vinyl chloride resin, the plasticizer for the vinyl chloride resin of the present invention, and optional components (the other plasticizers and the other additives) in a blender, planetary mixer, Banbury mixer, or the like. It can be prepared by mixing using a kneader.
• a molded article is obtained by molding the vinyl chloride resin composition of the present invention by a known molding method such as vacuum molding, compression molding, extrusion molding, calendar molding, press molding, blow molding, powder molding, and powder slush molding. receive.
• Molded articles obtained using the vinyl chloride resin composition of the present invention include, for example, insulating tapes, insulating sheets, wiring connectors, conductor covering materials, pipes such as water pipes, joints for pipes, gutters such as rain gutters, and window frames. Sidings, flat plates, corrugated sheets, automobile underbody coats, dashboards, instrument panels, consoles, door sheets, under carpets, trunk sheets, door trims and other automobile materials, various types of leather, decorative sheets, agricultural films, food packaging films, various foam products, hoses, medical tubes, food tubes, refrigerator gaskets, packings, wallpapers, floor materials, boots, curtains, shoe soles, gloves, waterstops, toys, veneers, blood bags, It can be used for infusion bags, tarpaulins, mats, waterproof sheets, civil engineering sheets, roofing, waterproof sheets, industrial tapes, glass films, erasers, and the like.
• the automotive dashboard includes a laminate portion of a vinyl chloride resin layer and a urethane resin layer, and a molded article obtained using the vinyl chloride resin composition of the present invention is particularly suitable for the vinyl chloride resin layer of the laminate. is. This is because in the vinyl chloride resin layer using the plasticizer of the present invention, the migration of the plasticizer in the vinyl chloride resin layer to the urethane resin layer is reduced, and the flexibility of the vinyl chloride resin layer can be maintained. is.
• the non-migratory property of the plasticizer of the present invention can be confirmed by the heating test described in Examples. Specifically, even after a laminate of a vinyl chloride resin layer and a urethane resin layer containing the vinyl chloride resin plasticizer of the present invention is subjected to a heat test, the plasticizer of the present invention remains in the vinyl chloride resin layer.
• the ratio (amount of plasticizer in vinyl chloride resin layer after heat test/amount of plasticizer in vinyl chloride resin layer before heat test ⁇ 100) can be 90% or more.
• the upper limit of the residual rate is not particularly limited, it is, for example, 100%
• the laminate of the vinyl chloride resin layer containing the vinyl chloride resin plasticizer of the present invention and the urethane resin layer will be referred to as the "laminate of the present invention", and each layer will be described.
• the vinyl chloride resin layer is obtained by molding the vinyl chloride resin composition of the present invention, and the components contained in the vinyl chloride resin composition and the molding method are as described above.
• the thickness of the vinyl chloride resin layer may be set arbitrarily, and is, for example, 0.2 to 2.0 mm, preferably 0.5 to 1.5 mm.
• the urethane resin layer is a layer made of polyurethane foam, and can be formed using a foam raw material containing polyol, polyisocyanate, a cross-linking agent, a catalyst, a foaming agent, a foam stabilizer, and the like.
• the polyol is not particularly limited, and known polyols used for producing polyurethane foams can be used.
• specific examples of the polyol include polyether polyols such as polypropylene glycol (PPG), polyethylene glycol (PEG), and polyoxytetramethylene glycol (PTMG); polyester polyols, polymer polyols, and the like. is preferred.
• PPG polypropylene glycol
• PEG polyethylene glycol
• PTMG polyoxytetramethylene glycol
• polyester polyols polymer polyols, and the like. is preferred.
• One type of polyol may be used alone, or two or more types may be used in combination.
• a diphenylmethane diisocyanate (hereinafter sometimes abbreviated as "MDI”) system and a tolylene diisocyanate (hereinafter sometimes abbreviated as "TDI”) system may be used in combination.
• MDI series include 2,2'-MDI, 2,4'-MDI, 4,4'-MDI, polymethylene polyphenylene polyisocyanate, and urethane modified products thereof.
• TDI series include 2,4-TDI, 2,6-TDI, and carbodiimide modified products thereof.
• cross-linking agent a cross-linking agent that is usually used in the production of polyurethane foam can be used without particular limitation.
• Compounds having a molecular weight of less than 500 and having at least two active hydrogen groups, such as low-molecular-weight alcohols, low-molecular-weight amines, and low-molecular-weight aminoalcohols, can be used as the cross-linking agent.
• Said cross-linking agent is preferably a low molecular weight aminoalcohol that reacts slowly with isocyanate groups, more preferably diethanolamine.
• the amount of the cross-linking agent to be blended is preferably 10 parts by mass or less, particularly 5 parts by mass or less (usually 1 part by mass or more) per 100 parts by mass of the polyol.
• a catalyst that is usually used in the production of polyurethane foam can be used without particular limitation.
• Tertiary amines, diazabicycloalkene compounds and salts thereof, organometallic compounds, and the like can be used as this catalyst, and tertiary amines are preferred.
• tertiary amine examples include triethylenediamine, triethylamine, tri-n-butylamine, bis(2-dimethylaminoethyl)ether, N,N,N',N'-tetramethylhexamethylenediamine and 1,2-dimethylimidazole. etc.
• organometallic compounds include metal salts of various metals such as tin, lead, and zirconium with organic acids such as octenoic acid and naphthenic acid, such as dibutyltin dilaurate, dibutyltin diacetylacetonate, and zirconium tetraacetylacetonate. are mentioned.
• the blending amount of the catalyst is preferably 0.03 to 2.0 parts by mass, particularly 0.03 to 1.5 parts by mass, based on 100 parts by mass of the polyol.
• the amount of the catalyst is 0.03 to 2.0 parts by mass, the foam raw material can be easily cured and the moldability is good.
• any foaming agent normally used in the production of polyurethane foam can be used without particular limitation.
• Water is often used as a blowing agent, and in addition to water, for example, two types of inert low boiling point solvents and reactive blowing agents can be used.
• inert low boiling point solvent examples include dichloromethane, hydrochlorofluorocarbon, hydrofluorocarbon, isopentane, and the like.
• Examples of the reactive foaming agent include azo compounds that decompose at a temperature higher than room temperature to generate gas.
• One of these foaming agents may be used alone, or two or more thereof may be used in combination.
• the blending amount of the foaming agent is preferably 1.0 to 5.0 parts by mass, particularly 1.5 to 4.0 parts by mass, based on 100 parts by mass of the polyol.
• foam stabilizer a foam stabilizer that is usually used in the production of polyurethane foam can be used without particular limitation.
• foam stabilizers include polydimethylsiloxane/polyalkylene oxide block copolymers and vinylsilane/polyalkylene polyol copolymers.
• the amount of the foam stabilizer compounded is preferably 3.0 parts by mass or less, particularly 2.0 parts by mass or less (usually 0.5 parts by mass or more) when the polyol is 100 parts by mass.
• anti-aging agents such as antioxidants and ultraviolet absorbers
• fillers such as calcium carbonate and barium sulfate
• internal release agents such as flame retardants, plasticizers, colorants, anti-aging agents, etc.
• additives and auxiliaries such as fungicides can be used as required.
• the method for forming the polyurethane foam layer is not particularly limited, and for example, a foam raw material is placed in the space between the upper mold and the lower mold by vacuum molding or the like under the condition that the isocyanate index is 70 to 140, particularly 80 to 120. It can be formed by injecting, reacting and curing. Also, if necessary, the foam raw material and/or the mold can be heated to accelerate the reaction and curing. Further, the foam raw material is injected into the space between the molds, preferably coated with a release agent, using at least one mixing head, and is usually reacted at a temperature ranging from room temperature to about 70° C. to foam. , can be formed by curing.
• the thickness of the urethane resin layer may be set arbitrarily, for example 5 to 15 mm, preferably 7 to 12 mm.
• the values of acid value and viscosity are values evaluated by the following methods. ⁇ Method for measuring acid value> It was measured by a method according to JIS K0070-1992. ⁇ Method for measuring viscosity> It was measured by a method according to JIS K6901-1986.
• the number average molecular weight of polyester is a value converted to polystyrene based on GPC measurement, and the measurement conditions are as follows.
• [GPC measurement conditions] Measuring device: High-speed GPC device “HLC-8320GPC” manufactured by Tosoh Corporation Column: "TSK GURDCOLUMN SuperHZ-L” manufactured by Tosoh Corporation + "TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZ-2000” manufactured by Tosoh Corporation + “TSK gel SuperHZ-2000” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "EcoSEC Data Analysis version 1.07" manufactured by Tosoh Corporation Column temperature: 40°C Developing solvent: tetrahydrofuran Flow rate: 0.35 mL/min Measurement sample: 7.5 mg of the sample was dissolved in
• Example 1 Synthesis of polyester plasticizer A
• a reaction vessel was charged with 597 g (4.09 mol) of adipic acid, 448 g (3.80 mol) of 3-methyl 1,5-pentanediol, 177 g (1.23 mol) of isononyl alcohol, and 0 of tetraisopropyl titanate as an esterification catalyst. 0.06 g was placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, and the temperature was raised stepwise to 230° C. while stirring under a nitrogen stream. Heating was continued at 230° C. until the acid value was 4 or less, and the water produced was continuously removed. After the reaction, polyester plasticizer A (Mn 2,734, acid value 0.5, viscosity 3,000 mPa s (25 ° C.), isononyl alcohol content of 1920 mass ppm) was obtained in an amount of 945 g.
• the amount of isononyl alcohol remaining in the obtained polyester plasticizer A was measured by GC under the following conditions: Measuring instrument: GC-2010PLUS (manufactured by Shimadzu Corporation) Column: DB-5 (0.25 mm ⁇ 30 m ⁇ 0.25 ⁇ m) Vaporization chamber temperature: 250°C Detector temperature: 320°C Column temperature conditions: 40°C (10°C/min) ⁇ 250°C (20°C/min) ⁇ 315 (holding for 34 minutes) Sample concentration: 50mg/ml acetone
• Vinyl chloride resin (polymerization degree 1,000, ZEST1000Z, manufactured by Shin-Daiichi Vinyl Co., Ltd.) 100 parts by mass, 50 parts by mass of the obtained polyester plasticizer A, filler (Greg MP-677D (calcium / zinc-based composite stabilizer agent) and Nisshin Boeki Co., Ltd.) were mixed to obtain a vinyl chloride resin composition (1).
• the following evaluation was performed using the obtained vinyl chloride resin composition (1).
• the resulting sheet was evaluated for 100% modulus (tensile stress at 100% elongation) and elongation at break according to JISK6251:2010. Specifically, using a sheet with a thickness of 1.0 mm, a tensile test was performed under the following conditions to evaluate 100% modulus and elongation at break. Table 1 shows the results.
• the elongation at break is the value obtained by subtracting the initial distance between chucks of 20 mm from the distance between chucks when a 1.0 mm thick sheet is tensile-broken, divided by the distance between chucks of 20 mm, and expressed as a percentage.
• Measuring equipment Tensilon universal material testing machine (manufactured by Orientec Co., Ltd.) Sample shape: Dumbbell shape No. 3 Distance between chucks: 20mm Tensile speed: 200 mm/min Measurement atmosphere: temperature 23 degrees, humidity 50%
• the prepared dumbbell test piece was subjected to a heat aging test at 136°C for 168 hours according to JISK6257:2017.
• the weight of the dumbbell test piece was measured before and after the heat aging test, and the weight loss rate ((mass before heat aging test ⁇ mass after heat aging test)/mass before heat aging test) was calculated.
• Table 1 shows the results. The smaller the weight loss rate, the more the polyester plasticizer A remains in the molded article even after the heat aging test, and the polyester plasticizer A can be expected to have a heat resistance effect.
• the elongation at break was evaluated in the same manner as in the evaluation of the plasticizing effect, and the elongation rate of the dumbbell test piece after the heat aging test/the dumbbell test piece before the heat aging test The elongation rate was evaluated as "remaining elongation rate". Table 1 shows the results. The higher the elongation retention rate, the more the plasticizing effect can be maintained even after the heat aging test, and it can be said that the vinyl chloride resin composition has excellent heat resistance.
• ABS acrylonitrile-butadiene-styrene resin
• HIPS high-impact polystyrene resin
• AS acrylonitrile-styrene resin
• PU polyurethane resin
• a mixed liquid was prepared by mixing the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) at a ratio of index 98.
• the prepared mixed solution is poured onto a vinyl chloride resin molding sheet laid in a mold of 200 mm ⁇ 300 mm ⁇ 10 mm, and the mold is covered with an aluminum plate of 348 mm ⁇ 255 mm ⁇ 10 mm from above, The mold was closed.
• a foamed polyurethane molded article (thickness: 9 mm, density: 0.18 g/cm 3 ) was formed on the vinyl chloride resin molded sheet (thickness: 1 mm) as the skin.
• a lined laminate was formed in the mold. This laminate was removed from the mold to produce a laminate comprising a foamed urethane resin layer and a vinyl chloride resin layer.
• the obtained laminate was placed in an oven and heated at a temperature of 130°C for 600 hours. After heating, only the vinyl chloride resin layer was peeled off from the laminate, and 20 mg of the peeled vinyl chloride resin layer was dissolved in tetrahydrofuran (THF).
• THF tetrahydrofuran
• the plasticizer content (%) in the vinyl chloride resin layer after heat treatment was measured by analyzing the obtained THF solution under the above-described GPC measurement conditions. The plasticizer content rate obtained by the measurement was divided by the plasticizer content rate in the vinyl chloride resin layer before heat treatment to calculate the plasticizer residual rate.
• Example 2 Synthesis of polyester plasticizer B
• a reaction vessel was charged with 597 g (4.09 mol) of adipic acid, 448 g (3.80 mol) of 3-methyl 1,5-pentanediol, 177 g (1.23 mol) of isononyl alcohol, and 0 of tetraisopropyl titanate as an esterification catalyst. 0.06 g was placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, and the temperature was raised stepwise to 230° C. while stirring under a nitrogen stream. Heating was continued at 230° C. until the acid value was 4 or less, and the water produced was continuously removed.
• polyester plasticizer B Mn 2,738, acid value 0.5, a viscosity of 2,990 mPa ⁇ s (25° C.), and an isononyl alcohol content of 1562 mass ppm
• a vinyl chloride resin composition (2) was prepared and evaluated in the same manner as in Example 1, except that plasticizer B was used instead of plasticizer A. Table 1 shows the results.
• Example 3 Synthesis of polyester plasticizer C
• a reaction vessel was charged with 597 g (4.09 mol) of adipic acid, 448 g (3.80 mol) of 3-methyl 1,5-pentanediol, 177 g (1.23 mol) of isononyl alcohol, and 0 of tetraisopropyl titanate as an esterification catalyst. 0.06 g was placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, and the temperature was raised stepwise to 230° C. while stirring under a nitrogen stream. Heating was continued at 230° C. until the acid value was 4 or less, and the water produced was continuously removed.
• polyester plasticizer C Mn 2,697, acid value 0.6, a viscosity of 2,980 mPa ⁇ s (25° C.), and an isononyl alcohol content of 792 mass ppm
• a vinyl chloride resin composition (3) was prepared and evaluated in the same manner as in Example 1, except that plasticizer C was used instead of plasticizer A. Table 1 shows the results.
• Example 4 Synthesis of polyester plasticizer D
• a reaction vessel was charged with 597 g (4.09 mol) of adipic acid, 448 g (3.80 mol) of 3-methyl 1,5-pentanediol, 177 g (1.23 mol) of isononyl alcohol, and 0 of tetraisopropyl titanate as an esterification catalyst. 0.06 g was placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, and the temperature was raised stepwise to 230° C. while stirring under a nitrogen stream. Heating was continued at 230° C. until the acid value was 4 or less, and the water produced was continuously removed.
• polyester plasticizer D Mn 2,794, acid value 0.7, a viscosity of 2,943 mPa ⁇ s (25° C.), and an isononyl alcohol content of 522 mass ppm
• a vinyl chloride resin composition (4) was prepared and evaluated in the same manner as in Example 1, except that plasticizer D was used instead of plasticizer A. Table 1 shows the results.
• Example 5 Synthesis of polyester plasticizer E
• a reaction vessel was charged with 597 g (4.09 mol) of adipic acid, 265 g (2.25 mol) of 3-methyl 1,5-pentanediol, 80 g (0.77 mol) of neopentyl glycol, 73 g of 1,4-butanediol ( 0.81 mol), 114 g (0.88 mol) of 2-ethylhexanol, 54 g (0.08 mol) of coconut oil, 0.06 g of tetraisopropyl titanate as an esterification catalyst, a thermometer, stirrer, and reflux condenser.
• polyester plasticizer E Mn 2,995, acid value 0.6, a viscosity of 2,910 mPa ⁇ s (25° C.), and a 2-ethylhexanol content of 693 mass ppm
• a vinyl chloride resin composition (5) was prepared and evaluated in the same manner as in Example 1, except that plasticizer E was used instead of plasticizer A. Table 1 shows the results.
• Example 6 Synthesis of polyester plasticizer F
• a reaction vessel was charged with 657 g (4.50 mol) of adipic acid, 231 g (2.57 mol) of 2-methyl-1,3-propanediol, 154 g (1.49 mol) of neopentyl glycol, and 194 g (1.49 mol) of isononyl alcohol. 35 mol), and 0.06 g of tetraisopropyl titanate as an esterification catalyst were placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and heated to 230° C. while stirring under a nitrogen stream.
• polyester plasticizer F Mn 2,182, acid value 0.2, a viscosity of 3,140 mPa ⁇ s (25° C.), and an isononyl alcohol content of 753 mass ppm
• a vinyl chloride resin composition (6) was prepared and evaluated in the same manner as in Example 1, except that plasticizer F was used instead of plasticizer A. Table 1 shows the results.
• Example 7 Synthesis of polyester plasticizer G
• a reaction vessel was charged with 615 g (4.21 mol) of adipic acid, 70 g (0.78 mol) of 1,4-butanediol, 322 g (3.10 mol) of neopentyl glycol, and 177 g (1.36 mol) of 2-ethylhexanol.
• 56 g (0.08 mol) of coconut oil, and 0.06 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and a nitrogen stream was added.
• the temperature was gradually raised to 230° C. while stirring at the bottom. Heating was continued at 230° C. until the acid value was 4 or less, and the water produced was continuously removed. After the reaction, excess 2-ethylhexanol was distilled off under reduced pressure at 230-200° C. to obtain a polyester. The obtained polyester was subjected to steam stripping treatment by supplying steam at 160° C.
• polyester plasticizer G Mn 2,144, acid value 0.6, a viscosity of 2,950 mPa ⁇ s (25° C.), and a 2-ethylhexanol content of 461 mass ppm
• a vinyl chloride resin composition (7) was prepared and evaluated in the same manner as in Example 1, except that plasticizer G was used instead of plasticizer A. Table 1 shows the results.
• Example 8 Synthesis of polyester plasticizer H
• a reaction vessel was charged with 672 g (4.60 mol) of adipic acid, 236 g (2.62 mol) of 1,4-butanediol, 182 g (1.75 mol) of neopentyl glycol, 133 g (0.92 mol) of isononyl alcohol, 0.06 g of tetraisopropyl titanate as an esterification catalyst was placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and gradually heated to 230° C. while stirring under a nitrogen stream. heated up. Heating was continued at 230° C.
• polyester plasticizer H Mn 2,770, acid value 0.6, a viscosity of 9,810 mPa ⁇ s (25° C.), and an isononyl alcohol content of 669 mass ppm
• a vinyl chloride resin composition (8) was prepared and evaluated in the same manner as in Example 1, except that plasticizer H was used instead of plasticizer A. Table 1 shows the results.
• Example 9 Synthesis of polyester plasticizer I
• a reaction vessel was charged with 579 g (3.97 mol) of adipic acid, 167 g (1.85 mol) of 1,4-butanediol, 289 g (2.78 mol) of neopentyl glycol, 176 g (0.88 mol) of lauric acid and an ester.
• 0.06 g of tetraisopropyl titanate as a conversion catalyst was placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised stepwise to 230° C. while stirring under a nitrogen stream. I warmed up.
• polyester plasticizer I Mn 2,400, acid value 0.4 and a viscosity of 4,350 mPa ⁇ s (25° C.) was obtained in an amount of 958 g.
• a vinyl chloride resin composition (9) was prepared and evaluated in the same manner as in Example 1, except that plasticizer I was used instead of plasticizer A. Table 1 shows the results.
• polyester plasticizer I (Mn2,242, acid value 0.2, viscosity 3,250 mPa s (25° C.), 2- 861 g of ethylhexanol content (3929 mass ppm) was obtained.
• a vinyl chloride resin composition (1') was prepared and evaluated in the same manner as in Example 1, except that plasticizer I was used instead of plasticizer A. Table 2 shows the results.
• Polyester plasticizer J (Mn 2,031, acid value 0.6, viscosity 2,940 mPa s (25 ° C.), isononyl alcohol content 3260 ppm by mass) was obtained.
• a vinyl chloride resin composition (2') was prepared and evaluated in the same manner as in Example 1, except that plasticizer J was used instead of plasticizer A. Table 2 shows the results.
• Polyester plasticizer K (Mn 2,725, acid value 0.2, viscosity 3,228 mPa s (25 ° C.), isononyl alcohol content 4011 mass ppm) was obtained in an amount of 924 g.
• a vinyl chloride resin composition (3') was prepared and evaluated in the same manner as in Example 1, except that plasticizer K was used instead of plasticizer A. Table 2 shows the results.
• Polyester plasticizer L (Mn 2,814, acid value 0.6, viscosity 1,552 mPa s (25 ° C.), 2-ethylhexanol content of 1211 mass ppm) was obtained in an amount of 919 g.
• a vinyl chloride resin composition (4') was prepared and evaluated in the same manner as in Example 1, except that plasticizer L was used instead of plasticizer A. Table 2 shows the results.

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