Classifications

• • 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
• • 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
  • 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
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • 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
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
• • 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
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
  • C08G63/21—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
• • 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
  • C08G63/88—Post-polymerisation treatment
  • C08G63/90—Purification; Drying

Definitions

• the present invention relates to a plasticizer for vinyl chloride resin, a vinyl chloride resin composition, and a molded product thereof.
• Vinyl chloride resin is one of the typical plastics, and because it has physical properties such as low cost and excellent heat resistance, its applications are wide-ranging. Since vinyl chloride resin has a hard and brittle property, it is usually used after adding a plasticizer to soften the vinyl chloride resin.
• esters of polybasic acids such as phthalates, adipates, and trimellitic acids are known as typical plasticizers used for vinyl chloride resins, and phthalates are used from the viewpoint of price and performance balance. Esters were often used.
• Trimellitic acid esters which have higher heat resistance than phthalates, are used in applications that require heat resistance, which cannot be handled by phthalates (for example, Patent Document 1).
• tri-2-ethylhexyl trimellitic acid, trinormaloctyltrimellitic acid, trinormaldecyltrimellitic acid, triisononyl trimellitic acid, triisodecyl ester of trimellitic acid and the like are plasticizers having extremely high heat resistance. Therefore, it is widely used in heat-resistant electric wires, wire harnesses for automobiles, dashboards for automobiles, and the like.
• Patent Document 2 discloses a plasticizer for polyester vinyl chloride resin.
• An object to be solved by the present invention is to provide a plasticizer for vinyl chloride resin having an excellent balance of non-migration property, fogging resistance, flexibility, heat resistance and cold resistance.
• polyester containing a certain amount or more of low molecular weight components while reducing low molecular weight components is excellent as a plasticizer for vinyl chloride resin.
• the present invention has been completed.
• 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 which is a polyester that uses an acid as a reaction raw material. The polyester has a number average molecular weight in the range of 500 to 6,000, and a component having a molecular weight of 600 or less is measured by gel permeation chromatography. It relates to a plasticizer for a vinyl chloride resin having an area ratio in the range of 0.5 to 3.0% by mass.
• the plasticizer for vinyl chloride resin of the present invention has 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. It is a polyester using to 21 monocarboxylic acids as a reaction raw material, and the polyester has a number average molecular weight of 500 to 6,000, and a component having a molecular weight of 600 or less has an area ratio of 0. It is in the range of 5 to 3.0% by mass.
• the polyester which is the plasticizer for vinyl chloride resin of the present invention may be simply referred to as "the polyester of the present invention" below.
• the polyester of the present invention has a number average molecular weight in the range of 500 to 6,000 and a component having a molecular weight of 600 or less in the range of 0.5 to 3.0% by mass to improve non-migration and fogging resistance. At the same time, flexibility and cold resistance can be guaranteed.
• the component of the polyester of the present invention having a molecular weight of 600 or less is preferably in the range of 1.0 to 3.0% by mass, more preferably in the range of 1.1 to 2.9% by mass, and further preferably 1. It is in the range of 1 to 2.8% by mass.
• the gel described in Examples that the polyester of the present invention has a number average molecular weight in the range of 500 to 6,000 and a component having a molecular weight of 600 or less in the range of 0.5 to 3.0 mass. Confirm by permeation chromatography (GPC) measurement.
• the polyester of the present invention has 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 4 to 21 carbon atoms. It is a polyester obtained by using a reaction raw material with an acid.
• reaction raw material means a raw material constituting the polyester of the present invention, and does not contain a solvent or a catalyst that does not constitute the polyester.
• the glycol having 2 to 18 carbon atoms is preferably an alkylene glycol having 2 to 18 carbon atoms or an 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-propylene glycol, 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 further preferably 1,2-propanediol. , 1,3-Butanediol, 1,4-Butanediol, Neopentyl Glycol, 2-Methyl-1,3-Propanediol, 3-Methyl-1,5-Pentanediol, 1,6-Hexanediol.
• the oxyalkylene glycol having 2 to 18 carbon atoms is, for example, one in which one of the carbon atoms of the alkylene glycol having 2 to 18 carbon atoms is replaced with an oxygen atom, and diethylene glycol, triethylene glycol, tetraethylene glycol, and the like. Examples thereof include dipropylene glycol and tripropylene glycol.
• the oxyalkylene glycol having 2 to 18 carbon atoms is preferably an oxyalkylene glycol having 3 to 10 carbon atoms, more preferably an oxyalkylene glycol having 4 to 10 carbon atoms, and further preferably diethylene glycol or tri. It is ethylene glycol.
• glycol having 2 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 aliphatic dicarboxylic acid having 4 to 14 carbon atoms is preferably an alkylene dicarboxylic acid having 4 to 14 carbon atoms, and more preferably an alkylene dicarboxylic acid having 6 to 12 carbon atoms.
• alkylene dicarboxylic acid 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. Can be mentioned. Of these, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid are more preferable, adipic acid and sebacic acid are even more preferable, and adipic acid is particularly preferable.
• the alkylene dicarboxylic acid having 4 to 14 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 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, dodecanol and the like.
• 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 acid having 2 to 21 carbon atoms include acetic acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, caproic acid, lauric acid, myristic acid, pentadecic acid, palmitic acid, margaric acid and stea. Acids, caproic acid and the like can be mentioned.
• 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, hydrogenated rapeseed oil fatty acid and the like. These are obtained by decomposing and hydrogenating oils obtained from palm, palm kernel, palm, olive, sunflower, and rapeseed, respectively, and all contain an aliphatic monocarboxylic acid having 8 to 21 carbon atoms 2 It is a mixture of long-chain aliphatic monocarboxylic acids of more than one species.
• the vegetable oil fatty acid which has not been hydrogenated may be used as long as the effect of the present invention is not impaired. Further, the vegetable oil fatty acid is not limited to the above.
• the polyester of the present invention has 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 reaction raw material may be an acid, and raw materials other than these may be used as long as the effects of the present invention are not impaired.
• the reaction raw material of the polyester of the present invention is 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.
• Substantially consisting of ⁇ 21 monocarboxylic acids more preferably glycols with 2-18 carbon atoms, aliphatic dicarboxylic acids with 4-14 carbon atoms, monoalcohols with 4-18 carbon atoms and / Alternatively, it is composed only of a monocarboxylic acid having 2 to 21 carbon atoms.
• the polyester of the present invention has a mixture of compounds represented by the following formulas (1) having different p values, a mixture of compounds represented by the following formulas (2) having different q values, and r values of each other. It comprises one or more selected from the group consisting of different mixtures of compounds represented by the following formula (3).
• G is a glycol residue having 2 to 18 carbon atoms.
• A is an aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms.
• S 11 and S 12 are independently monocarboxylic acid residues having 1 to 20 carbon atoms.
• S 21 and S 22 are independently monoalcohol residues 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 having 4 to 18 carbon atoms.
• p, q and r are each independently an integer.
• the "carboxylic acid residue” refers to the remaining organic group excluding the carboxyl group of the carboxylic acid. The number of carbon atoms in the “carboxylic acid residue” does not include the carbon atoms in the carboxy group.
• the "alcohol residue” refers to the remaining organic group obtained by removing the hydroxyl group from the alcohol.
• the "glycol residue” refers to the remaining organic group obtained by removing the hydroxyl group from the glycol.
• the glycol residue of G having 2 to 18 carbon atoms is a group corresponding to the glycol having 2 to 18 carbon atoms which is the reaction raw material of the polyester of the present invention.
• the aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms in 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 residues having 1 to 20 carbon atoms in S 11 , S 12 and S 31 are groups corresponding to the monocarboxylic acids having 2 to 21 carbon atoms which are the reaction raw materials of the polyester of the present invention.
• the monoalcohol residues having 4 to 18 carbon atoms in S 21 , S 22 and S 32 are the groups corresponding to the monoalcohols having 4 to 18 carbon atoms which are the reaction raw materials of the polyester of the present invention.
• each of p, q and r is not particularly limited, but is, for example, 30.
• the average value of p is, for example, in the range of 3 to 20
• the average value of q is in the range of, for example, 3 to 20
• the average value of r is, for example, in the range of 3 to 20.
• the average values of p, q and r can be confirmed from the number average molecular weight of polyester.
• the number average molecular weight (Mn) of the polyester of the present invention is 500 to 6,000, preferably 1,000 to 5,000, more preferably 1,500 to 4,000, and even more preferably 1. , 700-3,700.
• the number average molecular weight (Mn) of the polyester of the present invention is confirmed by the method described in Examples.
• 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 method described in Examples.
• the plasticizer for vinyl chloride resin of the present invention has glycols having 2 to 18 carbon atoms, aliphatic dicarboxylic acids having 4 to 14 carbon atoms, monoalcohols having 4 to 18 carbon atoms and / or 4 carbon atoms.
• Polyester is synthesized by reacting with ⁇ 21 monocarboxylic acids, the synthesized polyester is thin-film distilled, and a component having a molecular weight of 600 or less contained in the polyester after thin-film distillation is added to the total amount of polyester after thin-film distillation. It can be manufactured by setting it in the range of 5 to 3.0 mass.
• the method for synthesizing the polyester before thin film distillation is not particularly limited, and it can be produced by a known method, and can be produced by the following production method.
• 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 the formula (1) are collectively charged and reacted.
• Method 2 The dicarboxylic acid and glycol constituting each residue of the polyester represented by the formula (1) are reacted under the condition that the equivalent of the hydroxyl group is larger than the equivalent of the carboxyl group, and the hydroxyl group is at the end of the main chain.
• method after obtaining the polyester the reaction of a monocarboxylic acid constituting the obtained polyester resin and S 11 and S 12 having a.
• the polyester represented by the formula (2) can be obtained, for example, by the method shown below.
• Method 3 A method in which monoalcohol, dicarboxylic acid and glycol constituting each residue of the polyester represented by the formula (2) are collectively charged and reacted.
• Method 4 The dicarboxylic acid and glycol constituting each residue of the polyester represented by the formula (2) are reacted under the condition that the equivalent of the carboxyl group is larger than the equivalent of the hydroxyl group to form the carboxyl group in 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 monoalcohol, monocarboxylic acid, dicarboxylic acid and glycol constituting each residue of the polyester represented by the formula (3) are collectively charged and reacted.
• Method 5 The dicarboxylic acid and glycol constituting each residue of the polyester represented by the formula (3) are reacted under the condition that the equivalent of the carboxyl group and the equivalent of the hydroxyl group are the same to form the carboxyl group and the hydroxyl group, respectively.
• the reaction may be carried out in the presence of an esterification catalyst, for example, in the temperature range of 180 to 250 ° C. for 5 to 25 hours.
• an esterification catalyst for example, in the temperature range of 180 to 250 ° C. for 5 to 25 hours.
• the 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 used may be appropriately set, but is usually 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 material.
• an evaporative raw material is continuously supplied on a surface heated to a certain temperature under reduced pressure to form a uniform thin film, and the evaporative raw material is heated only while it is on the surface, relative to each other.
• This is a distillation method in which a component having a relatively low molecular weight is instantaneously evaporated and a component having a relatively high molecular weight is recovered from the surface.
• the thin film distillation of the synthesized polyester can be carried out by using, for example, a thin film distillation apparatus, a thin film evaporator, or the like.
• the thin-film distillation apparatus includes a flow-down membrane distillation apparatus, a centrifugal distillation apparatus, and the like, but is not particularly limited, and any of them can be used.
• the temperature during thin film distillation is, for example, in the range of 80 to 280 ° C, preferably in the range of 150 to 250 ° C, and more preferably in the range of 180 to 250 ° C.
• the degree of vacuum during thin film distillation is, for example, in the range of 0.1 to 300 Pa, preferably in the range of 0.1 to 150 Pa, and more preferably in the range of 0.1 to 100 Pa.
• the vinyl chloride resin composition of the present invention contains the plasticizer for vinyl chloride resin and the vinyl chloride resin of the present invention.
• the vinyl chloride resin includes a homopolymer of vinyl chloride, a homopolymer of vinylidene chloride, a copolymer containing vinyl chloride as an essential component, a copolymer 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 the comonomer that can be copolymerized include ⁇ - such as ethylene, propylene, and 1-butene.
• Olefins such as butadiene, isoprene; Vinyl alcohol, styrene, acrylonitrile, vinyl acetate, vinyl propionate, fumaric acid, fumaric acid ester, maleic acid, maleic acid ester, maleic acid anhydride, acrylic acid, acrylic acid ester, Examples thereof include methacrylic acid, methacrylic acid ester, and isoprenol.
• the degree of polymerization of the vinyl chloride resin is usually 300 to 5,000, preferably 400 to 3,500, and more preferably 700 to 3,000.
• the degree of polymerization of the vinyl chloride resin is within the above range, a molded product having high heat resistance can be obtained, and a vinyl chloride resin composition having excellent processability can be obtained.
• the vinyl chloride resin can be produced by a known method, and examples thereof include suspension polymerization in the presence of an oil-soluble polymerization catalyst, emulsion polymerization in the presence of a water-soluble polymerization catalyst in an aqueous medium, and the like.
• a commercially available product may be used as the vinyl chloride resin.
• Commercially available vinyl chloride resins include TH-640, TH-700, TH-800 (above, manufactured by Taiyo PVC Co., Ltd.); S-1004, S-1008, PSH-10 (above, manufactured by Kaneka Corporation).
• TK-1300 aboveve, manufactured by Shin-Etsu Polymer Co., Ltd.
• ZEST800Z, ZEST1000Z, ZEST1300Z aboveve, manufactured by Shin-Etsu Polymer Co., Ltd.
• the content of the plasticizer for vinyl chloride resin of the present invention in the vinyl chloride resin composition of the present invention is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin from the viewpoint of compatibility with the vinyl chloride resin and the like. It is in the range of parts, more preferably in the range of 30 to 100 parts by mass, further preferably in the range of 40 to 80 parts by mass, and particularly preferably in the range of 50 to 80 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 contain plasticizers other than the plasticizer for vinyl chloride resin of the present invention (other plasticizers), and other plasticizers. It may contain an additive or the like.
• plasticizer examples include benzoic acid esters such as diethylene glycol dibenzoate; dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and the like.
• benzoic acid esters such as diethylene glycol dibenzoate; dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and the like.
• Phthalate esters such as diundecyl phthalate (DUP), ditridecyl phthalate (DTDP); terephthalates such as bis terephthalate (2-ethylhexyl) (DOTP); isophthalates such as bis isophthalate (2-ethylhexyl) (DOIP) Acid Esters; Phthalate Esters such as Tetra-2-ethylhexyl Pyromatate (TOPM); Di-2-ethylhexyl adipate (DOA), Disononyl Adipate (DINA), Diisodecyl adipate (DIDA), Di-Sebasicate Aliphatic dibasic acid esters such as 2-ethylhexyl (DOS) and diisononyl sebacate (DINS); phthalates such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP); many such as pentaeryth
• Alkyl esters of valence alcohols polyesters with a molecular weight of 800-4,000 synthesized by polyesterification of dibasic acids such as adipic acid and glycols; epoxidized esters such as epoxidized soybean oil and epoxidized flaxseed oil; hexahydrophthalates Alicyclic dibasic acid such as acid diisononyl ester; fatty acid glycol ester such as dicapric acid 1.4-butanediol; tributyl acetylcitrate (ATBC); chlorinated paraffin chlorinated paraffin wax or n-paraffin; chlorinated Chlorinated fatty acid esters such as stearate esters; higher fatty acid esters such as butyl oleate and the like can be mentioned.
• dibasic acids such as adipic acid and glycols
• epoxidized esters such as epoxidized soybean oil and epoxidized flaxseed oil
• the content of the other plasticizer is, for example, 10 to 300 parts by mass with respect to 100 parts by mass of the plasticizer for vinyl chloride resin of the present invention.
• the range is preferably 20 to 200 parts by mass.
• Examples of the other additives include flame retardants, stabilizers, stabilizing aids, coloring agents, processing aids, fillers, antioxidants (antioxidants), ultraviolet absorbers, light stabilizers, lubricants, and antistatic agents.
• Examples thereof include an inhibitor, a cross-linking aid, and the like.
• the flame retardant examples include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, and zinc borate; cresyldiphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, and trisdichloropropyl phos. Phosphorus compounds such as fate; halogen compounds such as chlorinated paraffin are exemplified.
• the flame retardant is blended in the vinyl chloride resin composition, the blending amount is usually in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
• the stabilizer examples include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinolate, calcium stearate, barium laurate, barium lysinolate, barium stearate, zinc octylate, zinc laurate, zinc lysinolate.
• Metal soap compounds such as zinc stearate; organic tin compounds such as dimethyltinbis-2-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutylmaleate, dibutyltin dilaurate; antimony mercaptide compounds; lanthanum oxide, water Examples thereof include lanthanoid-containing compounds such as lanthanum oxide.
• the blending amount thereof is usually in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass 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.
• phosphite compounds such as triphenylphosphite, monooctyldiphenylphosphite and tridecylphosphite
• beta-diketone compounds such as acetylacetone and benzoylacetone
• glycerin examples include polyol compounds such as glycol; perchlorate compounds such as barium perchlorate salt and sodium perchlorate salt; hydrotalcite compounds; zeolite and the like.
• the colorant examples include carbon black, lead sulfide, white carbon, titanium white, lithopone, Benigara, antimony sulfide, chrome yellow, chrome green, cobalt blue, molybdenum orange and the like.
• the blending amount is usually in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
• processing aid examples include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bisstearic acid amide, butyl steaerate, calcium stearate and the like.
• the processing aid is blended in the vinyl chloride resin composition, the blending amount is usually in the range of 0.1 to 20 parts by mass with respect to 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 metal; glass spheres, graphite, aluminum hydroxide, and barium sulfate. , Magnesium oxide, magnesium carbonate, magnesium silicate, calcium silicate and the like are exemplified.
• the blending amount is usually in the range of 1 to 100 parts by mass with respect to 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, and 2-hydroxy-4-methoxy.
• Phenolic compounds such as benzophenone; sulfur compounds such as alkyldisulfide, thiodipropionic acid ester, benzothiazole; trisnonylphenylphosphite, diphenylisodecylphosphite, triphenylphosphite, tris (2,4-di-tert) -Phenol acid compounds such as butylphenyl) phosphite; organic metal compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate are exemplified.
• the antioxidant is blended in the vinyl chloride resin composition, the blending amount thereof is usually in the range of 0.2 to 20 parts by mass with respect to 100 parts by mass
• the ultraviolet absorber examples include salicylate compounds such as phenylsalicylate and p-tert-butylphenylsalicylate; benzophenones such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone.
• System compounds In addition to benzotriazole-based compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, cyanoacrylate-based compounds and the like are exemplified.
• the ultraviolet absorber is blended in the vinyl chloride resin composition, the blending amount thereof is usually in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
• the light stabilizer examples include hindered amine-based light stabilizers. Specifically, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2 , 2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) ) -4-Hydrikyphenyl] methyl] butylmalonate, bisdecanoate (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester and 1,1-dimethylethylhydroperoxide And octane reaction product, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidinol and
• the lubricant examples include fatty acid metal salts such as silicone, liquid paraffin, barafin wax, metal stearate and metal laurate; fatty acid amides, fatty acid wax, higher fatty acid wax and the like.
• the blending amount is usually in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
• the antistatic agent examples include an alkyl sulfonate type, an alkyl ether carboxylic acid type or a dialkyl sulfosuccinate type anionic antistatic agent; a nonionic antistatic agent such as a polyethylene glycol derivative, a sorbitan derivative and a diethanolamine derivative; an alkylamide amine.
• a nonionic antistatic agent such as a polyethylene glycol derivative, a sorbitan derivative and a diethanolamine derivative
• an alkylamide amine examples include quaternary ammonium salts such as type and alkyldimethylbenzyl type, cationic antistatic agents such as alkylpyridinium type organic acid salts or hydrochlorides; and amphoteric antistatic agents such as alkylbetaine type and alkylimidazolin type. ..
• the blending amount thereof is usually in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
• cross-linking aid examples include polyfunctional monomers such as tetraethylene glycol dimethacrylate, divinylbenzenediallyl phthalate, triallyl isocyanurate, trimethylolpropane trialilate, tetramethylolmethanetetramethacrylate, and trimethoxyethoxyvinylsilane.
• the cross-linking aid is blended in the vinyl chloride resin composition, the blending amount thereof is usually in the range of 0.5 to 30 parts by mass with respect to 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 comprises a vinyl chloride resin, a plasticizer for vinyl chloride resin of the present invention, and optional components (the other plasticizer and the other additive), such as a blender, a planetary mixer, and a Banbury mixer. It can be prepared by mixing using a kneader.
• a molded product can be 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, calender molding, press molding, blow molding, powder molding and the like.
• Molded products obtained by using the vinyl chloride resin composition of the present invention include, for example, insulating tapes, insulating sheets, wiring connectors, wire coating materials, pipes such as water pipes, joints for pipes, and gutters such as rain gutters.
• Window frame siding flat plate, corrugated sheet, automobile underbody coat, dashboard, instrument panel, console, door sheet, undercarpet, trunk sheet, door trim and other automobile packaging, various leathers, decorative sheet, for agriculture Films, food packaging films, various foam products, hoses, medical tubes, food tubes, refrigerator gaskets, packings, wallpaper, flooring, boots, curtains, shoe soles, gloves, waterproof boards, toys, veneers , Blood bag, infusion bag, tarpaulin, mats, impermeable sheet, civil engineering sheet, roofing, waterproof sheet, industrial tape, glass film, erasing and the like.
• the acid value and the viscosity are the values evaluated by the following methods.
• the number average molecular weight of polyester is a value converted into 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 velocity: 0.35 mL / min Measurement sample: 7.5 mg of the sample was dissolved in 10
• Example 1 Synthesis of polyester plasticizer A
• adipic acid In the reaction vessel, 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 tetraisopropyl titanate 0 as an esterification catalyst. .06 g was placed in a four-necked flask having an internal volume of 2 liters equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually raised to 230 ° C. while stirring under a nitrogen stream. Heating was continued at 230 ° C.
• Vinyl Chloride Resin Composition (1) 100 parts by mass of vinyl chloride resin (polymerization degree 1,000, ZEST1000Z, manufactured by Shin-Daiichi PVC Co., Ltd.), 50 parts by mass of the obtained polyester plasticizer A, filler (Greg MP-677D (calcium / zinc-based composite stable) Agent) and 4 parts by mass (manufactured by Nittatsu Trading 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 kneaded vinyl chloride resin composition (1) After kneading the vinyl chloride resin composition (1) prepared by two rolls heated to 170 ° C. for 10 minutes, the kneaded vinyl chloride resin composition (1) can be obtained as a molded product having a thickness of 1.0 mm. Molding was performed using a mold (1.0 mm thick mold) and a press machine heated to 170 ° C. to prepare a 1.0 mm thick sheet.
• the obtained sheet was evaluated for 100% modulus (tensile stress at 100% elongation) and elongation at break according to JISK6251: 2010. Specifically, a tensile test was carried out under the following conditions using a sheet having a thickness of 1.0 mm, and 100% modulus and elongation at break were evaluated. The results are shown in Table 1. The breaking elongation is expressed as a percentage by dividing the value obtained by subtracting the initial chuck distance of 20 mm from the chuck distance when the 1.0 mm thick sheet is tensilely broken by the chuck distance of 20 mm.
• Measuring equipment Tensilon universal material testing machine (manufactured by Orientec Co., Ltd.) Sample shape: Dumbbell-shaped No. 3 Chuck distance: 20 mm
• the kneaded vinyl chloride resin composition (1) After kneading the vinyl chloride resin composition (1) prepared by two rolls heated to 170 ° C. for 10 minutes, the kneaded vinyl chloride resin composition (1) can be obtained as a molded product having a thickness of 1.0 mm. Molding was performed using a mold (1.0 mm thick mold) and a press machine heated to 170 ° C. to prepare a 1.0 mm thick sheet. From the prepared 1.0 mm thick sheet, a dumbbell-shaped No. 3 dumbbell test piece was prepared according to JISK6251: 2010.
• the prepared dumbbell test piece was subjected to a heat aging test at 136 ° C. for 168 hours according to JIS K6257: 2017.
• the masses of the dumbbell test pieces before and after the heat aging test were measured, and the weight loss rate ((mass before the heat aging test-mass after the heat aging test) / mass before the heat aging test) was calculated.
• the results are shown in Table 1. The smaller the weight loss rate, the more the polyester plasticizer A remains in the molded product even after the heat aging test, and the effect of heat resistance by the polyester plasticizer A can be expected.
• the breaking elongation rate was evaluated in the same manner as in the evaluation of the plasticization 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 growth rate was evaluated as the "remaining growth rate”. The results are shown in Table 1. It can be said that the higher the elongation residual ratio, the more the plasticizing effect can be maintained even after the heat aging test, and the vinyl chloride resin composition has excellent heat resistance.
• the kneaded vinyl chloride resin composition (1) After kneading the vinyl chloride resin composition (1) prepared by two rolls heated to 170 ° C. for 10 minutes, the kneaded vinyl chloride resin composition (1) can be obtained as a molded product having a thickness of 1.0 mm. Molding was performed using a mold (1.0 mm thick mold) and a press machine heated to 170 ° C. to prepare a 1.0 mm thick sheet. With respect to the obtained sheet, a test piece was prepared according to the test method specified in JIS K6773: 2007, and the flexible temperature (unit: ° C.) was evaluated using a Crashberg flexible temperature measuring tester. The results are shown in Table 1. The lower the softening temperature, the better the cold resistance.
• the kneaded vinyl chloride resin composition (1) After kneading the vinyl chloride resin composition (1) prepared by two rolls heated to 170 ° C. for 10 minutes, the kneaded vinyl chloride resin composition (1) can be obtained as a molded product having a thickness of 1.0 mm. Molding was performed using a mold (1.0 mm thick mold) and a press machine heated to 170 ° C. to prepare a 1.0 mm thick sheet. The obtained 1.0 mm-thick sheet was punched into a size of 6.0 mm ⁇ 38 mm and used as a test piece.
• This test piece is divided into two acrylonitrile-butadiene-styrene resin (ABS) plates, two impact-resistant polystyrene resin (HIPS) plates, two acrylonitrile-styrene resin (AS) plates, and two polyurethane resins (PU). ) It was sandwiched between each of the plates and held at 70 ° C. for 72 hours while applying a load of 0.22 kg / cm 2. The degree of contamination due to the transfer of the plasticizer to each of the ABS plate, the HIPS plate, the AS plate, and the PU plate was visually evaluated according to the following criteria. The results are shown in Table 1.
• the kneaded vinyl chloride resin composition (1) After kneading the vinyl chloride resin composition (1) prepared by two rolls heated to 170 ° C. for 10 minutes, the kneaded vinyl chloride resin composition (1) can be obtained as a molded product having a thickness of 1.0 mm. Molding was performed using a mold (1.0 mm thick mold) and a press machine heated to 170 ° C. to prepare a 1.0 mm thick sheet. Two 1.0 mm thick sheets cut into a size of 5 cm ⁇ 5 cm were prepared from this sheet. The two prepared sheets were stacked and left at 70 ° C. and a relative humidity of 95% for 30 days.
• the fogging resistance of the polyesterplasticizer A was evaluated according to DIN75201. Specifically, 10 g of the polyesterplasticizer A was placed in a glass sample bottle and the temperature was adjusted to 100 ° C. (Thermo Scientific Horizon Fog Testing System). It was set in PC-FTS / PC200-A25). The sample bottle was covered with aluminum foil and then heat-treated at 100 ° C. for 16 hours. After the heat treatment, the mixture was cooled to 21 ° C. and allowed to stand for 4 hours. Fogging resistance was evaluated by the increased weight of the aluminum foil. The results are shown in Table 1. The lower the weight gain, the better the fogging resistance.
• Example 2 Synthesis of polyester plasticizer B
• adipic acid In the reaction vessel, 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, thermometer, stirrer, and reflux condenser.
• polyester plasticizer B (Mn3). , 137, acid value 0.5, viscosity 3,244 mPa ⁇ s (25 ° C.)) was obtained in an amount of 898 g.
• the component of the obtained polyester plasticizer B having a molecular weight of 600 or less was 1.9% by mass.
• the coconut oil is mainly composed of lauric acid (12 carbon atoms), octanic acid (8 carbon atoms), capric acid (10 carbon atoms), myristic acid (14 carbon atoms), and palmitic acid (14 carbon atoms). It is a mixture containing 16) carbon atoms, octadecanoic acid (18 carbon atoms) and the like.
• the vinyl chloride resin composition (2) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer B was used instead of the plasticizer A. The results are shown in Table 1.
• Example 3 Synthesis of polyester plasticizer C
• adipic acid 489 g (3.35 mol) of adipic acid, 412 g (3.49 mol) of 3-methyl 1,5-pentanediol, 35 g (0.27 mol) of 2-ethylhexanol, 222 g of coconut oil (0.33).
• 0.06 g of tetraisopropyl titanate as an esterification catalyst was placed in a four-necked flask with an internal volume of 2 liters equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature reached 230 ° C. while stirring under a nitrogen stream.
• the temperature was raised stepwise, and heating was continued at 230 ° C. until the acid value became 4 or less, and the produced water was continuously removed.
• excess 2-ethylhexanol was distilled off under reduced pressure at 230 to 200 ° C., and then treated with a thin film distillation apparatus under the conditions of 230 ° C., 30 Pa, 1.8 kg / hr to obtain a polyester plasticizer C (Mn3).
• 028, acid value 0.4, viscosity 2,230 mPa ⁇ s (25 ° C.)) was obtained in 873 g.
• the component of the obtained polyester plasticizer C having a molecular weight of 600 or less was 1.8% by mass.
• the vinyl chloride resin composition (3) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer C was used instead of the plasticizer A. The results are shown in Table 1.
• Example 4 Preparation of polyester plasticizer D
• adipic acid In the reaction vessel, 596 g (4.08 mol) of adipic acid, 284 g (2.73 mol) of neopentyl glycol, 61 g (0.68 mol) of 1,4-butanediol, 282 g (2.17 mol) of 2-ethylhexanol.
• 0.06 g of tetraisopropyl titanate as an esterification catalyst was placed in a four-necked flask with an internal volume of 2 liters equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually increased to 230 ° C. while stirring under a nitrogen stream.
• polyester plasticizer D (Mn1). , 976, acid value 0.3, viscosity 1,578 mPa ⁇ s (25 ° C.)) was obtained in an amount of 849 g.
• the component of the obtained polyester plasticizer D having a molecular weight of 600 or less was 2.0% by mass.
• the vinyl chloride resin composition (4) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer D was used instead of the plasticizer A. The results are shown in Table 1.
• Example 5 Synthesis of polyester plasticizer E
• adipic acid In the reaction vessel, 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, thermometer, stirrer, and reflux condenser.
• the vinyl chloride resin composition (5) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer E was used instead of the plasticizer A. The results are shown in Table 1.
• Example 6 Synthesis of polyester plasticizer F
• adipic acid In the reaction vessel, 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, thermometer, stirrer, and reflux condenser.
• the vinyl chloride resin composition (6) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer F was used instead of the plasticizer A. The results are shown in Table 1.
• Example 7 Synthesis of polyester plasticizer G
• adipic acid In the reaction vessel, 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, thermometer, stirrer, and reflux condenser.
• the vinyl chloride resin composition (7) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer G was used instead of the plasticizer A. The results are shown in Table 1.
• Example 8 Synthesis of polyester plasticizer H
• adipic acid In the reaction vessel, 680.3 g (4.66 mol) of adipic acid, 394.2 g (4.38 mol) of 2-methyl 1,3-propanediol, 168.7 g (0.88 mol) of isononyl alcohol, esterification. 0.06 g of tetraisopropyl titanate as a catalyst was placed in a four-necked flask with an internal volume of 2 liters equipped with a thermometer, a stirrer, and a reflux cooler, and the temperature was gradually raised to 230 ° C. while stirring under a nitrogen stream. Then, heating was continued at 230 ° C.
• polyester plasticizer H (Mn3, Mn3) was treated with a thin film distillation apparatus under the conditions of 230 ° C., 30 Pa, 1.8 kg / hr. 872 g of 331, acid value 0.2, viscosity 6,360 mPa ⁇ s (25 ° C.) was obtained.
• the component of the obtained polyester plasticizer H having a molecular weight of 600 or less was 1.7% by mass.
• the vinyl chloride resin composition (8) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer H was used instead of the plasticizer A. The results are shown in Table 1.
• Example 9 Synthesis of polyester plasticizer I
• 584 g (4.0 mol) of adipic acid and 418 g (5.5 mol) of 1,2-propanediol were added to a four-necked flask with an internal volume of 2 liters equipped with a thermometer, agitator, and a reflux condenser.
• the temperature was gradually raised to 220 ° C. while being charged in a flask and stirred under a nitrogen stream.
• 410 g (2.0 mol) of hydrogenated coconut oil cured fatty acid and 0.1 g of tetraisopropoxytitanium as an esterification catalyst were added, and the water produced was continuously removed.
• the reaction product was distilled off under reduced pressure at the same temperature, and then the obtained reaction product was treated with a thin film distillation apparatus under the conditions of 230 ° C., 30 Pa, 0.6 kg / hr, whereby the polyester plasticizer I (Mn 2,160, A viscosity of 792 mPa ⁇ s, an acid value of 0.3, and a hydroxyl value of 5.6) were obtained.
• the component of the obtained polyester plasticizer I having a molecular weight of 600 or less was 2.9% by mass.
• the vinyl chloride resin composition (9) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer I was used instead of the plasticizer A. The results are shown in Table 2.
• Example 10 Synthesis of polyester plasticizer J
• the reaction product was distilled off under reduced pressure at the same temperature, and then the obtained reaction product was treated with a thin film distillation apparatus under the conditions of 230 ° C., 30 Pa, 0.6 kg / hr to obtain a polyester plasticizer J (Mn2,172, A viscosity of 963 mPa ⁇ s, an acid value of 0.2, and a hydroxyl value of 5.2) were obtained.
• the component of the obtained polyester plasticizer J having a molecular weight of 600 or less was 2.8% by mass.
• the vinyl chloride resin composition (10) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer J was used instead of the plasticizer A. The results are shown in Table 2.
• Example 11 Synthesis of polyester plasticizer K
• 808 g (4.0 mol) of sebacic acid and 418 g (5.5 mol) of 1,2-propanediol were added to a four-necked flask with an internal volume of 2 liters equipped with a thermometer, agitator, and a reflux condenser. The temperature was gradually raised to 220 ° C. while being charged in a flask and stirred under a nitrogen stream. Then, 410 g (2.0 mol) of hydrogenated coconut oil fatty acid and 0.1 g of tetraisopropoxytitanium as an esterification catalyst were added, and the water produced was continuously removed.
• the reaction product was distilled off under reduced pressure at the same temperature, and then the obtained reaction product was treated with a thin film distillation apparatus under the conditions of 230 ° C., 30 Pa, 0.6 kg / hr to obtain a polyester plasticizer K (Mn2,125, A viscosity of 867 mPa ⁇ s, an acid value of 0.2, and a hydroxyl value of 9.0) were obtained.
• the component of the obtained polyester plasticizer K having a molecular weight of 600 or less was 2.9% by mass.
• the vinyl chloride resin composition (11) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer K was used instead of the plasticizer A. The results are shown in Table 2.
• Example 12 Synthesis of polyester plasticizer L
• 808 g (4.0 mol) of sebacic acid, 209 g (2.75 mol) of 1,3-propanediol, and 286 g (2.75 mol) of neopentyl glycol were placed in a thermometer, a stirrer, and a reflux condenser. The temperature was gradually raised to 220 ° C. while stirring under a nitrogen stream. Then, 400 g (2.0 mol) of lauric acid and 0.1 g of tetraisopropoxytitanium as an esterification catalyst were added, and the water produced was continuously removed.
• the reaction product was distilled off under reduced pressure at the same temperature, and then the obtained reaction product was treated with a thin film distillation apparatus under the conditions of 230 ° C., 30 Pa, 0.6 kg / hr to obtain a polyester plasticizer L (Mn2,262, A viscosity of 893 mPa ⁇ s, an acid value of 0.4, and a hydroxyl value of 4.9) were obtained.
• the component of the obtained polyester plasticizer L having a molecular weight of 600 or less was 2.7% by mass.
• the vinyl chloride resin composition (12) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer L was used instead of the plasticizer A. The results are shown in Table 2.
• Example 13 Synthesis of polyester plasticizer M
• 808 g (4.0 mol) of sebacic acid, 209 g (2.75 mol) of 1,2-propanediol, and 324.5 g (2.75 mol) of 1,6-hexanediol were placed in a thermometer and a stirrer.
• a four-necked flask with an internal volume of 2 liters equipped with a reflux condenser and the temperature was gradually raised to 220 ° C. while stirring under a nitrogen stream.
• the vinyl chloride resin composition (13) was prepared and evaluated in the same manner as in Example 1 except that the plasticizer M was used instead of the plasticizer A. The results are shown in Table 2.
• Example 1 Example 1 except that the plasticizer N (tri2 ethylhexyl trimellitate, acid value 0.1, viscosity 210 mPa ⁇ s (25 ° C.), monosizer W-705 manufactured by DIC Corporation) was used instead of the plasticizer A.
• the vinyl chloride resin composition (1') was prepared and evaluated in the same manner as above. The results are shown in Table 3.
• Example 2 Comparative Example 2 except that the plasticizer O (trinormal octal remetrite, acid value 0.1, viscosity 90 mPa ⁇ s (25 ° C.), monosizer W-755 manufactured by DIC Corporation) was used instead of the plasticizer A.
• a vinyl chloride resin composition (2') was prepared and evaluated in the same manner as above. The results are shown in Table 3.
• polyester plasticizer P Mn 3,048, acid value 0.2, viscosity 3,300 mPa ⁇ s (25 ° C.)). rice field.
• the component of the obtained polyester plasticizer P having a molecular weight of 600 or less was 3.7% by mass.
• a vinyl chloride resin composition (3') was prepared and evaluated in the same manner as in Example 1 except that the plasticizer P was used instead of the plasticizer A. The results are shown in Table 3.
• polyester plasticizer Q (Mn 2,655, acid value 0.5, viscosity 2,614 mPa ⁇ s (25 ° C.)). Obtained.
• the component of the obtained polyester plasticizer Q having a molecular weight of 600 or less was 3.7% by mass.
• a vinyl chloride resin composition (4') was prepared and evaluated in the same manner as in Example 1 except that the plasticizer Q was used instead of the plasticizer A. The results are shown in Table 3.
• polyester plasticizer R Mn 1,677, acid value 0.2, viscosity 1,033 mPa ⁇ s (25 ° C.)
• a vinyl chloride resin composition (5') was prepared and evaluated in the same manner as in Example 1 except that the plasticizer R was used instead of the plasticizer A. The results are shown in Table 3.
• polyester plasticizer S (Mn2). , 793, acid value 0.5, viscosity 2,870 mPa ⁇ s (25 ° C.)) was obtained in 926 g.
• the component of the obtained polyester plasticizer S having a molecular weight of 600 or less was 3.1% by mass.
• a vinyl chloride resin composition (6') was prepared and evaluated in the same manner as in Example 1 except that the plasticizer S was used instead of the plasticizer A. The results are shown in Table 3.
• polyester plasticizer T (Mn 3,766, acid value 0.2, viscosity 4,173 mPa ⁇ s (25 ° C.)) was obtained in an amount of 847 g.
• the component of the obtained polyester plasticizer T having a molecular weight of 600 or less was 0.1% by mass or less.
• a vinyl chloride resin composition (7') was prepared and evaluated in the same manner as in Example 1 except that the plasticizer T was used instead of the plasticizer A. The results are shown in Table 3.

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