Biomass plasticizer for vinyl chloride resins

Abstract

To provide a biomass plasticizer for a vinyl chloride-based resin which can impart excellent heat resistance and volatility resistance to a molding of a vinyl chloride-based resin composition, and can suppress an emission amount of carbon dioxide by employing a biomass plasticizer obtained from a biomass-derived raw material.SOLUTION: A biomass plasticizer for a vinyl chloride-based resin contains a mixture of two or more kinds of phthalic acid diesters represented by general formula (1), wherein a biomass degree of the biomass plasticizer for the vinyl chloride-based resin is within a range of 70-100%. In the formula, R1 and R2 are the same or different, and each represent a biomass-derived straight-chain alkyl group having 8 to 14 carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a biomass plasticizer for vinyl chloride resins, a vinyl chloride resin composition containing the same, and a molded article obtained from the vinyl chloride resin composition. [Background technology]

[0002] Polyvinyl chloride (PVC) is one of the most common plastics, and its properties, such as low cost and excellent heat resistance, give it a wide range of applications. When using PVC, because it is hard and brittle, plasticizers are usually added to make the PVC more flexible before use.

[0003] As plasticizers used in polyvinyl chloride resins, higher alkyl esters of polybasic acids such as phthalates, adipicates, and trimelliticates derived from petroleum are known, and phthalates were often used due to the balance between price and performance.

[0004] In recent years, with the growing demand for a circular economy, there has been a desire to move away from petroleum-derived materials in the materials sector, and the use of biomass has attracted attention. Biomass is an organic compound produced through photosynthesis from carbon dioxide and water, and by utilizing it, it can be converted back into carbon dioxide and water, making it a so-called carbon-neutral material. Recently, the practical application of biomass chemical products made from these biomass raw materials has been progressing rapidly, and attempts are also being made to manufacture general-purpose chemicals from these biomass raw materials.

[0005] Patent Document 1 discloses a plasticizer for vinyl chloride resins derived from hydrogenated vegetable oil fatty acids and a vinyl chloride resin composition using the same. However, this vinyl chloride resin plasticizer had insufficient flexibility and other performance characteristics under low-temperature conditions. Patent Document 2 discloses isosorbide epoxy diester as a plasticizer for vinyl chloride resins. This plasticizer uses biomass-derived isosorbide and unsaturated fatty acids as raw materials. However, this plasticizer had insufficient performance as a plasticizer for vinyl chloride resins. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Patent No. 6954509 [Patent Document 2] International Publication No. 2016 / 046490 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The problem that this invention aims to solve is to provide a biomass plasticizer for vinyl chloride resins that can impart excellent heat resistance and volatility to molded vinyl chloride resin compositions, and can also suppress carbon dioxide emissions by incorporating a biomass plasticizer obtained from biomass-derived raw materials. [Means for solving the problem]

[0008] In view of the current situation, the inventors diligently conducted studies to solve the above problems and found that a biomass plasticizer for vinyl chloride resins containing a mixture of two or more phthalate diesters having a specific structure, obtained from biomass-derived raw materials, is a biomass plasticizer for vinyl chloride resins having a specific biomass content that can impart excellent heat resistance and volatility to molded vinyl chloride resin compositions, thus completing the present invention.

[0009] That is, it provides a biomass plasticizer for vinyl chloride resins, which has the following items as the summary.

[0010] [Item 1] General formula (1) [Chemical formula] [In the formula, R 1 and R 2 are the same or different and each represents a linear alkyl group derived from biomass having 8 to 14 carbon atoms.] A biomass plasticizer for vinyl chloride resins containing a mixture of two or more phthalic acid diesters represented by , wherein the biomass content of the biomass plasticizer for vinyl chloride resins is in the range of 70 to 100%. The biomass plasticizer for vinyl chloride resins is characterized by this.

[0011] [Item 2] The biomass plasticizer for vinyl chloride resins according to [Item 1], wherein the phthalic acid diester is a mixture of three or more.

[0012] [Item 3] R 1 and R 2 described in the general formula (1) are 8 carbon atoms and / or 12 carbon atoms. The biomass plasticizer for vinyl chloride resins according to [Item 1] or [Item 2].

[0013] [Item 4] The biomass plasticizer for vinyl chloride resins is (a) di-n-octyl phthalate, (b) n-octyl n-dodecyl phthalate and (d) di-n-dodecyl phthalate, and the sum of (a), (b) and (d) is 100 mol%, and (a):(b):(d) is in the range of 0.5 to 10.0 mol%: 14.0 to 44.0 mol%: 39.0 to 85.0 mol%. The biomass plasticizer for vinyl chloride resins according to any one of [Item 1] to [Item 3].

[0014] [Item 5] The biomass plasticizer for vinyl chloride resins in item [4] is (a) di-n-octyl phthalate, (b) n-octyl-n-dodecyl phthalate and (d) di-n-dodecyl phthalate, The sum of (a), (b), and (d) is 100 mol%, and A biomass plasticizer for vinyl chloride resins as described in any of [Item 1] to [Item 4], wherein (a):(b):(d) = 1.0~9.0 mol%:18.0~42.0 mol%:49.0~81.0 mol%.

[0015] [Section 6] A biomass plasticizer for vinyl chloride resins according to [Item 1] or [Item 2], wherein the biomass plasticizer for vinyl chloride resins is (a) di-n-octyl phthalate, (b) n-octyl-n-dodecyl phthalate, (c) n-octyl-n-tetradecyl phthalate, (d) di-n-dodecyl phthalate, (e) n-dodecyl-n-tetradecyl phthalate, and (f) di-n-tetradecyl phthalate.

[0016] [Section 7] In the biomass plasticizer for vinyl chloride resins described in [Item 6], The sum of (a) to (f) is 100 mol%, and (a):(b):(c):(d):(e):(f) = 3.0~17.0 mol%:19.0~40.0 mol%:5.5~12.0 mol%:16.5~41.0 mol%:9.5~24.5 mol%:0.5~4.5 mol%, a biomass plasticizer for vinyl chloride resins as described in [Item 6].

[0017] [Section 8] In the biomass plasticizer for vinyl chloride resins described in [Item 7], The sum of (a) to (f) is 100 mol%, and (a):(b):(c):(d):(e):(f) = 4.0~16.0 mol%:24.0~38.0 mol%:7.0~11.0 mol%:21.0~39.0 mol%:12.0~23.0 mol%:1.0~4.0 mol%, a biomass plasticizer for vinyl chloride resins as described in [Item 7].

[0018] [Section 9] A biomass-derived plasticizer for vinyl chloride resins containing a mixture of two or more phthalate diesters represented by general formula (1), wherein the biomass content is 72.5 to 100%. (The biomass plasticizer for vinyl chloride resins according to any of items [1] to [8].)

[0019] [Section 10] A vinyl chloride resin composition characterized by comprising a vinyl chloride resin and a biomass plasticizer for vinyl chloride resins as described in any of [Item 1] to [Item 9].

[0020] [Section 11] The vinyl chloride resin composition according to item 10, characterized in that it contains 5 to 200 parts by mass of a biomass plasticizer for vinyl chloride resins described in any of items 1 to 9, per 100 parts by mass of vinyl chloride resin.

[0021] [Section 12] A vinyl chloride resin composition according to item

[10] or

[11] , characterized by containing 10 to 100 parts by mass of a biomass plasticizer for vinyl chloride resins according to any one of items [1] to [9] per 100 parts by mass of vinyl chloride resin.

[0022] [Section 13] A molded article obtained from a vinyl chloride resin composition according to any of items

[10] to

[12] . [Effects of the Invention]

[0023] By replacing the composition of the plasticizer for vinyl chloride resins that entirely depends on petroleum-derived plasticizers for vinyl chloride resins with biomass plasticizers for vinyl chloride resins derived from plants, the amount of petroleum resources used can be reduced, and the environmental load can be decreased by suppressing the carbon dioxide emissions during the production of plasticizers for vinyl chloride resins. The biomass plasticizer for vinyl chloride resins of the present invention is excellent in compatibility with vinyl chloride resins, thus having excellent plasticization efficiency and flexibility, capable of imparting excellent heat resistance and volatility resistance, and can be suitably used as a plasticizer having a specific biomass degree.

Embodiments for Carrying Out the Invention

[0024] The biomass plasticizer for vinyl chloride resins of the present invention is General formula (1)

Chemical formula

[0025] For the diester represented by general formula (1), R 1 and R 2 are the same or different and each includes a biomass-derived n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, preferably an n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, and more preferably an n-octyl group, n-dodecyl group, n-tetradecyl group. [[ID=了31]]

[0026] For the diester represented by general formula (1), R 1 and R 2In the case of identical or different linear alkyl groups derived from biomass with 1 to 7 carbon atoms, the heat resistance (loss due to volatilization) deteriorates, which is undesirable.

[0027] R of the diester represented by general formula (1) 1 and R 2 If the alkyl groups are the same or different, and each has 15 or more carbon atoms, and are derived from biomass, then cold resistance (flexibility temperature) deteriorates, which is undesirable.

[0028] R of phthalate diester represented by general formula (1) 1 and R 2 The method for describing mixed esters with different R groups is as exemplified in formula (2) below. 1 =n-octyl group, R 2 In the case of an =n-dodecyl group, it shall be referred to as phthalic acid =n-octyl=n-dodecyl in this specification and in the claims. [ka]

[0029] Specific examples of mixtures of two or more phthalate diesters represented by general formula (1) include: A mixture of di-n-octyl phthalate and di-n-decyl phthalate, a mixture of di-n-octyl phthalate and di-n-dodecyl phthalate, a mixture of di-n-octyl phthalate and di-n-tetradecyl phthalate, a mixture of di-n-decyl phthalate and di-n-dodecyl phthalate, a mixture of di-n-decyl phthalate and di-n-tetradecyl phthalate, a mixture of di-n-dodecyl phthalate and di-n-tetradecyl phthalate, a mixture of di-n-octyl phthalate, di-n-decyl phthalate and di-n-dodecyl phthalate A mixture of di-n-decyl phthalate, di-n-dodecyl phthalate, and di-n-tetradecyl phthalate; a mixture of di-n-octyl phthalate, di-n-decyl phthalate, di-n-dodecyl phthalate, and di-n-tetradecyl phthalate; a mixture of di-n-octyl phthalate, phthalate=n-octyl=n-decyl, and di-n-decyl phthalate; a mixture of di-n-octyl phthalate, phthalate=n-octyl=n-dodecyl, and di-n-dodecyl phthalate; a mixture of di-n-octyl phthalate, phthalate=n-octyl=n-tetradecyl, and di-n-tetradecyl phthalate; phthalate A mixture of di-n-decyl phthalate, n-decyl phthalate, n-dodecyl phthalate, a mixture of di-n-decyl phthalate, n-decyl phthalate, n-tetradecyl phthalate, a mixture of di-n-tetradecyl phthalate, n-dodecyl phthalate, n-tetradecyl phthalate, a mixture of di-n-tetradecyl phthalate, di-n-octyl phthalate, n-octyl phthalate, n-dodecyl phthalate, a mixture of di-n-decyl phthalate, n-decyl phthalate, n-dodecyl phthalate, -Octyl, phthalate=n-octyl=n-dodecyl, phthalate=n-octyl=n-tetradecyl, di-n-dodecyl phthalate, phthalate=n-dodecyl=n-tetradecyl, and mixture of di-n-tetradecyl phthalate, di-n-decyl phthalate, phthalate=n-decyl=n-dodecyl, phthalate=n-decyl=n-tetradecyl, di-n-dodecyl phthalate, phthalate=n-dodecyl=n-tetradecyl, and mixture of di-n-tetradecyl phthalate, di-n-octyl phthalate, phthalate=n-octyl=n-decyl, phthalate=n-octyl=n-dodecyl,Examples include n-octyl-n-tetradecyl phthalate, di-n-decyl phthalate, n-decyl-n-dodecyl phthalate, n-decyl-n-tetradecyl phthalate, di-n-dodecyl phthalate, n-dodecyl-n-tetradecyl phthalate, and mixtures of di-n-tetradecyl phthalate.

[0030] Among the specific examples of the mixture of two or more of the above phthalate diesters, a preferred example is a mixture of (a) di-n-octyl phthalate, (b) n-octyl-n-dodecyl phthalate, (c) n-octyl-n-tetradecyl phthalate, (d) di-n-dodecyl phthalate, (e) n-dodecyl-n-tetradecyl phthalate, and (f) di-n-tetradecyl phthalate.

[0031] Among the specific examples of the above-mentioned mixture of two or more phthalate diesters, more preferably the mixture is such that the total of the diester mixtures of (a), (b), and (d) is 100 mol%, and (a):(b):(d) = 0.5~10.0 mol%:14.0~44.0 mol%:39.0~85.0 mol%. Or the mixture is such that (a):(b):(c):(d):(e):(f) = 3.0~17.0 mol%:19.0~40.0 mol%:5.5~12.0 mol%:16.5~41.0 mol%:9.5~24.5 mol%:0.5~4.5 mol%.

[0032] Among the specific examples of the above-mentioned mixture of two or more phthalate diesters, particularly preferred is a mixture in which the total of the diester mixtures of (a), (b), and (d) is 100 mol%, and (a):(b):(d) = 1.0~9.0 mol%:18.0~42.0 mol%:49.0~81.0 mol%. Or a mixture in which (a):(b):(c):(d):(e):(f) = 4.0~16.0 mol%:24.0~38.0 mol%:7.0~11.0 mol%:21.0~39.0 mol%:12.0~23.0 mol%:1.0~4.0 mol%.

[0033] A mixture of two or more phthalate diesters represented by general formula (1) is not particularly limited by its manufacturing method, as long as it satisfies the requirements for plasticizer performance. For example, it can be easily obtained by adding phthalic acid or its anhydride derived from petroleum and / or biomass raw materials to two or more linear alcohols derived from biomass having 8 to 14 carbon atoms in an esterification reaction.

[0034] In esterification, water entrainers such as benzene, toluene, xylene, and cyclohexane can be used to promote the distillation of water produced by the reaction.

[0035] Furthermore, during the esterification reaction, the oxidative degradation of the diester compound and organic solvent (water entrainer) can generate oxygen-containing organic compounds such as oxides, peroxides, and carbonyl compounds, which adversely affect heat resistance, weather resistance, etc. Therefore, it is desirable to carry out the reaction under atmospheric pressure or reduced pressure in an inert gas atmosphere such as nitrogen gas or under an inert gas flow. After the esterification reaction is complete, it is recommended to remove excess raw materials by distillation under reduced pressure or atmospheric pressure.

[0036] The diester compound according to the present invention obtained by the above esterification method may subsequently be purified by base treatment (neutralization treatment) as needed, followed by washing with water, liquid-liquid extraction, distillation (reduced pressure, dehydration treatment), adsorption purification treatment, etc.

[0037] The base used in the base treatment is not particularly limited as long as it is a basic compound; for example, sodium hydroxide and sodium carbonate are examples.

[0038] Examples of adsorbents used in adsorption purification include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, and diatomaceous earth. These can be used individually or in combination of two or more as appropriate.

[0039] The above process can be carried out at room temperature, but it can also be done by heating it to around 40-90°C.

[0040] The biomass content of the biomass plasticizer for vinyl chloride resins of the present invention is measured by burning the sample to be measured to generate carbon dioxide, and the purified carbon dioxide is reduced with hydrogen using iron as a catalyst to produce graphite. This graphite is then processed using a tandem accelerator. 14 It is installed in a dedicated C-AMS device (manufactured by NEC Corporation), 14 The count of C, 13 C's flux ( 13 C / 12 C), 14 C's flux ( 14 C / 12 C) is measured, and from this measurement, the sample carbon relative to standard modern carbon is 14 The percentage of C concentration was calculated. For this measurement, oxalic acid (HOxII), provided by the U.S. National Institute of Standards (NIST), was used as the standard sample.

[0041] From the viewpoint of reducing the use of petroleum resources and mitigating environmental impact, a higher biomass content of a mixture of two or more phthalate diesters represented by general formula (1) is preferable, as it reduces the environmental impact by suppressing carbon dioxide emissions during the production of plasticizers for vinyl chloride resins. From the viewpoint of practicality, such as simplicity, the biomass content of a mixture of two or more phthalate diesters represented by general formula (1) is preferably 70-100%, and more preferably 72.5-100%. If the biomass content of a mixture of two or more phthalate diesters represented by general formula (1) is less than 70%, its contribution to suppressing carbon dioxide emissions during the production of plasticizers for vinyl chloride resins is small and undesirable.

[0042] Furthermore, a method for producing phthalic acid or its anhydride, which is a raw material for phthalic acid diesters represented by general formula (1), can be used, for example, by a known method described in Y. Tachibana, S. Kimura, K. Kasuya, Sci. Rep., 5, 8249 (2015), to produce phthalic acid or its anhydride from biomass-derived furfural. The biomass content of the phthalic acid or its anhydride obtained in this way is 99% or more.

[0043] The phthalic acid diester according to the present invention can be produced by carrying out an esterification reaction of the aforementioned phthalic acid or its anhydride with a linear alcohol derived from biomass having 8 to 14 carbon atoms using a known method. The biomass content of the phthalic acid diester obtained in this way is 99% or more.

[0044] The acid value of the phthalate diester represented by general formula (1) is preferably 0.1 mg KOH / g or less, more preferably 0.05 mg KOH / g or less, and particularly preferably 0.01 mg KOH / g or less. When the acid value is 0.1 mg KOH / g or less, the heat resistance of the phthalate diester represented by general formula (1) tends to improve further, and within this preferred range, it also has a positive effect on improving the thermal oxidation stability of the biomass plasticizer for vinyl chloride resins of the present invention.

[0045] [Vinyl chloride resin] The vinyl chloride resins used in this invention are homopolymers of vinyl chloride or vinylidene chloride, and copolymers of vinyl chloride or vinylidene chloride. Their production methods are conventionally known polymerization methods. For general-purpose vinyl chloride resins, a suspension polymerization method in the presence of an oil-soluble polymerization catalyst is used. For vinyl chloride paste resins, an emulsion polymerization method in an aqueous medium in the presence of a water-soluble polymerization catalyst is used. The degree of polymerization of these vinyl chloride resins is typically 300 to 5000, preferably 400 to 3500, and more preferably 700 to 3000. If the degree of polymerization is too low, heat resistance and other properties tend to decrease, while if it is too high, moldability tends to decrease.

[0046] In the case of copolymers, for example, ethylene, propylene, α-olefins having 2 to 30 carbon atoms such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl compounds such as vinyl acetate, vinyl propionate, alkyl vinyl ethers, polyfunctional monomers such as diallyl phthalate, and copolymers of these mixtures with vinyl chloride monomer, ethylene Examples include ethylene-acrylic acid ester copolymers such as ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene, butyl rubber, crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile-(α-methyl)styrene copolymer (ABS), styrene-butadiene copolymer, polyethylene, polymethyl methacrylate, and graft copolymers obtained by grafting vinyl chloride monomer onto mixtures thereof.

[0047] [Vinyl chloride resin composition] The content of the biomass plasticizer for vinyl chloride resins in the vinyl chloride resin composition according to the present invention is appropriately selected depending on the application, but is usually 5 to 200 parts by mass, preferably 10 to 100 parts by mass, per 100 parts by mass of vinyl chloride resin. If the amount is less than 5 parts by mass, it is difficult to obtain the desired plasticizing effect, and if it is added in excess of 200 parts by mass, bleeding to the surface of the molded product is severe, and in either case it is undesirable. However, when a filler or the like is added to the above vinyl chloride resin composition, the plasticizer can be added in excess of the above range because the filler itself absorbs oil. For example, if 100 parts by mass of calcium carbonate is added as a filler to 100 parts by mass of vinyl chloride resin, the plasticizer can be added in an amount of about 1 to 500 parts by mass.

[0048] The vinyl chloride resin composition according to the present invention can be used in combination with other known plasticizers along with the biomass plasticizer for vinyl chloride resins. In addition, additives such as stabilizers, stabilizing aids, antioxidants (anti-aging agents), ultraviolet absorbers, hindered amine-based light stabilizers, fillers, diluents, viscosity reducers, viscosity thickeners, processing aids, lubricants, antistatic agents, flame retardants, foaming agents, adhesives, and colorants may be added as needed.

[0049] Other plasticizers and additives besides the biomass plasticizer for vinyl chloride resins according to the present invention may be blended together with the biomass plasticizer for vinyl chloride resins, either individually or in combination of two or more as appropriate.

[0050] Known plasticizers that can be used in combination with the biomass plasticizer for vinyl chloride resins according to the present invention include, for example, benzoic acid esters such as diethylene glycol dibenzoate, dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), and bis(2-ethylhexyl) terephthalate (DOT P), phthalate esters such as bis(2-ethylhexyl) isophthalate (DOIP) (excluding diester mixtures represented by general formula (1) according to the present invention), aliphatic dibasic acid esters such as di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), diisononyl sebacate (DINS), tri-2-ethylhexyl trimellitate (T Trimellitate esters such as OTM, triisononyl trimellitate (TINTM), triisodecyl trimellitate (TIDTM), pyromellitate esters such as tetra-2-ethylhexyl pyromellitate (TOPM), phosphate esters such as tri-2-ethylhexyl phosphate (TOP), tricresyl phosphate (TCP), alkyl esters of polyhydric alcohols such as pentaerythritol, polyesters with molecular weights of 800-4000 synthesized by polyesterization of dibasic acids such as adipic acid with glycols, epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, epoxy esters such as 4,5-epoxy-1,2-cyclohexanedicarboxylate di-2-ethylhexyl, alicyclic dibasic acid esters such as 1,2-cyclohexanedicarboxylate diisononyl (DINCH) and 4-cyclohexen-1,2-dicarboxylate di-2-ethylhexyl, dicapric acid 1.Examples include fatty acid glycol esters such as 4-butanediol, citrate esters such as tributyl acetyl citrate (ATBC), trihexyl acetyl citrate (ATHC), triethylhexyl acetyl citrate (ATEHC), and trihexyl butyryl citrate (BTHC), isosorbide diesters, chlorinated paraffins obtained by chlorinating paraffin wax or n-paraffin, chlorinated fatty acid esters such as chlorinated stearate ester, and higher fatty acid esters such as butyl oleate. When incorporating the above-mentioned plasticizers, the recommended amount is approximately 1 to 100 parts by mass per 100 parts by mass of vinyl chloride resin.

[0051] Among known plasticizers that can be used in combination, epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil are particularly preferred because they can suppress discoloration during sterilization by ultraviolet irradiation or radiation irradiation. When incorporating the above-mentioned epoxidized vegetable oils, the recommended amount is 1 to 50 parts by mass, preferably 2 to 40 parts by mass, per 100 parts by mass of vinyl chloride resin.

[0052] Examples of stabilizers include metal soap compounds such as lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octoate, zinc laurate, zinc ricinoleate, and zinc stearate; organotin compounds such as dimethyl tin bis-2-ethylhexyl thioglycolate, dibutyl tin maleate, dibutyl tin bisbutyl maleate, and dibutyl tin dilaurate; and antimony mercaptide compounds. When incorporating stabilizers, the recommended amount of stabilizer per 100 parts by mass of vinyl chloride resin is approximately 0.1 to 20 parts by mass.

[0053] Of the aforementioned stabilizers, the combination of calcium stearate and zinc stearate is most preferred in terms of safety and other factors. The recommended amount is 0.1 to 10 parts by mass in total, preferably 0.2 to 6 parts by mass. There are no particular restrictions on the mixing ratio as long as it shows a stabilizing effect, but it is usually used in the range of 5:1 to 1:5.

[0054] Examples of stabilizing agents include phosphite compounds such as triphenyl phosphite, monooctyldiphenyl phosphite, and tridecyl phosphite; beta-diketone compounds such as acetylacetone and benzoylacetone; polyol compounds such as glycerin, sorbitol, pentaerythritol, and polyethylene glycol; perchlorate compounds such as barium perchlorate and sodium perchlorate; hydrotalcite compounds; and zeolites. When incorporating stabilizing agents, it is recommended to add approximately 0.1 to 20 parts by mass of the stabilizing agent per 100 parts by mass of the vinyl chloride resin.

[0055] Examples of antioxidants include phenolic compounds such as 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol)propionate]methane, and 2-hydroxy-4-methoxybenzophenone; sulfuric compounds such as alkyl disulfides, thiodipropionates, and benzothiazoles; phosphoric acid compounds such as trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, and tris(2,4-di-tert-butylphenyl) phosphite; and organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. When incorporating antioxidants, the recommended amount of antioxidant per 100 parts by mass of vinyl chloride resin is approximately 0.2 to 20 parts by mass.

[0056] Examples of UV absorbers include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate, benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone, benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, and cyanoacrylate compounds. When incorporating UV absorbers, the recommended amount of UV absorber per 100 parts by mass of vinyl chloride resin is approximately 0.1 to 10 parts by mass.

[0057] Examples of hindered amine-based light stabilizers include 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-hydroxyphenyl]methyl]butylmalonate, and bis(2,2,6,6-tetramethyl-1( Octyloxy)-4-piperidyl) ester and reaction products of 1,1-dimethylethyl hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, ester mixture of 2,2,6,6-tetramethyl-4-piperidinol and higher fatty acids, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate Luboxylate, polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, poly[{(6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}}, dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) Examples include polycondensates of ru-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, and N,N',N'',N'''-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidine-4-yl)amino)-triazine-2-yl)-4,7-diazadecane-1,10-diamine. Furthermore, when incorporating a light stabilizer, the recommended amount of light stabilizer per 100 parts by mass of vinyl chloride resin is approximately 0.1 to 10 parts by mass.

[0058] Examples of fillers include calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, metal oxides such as ferrite, glass, carbon, metal fibers and powders, glass spheres, graphite, aluminum hydroxide, barium sulfate, magnesium oxide, magnesium carbonate, magnesium silicate, and calcium silicate. When incorporating fillers, it is recommended to use approximately 1 to 100 parts by mass of filler per 100 parts by mass of vinyl chloride resin.

[0059] Examples of diluents include 2,2,4-trimethyl-1,3-pentanediol diisobutyrate and low-boiling-point aliphatic and aromatic hydrocarbons. When incorporating a diluent, it is recommended to use approximately 1 to 50 parts by mass of the diluent per 100 parts by mass of the vinyl chloride resin.

[0060] Examples of viscosity reducers include various nonionic surfactants, sulfosuccinate anionic surfactants, surfactant silicone compounds, soybean oil lecithin, monohydric alcohols, glycol ethers, and polyethylene glycols. When a viscosity reducer is added, it is recommended that the amount of the viscosity reducer be approximately 0.1 to 20 parts by mass per 100 parts by mass of vinyl chloride resin.

[0061] Examples of thickening agents include synthetic fine silica, bentonite, ultrafine precipitated calcium carbonate, metal soap, hydrogenated castor oil, polyamide wax, oxidized polyethylene, vegetable oil, granular acid ester surfactants, and nonionic surfactants. When incorporating a thickening agent, it is recommended to use approximately 1 to 50 parts by mass of the thickening agent per 100 parts by mass of vinyl chloride resin.

[0062] Examples of processing aids include liquid paraffin, polyethylene wax, stearic acid, stearate amide, ethylenebisstearate amide, butyl stearate, and calcium stearate. When incorporating processing aids, it is recommended to use approximately 0.1 to 20 parts by mass of the processing aid per 100 parts by mass of the vinyl chloride resin.

[0063] Examples of lubricants 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. When incorporating a lubricant, it is recommended to add approximately 0.1 to 10 parts by mass of the lubricant per 100 parts by mass of the vinyl chloride resin.

[0064] Examples of antistatic agents include anionic antistatic agents of the alkyl sulfonate, alkyl ether carboxylic acid, or dialkyl sulfosuccinate type; nonionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, and diethanolamine derivatives; cationic antistatic agents such as quaternary ammonium salts such as alkylamidoamine and alkyldimethylbenzyl types, and organic acid salts or hydrochlorides of alkylpyridinium type; and amphoteric antistatic agents such as alkyl betaine and alkylimidazoline types. When incorporating an antistatic agent, it is recommended to add approximately 0.1 to 10 parts by mass of the antistatic agent per 100 parts by mass of vinyl chloride resin.

[0065] Examples of flame retardants include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, and zinc borate; phosphorus compounds such as cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, and trisdichloropropyl phosphate; and halogen compounds such as chlorinated paraffin. When incorporating flame retardants, it is recommended that the amount of flame retardant be approximately 0.1 to 20 parts by mass per 100 parts by mass of vinyl chloride resin.

[0066] Examples of blowing agents include organic blowing agents such as azodicarbonamide and oxybisbenzenesulfonyl hydrazide, and inorganic blowing agents such as sodium bicarbonate. When incorporating a blowing agent, it is recommended to add approximately 0.1 to 30 parts by mass of the blowing agent per 100 parts by mass of the vinyl chloride resin.

[0067] Examples of colorants include carbon black, lead sulfide, white carbon, titanium white, lithopone, red ochre, antimony sulfide, chromium yellow, chromium green, phthalocyanine green, cobalt blue, phthalocyanine blue, and molybdenum orange. When incorporating colorants, it is recommended to use approximately 1 to 100 parts by mass of colorant per 100 parts by mass of vinyl chloride resin.

[0068] The vinyl chloride resin composition according to the present invention can be obtained by stirring and mixing or melting together the biomass plasticizer for vinyl chloride resins, vinyl chloride resin, and various additives as needed, according to the present invention, for example, by handling mixing, or by stirring and melting together using a stirring and mixing machine such as a pony mixer, butterfly mixer, planetary mixer, dissolver, twin-screw mixer, three-roll mill, mortar mixer, Henschel mixer, Banbury mixer, ribbon blender, or kneader such as a conical twin-screw extruder, parallel twin-screw extruder, single-screw extruder, cone kneader type kneader, or roll kneader, to obtain a vinyl chloride resin composition in powder, pellet, or paste form.

[0069] [Vinyl chloride resin molded product] The vinyl chloride resin composition according to the present invention can be molded into a desired shape by molding using conventionally known methods such as vacuum forming, compression molding, extrusion molding, injection molding, calendering, press molding, blow molding, powder molding, spread coating, dip coating, spray coating, paper casting, extrusion coating, gravure printing, screen printing, slush molding, rotational molding, casting, dip molding, and welding.

[0070] The shape of the molded body is not particularly limited, but examples include rod-shaped, sheet-shaped, film-shaped, plate-shaped, cylindrical, circular, elliptical, or special shapes such as star-shaped or polygonal shapes used for toys and ornaments.

[0071] <Evaluation of polyvinyl chloride resin molded products> (a) Soft temperature The flexible temperature of a vinyl chloride sheet containing a plasticizer for vinyl chloride resins is preferably -25°C or lower, and more preferably -30°C or lower. In this specification, the flexible temperature is the value measured by the method described in the examples below.

[0072] (b) Loss on volatilization The loss by volatilization of a vinyl chloride sheet containing a plasticizer for vinyl chloride resins is preferably 10% or less, and more preferably 2% or less. In this specification, loss by volatilization refers to the value measured by the method described in the examples below.

[0073] (c) Heat resistance (sheet coloring) evaluation The heat resistance (sheet coloring) evaluation (170°C, 60 minutes) of a vinyl chloride sheet containing a plasticizer for vinyl chloride resins is preferably slightly colored, and more preferably no coloring. In this specification, heat resistance (sheet coloring) refers to the value measured by the method described in the examples below.

[0074] (d) Evaluation of vinyl chloride sheets The evaluation of vinyl chloride sheets containing plasticizers for vinyl chloride resins is The performance is good when the flexibility temperature is -25°C or lower, the loss of volatilization is 10% or less, and the sheet is not colored. Preferably, When the flexible temperature is -25°C or lower, the loss due to volatilization is 2% or less, and the sheet is not colored; When the flexible temperature is -30°C or lower, the loss due to volatilization is 10% or less, and the sheet is not colored; Particularly preferred, When the flexible temperature is -30°C or lower, the loss due to volatilization is 2% or less, and the sheet is not colored; That is the case. [Examples]

[0075] The present invention will be further described in detail below with reference to examples, but the present invention is not limited to these examples. The abbreviations for the compounds in the examples and comparative examples, and the measurements of each property are as follows. <Compound used> n-Octanol: Manufactured by Shin-Nippon Rika Co., Ltd. Product name: "Conol 10WS" (Biomass content: 99% or higher) n-Dodecanol: Manufactured by Shin-Nippon Rika Co., Ltd. Product name: "Conol 20P" (Biomass content: 99% or more) • n-Tetradecanol: Manufactured by Shin-Nippon Rika Co., Ltd. Product name: "Conol 1495" (Biomass content: 99% or more) • Polyvinyl chloride resin: Manufactured by Shin-Daiichi Vinyl Chloride Co., Ltd. Product name: "Zest1000Z" (straight, degree of polymerization 1050) • DUP: Manufactured by Shin-Nippon Rika Co., Ltd. Product name: "Sansosizer DUP" (Diundecyl phthalate) (Biomass content: Less than 1%)

[0076] (1) Evaluation of diester properties The mixture of two or more phthalate diesters represented by general formula (1) according to the present invention, obtained in the following manufacturing example, was analyzed by the following method. Acid value: Measured in accordance with JIS K-0070 (1992). Hue: Measured in accordance with JIS K-4101 (Hazen) (1995).

[0077] (2) Gas chromatography analysis (hereinafter abbreviated as GC analysis) Model: Gas chromatograph GC-2025 (manufactured by Shimadzu Corporation) Detector: FID Column: Capillary column ZB-130m Column temperature: Increased from 60°C to 290°C, heating rate = 13°C / min, held for 23 minutes. Carrier gas: Helium Split ratio: 1:80 Sample: 50% acetone solution Injection volume: 0.5μl Determination: DOP was used as an internal standard for quantification.

[0078] (3) Preparation of polyvinyl chloride press sheet 100 parts by mass of polyvinyl chloride resin (straight, degree of polymerization 1050, trade name "Zest1000Z", manufactured by Shin-Daiichi Vinyl Chloride Co., Ltd.) were mixed with 0.3 parts by mass of calcium stearate (manufactured by Nacalai Tesque Co., Ltd.) and 0.2 parts by mass of zinc stearate (manufactured by Nacalai Tesque Co., Ltd.) as stabilizers. After stirring and mixing in a mortar mixer, 50 parts by mass of plasticizer were added and the mixture was handled and mixed until uniform to obtain a polyvinyl chloride resin composition. This resin composition was melt-kneaded using a 5 x 12 inch double roll at 160-166°C for 4 minutes to create a roll sheet. Subsequently, press molding was performed at 162-168°C for 10 minutes to produce a press sheet with a thickness of approximately 1 mm.

[0079] <Evaluation of physical properties of vinyl chloride resins> (4) Tensile properties: The 100% modulus, breaking strength, and breaking elongation of the press sheet were measured in accordance with JIS K-6723 (1995). A smaller 100% modulus value indicates better flexibility, while breaking strength and breaking elongation are indicators of the material's practical strength. Generally, a larger value indicates superior practical strength.

[0080] (5) Cold resistance: Measured using a Crushberg tester in accordance with JIS K-6773 (1999). The lower the flexibility temperature (°C), the better the cold resistance. The flexibility temperature here refers to the torsional stiffness ratio (3.17 × 10) as specified in JIS in the above measurement. 3 kg / cm 2 This refers to the low-temperature limit temperature at which ) is indicated. <Evaluation of flexibility temperature> [I]: -30℃ or less [II]: Over -30℃ and below -25℃ [III]: Exceeding -25℃

[0081] (6) Heat resistance: Evaluated based on loss due to volatilization and sheet coloration. a) Loss due to volatilization: The mass change of the roll sheet was measured after heating the roll sheet in a gear oven at 170°C for 60 minutes and 120 minutes, and the mass loss rate (mass %) was calculated using the following formula. The smaller the number, the higher the heat resistance. Loss of volatilization (%) = ((Mass before test - Mass after test) / Mass before test) × 100 <Evaluation of loss on volatilization (170°C, 120 minutes)> [I]: 2% or less [II]: More than 2% and less than 10% [III]: Exceeding 10% b) Sheet coloring: The degree of coloring of the rolled sheets was visually evaluated on a three-point scale after heating them in a gear oven at 170°C for 30 minutes and 60 minutes. <Evaluation of sheet coloring> [I]: No coloring [II]: △ Slightly colored [III]: × Colored

[0082] (7) Breeding: Based on the evaluation of breeding occurrence. The sheets were left in an environment of 25°C and 60% humidity for one week and evaluated visually. <Breeding Evaluation> [I]: No breeding occurred. [II]: △Slight breeding occurred [III]: × Breeding occurred

[0083] (8) Performance evaluation of polyvinyl chloride resin molded products For performance evaluation of polyvinyl chloride resin molded articles, the results of the evaluation of flexibility temperature, loss of volatilization (170°C, 120 minutes), and sheet coloring are evaluated as follows: if [III] is 1 or higher, it is considered unsuitable; if [II] is 1 or lower (other evaluations are [I]), it is considered good; and if all evaluations are [I], it is considered particularly good.

[0084] (9) Biomass The biomass content is measured by burning the sample to be measured to generate carbon dioxide, which is then purified in a vacuum line and reduced with hydrogen using iron as a catalyst to produce graphite. This graphite is then processed using a tandem accelerator. 14 It is installed in a dedicated C-AMS device (manufactured by NEC Corporation), 14 The count of C, 13 C's flux ( 13 C / 12 C),14 C's flux ( 14 C / 12 C) is measured, and from this measurement, the sample carbon relative to standard modern carbon is 14 The percentage of C concentration was calculated. For this measurement, oxalic acid (HOxII), provided by the U.S. National Institute of Standards (NIST), was used as the standard sample.

[0085] [Example 1] In a 1 L four-necked flask equipped with a thermometer, decanter, stirring blade, and reflux condenser, 1.0 mol of phthalic anhydride, 0.72 mol of n-octanol, 1.68 mol of n-dodecanol, and 0.20 g of tetraisopropyl titanate (manufactured by Nippon Soda Co., Ltd.) as an esterification catalyst were added. Furthermore, xylene equivalent to 10% by mass of the initial raw materials (14.3 g) was added as a water entrainer, and the esterification reaction was carried out at a reaction temperature of 185°C. The reaction was carried out under reduced pressure, refluxing the alcohol to remove the generated water from the system, until the acid value of the reaction solution reached 0.5 mg KOH / g. After the reaction was complete, the unreacted alcohol was removed from the system under reduced pressure, and then neutralization, washing with water, and dehydration were performed according to conventional methods to obtain 416.5 g of phthalic acid diester. The obtained phthalic acid diester had an acid value of 0.01 mg KOH / g, a color of 16, and a biomass content of 73.0%. As a result of quantitative analysis of each component by GC using DOP as a standard substance, it was confirmed that the mol% of (a) di-n-octyl phthalate, (b) n-octyl-n-dodecyl phthalate, and (d) di-n-dodecyl phthalate were in the ratio (a):(b):(d) = 9.0 mol%:42.0 mol%:49.0 mol%. The obtained phthalate diester was used as plasticizer 1 to prepare a vinyl chloride resin composition. Subsequently, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and cold resistance tests, heat resistance tests, and bleed tests were performed. The results are shown in Table 1.

[0086] [Example 2] 374.4 g of phthalate diester was obtained in the same manner as in Example 1, except that n-octanol (0.48 mol) and n-dodecanol (1.92 mol) were used. The obtained phthalate diester had an acid value of 0.01 mg KOH / g, a hue of 14, and a biomass content of 73.7%. Quantitative analysis of each component using DOP as a standard substance by GC confirmed that the mol% ratio of (a) di-n-octyl phthalate, (b) phthalate = n-octyl = n-dodecyl, and (d) di-n-dodecyl phthalate was (a):(b):(d) = 4.0 mol%:32.0 mol%:64.0 mol%. The obtained phthalate diester was used as plasticizer 2 to prepare a vinyl chloride resin composition. Subsequently, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and cold resistance tests, heat resistance tests, and bleed tests were conducted. The results are shown in Table 1.

[0087] [Example 3] 360.1 g of phthalate diester was obtained in the same manner as in Example 1, except that n-octanol (0.24 mol) and n-dodecanol (2.16 mol) were used instead. The obtained phthalate diester had an acid value of 0.01 mg KOH / g, a color of 13, and a biomass content of 74.3%. Quantitative analysis of each component using DOP as a standard substance by GC confirmed that the mol% ratio of (a) di-n-octyl phthalate, (b) phthalate=n-octyl=n-dodecyl, and (d) di-n-dodecyl phthalate was (a):(b):(d) = 1.0 mol%:18.0 mol%:81.0 mol%. The obtained phthalate diester was used as plasticizer 3 to prepare a vinyl chloride resin composition. Subsequently, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and cold resistance tests, heat resistance tests, and bleed tests were conducted. The results are shown in Table 1.

[0088] [Example 4] 343.5 g of phthalate diester was obtained in the same manner as in Example 1, except that n-octanol (0.96 mol), n-dodecanol (1.08 mol), and n-tetradecanol (0.36 mol) were used instead. The obtained phthalate diester had an acid value of 0.01 mg KOH / g, a hue of 18, and a biomass content of 72.7%. As a result of quantitative analysis of each component by GC using DOP as a standard substance, it was confirmed that the mol% of (a) di-n-octyl phthalate, (b) n-octyl-n-dodecyl phthalate, (c) n-octyl-n-tetradecyl phthalate, (d) di-n-dodecyl phthalate, (e) n-dodecyl-n-tetradecyl phthalate, and (f) di-n-tetradecyl phthalate were in the ratio (a):(b):(c):(d):(e):(f) = 16.0 mol%:37.2 mol%:10.8 mol%:21.6 mol%:12.6 mol%:1.8 mol%. The obtained phthalate diester was used as plasticizer 4 to prepare a vinyl chloride resin composition. Subsequently, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and cold resistance tests, heat resistance tests, and bleed tests were conducted. The results are shown in Table 1.

[0089] [Example 5] 443.6 g of phthalate diester was obtained in the same manner as in Example 1, except that n-octanol (0.48 mol), n-dodecanol (1.44 mol), and n-tetradecanol (0.48 mol) were used instead. The obtained phthalate diester had an acid value of 0.01 mg KOH / g, a hue of 15, and a biomass content of 74.3%. As a result of quantitative analysis of each component by GC using DOP as a standard substance, it was confirmed that the mol% of (a) di-n-octyl phthalate, (b) n-octyl-n-dodecyl phthalate, (c) n-octyl-n-tetradecyl phthalate, (d) di-n-dodecyl phthalate, (e) n-dodecyl-n-tetradecyl phthalate, and (f) di-n-tetradecyl phthalate were in the ratio (a):(b):(c):(d):(e):(f) = 4.0 mol%:24.8 mol%:7.2 mol%:38.5 mol%:22.3 mol%:3.2 mol%. The obtained phthalate diester was used as plasticizer 5 to prepare a vinyl chloride resin composition. Subsequently, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and cold resistance tests, heat resistance tests, and bleed tests were conducted. The results are shown in Table 1.

[0090] [Comparative Example 1] In a 1 L four-necked flask equipped with a thermometer, decanter, stirring blade, and reflux condenser, 1.0 mol of phthalic anhydride, 1.20 mol of n-octanol, 1.20 mol of n-dodecanol, and 0.20 g of tetraisopropyl titanate (manufactured by Nippon Soda Co., Ltd.) as an esterification catalyst were added. Furthermore, xylene equivalent to 10% by mass of the starting materials (14.3 g) was added as a water entrainer, and the esterification reaction was carried out at a reaction temperature of 185°C. The reaction was carried out under reduced pressure, refluxing the alcohol to remove the generated water from the system, until the acid value of the reaction solution reached 0.5 mg KOH / g. After the reaction was complete, the unreacted alcohol was removed from the system under reduced pressure, and then neutralization, washing with water, and dehydration were performed according to conventional methods to obtain 432 g of phthalic acid diester. The obtained phthalic acid diester had an acid value of 0.01 mg KOH / g, a hue of 14, and a biomass content of 71.4%. As a result of quantitative analysis of each component by GC using DOP as a standard substance, it was confirmed that the mol% of (a) di-n-octyl phthalate, (b) n-octyl-n-dodecyl phthalate, and (d) di-n-dodecyl phthalate were in the ratio (a):(b):(d) = 25.0 mol%:50.0 mol%:25.0 mol%. The obtained phthalate diester was used as plasticizer 6 to prepare a vinyl chloride resin composition. Subsequently, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and cold resistance tests, heat resistance tests, and bleed tests were conducted. The results are shown in Table 1.

[0091] [Comparative Example 2] 359.4 g of phthalate diester was obtained in the same manner as in Comparative Example 1, except that n-octanol (1.92 mol), n-dodecanol (0.36 mol), and n-tetradecanol (0.12 mol) were used instead. The obtained phthalate diester had an acid value of 0.01 mg KOH / g, a hue of 18, and a biomass content of 69.0%. As a result of quantitative analysis of each component by GC using DOP as a standard substance, it was confirmed that the mol% of (a) di-n-octyl phthalate, (b) n-octyl-n-dodecyl phthalate, (c) n-octyl-n-tetradecyl phthalate, (d) di-n-dodecyl phthalate, (e) n-dodecyl-n-tetradecyl phthalate, and (f) di-n-tetradecyl phthalate were in the ratio (a):(b):(c):(d):(e):(f) = 64.0 mol%:24.8 mol%:7.2 mol%:2.4 mol%:1.4 mol%:0.2 mol%. The obtained phthalate diester was used as plasticizer 7 to prepare a vinyl chloride resin composition. Subsequently, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and cold resistance tests, heat resistance tests, and bleed tests were conducted. The results are shown in Table 1.

[0092] [Comparative Example 3] 375.6 g of phthalate diester was obtained in the same manner as in Comparative Example 1, except that n-dodecanol (3.00 mol) and n-tetradecanol (1.00 mol) were used instead. The obtained phthalate diester had an acid value of 0.01 mg KOH / g, a color of 11, and a biomass content of 75.7%. Quantitative analysis of each component using DOP as a standard substance by GC confirmed that the mol% ratios of (d) di-n-dodecyl phthalate, (e) phthalate=n-dodecyl=n-tetradecyl, and (f) di-n-tetradecyl phthalate were (d):(e):(f) = 60.1 mol%:34.8 mol%:5.1 mol%. The obtained phthalate diester was used as plasticizer 8 to prepare a vinyl chloride resin composition. Subsequently, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and cold resistance tests, heat resistance tests, and bleed tests were conducted. The results are shown in Table 1.

[0093] [Comparative Example 4] Using only n-octanol (2.40 mol), a phthalate diester was obtained in the same manner as in Comparative Example 1. The obtained phthalate diester had a biomass content of 66.7%. The obtained phthalate di-n-ester was used as plasticizer 9 to prepare vinyl chloride resin compositions and vinyl chloride sheets, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 1.

[0094] [Comparative Example 5] When DUP was used as a plasticizer, the biomass content was less than 1%. Using DUP, polyvinyl chloride resin compositions and polyvinyl chloride sheets were prepared and subjected to tensile, cold resistance, and heat resistance tests. The results are summarized in Table 1.

[0095] [Table 1] (a): Di-n-octyl phthalate (b): Phthalic acid = n-octyl = n-dodecyl (c): Phthalic acid = n-octyl = n-tetradecyl (d): Di-n-dodecyl phthalate (e): Phthalic acid = n-dodecyl = n-tetradecyl (f): Di-n-tetradecyl phthalate

[0096] Table 1 shows that the biomass plasticizers for vinyl chloride resins according to the present invention, as described in Examples 1 to 5, have a low flexibility temperature of -33°C or lower, a loss on volatilization (170°C, 120 minutes) of 1.7 or less, no coloring in the sheet, and a biomass content of 70% or more. [Industrial applicability]

[0097] By replacing the composition of plasticizers for vinyl chloride resins, which are entirely dependent on petroleum-derived plasticizers, with the plant-derived biomass plasticizer for vinyl chloride resins according to the present invention, the amount of petroleum resources used can be reduced, and the environmental burden can be reduced by suppressing carbon dioxide emissions during the production of plasticizers for vinyl chloride resins. The biomass plasticizer for vinyl chloride resins according to the present invention has excellent compatibility with vinyl chloride resins, and therefore offers excellent plasticization efficiency and flexibility, can impart excellent heat resistance and cold resistance, and can be suitably used as a biomass plasticizer for vinyl chloride resins having a specific biomass content. The vinyl chloride resin composition and vinyl chloride resin molded articles, characterized by containing a biomass plasticizer for vinyl chloride resins according to the present invention, can be used, for example, in films, sheets, packaging containers (e.g., trays), wire covering materials, automotive interior and exterior materials, agricultural materials (e.g., greenhouses), hoses, pipes, wall materials, flooring materials, canvas, leather, toys, rubber gloves, and rubber boots, and are particularly suitable for use in food packaging sheets or food packaging stretch films.

Claims

1. General formula (1) 【Chemistry 1】 [In the formula, R1 and R2 are the same or different, each representing a linear alkyl group derived from biomass having 8 to 14 carbon atoms.] A biomass plasticizer for vinyl chloride resins comprising a mixture of two or more phthalate diesters represented by , wherein the biomass content of the biomass plasticizer for vinyl chloride resins is in the range of 70 to 100%, and the biomass plasticizer for vinyl chloride resins comprises (a) di-n-octyl phthalate, (b) phthalate=n-octyl=n-dodecyl, and (d) di-n-dodecyl phthalate, wherein the sum of (a), (b), and (d) is 100 mol%, and the ratio of (a):(b):(d) is in the range of 1.0 to 9.0 mol%:18.0 to 42.0 mol%:49.0 to 81.0 mol%.

2. General formula (1) 【Chemistry 2】 A biomass plasticizer for vinyl chloride resins comprising a mixture of two or more phthalate diesters represented by the formula [wherein R1 and R2 are the same or different, each representing a linear alkyl group derived from biomass having 8 to 14 carbon atoms], wherein the biomass content of the biomass plasticizer for vinyl chloride resins is in the range of 70 to 100%, and the biomass plasticizer for vinyl chloride resins comprises (a) di-n-octyl phthalate, (b) phthalate=n-octyl=n-dodecyl, (c) phthalate=n-octyl=n-tetradecyl, (d) di-n-dodecyl phthalate, (e) phthalate=n-dodecyl=n-tetradecyl, and (f) di-n-tetradecyl phthalate, wherein the total of (a) to (f) is 100 mol%, and A biomass plasticizer for vinyl chloride resins, characterized in that (a):(b):(c):(d):(e):(f) = 3.0-17.0 mol%:19.0-40.0 mol%:5.5-12.0 mol%:16.5-41.0 mol%:9.5-24.5 mol%:0.5-4.5 mol%.

3. A vinyl chloride resin composition characterized by comprising a vinyl chloride resin and a biomass plasticizer for vinyl chloride resins as described in claim 1 or claim 2.

4. A molded article obtained from the vinyl chloride resin composition described in claim 3.

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