Plasticizer composition for vinyl chloride resin, plastisol, and coated film thereof

Abstract

The present invention provides a chlorovinyl resin plasticizer composition capable of imparting excellent plasticization and cold resistance to a chlorovinyl resin plastisol, and excellent non-leaching properties. Specifically, the chlorovinyl resin plasticizer composition contains an aliphatic diester (A) of an aliphatic dicarboxylic acid having 2 to 12 carbon atoms and an aliphatic monoalcohol having 4 to 18 carbon atoms, an aromatic diester (B) of an aromatic monocarboxylic acid having 6 to 12 carbon atoms and a diol having 2 to 12 carbon atoms, and a phthalic acid ester (C), and satisfies aliphatic diester (A): aromatic diester (B) = 65:35 to 95:5 (mass ratio), and satisfies (aliphatic diester (A) + aromatic diester (B)): phthalic acid ester (C) = 5:95 to 35:65 (mass ratio).

Description

Technical Field

[0001] This invention relates to plasticizer compositions for vinyl chloride resins, plasticizer sols, and coatings thereof. Background Technology

[0002] In automobile manufacturing, to prevent water and rust, a sealant (so-called body sealant) is applied to the steel plates and joints of the automobile components. After applying the sealant, a mid-coat and a top coat are applied and then heat-cured.

[0003] The aforementioned sealant uses a suspension, or plastisol, formed by dispersing vinyl chloride resin particles in a liquid plasticizer. Phthalate esters such as diisononyl phthalate (DINP) are used as this plasticizer, but they suffer from insufficient plasticizing properties and cold resistance. To address this issue, the addition of aromatic compounds with long-chain alkyl groups as plasticizers has been proposed (e.g., Patent Documents 1 and 2).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2006 / 077131

[0007] Patent Document 2: International Publication No. 1997 / 039060 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] Even when phthalates and aromatic compounds with long-chain alkyl groups are added to the vinyl chloride resin plastisol, in addition to insufficient cold resistance, the compatibility between the plasticizer and the vinyl chloride resin is also insufficient, thus causing the problem of plasticizer exudation.

[0010] The problem to be solved by the present invention is to provide a plasticizer composition for vinyl chloride resin that can impart excellent plasticizing properties and cold resistance to vinyl chloride resin plastisol, and has excellent non-exudation properties.

[0011] Methods for solving problems

[0012] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by adding specific aliphatic diesters and aromatic diesters to phthalates in specific amounts, a plasticizer composition for vinyl chloride resin is obtained, which imparts excellent plasticizing and cold resistance to vinyl chloride resin plastisol and has excellent non-exudation properties of the plasticizer itself, thus completing the present invention.

[0013] Specifically, the present invention relates to a plasticizer composition for vinyl chloride resin comprising: an aliphatic diester (A) formed by an aliphatic dicarboxylic acid having 2 to 12 carbon atoms and an aliphatic monool having 4 to 18 carbon atoms; an aromatic diester (B) formed by an aromatic monocarboxylic acid having 6 to 12 carbon atoms and a diol having 2 to 12 carbon atoms; and a phthalate (C), wherein the mass ratio of the aliphatic diester (A) to the aromatic diester (B) satisfies aliphatic diester (A): aromatic diester (B) = 65:35 to 95:5, and the mass ratio of the aliphatic diester (A), the aromatic diester (B), and the phthalate (C) satisfies (aliphatic diester (A) + aromatic diester (B)) : phthalate (C) = 5:95 to 35:65.

[0014] Invention Effects

[0015] According to the present invention, a plasticizer composition for vinyl chloride resin can be provided, which can impart excellent plasticizing properties and cold resistance to vinyl chloride resin plastisol and has excellent non-exudation properties. Detailed Implementation

[0016] The following describes one embodiment of the present invention. The present invention is not limited to this embodiment, and can be implemented with appropriate modifications without impairing its effects.

[0017] [Plasticizer Composition for Vinyl Chloride Resins]

[0018] The plasticizer composition for vinyl chloride resin of the present invention (hereinafter, sometimes referred to as "the plasticizer composition of the present invention") contains: an aliphatic diester (A) formed by an aliphatic dicarboxylic acid having 2 to 12 carbon atoms and an aliphatic monool having 4 to 18 carbon atoms, an aromatic diester (B) formed by an aromatic monocarboxylic acid having 6 to 12 carbon atoms and a diol having 2 to 12 carbon atoms, and a phthalate ester (C).

[0019] The components contained in the plasticizer composition of the present invention will be described below.

[0020] (Aliphatic diester (A))

[0021] Aliphatic diesters (A) are diesters formed by aliphatic dicarboxylic acids with 2 to 12 carbon atoms and aliphatic monools with 4 to 18 carbon atoms.

[0022] Aliphatic diester (A) can improve the non-leakage properties of the plasticizer composition of the present invention.

[0023] The aliphatic dicarboxylic acids having 2 to 12 carbon atoms are preferably alkylene dicarboxylic acids having 2 to 12 carbon atoms, more preferably alkylene dicarboxylic acids having 4 to 12 carbon atoms, and even more preferably alkylene dicarboxylic acids having 5 to 11 carbon atoms.

[0024] Examples of aliphatic dicarboxylic acids with 2 to 12 carbon atoms include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid (dodecanoic acid), cyclohexanedicarboxylic acid, and hexahydrophthalic acid. Among these, adipic acid, azelaic acid, sebacic acid, and dodecanoic acid are preferred, adipic acid and sebacic acid are more preferred, and adipic acid is even more preferred.

[0025] The aliphatic dicarboxylic acids with 2 to 12 carbon atoms mentioned above can be used alone or in combination with two or more.

[0026] Aliphatic monools with 4 to 18 carbon atoms are preferably aliphatic monools with 6 to 18 carbon atoms, and more preferably aliphatic monools with 7 to 13 carbon atoms.

[0027] Examples of aliphatic monools with 4 to 18 carbon atoms include butanol, heptanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, isononol, nonanol, decanol, 2-propylheptanol, undecaneol, and dodecaneol.

[0028] The monools with 4 to 18 carbon atoms mentioned above can be used alone or in combination with two or more.

[0029] The aliphatic diester (A) is preferably a compound represented by the following general formula (A-1).

[0030] [Chemical Formula 1]

[0031]

[0032] (In the above formula (A-1),

[0033] A is an alkylene group having 2 to 10 carbon atoms.

[0034] R 11 and R 12 Each is an alkyl group having 4 to 18 carbon atoms.

[0035] In the above general formula (A-1), A corresponds to an aliphatic dicarboxylic acid residue, and R... 11 and R 12 These correspond to aliphatic monool residues, respectively.

[0036] Here, "carboxylic acid residue" refers to the organic group remaining after removing the carboxyl group from a carboxylic acid. It should be noted that the carbon number of a "carboxylic acid residue" is assumed to exclude the carbon atoms in the carboxyl group. Additionally, "alcohol residue" refers to the organic group remaining after removing the hydroxyl group from an alcohol.

[0037] The aliphatic diester (A) contained in the plasticizer composition of the present invention may be a single type or two or more types.

[0038] Aliphatic diesters (A) are, for example, substances obtained by the dehydration condensation reaction of an aliphatic dicarboxylic acid with an aliphatic monool, and can be manufactured by known methods. Alternatively, commercially available products can also be used.

[0039] (Aromatic diester (B))

[0040] Aromatic diesters (B) are diesters formed by aromatic monocarboxylic acids with 6 to 12 carbon atoms and diols with 2 to 12 carbon atoms.

[0041] Examples of aromatic monocarboxylic acids with 6 to 12 carbon atoms include benzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, tetramethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, cuminic acid, p-tert-butylbenzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, ethoxybenzoic acid, propoxybenzoic acid, naphtholic acid, nicotinic acid, furoic acid, and anisic acid. Benzoic acid is preferred among these.

[0042] The aromatic monocarboxylic acids with 6 to 12 carbon atoms mentioned above can be used alone or in combination with two or more.

[0043] The diols with 2 to 12 carbon atoms mentioned above are preferably alkylene diols with 2 to 12 carbon atoms or oxoalkylene diols with 2 to 12 carbon atoms.

[0044] Examples of alkylene glycols with 2 to 12 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentanediol), and 2,2-diethyl-1,3-propanediol (…). 3,3-Dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc.

[0045] The aforementioned alkylene glycols with 2 to 12 carbon atoms are preferably alkylene glycols with 3 to 10 carbon atoms, more preferably alkylene glycols with 3 to 6 carbon atoms, and even more preferably 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol.

[0046] The aforementioned alkylene glycols with 2 to 12 carbon atoms are, for example, substances obtained by replacing one carbon atom of the aforementioned alkylene glycols with 2 to 12 carbon atoms with an oxygen atom, and examples include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol.

[0047] The oxoalkylene glycols with 2 to 12 carbon atoms are preferably oxoalkylene glycols with 3 to 10 carbon atoms, more preferably oxoalkylene glycols with 4 to 10 carbon atoms, and even more preferably diethylene glycol or dipropylene glycol.

[0048] The diols with 2 to 12 carbon atoms mentioned above can be used alone or in combination with two or more.

[0049] The aromatic diester (B) is preferably a compound represented by the following general formula (B-1).

[0050] [Chemical Formula 2]

[0051]

[0052] (In the above formula (B-1),

[0053] G is an alkylene group having 2 to 12 carbon atoms or an oxoalkylene group having 2 to 12 carbon atoms.

[0054] In the above general formula (B-1), G corresponds to a diol residue.

[0055] Here, "diol residue" refers to the organic group remaining after the hydroxyl group is removed from the diol.

[0056] The aromatic diester (B) contained in the plasticizer composition of the present invention may be a single type or two or more types.

[0057] Aromatic diesters (B) are, for example, substances obtained by dehydration condensation of an aromatic monocarboxylic acid with a diol, and can be manufactured by known methods. Alternatively, commercially available products can also be used.

[0058] (Phenyl phthalate (C))

[0059] Phthalate (C) is, for example, a compound represented by the following general formula (C-1).

[0060] [Chemical Formula 3]

[0061]

[0062] (In the above formula (C-1),

[0063] R 31 and R 32 Each is an alkyl group having 1 to 15 carbon atoms.

[0064] Examples of phthalate esters (C) include dibutyl phthalate (DBP), di(2-ethylhexyl) phthalate (DOP), diisononyl phthalate (DINP), di(2-propylheptyl) phthalate (DPHP), diisodecyl phthalate (DIDP), di(undecyl) phthalate (DUP), di(tridecyl) phthalate (DTDP), bis(2-ethylhexyl) terephthalate (DOTP), and bis(2-ethylhexyl) isophthalate (DOIP).

[0065] The phthalate (C) contained in the plasticizer composition of the present invention may be a single type or two or more types.

[0066] Phthalate esters (C) are, for example, substances obtained by the dehydration condensation reaction of phthalic acid with aliphatic monools, and can be manufactured by known methods. Alternatively, commercially available products can also be used.

[0067] The plasticizer composition of the present invention may contain an aliphatic diester (A), an aromatic diester (B), and a phthalate (C), or may be substantially formed from an aliphatic diester (A), an aromatic diester (B), and a phthalate (C).

[0068] Here, "substantially formed" means that the proportions of the aliphatic diester (A), aromatic diester (B), and phthalate (C) in the plasticizer composition of the present invention are, for example, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, or 100% by mass.

[0069] In the plasticizer composition of the present invention, the mass ratio of aliphatic diester (A) to aromatic diester (B) satisfies aliphatic diester (A): aromatic diester (B) = 65:35 to 95:5, preferably aliphatic diester (A): aromatic diester (B) = 70:30 to 90:10.

[0070] By satisfying the above conditions in the mass ratio of aliphatic diester (A) to aromatic diester (B), the viscosity stability of the plasticizer of the present invention, described later, can be improved.

[0071] In the plasticizer composition of the present invention, the mass ratio of the total mass of aliphatic diester (A) and aromatic diester (B) to the mass of phthalate (C) satisfies (aliphatic diester (A) + aromatic diester (B)): phthalate (C) = 5:95 to 35:65, preferably (aliphatic diester (A) + aromatic diester (B)): phthalate (C) = 10:90 to 30:70.

[0072] [Plasmol]

[0073] The plasticizer sol of the present invention contains the plasticizer composition for vinyl chloride resin of the present invention and vinyl chloride resin.

[0074] The aforementioned vinyl chloride resins include homopolymers of vinyl chloride, homopolymers of vinylidene chloride, copolymers with vinyl chloride as an essential component, copolymers with vinylidene chloride as an essential component, etc.

[0075] When the vinyl chloride resin is a copolymer with vinyl chloride as an essential component or a copolymer with vinylidene chloride as an essential component, examples of copolymerizable comonomers include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl stearate; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; maleic esters such as diethyl maleate; fumarates such as dibutyl fumarate; alkyl (meth)acrylates such as methyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate; hydroxyalkyl (meth)acrylates such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, and N-dihydroxyethylmethacrylamide; acrylonitrile and vinylidene chloride.

[0076] From the viewpoint of physical properties such as resistance to chipping, the average degree of polymerization of vinyl chloride resin is preferably in the range of 500 to 2,500, and more preferably in the range of 800 to 2,300.

[0077] The vinyl chloride resin used to make the plastisol is usually in particulate form, with an average particle size in the range of, for example, 0.1 to 10 μm, preferably in the range of 0.1 to 5 μm, and more preferably in the range of 0.1 to 2 μm.

[0078] Vinyl chloride resin can be manufactured using known methods or commercially available products.

[0079] From the viewpoint of compatibility with vinyl chloride resin, the content of the plasticizer composition for vinyl chloride resin of the present invention in the plastisol of the present invention is preferably in the range of 10 to 150 parts by weight relative to 100 parts by weight of vinyl chloride resin, more preferably in the range of 30 to 120 parts by weight, further preferably in the range of 40 to 110 parts by weight, and particularly preferably in the range of 50 to 100 parts by weight.

[0080] The plasticizer of the present invention may contain vinyl chloride resin and the plasticizer composition for vinyl chloride resin of the present invention, or may contain plasticizers other than the plasticizer composition for vinyl chloride resin of the present invention (other plasticizers), other additives, etc., without impairing the effect of the present invention.

[0081] Other plasticizers mentioned above include, for example, benzoates such as diethylene glycol dibenzoate; pyromellitic esters such as tetra(2-ethylhexyl) pyromellitic acid tetra(2-ethylhexyl) ester (TOPM); aliphatic diesters such as di(2-ethylhexyl) adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di(2-ethylhexyl) sebacate (DOS), and diisononyl sebacate (DINS); and tri(2-ethylhexyl) phosphate (TOP) and tricresyl phosphate (TCP). Phosphate esters such as pentaerythritol; alkyl esters of polyols such as pentaerythritol; polyesters with molecular weights of 800–4,000 synthesized by polyesterification of dicarboxylic acids such as adipic acid with diols; epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil; alicyclic dicarboxylic acids such as diisononyl hexahydrophthalate; fatty acid diol esters such as 1,4-butanediol didecanoate; tributyl acetyl citrate (ATBC); chlorinated paraffin obtained by chlorinating paraffin and n-chain alkanes; chlorinated fatty acid esters such as chlorinated stearate; and higher fatty acid esters such as butyl oleate.

[0082] When the other plasticizers described above are used in the plastisol of the present invention, the content of such other plasticizers is, for example, in the range of 10 to 300 parts by weight, and preferably in the range of 20 to 200 parts by weight, relative to 100 parts by weight of the plasticizer for vinyl chloride resin of the present invention.

[0083] It should be noted that by using the plasticizer composition of the present invention, sufficient plasticizing properties can be obtained. Therefore, the plasticizer sol of the present invention can be made into a plasticizer sol that does not contain the other plasticizers mentioned above.

[0084] Other additives mentioned above include, for example, fillers.

[0085] Examples of fillers mentioned above include calcium carbonate, magnesium carbonate, barium sulfate, mica, graphite, talc, clay, glass flakes, glass beads, vermiculite, kaolinite, wollastonite, silicon dioxide, diatomaceous earth, gypsum, cement, converter slag, white sand, zeolite, cellulose powder, powdered rubber, gold vermiculite, potassium titanate, bentonite, aluminum nitride, silicon nitride, zinc oxide, titanium dioxide, calcium oxide, aluminum oxide, zinc oxide, iron oxide, magnesium oxide, titanium dioxide, magnesium hydroxide, aluminum hydroxide, and calcium silicate.

[0086] Fiber-like fillers such as calcium carbonate whiskers, ceramic short fibers, asbestos short fibers, glass fiber short fibers, potassium titanate short fibers, calcium silicate short fibers, aluminum silicate, carbon fiber short fibers, aramid fiber short fibers, and sepiolite; hollow fillers such as glass hollow spheres, silica hollow spheres, resin hollow spheres, and carbon inorganic hollow spheres; organic hollow fillers such as plastic hollow spheres formed from organic synthetic resins such as vinylidene chloride and acrylonitrile; and metal fillers such as aluminum fillers can also be used as fillers.

[0087] The content of filler in the plastisol of the present invention can be appropriately set according to the application, for example, in the range of 50 to 800 parts by weight relative to 100 parts by weight of vinyl chloride resin.

[0088] Other additives are not limited to fillers. Adhesives, viscosity modifiers, stabilizers, pigments, hygroscopic agents, antioxidants, UV absorbers, diluents, curing agents, leveling agents, anti-sagging agents, auxiliary resins, organic solvents, flame retardants, rust inhibitors, anti-aging agents, etc., may also be added as needed.

[0089] The plastisol of the present invention can be manufactured by known methods.

[0090] For example, the plastisol of the present invention can be prepared by mixing vinyl chloride resin, the vinyl chloride resin plasticizer composition of the present invention, and any components (the other plasticizers and other additives mentioned above) using a mixing machine such as a mixer, planetary mixer, or Banbury mixer.

[0091] The plastisol of the present invention can be applied to the desired location with any thickness by known coating methods such as brushing, roller coating, air spraying, electrostatic coating, and airless spraying, and then heated to form a coating film.

[0092] The plastisol of this invention can be used as coatings, inks, adhesives, sealants, etc. Furthermore, the plastisol of this invention can also be applied to molded products such as groceries, toys, industrial parts, and electrical components.

[0093] If the plasticizer of this invention is applied to paper, cloth, etc., it can be used to make artificial leather, mats, wallpaper, clothing, waterproof sheets, etc. If it is applied to metal sheets, it can be used to make corrosion-resistant metal sheets.

[0094] The plasticizer of the present invention is suitable for use in automobiles. Specifically, it is suitable for application to the back of the floor, wheel arches, front, rear fenders, front fenders, side beams (body fenders), etc. of automobiles. It is also suitable for application to the joints, seams, and edges of the steel plates constituting the vehicle body.

[0095] [Example]

[0096] The present invention will now be described in detail through examples and comparative examples.

[0097] It should be noted that the present invention is not limited to the following embodiments.

[0098] In the embodiments of this application, the acid value and viscosity values ​​are evaluated by the following method.

[0099] <Methods for determining acid value>

[0100] The determination was performed according to the method of JIS K0070:1992.

[0101] <Methods for measuring viscosity>

[0102] The determination was performed according to the method in JIS K6901:1986.

[0103] (Synthetic Example 1: Synthesis of the aromatic diester PGDB)

[0104] In a reaction vessel, 900 g (7.38 mol) of benzoic acid (manufactured by Kalama Corporation), 322 g (4.24 mol) of 1,2-propanediol (manufactured by Asahi Glass Co., Ltd.), and 0.373 g of tetraisopropyl titanate as an esterification catalyst were added to a 2-liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser. The mixture was heated to 230°C in stages under a nitrogen atmosphere with stirring. Heating was continued at 230°C until the acid value dropped below 2, continuously removing the generated water.

[0105] After the reaction, the unreacted propylene glycol was removed by vacuum distillation at 230–200 °C, thereby obtaining 949 g of propylene glycol dibenzoate (PGDB, acid value 0.02, viscosity 75 mPa·s (25 °C)) as an aromatic diester.

[0106] (Synthetic Example 2: Synthesis of the aromatic diester DEGDB)

[0107] In a reaction vessel, 783 g (6.42 mol) of benzoic acid (manufactured by Kalama Corporation), 374 g (3.53 mol) of diethylene glycol (manufactured by Mitsubishi Chemical Co., Ltd.), and 0.347 g of tetraisopropyl titanate as an esterification catalyst were added to a 2-liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser. The mixture was heated to 230°C in stages under a nitrogen atmosphere with stirring. Heating was continued at 230°C until the acid value dropped below 2, continuously removing the generated water.

[0108] After the reaction, the unreacted diethylene glycol was removed by vacuum distillation at 230–200 °C, thereby obtaining 943 g of diethylene glycol dibenzoate (DEGDB, acid value 0.02, viscosity 77 mPa·s (25 °C)) as an aromatic diester.

[0109] (Synthetic Example 3: Synthesis of the aromatic diester DPGDB)

[0110] In a reaction vessel, 780 g (6.39 mol) of benzoic acid (manufactured by Kalama Corporation), 471 g (3.51 mol) of dipropylene glycol (manufactured by Asahi Glass Co., Ltd.), and 0.378 g of tetraisopropyl titanate as an esterification catalyst were added to a 2-liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser. The mixture was heated to 230°C in stages under a nitrogen atmosphere with stirring. Heating at 230°C continued until the acid value dropped below 2, continuously removing the generated water.

[0111] After the reaction, the unreacted dipropylene glycol was removed by vacuum distillation at 230–200 °C, thereby obtaining 957 g of dipropylene glycol dibenzoate (DPGDB, acid value 0.01, viscosity 140 mPa·s (25 °C)) as an aromatic diester.

[0112] (Examples 1-9 and Comparative Examples 1-6: Preparation and Evaluation of Vinyl Chloride Resin Plaster)

[0113] When preparing vinyl chloride resin plastisol, the following plasticizer components are prepared:

[0114] DOA: Di(2-ethylhexyl) adipic acid ester

[0115] DINA: Diisononyl adipate

[0116] DOS: Di(2-ethylhexyl) sebacate

[0117] PGDB: Propylene glycol dibenzoate

[0118] DPGDB: Dipropylene glycol dibenzoate

[0119] DEGDB: Diethylene glycol dibenzoate

[0120] IDB: Isodecyl Benzoate

[0121] DINP: Diisononyl phthalate

[0122] Of the plasticizer components mentioned above, DOA is MONOCIZER W-240 manufactured by DIC Corporation, DINA is MONOCIZER W-242 manufactured by DIC Corporation, DOS is MONOCIZER W-280 manufactured by DIC Corporation, DINP is SANSOCIZER DINP manufactured by Shin Nippon Rikka Co., Ltd., and IDB is Jayflex MB-10 manufactured by Exxon Mobil.

[0123] 100 parts by weight of vinyl chloride resin (degree of polymerization 1,550, ZEST P21, manufactured by SHINDAI-ICHI VINYL CORPORATION), 100 parts by weight of the total plasticizer components shown in Tables 1 and 2, and 3 parts by weight of filler (Greg (Japanese: ゲレツゲ) ML-610 (calcium / zinc composite stabilizer), manufactured by Nichishin Trading Co., Ltd.) were mixed using a mixer at a stirring speed of 1100 rpm for 4 minutes. After standing for 30 minutes under reduced pressure to remove bubbles, a paste-sol-like vinyl chloride resin composition (vinyl chloride resin plastic sol) was prepared.

[0124] The obtained vinyl chloride resin plastisol was evaluated as follows. The results are shown in Tables 1 and 2.

[0125] (Evaluation of viscosity stability)

[0126] The viscosity stability of vinyl chloride resin plastisol was evaluated using a Type B rotational viscometer (manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K7117-1:1999.

[0127] Specifically, the viscosity of the vinyl chloride resin plasticized sol immediately after preparation was measured using a BM-type viscometer (rotor No. 3, 12 rpm, measurement temperature 25°C), and this initial sol viscosity was set as the initial sol viscosity. After measuring the initial sol viscosity, the sol was stored at 25°C for 7 days, and the sol viscosity was measured again after 7 days using the same method (sol viscosity after 7 days). The viscosity increase rate (sol viscosity after 7 days / initial sol viscosity) was calculated using the initial sol viscosity and the sol viscosity after 7 days, and the viscosity stability was evaluated according to the following criteria.

[0128] ○: The viscosity increase rate is less than 1.3 times.

[0129] ×: The viscosity increase rate is more than 1.3 times.

[0130] (Evaluation of the plasticizing properties of plasticizers)

[0131] After coating a glass plate with a 1 mm thick polyvinyl chloride resin plastisol, the plate is baked in an oven (WernerMathis AG, LTF-ST) at 140°C for 25 minutes to produce a 1.0 mm thick sheet.

[0132] The obtained sheet was evaluated according to JIS K6251:2010 for 100% modulus (tensile stress at 100% elongation) and elongation at break. Specifically, a 1.0 mm thick sheet was used, and tensile tests were performed under the following conditions to evaluate 100% modulus and elongation at break.

[0133] It should be noted that the elongation at break is the value obtained by subtracting the initial chuck distance of 20 mm from the chuck distance at the point of tensile fracture of a 1.0 mm thick sheet, divided by the chuck distance of 20 mm, and expressed as a percentage.

[0134] Testing equipment: Tensilon universal testing machine (manufactured by Orientec Co., Ltd.)

[0135] Sample shape: Dumbbell-shaped, No. 3

[0136] Chuck spacing: 20mm

[0137] Stretching speed: 200mm / minute

[0138] Measurement atmosphere: Temperature 23 degrees Celsius, humidity 50%

[0139] A lower 100% modulus value indicates a higher plasticizing effect on vinyl chloride resin. Additionally, a higher elongation at break indicates a higher plasticizing effect on vinyl chloride resin.

[0140] (Evaluation of the low-temperature flexibility of molded articles)

[0141] A 1.0 mm thick sheet was prepared using the same method as that used to evaluate the plasticizing properties.

[0142] For the obtained sheets, test pieces were prepared according to the test methods specified in JIS K6773:2007, and the softening temperature (unit: °C) was evaluated using a CLASH-BERG softening temperature tester. The lower the softening temperature, the better the cold resistance.

[0143] (Evaluation of the gelling properties of vinyl chloride resin compositions)

[0144] The dynamic viscoelasticity of the vinyl chloride resin composition was determined using a rheometer (HAAKE RS600, Thermo Scientific) at a frequency of 1 Hz, a strain of 1%, and a heating rate of 4 °C / min. Gelation properties were evaluated based on the temperature at which the storage modulus G' reaches its maximum value, according to the following criteria:

[0145] ○: The temperature at which the energy storage modulus G' reaches its maximum value is less than 140℃.

[0146] ×: The temperature at which the energy storage modulus G' reaches its maximum value is above 140℃.

[0147] (Evaluation of plasticizer compatibility)

[0148] A 1.0 mm thick sheet was prepared using the same method as for evaluating plasticizing properties. Two 1.0 mm thick sheets were then made from this sheet and cut into 5 cm × 5 cm pieces. The two sheets were overlapped and placed at 70°C and 95% relative humidity for 30 days. The surface condition of the sheets and the condition of the overlapping surfaces were then evaluated according to the following evaluation criteria.

[0149] 〇: Visually inspect the surface of the sheet and the overlapping surfaces of the sheets. No foreign matter (exudate) such as powder or sticky substances can be detected. Exudate cannot be detected even by touching the surface of the sheet and the overlapping surfaces of the sheets with your fingers.

[0150] ×: Visually inspect the surface of the sheet and the overlapping surfaces of the sheets to confirm the seepage, or touch the surface of the sheet and the overlapping surfaces of the sheets with your fingers to confirm the seepage.

[0151] [Table 1]

[0152]

[0153] [Table 2]

[0154]

[0155] As shown in Tables 1 and 2, in Comparative Example 2, where the plasticizer component contained an aliphatic diester but not an aromatic diester, gelation became insufficient. On the other hand, in Comparative Example 3, where the plasticizer component contained an aromatic diester but not an aliphatic diester, viscosity stability was not obtained. Furthermore, in Comparative Examples 4 and 5, although the plasticizer component contained both aliphatic and aromatic diesters, viscosity stability was not obtained due to the high amount of aromatic diester. Regarding Comparative Example 6, the plasticizer component contained an aromatic monoester, but compatibility was insufficient, and exudation occurred.

[0156] On the other hand, it was confirmed that Examples 1-9 had better plasticizing properties and cold resistance compared to Comparative Example 1, which did not contain the plasticizer of the present invention. In addition, it was found that compared to Comparative Example 6, which used an aromatic monoester, the plasticizing properties, cold resistance and compatibility were also excellent.

Claims

1. A plasticizer composition for vinyl chloride resin, comprising: an aliphatic diester A formed by an aliphatic dicarboxylic acid having 2-12 carbon atoms and an aliphatic monool having 4-18 carbon atoms; an aromatic diester B formed by an aromatic monocarboxylic acid having 6-12 carbon atoms and a diol having 2-12 carbon atoms; and a phthalate C. The mass ratio of the aliphatic diester A to the aromatic diester B satisfies an aliphatic diester A: aromatic diester B ratio of 65:35 to 95:

5. The mass ratio of the aliphatic diester A, the aromatic diester B, and the phthalate C satisfies (aliphatic diester A + aromatic diester B): phthalate C = 5:95 to 35:

65.

2. The plasticizer composition for vinyl chloride resin according to claim 1, wherein, The aliphatic dicarboxylic acid with 2 to 12 carbon atoms is selected from one or more of succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, and hexahydrophthalic acid.

3. The plasticizer composition for vinyl chloride resin according to claim 1 or 2, wherein, The aliphatic monools with 4 to 18 carbon atoms are selected from one or more of butanol, heptanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, isononol, nonanol, decanol, 2-propylheptanol, undecaneol, and dodecaneol.

4. The plasticizer composition for vinyl chloride resin according to claim 1 or 2, wherein, The aromatic monocarboxylic acid having 6 to 12 carbon atoms is selected from one or more of benzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, tetramethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, cuminic acid, p-tert-butylbenzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, ethoxybenzoic acid, propoxybenzoic acid, naphtholic acid, nicotinic acid, furoic acid, and anisic acid.

5. The plasticizer composition for vinyl chloride resin according to claim 1 or 2, wherein, The diol having 2 to 12 carbon atoms is selected from one or more of 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol.

6. The plasticizer composition for vinyl chloride resin according to claim 1 or 2, wherein, The phthalate ester (C) is selected from one or more of dibutyl phthalate, di(2-ethylhexyl) phthalate, diisononyl phthalate, di(2-propylheptyl) phthalate, diisodecyl phthalate, di(undecyl) phthalate, di(tridecyl) phthalate, bis(2-ethylhexyl) terephthalate, and bis(2-ethylhexyl) isophthalate.

7. A plasticizer sol comprising the plasticizer composition for vinyl chloride resin according to any one of claims 1 to 6 and vinyl chloride resin.

8. The plastisol according to claim 7, wherein, The content of the plasticizer composition for vinyl chloride resin is in the range of 10 to 150 parts by weight relative to 100 parts by weight of the vinyl chloride resin.

9. A coating film using the plastisol of claim 7 or 8.

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