JP2014189688A - Plasticizer for vinyl chloride-based resin including trimellitic acid triester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasticizer for a vinyl chloride-based resin having excellent cold resistance and heat resistance and good flexibility.SOLUTION: There is used, as a plasticizer for a vinyl chloride-based resin, a new trimellitic acid ester having a specific structure which is obtained by esterification reaction of trimellitic acid or an anhydride thereof and a mixture of an aliphatic saturated alcohol mainly composed of an aliphatic saturated alcohol having 9 carbon atoms.

Description

The present invention relates to a novel plasticizer for vinyl chloride resin and a vinyl chloride resin composition containing the same, and specifically includes a novel trimellitic acid triester excellent in cold resistance, heat resistance and flexibility. The present invention relates to a plasticizer for vinyl chloride resin.

The vinyl chloride resin was added with a plasticizer for the purpose of facilitating the molding process by imparting various performances including flexibility and lowering the processing temperature during molding such as extrusion and calendering. Often used as a vinyl chloride resin composition.

The performance required for the plasticizer used in such a vinyl chloride resin composition includes various properties such as flexibility, cold resistance, heat resistance, and electrical characteristics when the composition is used as a raw material. As typical plasticizers used in such vinyl chloride resin compositions, higher alkyl esters of polybasic acids such as phthalic acid esters, adipic acid esters and trimellitic acid esters are known, either alone or Used in combination of two or more. Up to now, phthalates are often used mainly in terms of price and performance balance, but in applications that require heat resistance that cannot be handled by phthalates, they have a performance balance equivalent to or better than that of phthalates. Trimellitic acid esters have been used. Among them, trimellitic acid tri-2-ethylhexyl (hereinafter referred to as “TOTM”), trimellitic acid triisononyl (hereinafter referred to as “TINTM”) and trimellitic acid triisodecyl ester (hereinafter referred to as “TIDTM”). Is expected to have compatibility close to that of phthalates and is a plasticizer with very good heat aging resistance. Therefore, it is frequently used for heat-resistant electric wires having a usable temperature of 105 ° C. or higher, vehicle dashboards, and the like.

However, in recent years, demands for cold resistance and heat resistance have become increasingly severe, and the above-mentioned TOTM, TINTM and TIDTM are insufficient in heat resistance and cold resistance, and none of them have achieved satisfactory performance. It is. Further, regarding the flexibility, the trimellitic acid ester that has been conventionally used is insufficient, and further improvement is desired.

An object of the present invention is to provide a novel trimellitic acid triester-based plasticizer for a vinyl chloride resin and a chloride containing the plasticizer, which can solve the above-mentioned problems and has excellent cold resistance and heat resistance and good flexibility. It is to provide a vinyl resin composition.

In view of the present situation, the present inventors have conducted intensive studies to solve the above problems, and as a result, trimellitic acid trimethyl ester obtained by esterifying a specific aliphatic saturated alcohol and trimellitic acid or its anhydride. The present inventors have found that an ester is a plasticizer for vinyl chloride resin that has excellent cold resistance and heat resistance and good flexibility, and has completed the present invention.

That is, the present invention provides the following new plasticizers for vinyl chloride resins and vinyl chloride resin compositions containing the same.

[Item 1] Vinyl chloride containing trimellitic acid triester obtained by esterification of trimellitic acid or an anhydride thereof and an aliphatic saturated alcohol mixture mainly containing an aliphatic saturated alcohol having 9 carbon atoms. A plasticizer for plastic resin,
The aliphatic saturated alcohol mixture is a linear aliphatic saturated alcohol having 9 to 9 carbon atoms having a content of 60 to 95% by weight and a branched chain having 9 to 40% by weight in the alcohol mixture. A plasticizer for a vinyl chloride resin, which is an aliphatic saturated alcohol mixture containing an aliphatic saturated alcohol.

[Item 2] The aliphatic saturated alcohol mixture contains a linear aliphatic saturated alcohol having 9 to 9 carbon atoms and a branched chain having 9 to 30 carbon atoms and a content of 70 to 90% by weight in the alcohol mixture. The plasticizer for vinyl chloride resin according to [Item 1], which is an aliphatic saturated alcohol mixture containing a chain aliphatic saturated alcohol.

[Item 3] Vinyl chloride containing trimellitic acid triester obtained by esterification of trimellitic acid or an anhydride thereof and an aliphatic saturated alcohol mixture mainly containing an aliphatic saturated alcohol having 9 carbon atoms. A plasticizer for plastic resin,
The aliphatic saturated alcohol mixture comprises (1) a step of producing a 9-carbon aldehyde by hydroformylation reaction of 1-octene, carbon monoxide and hydrogen, and (2) an alcohol obtained by hydrogenating a 9-carbon aldehyde. A plasticizer for a vinyl chloride resin, comprising an aliphatic saturated alcohol having a straight chain structure and a branched chain structure, which is produced by a production process including a step of reducing to a vinyl chloride resin.

[Item 4] A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer for vinyl chloride resin according to any one of [Item 1] to [Item 3].

The plasticizer for vinyl chloride resins of the present invention can be used as a plasticizer for vinyl chloride resins having excellent cold resistance and heat resistance and good flexibility. Furthermore, since the vinyl chloride resin composition of the present invention has good flexibility and is excellent in cold resistance and heat resistance, it is used for automobiles such as wire coating, interior materials, flooring, and various medical uses. It can be used as a vinyl chloride resin composition.

<Plasticizer for vinyl chloride resin>
Trimellitic acid triester (hereinafter referred to as “the present ester”) obtained by esterification of trimellitic acid according to the present invention or an anhydride thereof and an aliphatic alcohol mixture mainly containing an aliphatic saturated alcohol having 9 carbon atoms. Is easily obtained by esterifying a predetermined acid component and an alcohol component according to a conventional method, preferably in an inert gas atmosphere such as nitrogen, in the absence of a catalyst or in the presence of a catalyst.

[Fat saturated alcohol mixture]
The aliphatic saturated alcohol mixture mainly composed of an aliphatic saturated alcohol having 9 carbon atoms used in the present invention (hereinafter sometimes simply referred to as “aliphatic saturated alcohol mixture”) has a content in the alcohol mixture of 60 9 to 95% by weight, preferably 70 to 90% by weight of a linear saturated aliphatic alcohol having 9 carbon atoms, and 5 to 40% by weight, preferably 10 to 30% by weight of carbon atoms such as 2-methyloctanol. A branched chain saturated aliphatic alcohol. If the content of the linear saturated aliphatic alcohol having 9 carbon atoms is less than 60% by weight, the cold resistance and heat resistance are inferior and the flexibility tends to decrease. If the content exceeds 95% by weight, the alcohol is expensive. Therefore, it is economically unfavorable, and there is a concern that the molding processability is lowered.

Further, if the content of the branched saturated aliphatic alcohol having 9 carbon atoms is less than 5% by weight, the alcohol becomes expensive and not economically preferable. If it exceeds 40% by weight, the cold resistance and heat resistance are poor. , Tend to be less flexible.

In addition, the mixture of aliphatic saturated alcohol having 9 carbon atoms used in the present invention includes (1) a step of producing 9-aldehyde aldehyde by hydroformylation reaction of 1-octene, carbon monoxide and hydrogen, and (2) carbon. It can manufacture by the manufacturing process which comprises the process of hydrogenating the aldehyde of several 9 and reducing to alcohol.

In the hydroformylation reaction as the step (1), for example, an aldehyde having 9 carbon atoms can be produced by reacting 1-octene, carbon monoxide and hydrogen in the presence of a cobalt catalyst or a rhodium catalyst.

The hydrogenation in the step (2) can be reduced to an alcohol by hydrogenating an aldehyde having 9 carbon atoms by hydrogen pressurization in the presence of a noble metal catalyst such as a nickel catalyst or a palladium catalyst. . A reduction method using a reagent is also exemplified.

Specific examples of a mixture of aliphatic saturated alcohols mainly composed of aliphatic saturated alcohols having 9 carbon atoms obtained in the above production process include about 70% or more of linear nonanol and about 30% or less of branched chains. Lineball 9 (trade name, Shell Chemicals), which is a mixture of nonanol in the form of a ring.

[Esterification reaction]
In the esterification reaction of the aliphatic saturated alcohol mixture and trimellitic acid or anhydride thereof, the alcohol mixture is preferably, for example, from 3.05 mol to 1 mol of trimellitic acid or anhydride thereof. It is recommended to use 4.00 mol, more preferably 3.10 mol to 3.80 mol, in particular 3.15 mol to 3.60 mol.

Examples of the catalyst used in the esterification reaction include mineral acids, organic acids, Lewis acids, and alkali metals. More specifically, examples of the mineral acid include sulfuric acid, hydrochloric acid, and phosphoric acid, examples of the organic acid include p-toluenesulfonic acid and methanesulfonic acid, and examples of the Lewis acid include aluminum derivatives, tin derivatives, Examples include titanium derivatives, lead derivatives, zinc derivatives, etc., and examples of alkali metals include sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide, etc., and these are used alone or in combination of two or more. Is possible.

Among them, p-toluenesulfonic acid, tetraalkyl titanate having 3 to 8 carbon atoms, titanium oxide, titanium hydroxide, sodium alkoxide having 1 to 4 carbon atoms, sodium hydroxide, tin oxide having 3 to 12 carbon atoms, tin oxide, Tin hydroxide, zinc oxide, zinc hydroxide, lead oxide, lead hydroxide, aluminum oxide and aluminum hydroxide are particularly preferred. The amount used is preferably 0.01 wt% to 5.0 wt%, more preferably 0.02 wt% to 4.0 wt%, for example, with respect to the total weight of the acid component and alcohol component that are ester synthesis raw materials. It is recommended to use% by weight, in particular 0.03% to 3.0% by weight.

Examples of the esterification temperature include 100 ° C to 230 ° C, and the reaction is usually completed in 3 hours to 30 hours.

In esterification, it is possible to use water entraining agents such as benzene, toluene, xylene and cyclohexane in order to promote distillation of water produced by the reaction.

  Also, when oxygenated organic compounds such as oxides, peroxides, and carbonyl compounds are produced by oxidative degradation of raw materials, produced esters and organic solvents (water entraining agents) during the esterification reaction, the heat resistance, weather resistance, etc. are adversely affected. For this reason, it is desirable to carry out the reaction under normal or reduced pressure in an inert gas atmosphere such as nitrogen gas or in an inert gas stream. After completion of the esterification reaction, excess raw material is distilled off under reduced pressure or normal pressure.

The present ester obtained by the above esterification method may be subsequently purified by liquid-liquid extraction, vacuum distillation, adsorption purification, or the like, if necessary.

Examples of the adsorbent used for the adsorption purification include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, and diatomaceous earth.

The vinyl chloride resin composition of the present invention can be obtained by blending the above-described ester into a vinyl chloride resin as a plasticizer.

[Vinyl chloride resin]
The vinyl chloride resin used in the present invention is a homopolymer of vinyl chloride or vinylidene chloride and a copolymer of vinyl chloride or vinylidene chloride, and its production method is carried out by a conventionally known polymerization method. In the case of a vinyl resin, a suspension polymerization method can be mentioned in the presence of an oil-soluble polymerization catalyst, and in the case of a vinyl chloride paste resin, an emulsion polymerization method can be mentioned in an aqueous medium in the presence of a water-soluble polymerization catalyst. The degree of polymerization of these vinyl chloride resins is usually 300 to 5000, preferably 400 to 3500, and more preferably 700 to 3000. If the degree of polymerization is too low, heat resistance and the like are lowered, and if it is too high, moldability tends to be lowered.

In the case of a copolymer, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- C2-C30 α-olefins such as tridecene, 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, alkyl vinyl ether, etc. Copolymers of vinyl compounds, polyfunctional monomers such as diallyl phthalate, and mixtures thereof with vinyl chloride monomers, ethylene-acrylate copolymers such as ethylene-ethyl acrylate copolymers, ethylene-methacrylate esters Polymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyester Ren, butyl rubber, crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile- (α-methyl) styrene copolymer (ABS), styrene-butadiene copolymer, polyethylene, poly Examples thereof include a graft copolymer obtained by grafting vinyl chloride monomer onto methyl methacrylate and a mixture thereof.

[Vinyl chloride resin composition]
The content of the present ester in the vinyl chloride resin composition is appropriately selected according to its use, but is usually 1 to 100 parts by weight, preferably 5 to 100 parts by weight of the vinyl chloride resin. 50 parts by weight. If it is less than 1 part by weight, it is difficult to obtain a predetermined plasticizing effect, and if it exceeds 100 parts by weight, bleeding on the surface of the molded product is severe, which is not preferable in either case. However, when adding a filler etc. with respect to said vinyl chloride resin composition, since the filler itself absorbs oil, the said plasticizer can be mix | blended exceeding said range. For example, when 100 parts by weight of calcium carbonate as a filler is blended with 100 parts by weight of a vinyl chloride resin, about 1 to 500 parts by weight of the plasticizer can be blended.

In the vinyl chloride resin composition, other known plasticizers can be used in combination with the ester. If necessary, flame retardants, stabilizers, stabilization aids, colorants, processing aids, fillers, antioxidants (anti-aging agents), UV absorbers, light stabilizers such as hindered amines, lubricants or electrification Additives such as inhibitors can be blended.

Other plasticizers and additives other than the present ester may be used alone or in combination of two or more kinds together with the present ester.

Known plasticizers that can be used in combination with this ester include, for example, benzoic acid esters such as diethylene glycol dibenzoate, dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), and diisononyl phthalate (DINP). ), Diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), bis (2-ethylhexyl) terephthalate (DOTP), phthalic acid such as bis (2-ethylhexyl) isophthalate (DOIP) Esters, di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), diisononyl sebacate (DINS) Basic acid S , Trimellitic acid esters such as trimellitic acid tri-2-ethylhexyl (TOTM), trimellitic acid triisononyl (TINTM), trimellitic acid triisodecyl (TIDTM), pyromellitic acid tetra-2-ethylhexyl (TOPM), etc. Pyromellitic acid esters, phosphoric acid esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP), alkyl esters of polyhydric alcohols such as pentaerythritol, dibasic acids such as adipic acid and the like Polyesters having a molecular weight of 800 to 4000 synthesized by polyesterification with glycol, epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil, and alicyclic dibasic acids such as hexahydrophthalic acid diisononyl ester (DINCH) , Dicaprin 1. Fatty acid glycol esters such as 4-butanediol, acetyl tributyl citrate (ATBC), chlorinated paraffins chlorinated paraffin wax and n-paraffin, chlorinated fatty acid esters such as chlorinated stearate, Examples include higher fatty acid esters such as butyl oleate. The amount of the plasticizer is about 1 to 100 parts by weight.

Flame retardants include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, zinc borate, cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, trisdichloropropyl phosphate, etc. Illustrative are halogen compounds such as phosphorus compounds and chlorinated paraffins. The blending amount of the flame retardant with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 20 parts by weight.

Stabilizers include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octylate, zinc laurate, zinc ricinoleate, stearic acid Examples include metal soap compounds such as zinc, organotin compounds such as dimethyltin bis-2-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutylmaleate, and dibutyltin dilaurate, and antimony mercaptide compounds. The blending amount of the stabilizer with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 20 parts by weight.

Stabilization aids include phosphite compounds such as triphenyl phosphite, monooctyl diphenyl phosphite, tridecyl phosphite, beta diketone compounds such as acetylacetone and benzoylacetone, glycerin, sorbitol, pentaerythritol, polyethylene glycol, etc. Examples include polyol compounds, perchlorate compounds such as barium perchlorate and sodium perchlorate, hydrotalcite compounds, and zeolites. Moreover, the compounding quantity of the stabilization adjuvant with respect to 100 weight part of vinyl chloride-type resin is about 0.1-20 weight part.

Examples of the colorant include carbon black, lead sulfide, white carbon, titanium white, lithopone, benigara, antimony sulfide, chrome yellow, chrome green, cobalt blue, and molybdenum orange. Further, the blending amount of the colorant with respect to 100 parts by weight of the vinyl chloride resin is about 1 to 100 parts by weight.

Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bis stearic acid amide, butyl stearate, calcium stearate and the like. The blending amount of the processing aid with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 20 parts by weight.

Fillers include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, ferrite, fibers and powders such as glass, carbon, metal, glass spheres, graphite, aluminum hydroxide, barium sulfate, oxidation Examples include magnesium, magnesium carbonate, magnesium silicate, calcium silicate, and the like. Moreover, the compounding quantity of the filler with respect to 100 weight part of vinyl chloride resin is about 1 to 100 weight part.

Antioxidants include 2,6-di-tert-butylphenol, tetrakis [methylene-3- (3,5-tert-butyl-4-hydroxyphenol) propionate] methane, 2-hydroxy-4-methoxybenzophenone, and the like. Sulfur compounds such as phenolic compounds, alkyl disulfides, thiodipropionic esters, benzothiazoles, trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) ) Phosphinic compounds such as phosphites, organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. The blending amount of the antioxidant with respect to 100 parts by weight of the vinyl chloride resin is about 0.2 to 20 parts by weight.

Examples of ultraviolet 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, In addition to benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, cyanoacrylate compounds are exemplified. Moreover, the compounding quantity of the ultraviolet absorber with respect to 100 weight part of vinyl chloride-type resin is about 0.1-10 weight part.

Examples of hindered amine 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] butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester and 1,1-dimethylethyl Reaction product of hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidino And higher fatty acid ester mixtures, 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, 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- Polycondensate of 4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, N, N ′, N ″, N ′ ″ − Tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1 , 10-diamine, etc. The blending amount of the light stabilizer with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 10 parts by weight.

Examples of the lubricant include silicone, liquid paraffin, baraffin wax, fatty acid metal salts such as metal stearate and metal laurate, fatty acid amides, fatty acid wax, and higher fatty acid wax. The blending amount of the lubricant with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 10 parts by weight.

Antistatic agents include alkyl sulfonate type, alkyl ether carboxylic acid type or dialkyl sulfosuccinate type anionic antistatic agents, non-ionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, diethanolamine derivatives, alkylamidoamine type, alkyl Examples include quaternary ammonium salts such as dimethylbenzyl type, cationic antistatic agents such as alkylpyridinium type organic acid salts or hydrochlorides, amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. The blending amount of the antistatic agent with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 10 parts by weight.

The vinyl chloride resin composition of the present invention is obtained by stirring and mixing the ester, vinyl chloride resin and, if necessary, various additives using a stirrer such as a mortar mixer, a Henschel mixer, a Banbury mixer, or a ribbon blender. It can be set as a mixed powder of a resin composition.

On the other hand, the present ester, vinyl chloride resin and various additives as required are mixed with a kneader such as a conical twin screw extruder, a parallel twin screw extruder, a single screw extruder, a kneader type kneader, or a roll kneader. A pellet-like vinyl chloride resin composition can also be obtained by melt molding.

Furthermore, kneading machines such as the present ester, vinyl chloride paste resin and various additives as necessary, for example, conical twin screw extruder, parallel twin screw extruder, single screw extruder, kneader type kneader, roll kneader A paste-like vinyl chloride resin composition can also be obtained by melt molding.

[Vinyl chloride resin molding]
Conventionally known methods such as vacuum molding, compression molding, extrusion molding, injection molding, calendar molding, press molding, blow molding, powder molding, etc., for the vinyl chloride resin composition (mixed powder or pellets) according to the present invention Can be molded into a desired shape.

On the other hand, the above-mentioned pasty vinyl chloride resin composition is molded into a desired shape by molding using a conventionally known method such as spread molding, dipping molding, gravure molding, slush molding, or screen processing. Can do.

The shape of the molded body is not particularly limited, but, for example, rod-shaped, sheet-shaped, film-shaped, plate-shaped, cylindrical, circular, elliptical, etc., or special shapes such as toys, ornaments, such as stars, A polygonal shape is illustrated.

The molded body thus obtained includes pipes such as water pipes, joints for pipes, raindrops, etc., window frame siding, flat plate, corrugated sheet, automobile underbody coat, instrument panel, console, door seat. Automotive parts such as under carpets, trunk seats, door trims, various leathers, decorative sheets, agricultural films, food packaging films, electric wire coatings, various foam products, hoses, medical tubes, food tubes, refrigerators Gaskets, packing, wallpaper, flooring, boots, curtains, shoe soles, gloves, waterproofing boards, toys, decorative boards, blood bags, infusion bags, tarpaulins, mats, waterproof sheets, civil engineering sheets, roofing, tarpaulins It is useful for insulating sheets, industrial tapes, glass films, erasers, etc.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the symbol of the compound in an Example and a comparative example, and the measurement of each characteristic are as follows.

(1) Evaluation of physical properties of ester Esters obtained in the following production examples were analyzed by the following method.
Ester value: Measured according to JIS K-0070 (1992).
Acid value: measured in accordance with JIS K-0070 (1992).
Hue: Measured according to JIS K-4101 (Hazen) (1995).

(2) Production of vinyl chloride press sheet 100 parts by weight of vinyl chloride resin (straight, polymerization degree 1050, trade name “Zest1000Z”, manufactured by Shin Daiichi Vinyl Co., Ltd.), calcium stearate (Nacalai Tesque Co., Ltd.) as a stabilizer )) And zinc stearate (manufactured by Nacalai Tesque) are mixed in 0.3 and 0.2 parts by weight, stirred and mixed with a mortar mixer, and then added with 50 parts by weight of a plasticizer until uniform. Handling mixing was performed to obtain a vinyl chloride resin composition. This resin composition was melt-kneaded at 160 to 166 ° C. for 4 minutes using a 5 × 12 inch double roll to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168 ° C. for 10 minutes to produce a press sheet having a thickness of about 1 mm.

[Evaluation of physical properties of resin]
(3) Tensile test: Based on JIS K-6723 (1995), 100% modulus, breaking strength, and breaking elongation of the press sheet were measured. The smaller the value of 100% modulus, the better the flexibility.

(4) Cold resistance test: Measured according to JIS K-6773 (1999) using a Crushberg tester. The lower the softening temperature (° C), the better the cold resistance. The flexible temperature here refers to a temperature at a low temperature limit indicating a predetermined torsional rigidity (3.17 × 10 ³ kg / cm ² ) in the measurement.

(5) Heat resistance test: Based on evaluation of volatile loss and sheet coloring.
a) Volatilization loss: The weight change of the roll sheet after heating the roll sheet at 170 ° C. for 60 minutes and 120 minutes in a gear oven was measured, and the weight reduction rate (%) was calculated. The smaller the number, the higher the heat resistance.
Weight reduction rate (%) = ((weight before test−weight after test) / weight before test) × 100
b) Sheet coloring: The strength of the coloring degree after heating the roll sheet for 30 minutes at 170 ° C. for 60 minutes in a gear oven was visually evaluated in four stages.
A: Not colored, B: Slightly colored, B: Colored, X: Strongly colored.

[Production Example 1]
In a 2 L four-necked flask equipped with a thermometer, decanter, stirring blade and reflux condenser, trimellitic anhydride 96.0 g (0.5 mol), aliphatic saturated alcohol mixture (manufactured by Shell Chemicals, product name: 259 g (1.8 mol) of lineball 9), 10 g of xylene and 5.0 g of p-toluenesulfonic acid as an esterification catalyst were added, and the esterification reaction was carried out at a reaction temperature of 140 ° C. The reaction was carried out until the acid value of the reaction solution reached 0.5 mgKOH / g while refluxing xylene and alcohol under reduced pressure to remove the produced water out of the system. After completion of the reaction, unreacted alcohol was distilled off under reduced pressure, and then neutralized, washed with water and dehydrated according to a conventional method to obtain 245 g of the desired trimellitic acid triester (hereinafter referred to as “TL9TM”). It was.
The obtained TL9TM had an ester value of 285 mgKOH / g, an acid value of 0.01 mgKOH / g, and a hue of 15.

[Production Example 2]
Trimellitic acid tri-2-ethylhexyl (TOTM) in the same manner as in Production Example 1 except that 234 g of 2-ethylhexanol was added instead of 259 g of an aliphatic saturated alcohol mixture (manufactured by Shell Chemicals, product name: Lineball 9) 203.9 g was obtained.
The obtained TOTM had an ester value of 309 mgKOH / g, an acid value of 0.04 mgKOH / g, and a hue of 10.

[Production Example 3]
236 g of triisononyl trimellitic acid (TINTM) was obtained in the same manner as in Production Example 1 except that 259 g of isononyl alcohol was added instead of 259 g of an aliphatic saturated alcohol mixture (manufactured by Shell Chemicals, product name: Lineball 9).
The obtained TINTM had an ester value of 285 mgKOH / g, an acid value of 0.03 mgKOH / g, and a hue of 8.

[Production Example 4]
228 g of triisodecyl trimellitic acid (TIDTM) was obtained in the same manner as in Production Example 1 except that 285 g of isodecyl alcohol was added instead of 259 g of an aliphatic saturated alcohol mixture (manufactured by Shell Chemicals, product name: Lineball 9).
The obtained TIDTM had an ester value of 265 mgKOH / g, an acid value of 0.02 mgKOH / g, and a hue of 20.

[Example 1]
A vinyl chloride sheet was prepared using the trimellitic acid triester obtained in Production Example 1, and a tensile test, a cold resistance test, and a heat resistance test were measured. The obtained results are shown in Table 1.

[Comparative Example 1]
A vinyl chloride sheet was produced in the same manner as in Example 1 except that the trimellitic acid triester obtained in Production Example 2 was used instead of the trimellitic acid triester obtained in Production Example 1, and a tensile test, A cold resistance test and a heat resistance test were measured. The obtained results are shown in Table 1.

[Comparative Example 2]
A vinyl chloride sheet was produced in the same manner as in Example 1 except that the trimellitic acid triester obtained in Production Example 3 was used in place of the trimellitic acid triester obtained in Production Example 1, and a tensile test, A cold resistance test and a heat resistance test were measured. The obtained results are shown in Table 1.

[Comparative Example 3]
A vinyl chloride sheet was produced in the same manner as in Example 1 except that the trimellitic acid triester obtained in Production Example 4 was used instead of the trimellitic acid triester obtained in Production Example 1, and a tensile test, A cold resistance test and a heat resistance test were measured. The obtained results are shown in Table 1.

Trimellitic acid triester according to the present invention can be used as a plasticizer for vinyl chloride resin having excellent cold resistance and heat resistance and good flexibility, and a vinyl chloride resin composition containing the plasticizer The obtained molded product is very useful as a wire covering and automobile member that require high cold resistance, heat resistance and flexibility.

Claims (4)

Plastic for vinyl chloride resin containing trimellitic triester obtained by esterification of trimellitic acid or its anhydride and aliphatic saturated alcohol mixture mainly composed of aliphatic saturated alcohol having 9 carbon atoms An agent,
The aliphatic saturated alcohol mixture is a linear aliphatic saturated alcohol having 9 to 9 carbon atoms having a content of 60 to 95% by weight and a branched chain having 9 to 40% by weight in the alcohol mixture. A plasticizer for a vinyl chloride resin, which is an aliphatic saturated alcohol mixture containing an aliphatic saturated alcohol. The aliphatic saturated alcohol mixture contains 70 to 90% by weight of a linear aliphatic saturated alcohol having 9 to 9 carbon atoms and 10 to 30% by weight of a branched chain fatty acid having 9 carbon atoms. The plasticizer for a vinyl chloride resin according to claim 1, which is an aliphatic saturated alcohol mixture containing an aromatic saturated alcohol. Plastic for vinyl chloride resin containing trimellitic triester obtained by esterification of trimellitic acid or its anhydride and aliphatic saturated alcohol mixture mainly composed of aliphatic saturated alcohol having 9 carbon atoms An agent,
The aliphatic saturated alcohol mixture comprises (1) a step of producing a 9-carbon aldehyde by hydroformylation reaction of 1-octene, carbon monoxide and hydrogen, and (2) an alcohol obtained by hydrogenating a 9-carbon aldehyde. A plasticizer for a vinyl chloride resin, comprising an aliphatic saturated alcohol having a straight chain structure and a branched chain structure, which is produced by a production process including a step of reducing to a vinyl chloride resin. A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer for vinyl chloride resin according to any one of claims 1 to 3.