JP7131718B2 - Plasticizer for vinyl chloride resin, vinyl chloride resin composition, molded article and wire harness using the vinyl chloride resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a vinyl chloride resin plasticizer, a vinyl chloride resin composition, and a molded article and a wire harness using the vinyl chloride resin composition.

Vinyl chloride resin (PVC) is one of the representative plastics, and has physical properties such as being inexpensive and excellent in heat resistance, and therefore has a wide variety of uses. Since vinyl chloride resins are hard and brittle when used, they are usually softened by adding a plasticizer.
Higher alkyl esters of polybasic acids, such as phthalates, adipates, and trimellitates, are known plasticizers used in vinyl chloride resins. There were many cases where

As mentioned above, there are a wide variety of molded products that use vinyl chloride resin compositions with added plasticizers. A trimellitate ester plasticizer is often used as a plasticizer that can be expected to be compatible and has good heat resistance.
As for the trimellitate ester plasticizer, those capable of imparting properties other than heat resistance according to the use of the vinyl chloride resin composition have been developed. 1) has been proposed.

A vinyl chloride resin composition is also used as a wire coating material for a wire harness for a vehicle because the vinyl chloride resin is nonflammable. In the past, nonflammability and heat resistance were emphasized for wire harness coating materials. is now in demand. A trimellitate ester plasticizer corresponding to this movement has been proposed (Patent Document 2), but there is a problem that sufficient compatibility with vinyl chloride resin cannot be obtained.

JP 2016-169336 A WO2016/088841

The problem to be solved by the present invention is to provide a plasticizer that imparts excellent insulating properties to a vinyl chloride resin composition.

The inventors of the present invention conducted intensive studies to solve the above problems, and found that a trimellitate ester compound obtained using a specific raw material is a plasticizer that imparts excellent insulating properties to a vinyl chloride resin composition. The present invention was completed by discovering that

That is, the present invention provides a trimellitic acid ester plasticizer for vinyl chloride resins, which uses a saturated aliphatic alcohol and trimellitic acid as reaction raw materials, wherein the saturated aliphatic alcohol has 6 to 10 carbon atoms. containing a chain saturated fatty alcohol and a branched saturated fatty alcohol having 7 to 12 carbon atoms, wherein the linear saturated fatty alcohol having 6 to 10 carbon atoms and the branched saturated fatty alcohol having 7 to 12 carbon atoms A vinyl chloride resin plasticizer in which the ratio (mass ratio) is linear saturated aliphatic alcohol having 6 to 10 carbon atoms/branched saturated aliphatic alcohol having 7 to 12 carbon atoms = 3/97 to 49/51 It is a thing.

INDUSTRIAL APPLICABILITY The present invention can provide a plasticizer that imparts excellent insulating properties to a vinyl chloride resin composition.

An embodiment of the present invention will be described below. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention.

[Plasticizer for vinyl chloride resin]
The vinyl chloride resin plasticizer of the present invention is a trimellitic acid ester obtained by reacting a saturated aliphatic alcohol and trimellitic acid as raw materials, wherein the saturated aliphatic alcohol is a linear saturated fat having 6 to 10 carbon atoms. and a branched saturated aliphatic alcohol having 7 to 12 carbon atoms, the ratio of the linear saturated aliphatic alcohol having 6 to 10 carbon atoms and the branched saturated aliphatic alcohol having 7 to 12 carbon atoms ( The mass ratio) is linear saturated aliphatic alcohol having 6 to 10 carbon atoms/branched saturated aliphatic alcohol having 7 to 12 carbon atoms=3/97 to 49/51.
The trimellitate ester (hereinafter sometimes simply referred to as "the trimellitate ester of the invention"), which is the plasticizer for vinyl chloride resins of the present invention, can impart high electrical insulation to vinyl chloride resins.

The trimellitic acid ester of the present invention contains trimellitic acid and a saturated fatty alcohol as reaction raw materials. In the present invention, the term "reaction raw material" means a raw material that constitutes the trimellitate ester of the present invention. It means that it is not included.
In addition, even if an unsaturated aliphatic alcohol is used as a starting material and the carbon-carbon unsaturated bond of the unsaturated aliphatic alcohol is saturated by hydrogenation at any time, the resulting trimmerit Since the acid ester is substantially composed of saturated fatty alcohols, the reactants are saturated fatty alcohols.
The raw materials for reaction will be described below.

Trimellitic acid, which is a reaction raw material, also includes trimellitic anhydride.
The trimellitic acid may also be substituted, for example with an alkyl group having 1 to 6 carbon atoms.

Specific examples of trimellitic acid include 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, 3-methyl-1,2,4-benzene tricarboxylic acid, 3,5-dimethyl-1,2,4-benzenetricarboxylic acid, 3,5,6-trimethyl-1,2,4-benzenetricarboxylic acid, acid anhydrides thereof, and the like.
These trimellitic acids may be used singly or in combination of two or more. Moreover, these trimellitic acids can use a commercial item.

The saturated aliphatic alcohol as a reaction raw material may contain a linear saturated aliphatic alcohol having 6 to 10 carbon atoms and a branched saturated aliphatic alcohol having 7 to 12 carbon atoms, and other saturated aliphatic alcohols may be added. may contain.
Said saturated fatty alcohols preferably consist of linear saturated fatty alcohols having 6 to 10 carbon atoms and branched saturated fatty alcohols having 7 to 12 carbon atoms.

Here, "consisting of" means that the saturated aliphatic alcohol is a linear saturated aliphatic alcohol having 6 to 10 carbon atoms and a saturated aliphatic alcohol other than a branched saturated aliphatic alcohol having 7 to 12 carbon atoms. % or less.
When the saturated aliphatic alcohol consists of a linear saturated aliphatic alcohol having 6 to 10 carbon atoms and a branched saturated aliphatic alcohol having 7 to 12 carbon atoms, the linear saturated aliphatic alcohol having 6 to 10 carbon atoms and The content of the branched saturated fatty alcohol having 7 to 12 carbon atoms in the saturated fatty alcohol is, for example, 90% by mass or more, 95% by mass or more, or 99% by mass or more. Although the upper limit is not particularly limited, it is, for example, 100% by mass.

The linear saturated fatty alcohol is a saturated fatty alcohol having a straight carbon chain without branching. Moreover, the branched saturated fatty alcohol is a saturated fatty alcohol having a branched carbon chain.
Hereinafter, the linear saturated fatty alcohol may be simply referred to as "straight chain alcohol", and the branched saturated fatty alcohol may be simply referred to as "branched alcohol".

Among the saturated fatty alcohols, straight-chain alcohols having 6 to 10 carbon atoms are preferably straight-chain alcohols having 8 or 9 carbon atoms. Heat resistance can be improved by using a linear alcohol having 8 or 9 carbon atoms.

Specific examples of linear alcohols having 6 to 10 carbon atoms include 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol and 1-decanol, with 1-octanol and 1-nonanol being preferred.
These linear alcohols having 6 to 10 carbon atoms may be used singly or in combination of two or more. Commercially available straight-chain alcohols having 6 to 10 carbon atoms can also be used.

Among saturated fatty alcohols, branched alcohols having 7 to 12 carbon atoms are preferably branched alcohols having 8 to 10 carbon atoms.

The branched alcohol having 7 to 12 carbon atoms preferably includes a branched alcohol having 8 to 10 carbon atoms represented by the following formula (1).

（前記式（１）中、Ｒは炭素原子数１～６の直鎖アルキル基である。
ｐは０以上の整数であり、ｑは１以上の整数であり、ｐ、ｑ及びＲの炭素原子数の合計は７～９の範囲の整数である。）

(In formula (1) above, R is a linear alkyl group having 1 to 6 carbon atoms.
p is an integer of 0 or more, q is an integer of 1 or more, and the total number of carbon atoms of p, q and R is an integer in the range of 7-9. )

By using the branched alcohol having 8 to 10 carbon atoms represented by the formula (1), the trimellitate of the present invention can obtain high compatibility with the vinyl chloride resin.
In addition, when the saturated aliphatic alcohol is only a branched alcohol having a higher degree of branching than the branched alcohol having 8 to 10 carbon atoms represented by the above formula (1) (the alcohol has two or more branch points in the carbon chain), Sufficient compatibility with vinyl chloride resin cannot be obtained, and there is a possibility that the addition amount as a plasticizer cannot be increased.

The content of the branched alcohol having 8 to 10 carbon atoms represented by the formula (1) in the branched alcohol is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass. That's it. The upper limit of the content of the branched alcohol having 8 to 10 carbon atoms represented by the formula (1) is, for example, 100% by mass or less, preferably 90% by mass or less.

Specific examples of branched alcohols having 7 to 12 carbon atoms include branched alcohols having 8 carbon atoms such as 2-ethyl-1-hexanol and methyl-1-heptanol; 2-nonyl alcohol, 3-nonyl alcohol, 2,6 -dimethyl-4-heptanol, 2,4-dimethyl-1-heptanol, 2,2,5-trimethylhexanol, 3,5,5-trimethylhexanol, 2,3,4-trimethyl-2-hexanol, 4,6 -branched alcohols with 9 carbon atoms such as dimethyl-1heptanol, 2-methyl-2-octanol, 7-methyl-3-octanol; branched alcohols with 10 carbon atoms such as 3,5,5-trimethyl-1-heptanol Alcohol etc. are mentioned.
Among the above, mono-branched alcohols having 9 carbon atoms are preferred, and 2-propyl-1-hexanol, 2-ethyl-1-heptanol, 3-ethyl-1-heptanol, 2-methyl-1-octanol, 4-methyl -1-octanol, 5-methyl-1-octanol, 6-methyl-1-octanol and 7-methyl-1-octanol are more preferred.
These branched alcohols having 7 to 12 carbon atoms may be used singly or in combination of two or more.

Commercially available branched alcohols having 7 to 12 carbon atoms can be used, such as Oxocol 900 (manufactured by KH Neochem Co., Ltd.), EXXAL8, EXXAL9, EXXAL10, and EXXAL11 (manufactured by ExxonMobil Chemical Co., Ltd.). .
Commercially available branched higher alcohols may be mixtures containing two or more branched alcohols and small amounts of linear alcohols. For example, Oxocol 900 is mainly composed of monomethyloctyl alcohol and dimethylheptyl alcohol, which are branched alcohols having 9 carbon atoms, and other higher alcohols containing small amounts of normal nonyl alcohol, alcohol having 8 carbon atoms and alcohol having 10 carbon atoms. Alcohol.
When a commercially available branched higher alcohol is used as the branched alcohol, it should be used so as to satisfy the requirements for the mass ratio of the linear alcohol and the branched alcohol of the present invention.

Saturated fatty alcohols include straight chain alcohols of 6 to 10 carbon atoms and branched alcohols of 7 to 12 carbon atoms, preferably straight chain alcohols of 6 to 10 carbon atoms and branched alcohols of 7 to 12 carbon atoms. consists of alcohol.
By using a mixture of a straight-chain alcohol having 6 to 10 carbon atoms and a branched alcohol having 7 to 12 carbon atoms as the saturated aliphatic alcohol, it is possible to improve electrical insulation while ensuring heat resistance.

The ratio (mass ratio) of linear alcohol having 6 to 10 carbon atoms and branched alcohol having 7 to 12 carbon atoms in the saturated fatty alcohol is linear alcohol/branched alcohol = 3/97 to 49/51. , preferably linear alcohol/branched alcohol = 3/97 to 38/62.
Further, the ratio (molar ratio) of linear alcohol having 6 to 10 carbon atoms and branched alcohol having 7 to 12 carbon atoms in the saturated aliphatic alcohol is, for example, linear alcohol/branched alcohol = 3/97 to 56/ 44, preferably linear alcohol/branched alcohol = 3/97 to 48/52.

The trimellitic acid ester of the present invention can be produced, for example, by subjecting trimellitic acid and a saturated aliphatic alcohol to an esterification reaction in the presence of an esterification catalyst.
Examples of the esterification catalyst include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin-based catalysts such as dibutyltin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid.
The amount of the esterification catalyst to be used may be appropriately set, but it is usually used in the range of 0.001 to 0.1 parts by mass with respect to the total amount of 100 parts by mass of the reaction raw materials.
In addition, the esterification catalyst is not essential in the esterification reaction, and the esterification catalyst may not be used.

The reaction temperature and reaction time in the esterification reaction may be appropriately set, and for example, conditions of 2 to 25 hours at a temperature range of 100 to 250° C. can be employed.
Moreover, a solvent may or may not be used in the esterification reaction. When a solvent is used for the esterification reaction, the solvent is not particularly limited as long as it does not inhibit the esterification reaction, and aromatic solvents such as toluene and xylene and ether solvents such as tetrahydrofuran can be used. The amount of solvent to be used may be appropriately set.

The trimellitate ester of the present invention is, for example, a mixture of compounds represented by the following formula (A), wherein at least one of R ¹ , R ² and R ³ is a linear alkyl group having 6 to 10 carbon atoms. and at least one of R ¹ , R ² and R ³ is a branched alkyl group having 7 to 12 carbon atoms, including trimellitate esters. The ratio of the linear alkyl group having 6 to 10 carbon atoms and the branched alkyl group having 7 to 12 carbon atoms of R ¹ , R ² and R ³ in the entire mixture is the ratio of the linear alcohol and the branched alcohol in the reaction raw material. is obtained in such a way as to correspond to

（前記式（Ａ）中、
Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に水素原子、炭素原子数６～１０の直鎖アルキル基、又は炭素原子数７～１２の分岐アルキル基である。）

(In the above formula (A),
R ¹ , R ² and R ³ are each independently a hydrogen atom, a linear alkyl group having 6 to 10 carbon atoms, or a branched alkyl group having 7 to 12 carbon atoms. )

[Vinyl chloride resin composition]
The vinyl chloride resin composition of the present invention contains the vinyl chloride resin plasticizer and vinyl chloride resin of the present invention. In the present invention, vinyl chloride resins include vinyl chloride homopolymers, vinylidene chloride homopolymers, copolymers containing vinyl chloride as an essential component, copolymers containing vinylidene chloride as an essential component, and the like.
When the vinyl chloride resin is a copolymer containing vinyl chloride as an essential component or a copolymer containing vinylidene chloride as an essential component, examples of comonomers that can be copolymerized include ethylene, propylene, α- Olefins; conjugated dienes such as butadiene and isoprene; vinyl alcohol, styrene, acrylonitrile, vinyl acetate, vinyl propionate, fumaric acid, fumaric acid ester, maleic acid, maleic acid ester, maleic anhydride, acrylic acid, acrylic acid ester, Methacrylic acid, methacrylic acid esters, isoprenol and the like can be mentioned.

When the vinyl chloride resin is a copolymer containing vinyl chloride as an essential component or a copolymer containing vinylidene chloride as an essential component, the copolymerization format is not particularly limited, and may be block or random. good.

The degree of polymerization of the vinyl chloride resin is generally 300-5,000, preferably 400-3,500, more preferably 700-3,000. When the degree of polymerization of the vinyl chloride resin is in this range, it is possible to obtain a molded product with high heat resistance and to obtain a vinyl chloride resin composition having excellent workability.

Vinyl chloride resins can be produced by known methods, such as suspension polymerization in the presence of an oil-soluble polymerization catalyst and emulsion polymerization in an aqueous medium in the presence of a water-soluble polymerization catalyst.
A commercial item may be used for the vinyl chloride resin.

The content of the vinyl chloride resin plasticizer of the present invention in the vinyl chloride resin composition of the present invention is 10 to 100 parts by mass based on 100 parts by mass of the vinyl chloride resin from the viewpoint of compatibility with the vinyl chloride resin. It is preferably 30 to 100 parts by mass, more preferably 40 to 80 parts by mass, and particularly preferably 50 to 80 parts by mass.

The vinyl chloride resin composition of the present invention may contain the vinyl chloride resin and the plasticizer for the vinyl chloride resin of the present invention, and a plasticizer other than the plasticizer for the vinyl chloride resin of the present invention (other plasticizers) and other additives. It may contain agents and the like.

Examples of the other plasticizers include benzoic acid esters such as diethylene glycol dibenzoate; dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), and diisodecyl phthalate (DIDP). , diundecyl phthalate (DUP), ditridecyl phthalate (DTDP) and other phthalates; bis(2-ethylhexyl) terephthalate (DOTP) and other terephthalates; bis(2-ethylhexyl) isophthalate (DOIP) isophthalic acid esters such as; pyromellitic acid esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA) , di-2-ethylhexyl sebacate (DOS), diisononyl sebacate (DINS) and other aliphatic dibasic acid esters; tri-2-ethylhexyl phosphate (TOP), phosphate esters such as tricresyl phosphate (TCP) Epoxidized soybean oil, epoxidized linseed oil Epoxidized esters such as; cycloaliphatic dibasic acids such as hexahydrophthalic acid diisononyl ester; fatty acid glycol esters such as 1.4-butanediol dicaprate; acetyl tributyl citrate (ATBC); - chlorinated paraffins obtained by chlorinating paraffin; chlorinated fatty acid esters such as chlorinated stearate; and higher fatty acid esters such as butyl oleate.

When the other plasticizer is used in the vinyl chloride resin composition of the present invention, the content of the other plasticizer is, for example, 10 to 300 parts by mass with respect to 100 parts by mass of the vinyl chloride resin plasticizer of the present invention. and preferably 20 to 200 parts by mass.

Examples of other additives include flame retardants, stabilizers, stabilizing aids, colorants, processing aids, fillers, antioxidants (antiaging agents), ultraviolet absorbers, light stabilizers, lubricants, and electrification agents. Examples include inhibitors, cross-linking aids, and the like.

Examples of the flame retardant include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, zinc borate; cresyldiphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, trisdichloropropyl phosphate Phosphorus compounds such as phate; halogen compounds such as chlorinated paraffin, and the like are exemplified.
When the flame retardant is added to the vinyl chloride resin composition, the amount thereof is usually 0.1 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.

Examples of the stabilizer include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octylate, zinc laurate, and zinc ricinoleate. , zinc stearate and other metal soap compounds; dimethyltin bis-2-ethylhexyl thioglycolate, dibutyltin maleate, dibutyltin bisbutyl maleate, dibutyltin dilaurate and other organotin compounds; antimony mercaptide compounds; lanthanum oxide, water Examples include lanthanoid-containing compounds such as lanthanum oxide.
When the stabilizer is blended into the vinyl chloride resin composition, the blending amount is usually 0.1 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.

Examples of the stabilizing aid include phosphite compounds such as triphenylphosphite, monooctyldiphenylphosphite and tridecylphosphite; beta-diketone compounds such as acetylacetone and benzoylacetone; glycerin, sorbitol, pentaerythritol and polyethylene. polyol compounds such as glycol; perchlorate compounds such as barium perchlorate and sodium perchlorate; hydrotalcite compounds;
When the stabilizing aid is added to the vinyl chloride resin composition, the amount thereof is usually 0.1 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.

Examples of the coloring agent include carbon black, lead sulfide, white carbon, titanium white, lithopone, safflower, antimony sulfide, chrome yellow, chrome green, cobalt blue, and molybdenum orange.
When the coloring agent is blended into the vinyl chloride resin composition, the blending amount is usually 1 to 100 parts by mass per 100 parts by mass of the vinyl chloride resin.

Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearamide, ethylene bis stearamide, butyl stearate, and calcium stearate.
When the processing aid is blended into the vinyl chloride resin composition, the blending amount is usually 0.1 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.

Examples of the filler include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, and ferrite; fibers and powders such as glass, carbon, and metals; glass spheres, graphite, aluminum hydroxide, and barium sulfate. , magnesium oxide, magnesium carbonate, magnesium silicate, and calcium silicate.
When the filler is blended into the vinyl chloride resin composition, the blending amount is usually 1 to 100 parts by mass per 100 parts by mass of the vinyl chloride resin.

Examples of the antioxidant include 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol)propionate]methane, 2-hydroxy-4-methoxy Phenolic compounds such as benzophenone; Sulfur compounds such as alkyl disulfide, thiodipropionate, benzothiazole; -butylphenyl)phosphite; and organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate.
When the antioxidant is blended into the vinyl chloride resin composition, the blending amount is usually 0.2 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.

Examples of the ultraviolet absorber include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenones such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone; 5-methyl-1H-benzotriazole, 1-dioctylaminomethylbenzotriazole, and other benzotriazole compounds, as well as cyanoacrylate compounds.
When the ultraviolet absorber is blended into the vinyl chloride resin composition, the blending amount is usually 0.1 to 10 parts by mass per 100 parts by mass of the vinyl chloride resin.

As the light stabilizer, a hindered amine light stabilizer can be exemplified. Specifically, for example, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2 , 2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl )-4-hydroxyphenyl]methyl]butylmalonate, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) ester and 1,1-dimethylethyl hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidinol and ester mixtures of 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, a 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-1,6-hexa Polycondensate of methylenediamine 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 and the like are exemplified. .
When the light stabilizer is blended into the vinyl chloride resin composition, the blending amount is usually 0.1 to 10 parts by mass per 100 parts by mass of the vinyl chloride resin.

Examples of the lubricant 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 the lubricant is added to the vinyl chloride resin composition, the amount thereof is usually 0.1 to 10 parts by mass per 100 parts by mass of the vinyl chloride resin.

Examples of the antistatic agent include alkylsulfonate-type, alkylethercarboxylic acid-type, or dialkylsulfosuccinate-type anionic antistatic agents; nonionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, and diethanolamine derivatives; type, quaternary ammonium salts such as alkyldimethylbenzyl type, alkylpyridinium type organic acid salts or hydrochlorides; amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. .
When the antistatic agent is added to the vinyl chloride resin composition, the amount thereof is usually 0.1 to 10 parts by mass per 100 parts by mass of the vinyl chloride resin.

Examples of the cross-linking aid include polyfunctional monomers such as tetraethylene glycol dimethacrylate, divinylbenzene diallyl phthalate, triallyl isocyanurate, trimethylolpropane triarylate, tetramethylolmethane tetramethacrylate, and trimethoxyethoxyvinylsilane.
When the cross-linking aid is blended into the vinyl chloride resin composition, the blending amount is usually 0.5 to 30 parts by mass per 100 parts by mass of the vinyl chloride resin.

The vinyl chloride resin composition of the present invention can be produced by a known method.
For example, the vinyl chloride resin composition of the present invention can be obtained by mixing the vinyl chloride resin, the plasticizer for the vinyl chloride resin of the present invention, and optional components (the other plasticizer and the other additives) in a blender, planetary mixer, Banbury mixer, or the like. It can be prepared by mixing using a kneader.

A molded article can be obtained by molding the vinyl chloride resin composition of the present invention by a known molding method such as vacuum molding, compression molding, extrusion molding, calender molding, press molding, blow molding, and powder molding.

Molded articles obtained using the vinyl chloride resin composition of the present invention include, for example, insulating tapes, insulating sheets, wiring connectors, conductor covering materials, pipes such as water pipes, joints for pipes, and gutters such as rain gutters. , window frame siding, flat plate, corrugated sheet, automobile underbody coat, dashboard, instrument panel, console, door seat, under carpet, trunk seat, door trims, various leathers, decorative sheets, agriculture Films, food packaging films, foamed products, hoses, medical tubes, food tubes, refrigerator gaskets, packings, wallpapers, flooring materials, boots, curtains, shoe soles, gloves, waterstops, toys, decorative panels , blood bags, infusion bags, tarpaulins, mats, waterproof sheets, civil engineering sheets, roofing, waterproof sheets, industrial tapes, glass films, erasers, and the like.

Molded articles obtained from the vinyl chloride resin composition of the present invention can exhibit excellent electrical insulation due to the plasticizer for vinyl chloride resin of the present invention. It can be suitably used for the insulation coating layer of the higher harness provided.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. In the examples, "parts" and "%" are based on mass unless otherwise specified. Moreover, the acid value, hydroxyl value and viscosity were measured according to the following methods.

In the examples of the present application, the values of acid value, hydroxyl value and viscosity are values evaluated by the following methods.
<Method for measuring acid value>
It was measured by a method according to JIS K0070-1992.
<Method for measuring hydroxyl value>
It was measured by a method according to JIS K0070-1992.
<Method for measuring viscosity>
It was measured by a method according to JIS K6901-1986.

Example 1
(Preparation of trimellitate ester plasticizer)
211 g (1.10 mol) of trimellitic anhydride, 158 g (1.21 mol) of n-octanol, 349 g (2.42 mol, isononyl alcohol as the main component, manufactured by KH Neochem Co., Ltd.) of Oxocol 900, esterified 0.144 g of tetraisopropyl titanate as a catalyst was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser. The temperature is gradually raised to 230° C. while stirring under a nitrogen stream, and the heating is continued at 230° C. until the acid value of the reaction solution becomes 2 or less, the water to be purified is continuously removed, and the ester compound (1) is (acid value 0.03, hydroxyl value 0.00, viscosity 163 mPa·s) was obtained in an amount of 527 g.
The mass ratio of the linear alcohol having 6 to 10 carbon atoms and the branched alcohol having 7 to 12 carbon atoms in the alcohol used for the production of the ester compound was linear alcohol/branched alcohol=36:64.

Regarding the resulting ester compound (1), the mass ratio of the linear alcohol having 6 to 10 carbon atoms and the branched alcohol having 7 to 12 carbon atoms forming an ester with trimellitic acid is It was confirmed by gas chromatography (hereinafter abbreviated as GC), gas chromatograph mass spectrometry (hereinafter abbreviated as GCMS), and nuclear magnetic resonance (hereinafter abbreviated as NMR) that they corresponded to the ratio of alcohol and branched alcohol. Specifically, the obtained ester compound (1) was hydrolyzed, and GC measurement, GCMS measurement and NMR measurement were performed under the following conditions to determine the straight line having 6 to 10 carbon atoms forming an ester with trimellitic acid. The mass ratio of chain alcohols to branched alcohols with 7 to 12 carbon atoms was evaluated. As a result, it was confirmed that the mass ratio of the straight-chain alcohol and the branched alcohol forming an ester with trimellitic acid corresponded to the proportion of the straight-chain alcohol and the branched alcohol in the reaction raw materials.
[GC measurement conditions]
Measuring device: Gas chromatograph GC-2010 (manufactured by Shimadzu Corporation)
Detector: FID
Column: Capillary column ZB-5 (0.25 mm × 30 m, 0.25 μm)
Column temperature: 50°C → 300°C (heating rate 10°C/min) → (5min Hold)
Carrier gas: helium [GC-MS measurement conditions]
Measuring device: Gas chromatograph mass spectrometer GCMS-QP2010Plus (manufactured by Shimadzu Corporation)
Column: Capillary column ZB-5 (0.25 mm × 30 m, 0.25 μm)
Column temperature: 50°C → 300°C (10°C/min) → (5min Hold)
Carrier gas: helium [NMR measurement conditions]
Apparatus: ECA 500 manufactured by JEOL Ltd.
Measurement mode: Decoupling solvent with reverse gate: Deuterated chloroform Pulse angle: 30° pulse Sample concentration: 30 wt%
Cumulative count: 2000

The electrical resistance of the resulting ester compound (1) was evaluated according to JIS C2320 using a liquid sample electrode (SME-8330, manufactured by Hioki Electric Co., Ltd.).
As a result, the electric resistance of the ester compound (1) was 3.03×10 ¹² Ω·cm.

(Preparation of vinyl chloride resin composition)
Vinyl chloride resin (polymerization degree 1300, ZEST1300, manufactured by Shin Daiichi Vinyl Co., Ltd.) 100 parts by mass, plasticizer (ester compound (1)) 50 parts by mass, filler (Greg MP-677D (calcium / zinc-based composite stabilizer ) and Nisshin Trading Co., Ltd.) were mixed to obtain a vinyl chloride resin composition (1).
The following evaluations were performed using the vinyl chloride resin composition (1) produced.

(Evaluation of plasticizing performance of plasticizer)
After kneading the vinyl chloride resin composition (1) prepared with two rolls heated to 170° C. for 10 minutes, a molded product having a thickness of 1.0 mm is obtained from the vinyl chloride resin composition (1) after kneading. Molding was performed using a mold (1.0 mm thick mold) and a press heated to 170° C. to produce a sheet with a thickness of 1.0 mm.

The resulting sheet was evaluated for 100% modulus (tensile stress at 100% elongation) and elongation at break according to JISK6251. Specifically, using a sheet with a thickness of 1.0 mm, a tensile test was performed under the following conditions to evaluate 100% modulus and elongation at break. Table 1 shows the results.
The elongation at break is the value obtained by subtracting the initial distance between chucks of 20 mm from the distance between chucks when a 1.0 mm thick sheet is tensile-broken, divided by the distance between chucks of 20 mm, and expressed as a percentage.
Measuring equipment: Tensilon universal material testing machine (manufactured by Orientec Co., Ltd.)
Sample shape: Dumbbell shape No. 3 Distance between chucks: 20mm
Tensile speed: 200 mm/min Measurement atmosphere: temperature 23 degrees, humidity 50%

A lower 100% modulus value indicates a higher effect of plasticizing the vinyl chloride resin. Also, the higher the elongation at break, the higher the effect of plasticizing the vinyl chloride resin.

(Evaluation of heat resistance performance of molded product)
After kneading the vinyl chloride resin composition (1) prepared with two rolls heated to 170° C. for 10 minutes, a molded product having a thickness of 1.0 mm is obtained from the vinyl chloride resin composition (1) after kneading. Molding was performed using a mold (1.0 mm thick mold) and a press heated to 170° C. to produce a sheet with a thickness of 1.0 mm. A dumbbell-shaped No. 3 dumbbell test piece was produced from the produced sheet having a thickness of 1.0 mm according to JISK6251.

A heat aging test at 158° C. for 120 hours was performed on the prepared dumbbell test piece according to JISK6257. The weight of the dumbbell test piece was measured before and after the heat aging test, and the weight loss rate ((mass before heat aging test−mass after heat aging test)/mass before heat aging test) was calculated. Table 1 shows the results.
The smaller the weight loss rate, the more the ester compound (1) remains in the molded article even after the heat aging test, and the heat resistance effect of the ester compound (1) can be expected.

The prepared dumbbell test piece was subjected to a tensile test before and after the heat aging test according to the conditions of JISK6251, and the elongation rate of the dumbbell test piece before and after the heat aging test was measured. Elongation rate/elongation rate before heat aging test) was calculated. Table 1 shows the results.
The higher the elongation retention rate, the more the plasticizing effect can be maintained even after the heat aging test, and it can be said that the vinyl chloride resin composition has excellent heat resistance.

The 100% modulus of the dumbbell test piece after the heat aging test was evaluated in the same manner as the evaluation of the plasticizing effect. Table 1 shows the results.

(Evaluation of insulation performance of molded product)
After kneading the vinyl chloride resin composition (1) prepared with two rolls heated to 170° C. for 10 minutes, a molded product having a thickness of 1.0 mm is obtained from the vinyl chloride resin composition (1) after kneading. Molding was performed using a mold (1.0 mm thick mold) and a press heated to 170° C. to produce a sheet with a thickness of 1.0 mm.
The volume resistivity at 30° C. of the produced sheet having a thickness of 1.0 mm was evaluated according to JISK6723. Table 1 shows the results.

Example 2
Trimellitic anhydride 211 g (1.10 mol), n-octanol 222 g (1.71 mol), Oxocol 900 277 g (1.92 mol, isononyl alcohol as the main component, manufactured by KH Neochem Co., Ltd.), esterification catalyst 0.142 g of tetraisopropyl titanate was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser. The temperature is gradually raised to 230° C. while stirring under a nitrogen stream, and the heating is continued at 230° C. until the acid value of the reaction solution becomes 2 or less, the water to be purified is continuously removed, and the ester compound (2) is (acid value 0.03, hydroxyl value 0.20, viscosity 142 mPa·s) was obtained in an amount of 529 g.
The mass ratio of the linear alcohol having 6 to 10 carbon atoms and the branched alcohol having 7 to 12 carbon atoms in the alcohol used for the production of the ester compound is linear alcohol/branched alcohol = 48:52. . Regarding the resulting ester compound (2), the mass ratio of the straight-chain alcohol and the branched alcohol forming an ester with trimellitic acid was evaluated in the same manner as in Example 1. I have verified that the proportions are correct.

The electrical resistance of the resulting ester compound (2) was evaluated according to JIS C2320 using a liquid sample electrode (SME-8330, manufactured by Hioki Electric Co., Ltd.).
As a result, the electric resistance of the ester compound (2) was 2.83×10 ¹² Ω·cm.

The plasticizing effect, the heat resistance of the molded article, and the insulation properties of the molded article were evaluated in the same manner as in Example 1, except that the ester compound (2) was used instead of the ester compound (1) as the plasticizer. . Table 1 shows the results.

Example 3
211 g (1.10 mol) of trimellitic anhydride, 191 g (1.21 mol) of 2-propylheptanol, 349 g of Oxocol 900 (2.42 mol, isononyl alcohol as main component, manufactured by KH Neochem Co., Ltd.), ester 0.144 g of tetraisopropyl titanate as a conversion catalyst was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser. The temperature was gradually raised to 230° C. while stirring under a nitrogen stream, and the heating was continued at 230° C. until the acid value of the reaction solution became 2 or less. (acid value 0.02, hydroxyl value 0.00, viscosity 234 mPa·s) was obtained in an amount of 571 g.
The mass ratio of the linear alcohol having 6 to 10 carbon atoms and the branched alcohol having 7 to 12 carbon atoms in the alcohol used for the production of the ester compound is linear alcohol/branched alcohol=5:95. . Regarding the resulting ester compound (3), the mass ratio of the straight-chain alcohol and the branched alcohol forming an ester with trimellitic acid was evaluated in the same manner as in Example 1. I have verified that the proportions are correct.

The electrical resistance of the resulting ester compound (3) was evaluated according to JIS C2320 using a liquid sample electrode (SME-8330, manufactured by Hioki Electric Co., Ltd.).
As a result, the electric resistance of the ester compound (3) was 11.9×10 ¹² Ω·cm.

The plasticizing effect, the heat resistance of the molded article, and the insulation properties of the molded article were evaluated in the same manner as in Example 1, except that the ester compound (3) was used instead of the ester compound (1) as the plasticizer. . Table 1 shows the results.

Example 4
672 g (3.50 mol) of trimellitic anhydride, 16.7 g (0.116 mol) of n-nonanol, 501 g (3.85 mol) of n-octanol, 13.5 g (0.116 mol) of n-heptanol, and oxocol 900 1110 g (7.70 mol, isononyl alcohol as the main component, manufactured by KH Neochem Co., Ltd.), 15.1 g of an aliphatic saturated alcohol mixture (manufactured by ExxonMobil, product name: EXXAL8), 0.1 g of tetraisopropyl titanate as an esterification catalyst. 458 g was charged to a 1 liter four-necked flask equipped with a thermometer, stirrer and reflux condenser. The temperature was raised stepwise to 230°C while stirring under a nitrogen stream, and heating was continued at 230°C until the acid value of the reaction solution became 2 or less, and the water to be purified was continuously removed to obtain the ester compound (4). (acid value 0.02, hydroxyl value 0.02, viscosity 162 mPa·s) was obtained in an amount of 1858 g.
The mass ratio of the linear alcohol having 6 to 10 carbon atoms and the branched alcohol having 7 to 12 carbon atoms in the alcohol used for the production of the ester compound is linear alcohol/branched alcohol=37:63. . Regarding the resulting ester compound (4), the mass ratio of the straight-chain alcohol and the branched alcohol forming an ester with trimellitic acid was evaluated in the same manner as in Example 1. I have verified that the proportions are correct.

The electrical resistance of the resulting ester compound (4) was evaluated according to JIS C2320 using a liquid sample electrode (SME-8330, manufactured by Hioki Electric Co., Ltd.).
As a result, the electric resistance of the ester compound (4) was 2.97×10 ¹² Ω·cm.

The plasticizing effect, the heat resistance of the molded article, and the insulation properties of the molded article were evaluated in the same manner as in Example 1, except that the ester compound (4) was used instead of the ester compound (1) as the plasticizer. . Table 1 shows the results.

Example 5
403 g (2.10 mol) of trimellitic anhydride, 365 g (2.31 mol) of 2-propylheptanol, 666 g of Oxocol 900 (4.62 mol, isononyl alcohol as the main component, manufactured by KH Neochem Co., Ltd.), 2 10.0 g (0.0693 mol) of ethylhexanol and 0.287 g of tetraisopropyl titanate as an esterification catalyst were placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser. The temperature was gradually raised to 230°C while stirring under a nitrogen stream, and the heating was continued at 230°C until the acid value of the reaction solution became 2 or less, and the water to be purified was continuously removed to obtain the ester compound (5). (acid value 0.01, hydroxyl value 0.30, viscosity 227 mPa·s) was obtained in an amount of 1121 g.
The mass ratio of the linear alcohol having 6 to 10 carbon atoms and the branched alcohol having 7 to 12 carbon atoms in the alcohol used for the production of the ester compound is linear alcohol/branched alcohol=4:96. . Regarding the resulting ester compound (5), the mass ratio of the straight-chain alcohol and the branched alcohol forming an ester with trimellitic acid was evaluated in the same manner as in Example 1. I have verified that the proportions are correct.

The electrical resistance of the resulting ester compound (5) was evaluated according to JIS C2320 using a liquid sample electrode (SME-8330, manufactured by Hioki Electric Co., Ltd.).
As a result, the electric resistance of the ester compound (5) was 11.7×10 ¹² Ω·cm.

The plasticizing effect, the heat resistance of the molded article, and the insulation properties of the molded article were evaluated in the same manner as in Example 1, except that the ester compound (5) was used instead of the ester compound (1) as the plasticizer. . Table 1 shows the results.

Example 6
211 g (1.10 mol) of trimellitic anhydride, 523 g (3.63 mol, isononyl alcohol as the main component, manufactured by KH Neochem Co., Ltd.) of Oxocol 900, 0.147 g of tetraisopropyl titanate as an esterification catalyst, and a thermometer. , a stirrer and a reflux condenser. The temperature was gradually raised to 230° C. while stirring under a nitrogen stream, and the heating was continued at 230° C. until the acid value of the reaction solution became 2 or less. (acid value 0.02, hydroxyl value 0.30, viscosity 215 mPa·s) was obtained in an amount of 575 g.
The mass ratio of the linear alcohol having 6 to 10 carbon atoms and the branched alcohol having 7 to 12 carbon atoms in the alcohol used for the production of the ester compound is linear alcohol/branched alcohol=7:93. . Regarding the resulting ester compound (6), the mass ratio of the straight-chain alcohol and the branched alcohol forming an ester with trimellitic acid was evaluated in the same manner as in Example 1. I have verified that the proportions are correct.

The electrical resistance of the resulting ester compound (6) was evaluated according to JIS C2320 using a liquid sample electrode (SME-8330, manufactured by Hioki Electric Co., Ltd.).
As a result, the electric resistance of the ester compound (6) was 8.20×10 ¹² Ω·cm.

Comparative example 1
211 g (1.10 mol) of trimellitic anhydride, 473 g (3.30 mol) of n-octanol, 0.137 g of tetraisopropyl titanate as an esterification catalyst, and an internal volume of 1 liter equipped with a thermometer, a stirrer and a reflux condenser. was charged in a four-necked flask. The temperature is gradually raised to 230° C. while stirring under a nitrogen stream, and the heating is continued at 230° C. until the acid value of the reaction solution becomes 2 or less, the water to be purified is continuously removed, and the ester compound (1′ ) (oxidation 0.06, hydroxyl value 0.10, viscosity 90 mPa·s (25° C.)) was obtained in an amount of 511 g.

The electrical resistance of the resulting ester compound (1′) was evaluated according to JIS C2320 using a liquid sample electrode (SME-8330, manufactured by Hioki Electric Co., Ltd.).
As a result, the electric resistance of the ester compound (1′) was 0.91×10 ¹² Ω·cm.

In the same manner as in Example 1, except that the ester compound (1′) was used instead of the ester compound (1) as the plasticizer, the plasticizing effect, the heat resistance of the molded product, and the insulation properties of the molded product were evaluated. did. Table 1 shows the results.

Comparative example 2
Trimellitic anhydride 211 g (1.10 mol), n-octanol 315 g (2.42 mol), Oxocol 900 174 g (1.21 mol, isononyl alcohol as the main component, KH Neochem Co., Ltd.), esterification catalyst 0.140 g of tetraisopropyl titanate was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser. The temperature is gradually raised to 230° C. while stirring under a nitrogen stream, and the heating is continued at 230° C. until the acid value of the reaction solution becomes 2 or less, the water to be purified is continuously removed, and the ester compound (2′ ) (acid value 0.03, hydroxyl value 0.10, viscosity 123 mPa·s) was obtained in an amount of 520 g.
The mass ratio of the linear alcohol having 6 to 10 carbon atoms and the branched alcohol having 7 to 12 carbon atoms in the alcohol used for the production of the ester compound is linear alcohol/branched alcohol = 67:33. .

The electrical resistance of the resulting ester compound (2′) was evaluated in accordance with JIS C2320 using a liquid sample electrode (SME-8330, manufactured by Hioki Electric Co., Ltd.).
As a result, the electric resistance of the ester compound (2') was 2.71×10 ¹² Ω·cm.

In the same manner as in Example 1, except that the ester compound (2′) was used instead of the ester compound (1) as the plasticizer, the plasticizing effect, the heat resistance of the molded product, and the insulation properties of the molded product were evaluated. did. Table 1 shows the results.

Claims (7)

A plasticizer for a vinyl chloride resin, which is a trimellitate ester in which a saturated aliphatic alcohol and trimellitic acid are reacted as raw materials,
The saturated fatty alcohol is a linear saturated fatty alcohol having 6 to 10 carbon atoms, 2-propyl-1-hexanol, 2-ethyl-1-heptanol, 3-ethyl-1-heptanol, 2-methyl- one or more branched saturated aliphatics selected from the group consisting of 1-octanol, 4-methyl-1-octanol, 5-methyl-1-octanol, 6-methyl-1-octanol and 7-methyl-1-octanol including alcohol ;
The ratio (mass ratio) of the linear saturated fatty alcohol having 6 to 10 carbon atoms and the branched saturated fatty alcohol is: linear saturated fatty alcohol having 6 to 10 carbon atoms/branched saturated fatty alcohol = 3 /97 to 38/62 plasticizer for vinyl chloride resin. 2. The vinyl chloride resin plasticizer according to claim 1 , wherein the linear saturated aliphatic alcohol having 6 to 10 carbon atoms is a linear saturated aliphatic alcohol having 8 or 9 carbon atoms. 3. The straight-chain saturated fatty alcohol of claim 1 or 2, wherein the straight-chain saturated fatty alcohol having 6 to 10 carbon atoms is one or more straight-chain saturated fatty alcohols selected from the group consisting of 1-octanol and 1-nonanol. Plasticizer for vinyl chloride resin. A vinyl chloride resin composition comprising the plasticizer for vinyl chloride resin according to any one of claims 1 to 3 and a vinyl chloride resin. 5. The vinyl chloride resin composition according to claim 4 , wherein the content of said plasticizer for vinyl chloride resin is 10 to 100 parts by mass with respect to 100 parts by mass of said vinyl chloride resin. A molded article of the vinyl chloride resin composition according to claim 4 or 5 . A wire harness comprising a conductor and an insulating coating layer covering the conductor,
A wire harness in which the insulating coating layer comprises the vinyl chloride resin composition according to claim 4 or 5 .