JP2017082108A - Plasticizer for vinyl chloride-based resin containing 4-cyclohexane-1,2-dicarboxylic acid diester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasticizer for vinyl chloride-based resin good in flexibility and excellent in heat resistance and cold resistance, especially a plasticizer for vinyl chloride-based resin having largely improved heat resistance and suitable for a vinyl chloride-based resin composition requiring excellent heat resistance.SOLUTION: Heat resistance of a vinyl chloride-based resin composition can be largely improved by using 4-cyclohexene-1,2-dicarboxylic acid diester having a specific structure as a plasticizer for vinyl chloride-based resin.SELECTED DRAWING: None

Description

  The present invention relates to a novel plasticizer for vinyl chloride resin and a vinyl chloride resin composition containing the same, and more specifically, includes a novel 4-cyclohexene-1,2-dicarboxylic acid diester excellent in heat resistance. The present invention relates to a plasticizer for vinyl chloride resin.

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

  Functions required for the plasticizer used in such a vinyl chloride resin composition include various performances such as flexibility, cold resistance, heat resistance, and electrical characteristics when the composition is used as a raw material. It is in the place which gives or exhibits. As a plasticizer for such a vinyl chloride resin composition, for example, phthalate ester plasticizers for vinyl chloride represented by di-2-ethylhexyl phthalate (DOP) and diisononyl phthalate (DINP) are widely used. Has been used.

  However, in recent years, testicular toxicity has been observed when DOP is administered to rodents in large quantities, while the safety of chemicals has been highlighted. In accordance with the precautionary principle, infants are mainly used in Japan, Europe and the United States. The use of phthalate ester compounds such as DOP is restricted as a protection target, and non-phthalate ester plasticizers are also desired in the market in the plasticizer field.

  To date, as non-phthalate ester plasticizers, tributyl acetyl citrate (hereinafter referred to as “ATBC”), di-2-ethylhexyl adipate (hereinafter referred to as “DOA”), tri-2-ethyl trimellitic acid Although plasticizers such as hexyl (hereinafter referred to as “TOTM”) have been developed (Patent Documents 1 to 3), among these plasticizers, the above ATBC and DOA are compared with phthalate ester plasticizers. Therefore, there is a problem that heat resistance is largely insufficient. In addition, TOTM has a heat resistance equivalent to or higher than that of phthalate esters, and is expected to be a good heat-resistant plasticizer that can replace phthalate ester plasticizers. Compared with, the flexibility was insufficient, and there were restrictions on usage. Therefore, the actual situation is that the phthalate plasticizer has not yet been completely replaced by the non-phthalate plasticizer.

  Under these circumstances, in recent years, alicyclic dicarboxylic acid diester plasticizers have softness, heat resistance (volatility resistance) and cold resistance similar to phthalate ester plasticizers, and well-balanced non-phthalates. Attention has been focused on acid ester plasticizers. For example, alicyclic dicarboxylic acid diester plasticizers such as diisononyl 1,2-cyclohexanedicarboxylate (hereinafter referred to as “DINCH”) have begun to be used. (Patent Document 4).

In addition, cyclohexene dicarboxylic acid diester plasticizer, which is the same alicyclic dicarboxylic acid diester plasticizer, has characteristics not found in other ester plasticizers such as low viscosity,
It is attracting attention for various applications (Patent Document 5).

  On the other hand, the demand for cold resistance and heat resistance has become increasingly severe in any application, not limited to applications in recent years, and the above-mentioned alicyclic dicarboxylic acid diester plasticizers cannot be handled by conventional products. Therefore, the development of an alicyclic dicarboxylic acid diester plasticizer that satisfies the above requirements, that is, improved cold resistance and heat resistance has been awaited.

JP 2000-226482 A JP 2002-194159 A JP2013-147520A JP-T-2001-526252 JP 2004-002695 A

  An object of the present invention is to solve the above-mentioned problems, that is, a plasticizer for vinyl chloride resin based on 4-cyclohexene-1,2-dicarboxylic acid diester, which is excellent in cold resistance and heat resistance and has good flexibility, and The object is to provide a vinyl chloride resin composition containing the plasticizer.

  In the previous invention (Japanese Patent Application No. 2014-148463), the inventors of the present invention are saturated aliphatic compounds mainly composed of 4-cyclohexene-1,2-dicarboxylic acid or an anhydride thereof and a saturated aliphatic alcohol having 9 carbon atoms. The plasticizer for vinyl chloride resin containing 4-cyclohexene-1,2-dicarboxylic acid diester obtained by esterification reaction with a mixture of alcohol is the original plasticizer performance, that is, plasticization performance and flexibility However, as described above, there has been a need for further improvement in heat resistance in some applications, as the trend toward resource conservation has accelerated. It was.

  Therefore, in view of the present situation, the present inventors have conducted intensive studies to solve the above problems, and as a result, 4-cyclohexene-1,2-dicarboxylic acid diester having a specific structure is related to the previous invention. The inventors have found that further improvement in heat resistance is possible without impairing the performance and cold resistance of the cyclohexene-1,2-dicarboxylic acid diester as a plasticizer, and have 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] Consisting of 4-cyclohexene-1,2-dicarboxylic acid diester represented by the following general formula (1), R ¹ and R ² are mainly composed of an alkyl group having 9 to 11 carbon atoms, and having 9 carbon atoms. The ratio of alkyl group / alkyl group having 10 carbon atoms / alkyl group having 11 carbon atoms (molar ratio) is in the range of 8-28 / 32-52 / 28-48, and the alkyl group constituting R ¹ and R ² A plasticizer for vinyl chloride resin, wherein the ratio (molar ratio) of linear alkyl groups to the total amount of is 50 to 99%.

(In the formula, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group.)

[Claim 2] The plasticizer for a vinyl chloride resin according to [Claim 1], wherein the ratio of the alkyl group is in the range of 10 to 26/34 to 50/30 to 46.

[Claim 3] The plasticizer for a vinyl chloride resin according to [Claim 2], wherein the ratio of the alkyl group is in the range of 12 to 24/36 to 48/32 to 44.

[Claim 4] The plasticizer for a vinyl chloride resin according to any one of [Claim 1] to [Claim 3], wherein the ratio of the linear alkyl group in the alkyl group is 55 to 95%.

CLAIM | ITEM 5 The plasticizer for vinyl chloride-type resins as described in [Claim 4] whose ratio of the linear alkyl group in an alkyl group is 60 to 95%.

[Item 6] The plasticizer for a vinyl chloride resin according to [Item 5], wherein the ratio of the linear alkyl group in the alkyl group is 70 to 95%.

[Item 7] A process for producing 4-cyclohexene-1,2-dicarboxylic acid diester for use in the plasticizer for vinyl chloride resins according to any one of [Item 1] to [Item 6], -Cyclohexene-1,2-dicarboxylic acid or an anhydride thereof and a saturated aliphatic alcohol having 9 to 11 carbon atoms as main components, and the ratio (molar ratio) of each alcohol having 9, 10 and 11 carbon atoms is 10 to 10. A mixture of saturated aliphatic alcohols in the range of 25/35 to 50/30 to 45 and having a ratio (molar ratio) of linear saturated aliphatic alcohols in the saturated aliphatic alcohols of 50 to 99% And a method for producing 4-cyclohexene-1,2-dicarboxylic acid diester.

[Item 8] A step in which the mixture of saturated aliphatic alcohols (1) produces an aldehyde having 9 to 11 carbon atoms by hydroformylation reaction of 1-octene, 1-nonene, 1-decene, carbon monoxide and hydrogen. And (2) The production method according to [7], which is obtained by a method comprising a step of hydrogenating an aldehyde having 9 to 11 carbon atoms to reduce it to an alcohol.

[Item 9] 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 6].

[Item 10] A vinyl chloride resin molded product, which is a molded product of the vinyl chloride resin composition according to [Item 9].

  The plasticizer for vinyl chloride resin according to the present invention can greatly improve heat resistance, that is, volatility while maintaining good plasticizing performance, flexibility, and excellent cold resistance. As a plasticizer that can meet the heat resistance requirement, it can be used in various applications. Moreover, the vinyl chloride-type resin composition which can respond to the request | requirements, such as resource saving in recent years, can be obtained by including the plasticizer for vinyl chloride-type resins.

<Plasticizer for vinyl chloride resin>
The plasticizer for vinyl chloride resin of the present invention is characterized by comprising 4-cyclohexene-1,2-dicarboxylic acid diester having a specific structure represented by the following general formula (1).

In the formula, R ¹ and R ² are the same or different and represent a linear or branched alkyl group, mainly composed of an alkyl group having 9 to 11 carbon atoms, and an alkyl group / carbon having 9 carbon atoms. The ratio (molar ratio) of several 10 alkyl groups to 11 carbon atoms is 8 to 28/32 to 52/28 to 48, preferably 10 to 26/34 to 50/30 to 46, more preferably 12 to The ratio (molar ratio) of the linear alkyl group to the total amount of the alkyl groups represented by R ¹ and R ² is in the range of 24/36 to 48/32 to 44, preferably 50 to 99%, preferably 55 to 95%, more preferably 60 to 95%, particularly preferably 70 to 95%. Naturally, the sum of the numerical values of the ratios of the respective alkyl groups is 100. Satisfying such a ratio means that the plasticizer for vinyl chloride resin of the present invention comprises a mixture of 4-cyclohexene-1,2-dicarboxylic acid diester represented by the general formula (1), and The ratio is defined assuming the total amount of alkyl groups in the entire mixture. The alkyl group represented by R ¹ and R ² be selected from the range of 7 to 13 carbon atoms from the viewpoint of the effect of the present invention.

  The 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter referred to as “the present ester”) according to the present invention is not particularly limited by its production method as long as it satisfies the performance as a plasticizer. However, it can be 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, without a catalyst or in the presence of a catalyst.

[Alcohol component]
The alcohol component used in the esterification reaction is mainly composed of a saturated aliphatic alcohol having 9 to 11 carbon atoms, and the ratio of the alkyl group having 9 carbon atoms / the alkyl group having 10 carbon atoms / the alkyl group having 11 carbon atoms (molar ratio). ) Is in the range of 8-28 / 32-52 / 28-48, preferably 10-26 / 34-50 / 30-46, more preferably 12-24 / 36-48 / 32-44 It is a mixture of alcohol. The term “mainly” means that the ratio (molar ratio) of the aliphatic saturated alcohol having 9 to 11 carbon atoms in the saturated aliphatic alcohol is 90% or more, preferably 95% or more. The saturated aliphatic alcohol is a raw material alcohol that becomes an alkyl group constituting the 4-cyclohexene-1,2-dicarboxylic acid diester represented by the general formula (1), that is, the above description is synonymous with the description of the alkyl group. It becomes.

  The mixture of the saturated aliphatic alcohols has a linear saturated aliphatic alcohol ratio (linear ratio, molar ratio) in the saturated aliphatic alcohol of 50 to 99%, preferably 55 to 95%. More preferably, it is 60 to 95%, particularly preferably 70 to 95%.

  As the details of the embodiment of the mixture of saturated fatty alcohols used in the present invention, the mixture of saturated aliphatic alcohols is mainly a mixture of saturated aliphatic alcohols having 9 to 11 carbon atoms, and further has 9, 10, 11 carbon atoms. The ratio (molar ratio) occupied by each alcohol of 8-28 / 32-52 / 28-48, preferably 10-26 / 34-50 / 30-46, more preferably 12-24 / 36-48 / 32 The ratio (molar ratio) of the linear saturated aliphatic alcohol is 50 to 99%, preferably 55 to 95%, more preferably 60 to 95%, and particularly preferably 70 to 44. A mode of 95% is recommended.

  As a requirement that contributes to greatly improving the heat resistance, which is the object of the present invention, while maintaining excellent flexibility and cold resistance effects, a linear saturated aliphatic alcohol occupying in a mixture of saturated aliphatic alcohols It is important that the ratio of at least 50% or more and the ratio (molar ratio) of each alcohol having 9, 10, and 11 carbon atoms to be in the range of 8 to 28/32 to 52/28 to 48 .

  It is mainly composed of a saturated aliphatic alcohol having 9 to 11 carbon atoms and used in the present invention, and the ratio (molar ratio) of each alcohol having 9, 10, and 11 carbon atoms is in the range of 8 to 28/32 to 52/28 to 48. And a mixture of saturated aliphatic alcohols in which the ratio (molar ratio) of the linear saturated aliphatic alcohol is 50 to 99% is (1) 1-octene, 1-nonene, A step of producing an aldehyde having 9 to 11 carbon atoms by hydroformylation reaction of 1-decene, carbon monoxide and hydrogen, and (2) a step of hydrogenating the aldehyde having 9 to 11 carbon atoms and reducing it to an alcohol. The saturated aliphatic alcohol according to the present invention can be produced by the production method, and the saturated aliphatic alcohol obtained by the production method is used as it is or contained. It can be a mixture of that.

  The hydroformylation reaction in the step (1) is, for example, having 9 to 11 carbon atoms by reacting 1-octene, 1-nonene, 1-decene, carbon monoxide and hydrogen in the presence of a cobalt catalyst or a rhodium catalyst. Aldehydes can be produced.

  The hydrogenation in the step (2) can be reduced to an alcohol by hydrogenating an aldehyde having 9 to 11 carbon atoms under hydrogen pressure in the presence of a noble metal catalyst such as a nickel catalyst or a palladium catalyst. . Specific examples of commercially available products include Neodol 911 manufactured by Shell Chemicals.

[Esterification reaction]
The esterification reaction according to the present invention means an esterification reaction between the alcohol component and the acid component 4-cyclohexene-1,2-dicarboxylic acid or an anhydride thereof, and when performing the esterification reaction, The alcohol component is, for example, preferably 2.00 mol to 5.00 mol, more preferably 2.01 mol to 3.00 mol, per mol of 4-cyclohexene-1,2-dicarboxylic acid or its anhydride. In particular, it is recommended to use 2.02 mol to 2.50 mol.

  When a catalyst is used for the esterification reaction, examples of the catalyst include mineral acids, organic acids, Lewis acids and the like. 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, A titanium derivative, a lead derivative, a zinc derivative, etc. are illustrated and it is possible to use these 1 type or 2 types or more together.

  Among them, p-toluenesulfonic acid, tetraalkyl titanate having 3 to 8 carbon atoms, titanium oxide, titanium hydroxide, fatty acid tin 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.

  4-cyclohexene-1,2-dicarboxylic acid or its anhydride, which is the acid component of the raw material of this ester, is not particularly limited, and is produced by a known method, commercially available, available as a reagent, etc. Can be used. For example, Rikasit TH (trade name, Shin Nippon Rika Co., Ltd.) is exemplified as a commercial product. 4-Cyclohexene-1,2-dicarboxylic acid anhydride is usually obtained by Diels-Alder reaction of maleic anhydride and 1,3-butadiene. From the viewpoint of the esterification reaction, it is recommended to use 4-cyclohexene-1,2-dicarboxylic anhydride.

  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, it is recommended that excess raw materials be distilled off under reduced pressure or normal pressure.

  The ester obtained by the above esterification method may be subsequently purified by base treatment (neutralization treatment) → water washing treatment, liquid-liquid extraction, distillation (decompression, dehydration treatment), adsorption treatment, etc., if necessary. .

  The base used for the base treatment is not particularly limited as long as it is a basic compound, and examples thereof include sodium hydroxide and sodium carbonate.

  Examples of the adsorbent used for the adsorption treatment include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, and diatomaceous earth. They can be used alone or in combination of two or more.

  The purification treatment after the esterification may be performed at room temperature, but may be performed by heating to about 40 to 90 ° C.

<Vinyl chloride resin composition>
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 present ester within the range where the effects of the present invention are exhibited. In addition, known flame retardants, stabilizers, stabilization aids, colorants, processing aids, fillers, antioxidants (anti-aging agents), UV absorbers, which are usually used for plastics as required Additives such as light stabilizers such as hindered amines, lubricants or antistatic agents can be blended within the range where the effects of the present invention are exhibited.

  Other plasticizers and additives other than the present ester may be used alone or in combination of two or more 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, and dibasic acids such as adipic acid Polyesters having a molecular weight of 800 to 4000 synthesized by polyesterification with glycol, epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, and di-2-butyl 4,5-epoxy-1,2-cyclohexanedicarboxylate Ethoxy hexyl ester etc. Cyesters, alicyclic dibasic esters such as hexahydrophthalic acid diisononyl ester (DINCH), 4-cyclohexene-1,2-dicarboxylic acid di-2-ethylhexyl, and dicapric acid-1,4-butanediol Fatty acid glycol esters, citrate esters such as tributyl acetyl citrate (ATBC), trihexyl acetyl citrate (ATHC), triethylhexyl acetyl citrate (ATEHC), trihexyl butyl citrate (BTHC), isosorbide diesters, paraffin wax, Examples include chlorinated n-paraffin chlorinated paraffins, chlorinated fatty acid esters such as chlorinated stearates, and higher fatty acid esters such as butyl oleate. When the plasticizer that can be used in combination is blended, the blending amount is recommended to be about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

  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. Moreover, when mix | blending a flame retardant, about 0.1-20 weight part is recommended as the compounding quantity of the flame retardant with respect to 100 weight part of vinyl chloride resin.

  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. Moreover, when mix | blending a stabilizer, about 0.1-20 weight part is recommended for the compounding quantity of the stabilizer with respect to 100 weight part of vinyl chloride resin.

  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. In addition, when the stabilizing aid is blended, the blending amount of the stabilizing aid with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 20 parts by weight.

  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. Moreover, when mix | blending a coloring agent, about 1-100 weight part of the compounding quantity of the coloring agent with respect to 100 weight part of vinyl chloride resin is recommended.

  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. Moreover, when mix | blending a processing aid, about 0.1-20 weight part is recommended as the compounding quantity of the processing aid with respect to 100 weight part of vinyl chloride-type resin.

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

  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. Moreover, when mix | blending antioxidant, about 0.2-20 weight part of the compounding quantity of antioxidant with respect to 100 weight part of vinyl chloride resin is recommended.

  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, when mix | blending a ultraviolet absorber, about 0.1-10 weight part is recommended as the compounding quantity of the ultraviolet absorber with respect to 100 weight part of vinyl chloride-type resin.

  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 In addition, when a light stabilizer is blended, the blending amount of the light stabilizer with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

  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 wax, and higher fatty acid wax. When a lubricant is blended, the blending amount of the lubricant with respect to 100 parts by weight of the vinyl chloride resin is recommended to be 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. In addition, when blending an antistatic agent, the blending amount of the antistatic agent with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

  The vinyl chloride resin composition of the present invention comprises the present ester, vinyl chloride resin and other known plasticizers and various additives as required, for example, handling mixing, pony mixer, butterfly mixer, planetary mixer, dissolver. The mixture is stirred and mixed with a stirrer / mixer such as a twin-screw mixer, a three-roll mill, a mortar mixer, a Henschel mixer, a Banbury mixer, or a ribbon blender to obtain a mixed powder of a vinyl chloride resin composition.

  In addition, the present ester, vinyl chloride resin, and other known plasticizers and various additives as necessary, for example, conical twin screw extruder, parallel twin screw extruder, single screw extruder, cone kneader kneader, roll A pellet-like vinyl chloride resin composition can also be obtained by melt mixing with a kneader such as a kneader.

  Furthermore, the present ester, vinyl chloride paste resin, and other known plasticizers and various additives as required, such as pony mixer, butterfly mixer, planetary mixer, ribbon blender, kneader, dissolver, twin screw mixer, Henschel mixer Further, it is possible to obtain a paste-like vinyl chloride resin composition by uniformly mixing with a mixer such as a three-roll mill and defoaming under reduced pressure as necessary.

[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 paste-like vinyl chloride resin composition includes spread coating, dip coating, spray coating, paper casting, extrusion coating, gravure printing method, screen printing method, slush molding, rotational molding, casting, dip molding, etc. A desired shape can be formed by molding using a conventionally known method.

  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 and the like.

  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) Ratio of carbon number of alkyl group and linear alkyl group The ratio of carbon number of alkyl group and linear alkyl group in the plasticizer used in Examples and Comparative Examples of the present invention was used in the production thereof. The composition in the raw material alcohol was measured by gas chromatography (hereinafter abbreviated as GC), and the result was defined as the ratio of the number of carbon atoms in the plasticizer to the linear alkyl group. The measuring method of the raw material alcohol by GC is as follows.
<< GC measurement conditions >>
Model: Gas chromatograph GC-17A (manufactured by Shimadzu Corporation)
Detector: FID
Column: Capillary column ZB-1 30m
Column temperature: raised from 60 ° C to 290 ° C. Temperature increase rate = 13 ° C./min Carrier gas: helium Sample: 50% acetone solution Injection volume: 1 μl
Quantification: Quantification was performed using n-propyl benzoate as an internal standard substance.
In selecting the internal standard substance, it was confirmed in advance that n-propyl benzoate was less than the detection limit by GC in the raw material alcohol.
In the above esterification reaction, there is no difference in reactivity depending on the structure of the raw alcohol within the scope of the present invention, and there is no difference in the composition ratio of the raw alcohol used and the composition ratio of the alkyl group in the ester. Has been confirmed in advance.

(2) Physical property evaluation of ester The ester obtained by the following manufacture example analyzed by the following method.
Ester value: Measured according to JIS K-0070 (1992).
Acid value: measured in accordance with JIS K-0070 (1992).
Number of colors: Measured according to JIS K-0071 (Hazen) (1998) to determine the Hazen unit color number.

(3) Production of vinyl chloride sheet (tensile property, cold resistance, heat resistance test sheet)
Calcium stearate (manufactured by Nacalai Tesque Co., Ltd.) and zinc stearate (manufactured by Nacalai Tesque Co., Ltd.) and 0.3 and 0.2 are added as stabilizers to 100 parts by weight of a vinyl chloride resin having a polymerization degree of 1050 or 2500, respectively. After blending parts by weight and stirring and mixing with a mortar mixer, 50 parts by weight of a plasticizer was added and handled and mixed until uniform to obtain a vinyl chloride resin composition. When a vinyl chloride resin having a polymerization degree of 1050 is used with a 5 × 12 inch double roll, the obtained resin composition is melt-kneaded at 160 to 166 ° C. for 4 minutes. When used, it was melt-kneaded at 180-186 ° C. for 5 minutes to produce a roll sheet. Subsequently, when a vinyl chloride resin having a polymerization degree of 1050 is used, press molding is performed at 162 to 168 ° C. for 10 minutes, and when a vinyl chloride resin having a polymerization degree of 2500 is used, a press molding is performed at 167 to 173 ° C. for 10 minutes. A 1 mm press sheet was produced.

[Evaluation of physical properties of resin]
(4) Tensile properties: 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, and the breaking strength and breaking elongation are measures of practical strength of the material. Generally, the larger the value, the more practical the strength. It can be said that it is excellent.

(5) Cold resistance: Measured according to JIS K-6773 (1999) using a crashberg 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.

(6) Heat resistance: Based on evaluation of volatile loss and sheet coloring.
a) Volatilization loss: The change in weight of the sheet after heating the roll sheet for 60 minutes at 170 ° C. for 120 minutes in a gear oven was measured, and the volatilization loss (%) was calculated according to the following formula.
The smaller the value of volatilization loss, the higher the heat resistance.
Volatilization loss (%) = ((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 6 stages.
◎: No coloring, ○: Slightly colored, ○ △: Slightly colored,
Δ: Coloring, ×: Strong coloring, XX: Remarkable coloring

[Production Example 1]
In a 2 L four-necked flask equipped with a thermometer, decanter, stirring blade, and reflux condenser, 152 g (1.0 mol) of 4-cyclohexene-1,2-dicarboxylic anhydride and a ratio of 9/10/11 carbon atoms Is 19/43/38, the total linearity is 84%, mixed saturated fatty alcohol having 9 to 11 carbon atoms (manufactured by Shell Chemicals: Neodol 911), 384 g (2.4 mol), and ester P-Toluenesulfonic acid 5.0 g was added as an oxidization catalyst, and the reaction temperature was 140 ° C. to carry out the esterification reaction. The reaction was continued until the acid value of the reaction solution reached 0.5 mgKOH / g while the generated water was removed from the system by refluxing the alcohol under reduced pressure. After completion of the reaction, unreacted alcohol was distilled out of the system under reduced pressure, and then neutralized, washed with water and dehydrated according to a conventional method to obtain the desired 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter referred to as “ester 1”). ) 400 g was obtained.
The obtained ester 1 had an ester value of 247 mgKOH / g, an acid value of 0.02 mgKOH / g, and a color number of 5.

[Production Example 2]
In place of 384 g of the mixed saturated aliphatic alcohol having 9 to 11 carbon atoms (Neodol 911), the weight of the linear saturated aliphatic alcohol having 9 carbon atoms is 87.2% and the branched saturated aliphatic alcohol having 9 carbon atoms is 11. 4-Cyclohexene-1,2-dicarboxylic acid was prepared in the same manner as in Production Example 1 except that 346 g (2.4 mol) of a mixed saturated aliphatic alcohol containing 7% by weight (manufactured by Shell Chemicals: Lineball 9) was added. 374 g of an acid diester (hereinafter referred to as “ester 2”) was obtained.
The obtained ester 2 had an ester value of 262 mgKOH / g, an acid value of 0.04 mgKOH / g, and a color number of 15.

[Production Example 3]
4-cyclohexene-1, which was carried out in the same manner as in Production Example 1 except that 346 g (2.4 mol) of isononyl alcohol was added instead of 384 g of the mixed saturated aliphatic alcohol having 9 to 11 carbon atoms (Neodol 911). 380 g of 2-dicarboxylic acid diester (hereinafter referred to as “ester 3”) was obtained.
The obtained ester 2 had an ester value of 264 mgKOH / g, an acid value of 0.02 mgKOH / g, and a color number of 5.

[Example 1]
As described in “(3) Preparation of vinyl chloride sheet” above, a vinyl chloride resin having a polymerization degree of 1050 (straight, trade name “Zest1000Z”, manufactured by Shin Daiichi PVC Co., Ltd.) using ester 1 as a plasticizer. ) Based vinyl chloride resin compositions were prepared, vinyl chloride sheets were prepared from the resulting vinyl chloride resin compositions, and subjected to a tensile test, a cold resistance test, and a heat resistance test. The obtained results are shown in Table 1.

[Example 2]
The same procedure as in Example 1 was performed except that a vinyl chloride resin having a polymerization degree of 2500 (straight, trade name “Zest 2500Z”, manufactured by Shin Daiichi PVC Co., Ltd.) was used instead of the vinyl chloride resin having a polymerization degree of 1050. After preparing a vinyl chloride resin composition, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and a tensile test, a cold resistance test, and a heat resistance test were performed. The results obtained are summarized in Table 1.

[Comparative Example 1]
Except that ester 2 was used instead of ester 1, it was carried out in the same manner as in Example 1 to prepare a vinyl chloride resin composition. Then, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and subjected to a tensile test and cold resistance. And a heat resistance test were conducted. The results obtained are summarized in Table 1.

[Comparative Example 2]
Except that ester 3 was used instead of ester 1, the same procedure as in Example 1 was carried out to prepare a vinyl chloride resin composition, and then a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and subjected to a tensile test. A cold resistance test and a heat resistance test were conducted. The results obtained are summarized in Table 1.

[Comparative Example 3]
The same procedure as in Example 2 was conducted except that ester 3 was used instead of ester 1, and after preparing a vinyl chloride resin composition, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and a tensile test was conducted. A cold resistance test and a heat resistance test were conducted. The results obtained are summarized in Table 1.

[Comparative Example 4]
Obtained after preparing a vinyl chloride resin composition in the same manner as in Example 1 except that di-2-ethylhexyl phthalate (manufactured by Shin Nippon Rika Co., Ltd .: Sansosizer DOP) was used instead of ester 1. A vinyl chloride sheet was prepared from the vinyl chloride resin composition and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

From the results of Table 1, it is apparent that the vinyl chloride resin compositions (Examples 1 and 2) in which the 4-cyclohexene-1,2-dicarboxylic acid diester of the present invention is blended as a plasticizer are blended with conventionally known plasticizers. It can be seen that, compared with the resin compositions (Comparative Examples 2 to 4), the flexibility is good and the cold resistance and heat resistance are very excellent. Moreover, when compared with a resin composition (Comparative Example 1) containing 4-cyclohexene-1,2-dicarboxylic acid diester outside the scope of the present invention as a plasticizer, it has good or excellent flexibility and cold resistance effects. It can be seen that the heat resistance is further improved while holding.

The 4-cyclohexene-1,2-dicarboxylic acid diester of the present invention can be used as a plasticizer for a vinyl chloride resin having excellent cold resistance and heat resistance and good flexibility, and contains a chloride containing the plasticizer. Molded products obtained from vinyl-based resin compositions are used for electric wire coating, automotive parts, and general film sheets (lamination, packaging, vehicles, sundries, etc.) that require high cold resistance, heat resistance, and flexibility. , Agricultural film applications, leather applications, compound applications, flooring applications, wallpaper applications, footwear applications, sealant applications, textile applications, hose applications, gasket applications, building materials applications, paint applications, adhesive applications, paste applications, medical Very useful for applications.

Claims (9)

It consists of 4-cyclohexene-1,2-dicarboxylic acid diester represented by the following general formula (1), and the alkyl group constituting the diester is mainly composed of an alkyl group having 9 to 11 carbon atoms, and an alkyl group having 9 carbon atoms. The ratio (molar ratio) of / alkyl group having 10 carbon atoms / alkyl group having 11 carbon atoms is in the range of 8 to 28/32 to 52/28 to 48, and is based on the total amount of alkyl groups constituting the dicarboxylic acid diester A plasticizer for vinyl chloride resin, wherein the ratio (molar ratio) of linear alkyl groups is 50 to 99%.

(In the formula, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group.) 2. The plasticizer for a vinyl chloride resin according to claim 1, wherein a ratio of the alkyl group is in a range of 10 to 26/34 to 50/30 to 46. 3. The plasticizer for a vinyl chloride resin according to claim 1 or 2, wherein a ratio of the linear alkyl group in the alkyl group is 55 to 95%. The plasticizer for a vinyl chloride resin according to claim 3, wherein the ratio of the linear alkyl group in the alkyl group is 60 to 95%. The plasticizer for a vinyl chloride resin according to claim 4, wherein a ratio of the linear alkyl group in the alkyl group is 70 to 95%. A method for producing 4-cyclohexene-1,2-dicarboxylic acid diester for use in the plasticizer for vinyl chloride resin according to any one of claims 1 to 5, comprising 4-cyclohexene-1,2-dicarboxylic acid The ratio (molar ratio) of each alcohol having 9, 10 and 11 carbon atoms is mainly 8 to 28/32 to 52/28 or more, mainly composed of an acid or its anhydride and a saturated aliphatic alcohol having 9 to 11 carbon atoms. 4-cyclohexene-1, characterized by carrying out an esterification reaction with a mixture of saturated aliphatic alcohols in the range of 48 and the linear chain ratio (molar ratio) of the saturated aliphatic alcohols of 50 to 99% A method for producing 2-dicarboxylic acid diester. (1) a step of producing an aldehyde having 9 to 11 carbon atoms by hydroformylation reaction of 1-octene, 1-nonene, 1-decene, carbon monoxide and hydrogen; The production method according to claim 6, which is obtained by a method comprising a step of hydrogenating an aldehyde having 9 to 11 carbon atoms to reduce it to an alcohol. 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 5. A vinyl chloride resin molded product, which is a molded product of the vinyl chloride resin composition according to claim 8.