JP2016222895A - Plasticizer for vinyl chloride resin comprising epoxy cyclohexane dicarboxylic acid diester, and soft vinyl chloride resin composition comprising the plasticizer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasticizer for a vinyl chloride resin with reduced deterioration of physical properties and coloration due to heat and light, having good flexibility, and further having improved cold resistance and heat resistance, and a soft vinyl chloride resin composition comprising thereof which is suitable for a long-term outdoor use or the like.SOLUTION: An epoxy cyclohexane dicarboxylic acid diester having a specific structure is found to be able to improve cold resistance and volatility resistance while maintaining an ability to prevent aging due to heat or light peculiar to a vinyl chloride resin without impairing compatibility with a resin, and thus plasticizing efficiency and flexibility. By the use of the epoxy cyclohexane dicarboxylic acid diester as a plasticizer, a vinyl chloride resin composition with reduced aging due to heat and light, having good flexibility, and further having improved cold resistance and heat resistance can be provided.SELECTED DRAWING: None

Description

  The present invention relates to a novel plasticizer for vinyl chloride resin and a soft vinyl chloride resin composition containing the same, and more specifically, deterioration of physical properties due to heat or light comprising an epoxycyclohexanedicarboxylic acid diester having a specific structure. Soft chloride suitable for long-term outdoor use containing a plasticizer for vinyl chloride resin with little coloring, good flexibility, and further improved cold resistance and heat resistance, that is, improved volatility resistance. The present invention relates to a vinyl resin composition.

  In many cases, a vinyl chloride resin is usually produced by adding a plasticizer to a vinyl chloride resin and molding the soft vinyl chloride resin composition.

  Various properties such as flexibility, cold resistance, heat resistance, and electrical properties are required for molded articles (molded products) obtained by molding a soft vinyl chloride resin composition containing such a plasticizer. It has been. Representative plasticizers for vinyl chloride resins include, for example, phthalate esters such as di-2-ethylhexyl phthalate (hereinafter referred to as “DOP”) and diisononyl phthalate (hereinafter referred to as “DINP”). These are plasticizers, and these plasticizers are used for general purposes.

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

  To date, as non-phthalate ester plasticizers, tributyl acetylcitrate (hereinafter referred to as “ATBC”), di-2-ethylhexyl adipate (hereinafter referred to as “DOA”), tri-2 trimellitic acid -Plasticizers such as ethylhexyl (hereinafter referred to as "TOTM") have been developed (Patent Documents 1 to 3). Among these plasticizers, the above ATBC and DOA are phthalate ester plasticizers. In comparison, there was a problem that heat resistance was greatly insufficient. In addition, TOTM has a heat resistance equivalent to or better than that of phthalates, and is expected to be a good heat-resistant plasticizer that can replace phthalate plasticizers. It has the disadvantage of being inferior, and it has not yet completely replaced phthalate plasticizers with non-phthalate plasticizers.

  Under such circumstances, in recent years, an alicyclic dicarboxylic acid diester plasticizer represented by diisononyl 1,2-cyclohexanedicarboxylate (hereinafter referred to as “DINCH”) has a flexibility close to that of a phthalic acid ester plasticizer. It has attracted attention as a non-phthalate plasticizer that has heat resistance and cold resistance and is well-balanced (Patent Document 4).

  In addition, epoxycyclohexanedicarboxylic acid diester represented by 4,2-epoxycyclohexane-1,2-dicarboxylic acid di-2-ethylhexyl (hereinafter referred to as “E-DEHCH”), which is a kind of alicyclic dicarboxylic acid diester, Compared with cyclohexanedicarboxylic acid diesters such as DINCH that do not contain an epoxy group, it is more compatible with vinyl chloride resins, has better plasticization efficiency, that is, better flexibility, and also has excellent bleeding and migration properties. But it is known as an excellent plasticizer. In particular, in applications intended for long-term outdoor use, the epoxy group contained in the structure has the effect of supplementing hydrogen chloride generated by the decomposition of vinyl chloride resin by heat and light. Used as a plasticizer that can suppress aging, that is, deterioration of physical properties and coloration of products, alone or in combination with other plasticizers, and is expected to be one of the non-phthalate ester plasticizers in the future. (Patent Document 5).

  On the other hand, in recent years, the demand for cold resistance and volatility has become increasingly severe for wire coating applications, etc., and there are an increasing number of cases where conventional DINCH and E-DEHCH cannot handle non-phthalate ester plasticizers. Therefore, development of a non-phthalate ester plasticizer that satisfies the above-described requirements, that is, improved cold resistance and volatile resistance has been awaited.

JP 2000-226482 A JP 2002-194159 A JP2013-147520A JP-T-2001-526252 JP 2001-081259 A

  An object of the present invention is to provide a plasticizer for a vinyl chloride resin comprising a novel epoxycyclohexanedicarboxylic acid diester that can solve the above-mentioned problems, that is, satisfies the requirements of more severe cold resistance and volatile resistance and has good flexibility. And a soft vinyl chloride resin composition containing the plasticizer.

  In view of the current situation, the present inventors have conducted intensive studies to solve the above problems, and as a result, the epoxycyclohexanedicarboxylic acid diester having a specific structure is compatible with the characteristic resin, that is, plasticization efficiency. The inventors have found that it is possible to improve cold resistance and volatility without impairing flexibility, and have completed the present invention.

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

[Item 1] A linear alkyl group composed of a 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester represented by the following general formula (1) and relative to the total amount of alkyl groups constituting the dicarboxylic acid diester: A plasticizer for a vinyl chloride resin, wherein the ratio (molar ratio) is 50 to 99%.
(In formula, R1 and R2 are the same or different, and represent a C7-C13 linear or branched alkyl group.)

[Claim 2] The plasticizer for vinyl chloride resin according to [Claim 1], wherein the alkyl group has 8 to 12 carbon atoms.

[Item 3] The alkyl group mainly comprises an alkyl group having 9 to 11 carbon atoms, and the ratio (molar ratio) of the alkyl group having 9 carbon atoms / the alkyl group having 10 carbon atoms / the alkyl group having 11 carbon atoms is 10 to 10. The plasticizer for vinyl chloride resin according to [Item 1] or [Item 2], which is in the range of 25/35 to 50/30 to 45.

[Claim 4] The plasticizer for vinyl chloride resin according to [Claim 1] or [Claim 2], wherein the alkyl group contains 90% or more (molar ratio) of an alkyl group having 9 carbon atoms.

[Claim 5] The plasticizer for vinyl chloride resin according to any one of [Claim 1] to [Claim 4], wherein the ratio of the linear alkyl group in the alkyl group is 55 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 60 to 95%.

CLAIM | ITEM 7 The plasticizer for vinyl chloride-type resins as described in [Claim 6] whose ratio of the linear alkyl group in an alkyl group is 70 to 95%.

[Claim 8] Any of [Claim 1] to [Claim 7] obtained by epoxidizing 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester with 4-cyclohexene-1,2-dicarboxylic acid diester A plasticizer for a vinyl chloride resin according to any one of the above.

[Item 9] The 4-cyclohexene-1,2-dicarboxylic acid diester esterifies 4-cyclohexene-1,2-dicarboxylic acid or an acid anhydride thereof with a saturated aliphatic alcohol having 7 to 13 carbon atoms. The saturated aliphatic alcohol is mainly composed of a saturated aliphatic alcohol having 9 to 11 carbon atoms, and the straight chain ratio (molar ratio) of the saturated aliphatic alcohol is 50 to 95%. Item 8. The plasticizer for vinyl chloride resins according to [Item 8].

[Item 10] A soft 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 9].

[Item 11] The soft vinyl chloride resin composition according to Item 10, wherein the content of the plasticizer for vinyl chloride resin is 20 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

[Item 12] The soft vinyl chloride resin composition according to Item 11, wherein the content of the plasticizer for the vinyl chloride resin is 30 to 150 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

[Item 13] A vinyl chloride-based molded article obtained from the soft vinyl chloride-based resin composition according to any one of [Item 10] to [Item 12].

  The plasticizer for vinyl chloride resin of the present invention is excellent in plasticization efficiency and flexibility because it is excellent in compatibility with vinyl chloride resin, and has greatly improved cold resistance and volatilization resistance compared to conventional ones. Therefore, using it as a plasticizer is very useful for obtaining a vinyl chloride resin molded product that meets the demands for heat resistance and cold resistance, which have become increasingly severe in recent years. Furthermore, since anti-aging ability by heat and light due to the effect of the epoxy group contained in the compound is also expected, it is useful particularly in applications that are used outdoors for a long period of time.

<Plasticizer for vinyl chloride resin>
The plasticizer for vinyl chloride resin of the present invention is characterized by comprising an epoxycyclohexanedicarboxylic acid diester having a specific structure represented by the following general formula (1).
In the formulas, ^{R 1} and ^{R 2} are the same or different, 7-13 carbon atoms, preferably represents a straight-chain or branched alkyl group of 8 to 12, and in Shikichu ^R 1, ^{R 2} The ratio of linear alkyl groups to the total amount of alkyl groups shown is from 50 to 99%, preferably from 55 to 95%, more preferably from 60 to 95%, particularly preferably from 70 to 95%.

  Furthermore, the alkyl group is mainly composed of an alkyl group having 9 to 11 carbon atoms, and the ratio (molar ratio) of the alkyl group having 9 carbon atoms / the alkyl group having 10 carbon atoms / the alkyl group having 11 carbon atoms is 10 to 25. / 35 to 50/30 to 45, or 90% or more (molar ratio) of an alkyl group having 9 carbon atoms.

  The epoxycyclohexanedicarboxylic acid diester of the present invention (hereinafter referred to as “the present epoxy” or “the present epoxy compound”) is not limited by the particular production method as long as it satisfies the performance as a plasticizer. For example, 4-cyclohexene-1,2-dicarboxylic acid or an acid anhydride thereof and a saturated fatty alcohol having a specific structure are esterified, and the resulting 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter, referred to as “dicyclohexene-1,2-dicarboxylic acid diester”). It may be easily obtained by epoxidizing "this ester" (sometimes referred to as "the present ester") under predetermined conditions. In addition, after epoxidation of 4-cyclohexene-1,2-dicarboxylic acid or its acid anhydride, the resulting 4,5-epoxycyclohexane-1,2-dicarboxylic acid or its acid anhydride and a saturated fat having a specific structure It can also be obtained by esterifying a group alcohol. Further, depending on the type of the saturated aliphatic alcohol, there is a method of obtaining by ester exchange reaction by adding the saturated aliphatic alcohol after esterification with a lower alcohol having about 1 to 6 carbon atoms in advance. From the viewpoint of practicality such as simplicity, the method of epoxidation after esterification is most preferable.

[Saturated fatty alcohol]
The saturated aliphatic alcohol used in the esterification reaction or transesterification reaction is a linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms, preferably 8 to 12 carbon atoms, more preferably 9 carbon atoms. -11 linear or branched saturated aliphatic alcohols, particularly preferably (i) 90% or more (molar ratio) of saturated aliphatic alcohols having 9 carbon atoms, more preferably 95% or more. A linear or branched saturated aliphatic alcohol, or (ii) mainly composed of a saturated aliphatic alcohol having 9 to 11 carbon atoms, an alkyl group having 9 carbon atoms / an alkyl group having 10 carbon atoms / an alkyl group having 11 carbon atoms. Is a saturated aliphatic alcohol having a ratio (molar ratio) of 10 to 25/35 to 50/30 to 45. The term “mainly” means that the ratio (molar ratio) of the saturated aliphatic alcohol having 9 to 11 carbon atoms in the entire 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 epoxycyclohexanedicarboxylic acid diester represented by the general formula (1), that is, the above description is synonymous with the description of the alkyl group.

  The saturated aliphatic alcohol has a linear saturated aliphatic alcohol ratio (molar ratio) in the alcohol of 50 to 99%, preferably 55 to 95%, more preferably 60 to 95%. Particularly preferred is 70 to 95%.

  The details of the embodiment of the saturated aliphatic alcohol according to the present invention include: (i) a ratio of a saturated aliphatic alcohol having 9 to 13 carbon atoms, which is a linear or branched saturated aliphatic alcohol having 9 to 13 carbon atoms. (Molar ratio) is 90% or more, preferably 95% or more, and the ratio (molar ratio) of the linear saturated aliphatic alcohol is 50 to 99%, preferably 55 to 95%, more preferably 60 to 95%, particularly preferably 70 to 95%, or (ii) a saturated aliphatic alcohol mainly composed of a linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms It is a mixture of alcohols, and the ratio (molar ratio) occupied by each alcohol having 9, 10, and 11 carbon atoms is in the range of 10-25 / 35-50 / 30-45, and linear saturated Occupying fatty alcohol Rate (mole ratio) 50 to 99%, preferably 55 to 95%, more preferably 60% to 95%, aspects such as particularly preferably 70% to 95% recommended.

  If a saturated aliphatic alcohol having less than 7 carbon atoms is included, sufficient cold resistance and volatile resistance are difficult to obtain, and if a saturated aliphatic alcohol having more than 13 carbon atoms is included, the compatibility with the resin is poor. This is not preferable because the plasticizing efficiency is lowered. Similarly, when the ratio of the linear saturated aliphatic alcohol is less than 50%, it is difficult to obtain sufficient cold resistance and volatility, and when the ratio of the linear saturated aliphatic alcohol exceeds 99% Since the compatibility with the resin is deteriorated and there is a concern that the plasticizing efficiency and the like are lowered, neither of them is preferable.

  A saturated aliphatic alcohol containing 90% or more of a saturated aliphatic alcohol having 9 carbon atoms and having a linear saturated aliphatic alcohol ratio of 50 to 99% is (1) 1-octene, carbon monoxide, It can be produced by a production method comprising a step of producing an aldehyde having 9 carbon atoms by a hydroformylation reaction with hydrogen, and (2) a step of hydrogenating the aldehyde having 9 carbon atoms to reduce it to an alcohol. The saturated aliphatic alcohol according to the present invention can be obtained by using or containing the saturated aliphatic alcohol obtained in the above as it is.

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

  The hydrogenation in the step (2) can be reduced to an alcohol by hydrogenating an aldehyde having 9 carbon atoms 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 Lineball 9 manufactured by Shell Chemicals.

  Similarly, it is mainly composed of a saturated aliphatic alcohol having 9 to 11 carbon atoms, and the ratio (molar ratio) of the alkyl group having 9 carbon atoms / the alkyl group having 10 carbon atoms / the alkyl group having 11 carbon atoms is 10-25 / 35-50. A saturated aliphatic alcohol having a ratio (molar ratio) of linear saturated aliphatic alcohol of 50 to 99% in a saturated aliphatic alcohol in the range of / 30 to 45 is (1) 1-octene, 1- A step of producing an aldehyde having 9 to 11 carbon atoms by hydroformylation reaction of nonene, 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 using the saturated aliphatic alcohol obtained by the production method as it is or contained. It can be Lumpur.

  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 is the above-mentioned alcohol for obtaining 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter referred to as “the present ester”) which is a raw material of the epoxidation reaction for obtaining the present epoxy compound. Means an esterification reaction of 4-cyclohexene-1,2-dicarboxylic acid or an acid anhydride thereof, and in performing the esterification reaction, the alcohol is, for example, 4-cyclohexene-1,2-dicarboxylic acid or Preferably, 2.00 mol to 5.00 mol, more preferably 2.01 mol to 3.00 mol, and particularly preferably 2.02 mol to 2.50 mol are used with respect to 1 mol of the acid anhydride. It is recommended.

  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 acid anhydride, which is the raw material of this ester, is not particularly limited, and those produced by known methods, commercially available products, those available as reagents, etc. are used. it can. For example, Rikacid 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, generated esters, and organic solvents (water entraining agents) during the esterification reaction, 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 (reduced pressure, dehydration treatment), adsorption purification, etc. as 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 purification 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.

  Although the said process may be performed at normal temperature under pressure reduction or a normal pressure, it can also carry out by heating to about 40-90 degreeC.

[Epoxidation reaction]
The epoxidation reaction according to the present invention means an epoxidation reaction of an unsaturated bond in the ester for obtaining the epoxy compound, and is usually “Organic Synthetic Chemistry, Vol. 23, No. 7, 612-619”. Page (1985) "or the like, and can be easily performed using a well-known epoxidation reaction.
Examples include (i) a method using an organic peracid such as peracetic acid or performic acid as the epoxidizing agent, and (ii) a method using hydrogen peroxide as the epoxidizing agent.

  More specifically, in the case of the method (i), for example, peracetic acid obtained by reacting hydrogen peroxide and acetic anhydride or acetic acid with a strong acid such as sulfuric acid as a catalyst is added to the ester, and 20 to 20 After stirring at 30 ° C for several hours, the temperature is gradually raised, and after reaching 50-60 ° C, the temperature can be maintained for 2-3 hours to complete the reaction. As the organic peracid, monoperphthalic acid, permetachlorobenzoic acid, pertrifluoroacetic acid and the like can be used in addition to the above.

  In the case of the method (ii), for example, epoxidation can be carried out by reacting with the present ester in the presence of an oxygen carrier such as formic acid or a strong acid catalyst such as sulfuric acid. More specifically, with respect to 1 mol of hydrogen peroxide, acetic acid or formic acid is used in a small amount of 0.5 mol or less and sulfuric acid is used as a catalyst in a small amount of 0.05 mol or less, and the temperature at 40 to 70 ° C. for 2 to 15 hours. This ester can be easily epoxidized by carrying out the reaction while maintaining. In addition to the above, phosphoric acid, hydrochloric acid, nitric acid, boric acid, or a salt thereof is well known as the catalyst, and a sulfonic acid type strongly acidic cation exchange resin or aluminum oxide is also effective.

  After completion of the epoxidation reaction, it may be purified by water phase removal, water washing treatment, liquid-liquid extraction, and dehydration treatment as necessary.

<Soft vinyl chloride resin composition>
The soft vinyl chloride resin composition of the present invention can be obtained by blending the above-described epoxy compound as a plasticizer with a vinyl chloride resin.

[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 the production method thereof is carried out by a conventionally known polymerization method. For example, in the case of a general-purpose vinyl chloride resin, a method of suspension polymerization in the presence of an oil-soluble polymerization catalyst can be used. For vinyl chloride paste resin, a method of emulsion polymerization in the presence of a water-soluble polymerization catalyst in an aqueous medium can be used. 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.

[Soft vinyl chloride resin composition]
The content of the present epoxy compound in the soft vinyl chloride resin composition according to the present invention is appropriately selected according to its use, but is preferably 20 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. More preferably, it is 30 to 150 parts by weight. If it is 20 parts by weight or more, sufficient flexibility can be obtained even in applications where flexibility is required, and in applications where further flexibility is required, flexibility can be imparted by adjusting the blending amount accordingly. However, in applications where there is concern about bleeding on the surface of the molded product, the amount of 200 parts by weight or less can be preferably used without concern. However, when adding a filler etc. with respect to said vinyl chloride resin composition, since the filler itself absorbs oil, the said plasticizer may be mix | blended exceeding said range. For example, when 100 parts by weight of calcium carbonate is added as a filler to 100 parts by weight of the vinyl chloride resin, the plasticizer may be added up to about 500 parts by weight.

  The soft vinyl chloride resin composition may be used in combination with other known plasticizers together with the epoxy compound. If necessary, flame retardants, stabilizers, stabilizing aids, colorants, processing aids, fillers, antioxidants (anti-aging agents), UV absorbers, light stabilizers such as hindered amines, lubricants or electrification In many cases, additives such as inhibitors are appropriately blended and used.

  Other plasticizers and additives other than the epoxy compound may be used alone or in combination of two or more with the epoxy compound.

  As other plasticizers that can be used in combination with the epoxy compound, known plasticizers conventionally used in this technical field can be used. For example, benzoic acid esters such as diethylene glycol dibenzoate, dibutyl phthalate ( DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), bis (2-ethylhexyl terephthalate) (DOTP), phthalic acid esters such as bis (2-ethylhexyl) isophthalate (DOIP), tetrahydrophthalic acid esters such as bis (2-ethylhexyl) 4-cyclohexene-1,2-dicarboxylate (DOTH), adipine Di-2-ethylhexyl acid (DOA , Aliphatic dibasic acid esters such as diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), diisononyl sebacate (DINS), and tri-2-ethylhexyl trimellitic acid (TOTM), trimellitic acid esters such as triisononyl trimellitic acid (TINTM), trimisolic acid trimisodecyl (TIDTM), pyromellitic acid esters such as pyromellitic acid tetra-2-ethylhexyl (TOPM), tri-phosphate Molecular weight synthesized by polyesterification of 2-ethylhexyl (TOP), tricresyl phosphate (TCP) and other phosphate esters, polyhydric alcohol alkyl esters such as pentaerythritol, dibasic acids such as adipic acid and glycols 800 ˜4000 polyesters, epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil, alicyclic dibasic esters such as DINCH, fatty acid glycol esters such as dicapric acid-1,4-butanediol, Citrate esters such as tributyl acetyl citrate (ATBC), trihexyl acetyl citrate (ATHC), triethylhexyl acetyl citrate (ATEHC), trihexyl butyryl citrate (BTHC), isosorbide diesters, paraffin wax and n-paraffin are chlorinated Chlorinated paraffins, chlorinated fatty acid esters such as chlorinated stearic acid esters, higher fatty acid esters such as butyl oleate, and the like. When blending other plasticizers that can be used in combination, the blending amount is appropriately selected within a range not impairing the effect of the plasticizer according to the present invention, and is usually 1 to 100 weights per 100 parts by weight of the vinyl chloride resin. About 1 part is recommended.

  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. When the flame retardant is blended, the blending amount of the flame retardant with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 20 parts by weight.

  Stabilizers include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octylate, zinc laurate, zinc ricinoleate, stearic acid Metal soap compounds such as organic acid compounds containing metals such as zinc, barium zinc stearate, barium zinc laurate, barium zinc ricinoleate, barium zinc octylate, calcium stearate zinc, calcium zinc laurate, ricinol Metal soap compounds such as organic acid compounds containing complex metals such as calcium oxide-zinc, calcium octylate-zinc, dimethyltin bis-2-ethylhexyl thioglycolate, dibutyltin maleate, dibu Dibutyltin bis-butyl maleate, organic tin compounds such as dibutyltin dilaurate, antimony mercaptan Tide compounds and the like. When the stabilizer is blended, the blending amount of the stabilizer with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 20 parts by weight.

  Stabilization aids include phosphite compounds such as triphenyl phosphite, monooctyl diphenyl phosphite, tridecyl phosphite, beta diketone compounds such as acetylacetone and benzoylacetone, glycerin, sorbitol, pentaerythritol, polyethylene glycol, etc. Examples include polyol compounds, perchlorate compounds such as barium perchlorate and sodium perchlorate, hydrotalcite compounds, and zeolites. 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. When blending a colorant, the blending amount of the colorant with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 1 to 100 parts by weight.

  Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bis stearic acid amide, butyl stearate, calcium stearate and the like. When the processing aid is blended, the blending amount of the processing 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.

  Fillers include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, ferrite, fibers and powders such as glass, carbon, metal, glass spheres, graphite, aluminum hydroxide, barium sulfate, oxidation Examples include magnesium, magnesium carbonate, magnesium silicate, calcium silicate, and the like. When the filler is blended, the blending amount of the filler with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 1 to 100 parts by weight.

  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-methoxybenzophenone, 5- In addition to benzotriazole compounds such as methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, cyanoacrylate compounds are exemplified. When the ultraviolet absorber is blended, the blending amount of the ultraviolet absorber 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 hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1 , 2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1- Dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester and 1,1-dimethylethyl Reaction product of hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidino And higher fatty acid ester mixtures, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6- Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, poly [ {(6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidyl) Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}}, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6) -Tetramethyl- Polycondensate of 4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, N, N ′, N ″, N ′ ″ − Tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1 10-diamine, etc. 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, baraffin 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. When the antistatic agent is blended, 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 soft vinyl chloride resin composition of the present invention is a mixture of the present epoxy compound, vinyl chloride resin and various additives as required, for example, by a stirrer such as a mortar mixer, Henschel mixer, Banbury mixer, ribbon blender, It can be set as a mixed powder of a soft vinyl chloride resin composition.

  In addition, the present epoxy compound, vinyl chloride resin, and various additives as required, for example, a conical twin screw extruder, a parallel twin screw extruder, a single screw extruder, a kneader type kneader, a roll kneader, etc. It is also possible to obtain a pellet-like soft vinyl chloride resin composition by melt molding.

  In addition, this epoxy compound, vinyl chloride paste resin and, if necessary, other plasticizers and various additives other than this epoxy compound, such as pony mixer, butterfly mixer, planetary mixer, ribbon blender, kneader, dissolver, biaxial It can also mix uniformly with mixers, such as a mixer, a Henschel mixer, and a three roll mill, and if necessary, defoaming can be performed under reduced pressure to obtain a paste-like soft vinyl chloride resin composition.

[Vinyl chloride molded body]
The soft vinyl chloride resin composition (mixed powder or pellet) according to the present invention is conventionally known such as vacuum molding, compression molding, extrusion molding, injection molding, calendar molding, press molding, blow molding, powder molding, etc. It can be formed into a desired shape by melt molding using the method.

  On the other hand, the paste-like soft vinyl chloride resin composition is molded into a desired shape by molding using a conventionally known method such as spread molding, dipping molding, gravure molding, slush molding, or screen processing. be able to.

  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 can be used for automobile underbody coats, instrument panels, consoles, door seats, under carpets, trunk seats, door trims, various leathers, decorative sheets, agricultural films and food packaging. Film, electric wire coating, various foam products, hoses, medical tubes, food tubes, refrigerator gaskets, packings, wallpaper, flooring, boots, curtains, shoe soles, gloves, waterproof plates, toys, decorative plates, blood It is useful for bags, infusion bags, tarpaulins, mats, waterproof sheets, civil engineering sheets, roofing, waterproof sheets, insulating sheets, industrial tapes, glass films, erasers, etc.

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

(1) 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 esterification reaction described above, there is no difference in reactivity depending on the structure of the raw material alcohol within the scope of the present invention, and there is a difference in the composition ratio of the raw material alcohol used and the composition ratio of the alkyl group in the ester and the epoxy. It has been confirmed beforehand that there is no.

(2) Physical property evaluation of this epoxy compound 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).
Iodine value: measured according to JIS K-0070 (1992).
Oxirane Oxygen: Measured according to the standard oil and fat analysis test method 2.3.7.1-2013 “oxirane oxygen determination method (1)”.
Hue: Measured according to JIS K-0071 (1998) to determine the Hazen unit color number.

(3) Molding processability About 0.01 g of a sample prepared by mixing 10 g of a plasticizer into 2 g of vinyl chloride resin (straight, polymerization degree 1050, trade name “Zest1000Z”, manufactured by Shin Daiichi PVC Co., Ltd.) on a slide glass The solution was added dropwise, covered with a cover glass, and set on a trace melting point measuring device. The temperature is raised at a rate of 5 ° C./min, the state of the vinyl chloride resin particles is observed to change with heating, and the temperature at which the vinyl chloride resin particles begin to melt and the temperature at which the particles become transparent start to gel. The temperature and the gelation end temperature were used, and the average value was used as the gelation temperature. The lower the gelation temperature, the faster the plasticizer absorption rate and the better the processability.

(4) Preparation of vinyl chloride sheet (tensile properties, cold resistance, heat resistance test sheet)
Calcium stearate (manufactured by Nacalai Tesque) and zinc stearate (Nacalai) as stabilizers were added to 100 parts by weight of vinyl chloride resin (straight, polymerization degree 1050, trade name “Zest1000Z”, manufactured by Shin Daiichi Vinyl Co., Ltd.). After mixing 0.3 and 0.2 parts by weight of Tesque Co., Ltd. and stirring and mixing with a mortar mixer, add 50 parts by weight of a plasticizer and handle and mix until uniform. did. This resin composition was melt-kneaded at 160 to 166 ° C. for 4 minutes using a 5 × 12 inch double roll to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168 ° C. for 10 minutes to produce a press sheet having a thickness of about 1 mm.

[Evaluation of physical properties of resin]
(5) 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.

(6) 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.

(7) 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]
To a 2 L four-necked flask equipped with an esterification reaction thermometer, a decanter, a stirring blade, and a reflux condenser, 182.6 g of 4-cyclohexene-1,2-dicarboxylic anhydride (1.2 mol, Shin Nippon Rika Co., Ltd.) Sliced fatty alcohol (shell) containing 95.1% by weight of a linear saturated aliphatic alcohol having 9 carbon atoms and 11.7% by weight of a branched saturated aliphatic alcohol having 9 carbon atoms. Chemicals Co., Ltd .: 416 g (2.9 mol) of lineball 9) and 0.24 g of tetraisopropyl titanate as an esterification catalyst were added, and the esterification reaction was carried out at a reaction temperature of 200 ° C. 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”). 449 g was obtained.
The obtained ester 1 had an ester value of 254 mgKOH / g, an acid value of 0.04 mgKOH / g, and a hue of 15.

Epoxidation reaction Next, 423 g (1.0 mol) of ester 1 obtained by the above esterification reaction was charged into a 1 L four-necked flask equipped with an upper thermometer, stirring blades, and a cooling tube, and the temperature was adjusted to 60 to 70 ° C. The temperature rose. After the temperature rise, 60% hydrogen peroxide water 76.6 g (1.35 mol), 76% formic acid 18.3 g (0.30 mol), and 75% phosphoric acid 1.47 g (0.01 mol) 2.25 g. Drip slowly over time. After completion of the dropwise addition, the temperature was further maintained for 4 hours, and the reaction was completed by aging. After completion of the reaction, the aqueous phase was removed out of the system, and then washed and dehydrated according to a conventional method to obtain 397 g of the desired 4,5-epoxycyclohexanedicarboxylic acid diester (hereinafter referred to as “epoxy 1”).
Resulting epoxy 1, ester value: 256mgKOH / g, acid number: 0.06mgKOH / g, iodine value: 2.5gI ₂ / 100g, oxirane oxygen: 3.5%, color: 10.

[Production Example 2]
Instead of 416 g of saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9), the ratio of carbon number 9/10/11 is 19/43/38, and the total linearity is 84%. No. 11 mixed saturated aliphatic alcohol (manufactured by Shell Chemicals: Neodol 911), except that 400 g (2.5 mol) was added, the same as in Production Example 1, and 4,5-epoxycyclohexanedicarboxylic acid diester (hereinafter, 404 g) was obtained.
The resulting epoxy 2, ester value: 242mgKOH / g, acid number: 0.04 mgKOH / g, iodine value: 1.9gI ₂ / 100g, oxirane oxygen: 3.1%, color: 10.

[Production Example 3]
Similar to Production Example 1 except that 251 g (1.7 mol) of n-nonyl alcohol and 167 g (1.2 mol) of isononyl alcohol were added instead of 416 g of saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9). And 390 g of 4,5-epoxycyclohexanedicarboxylic acid diester (hereinafter referred to as “epoxy 3”) was obtained.
The resulting epoxy 3, ester value: 250 mgKOH / g, acid number: 0.02 mg KOH / g, iodine value: 1.9gI ₂ / 100g, oxirane oxygen: 3.3%, color number: 10.

[Production Example 4]
4,5-epoxycyclohexane was carried out in the same manner as in Production Example 1 except that 374 g (2.9 mol) of 2-ethylhexanol was added instead of 416 g of saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9). 390 g of dicarboxylic acid diester (hereinafter referred to as “epoxy 4”) was obtained.
The resulting epoxy 4, ester value: 273mgKOH / g, acid number: 0.04 mgKOH / g, iodine value: 3.3gI ₂ / 100g, oxirane oxygen: 3.5%, color: 10.

[Production Example 5]
4,5-epoxycyclohexanedicarboxylic acid was produced in the same manner as in Production Example 1 except that 416 g (2.9 mol) of isononyl alcohol was added instead of 416 g of saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9). 379 g of an acid diester (hereinafter referred to as “epoxy 5”) was obtained.
The resulting epoxy 5, ester value: 255mgKOH / g, acid number: 0.05 mg KOH / g, iodine value: 1.6gI ₂ / 100g, oxirane oxygen: 3.4%, color: 10.

[Production Example 6]
4,5-epoxycyclohexanedicarboxylic acid was prepared in the same manner as in Production Example 1 except that 459 g (2.9 mol) of isodecyl alcohol was added instead of 416 g of saturated aliphatic alcohol (manufactured by Shell Chemicals: Lineball 9). 410 g of acid diester (hereinafter referred to as “epoxy 6”) was obtained.
The resulting epoxy 6, ester value: 239mgKOH / g, acid number: 0.05 mg KOH / g, iodine value: 2.0gI ₂ / 100g, oxirane oxygen: 3.1%, color: 10.

[Example 1]
According to the method described in the above “(3) Molding processability”, the moldability (gelling temperature) was measured using the epoxycyclohexanedicarboxylic acid diester (epoxy 1) obtained in Production Example 1. The obtained results are shown in Table 1.
Subsequently, as described in “(4) Production of vinyl chloride sheet” above, a soft vinyl chloride resin composition was prepared using epoxy 1 as a plasticizer, and chlorinated from the obtained soft vinyl chloride resin composition. A vinyl sheet was prepared 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 conducted except that epoxy 2 was used in place of epoxy 1 to measure molding processability. Subsequently, a soft vinyl chloride resin composition was prepared, and the resulting soft vinyl chloride resin was obtained. A vinyl chloride sheet was prepared from the composition and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

[Example 3]
The same procedure as in Example 1 was conducted except that epoxy 3 was used in place of epoxy 1, the moldability was measured, a soft vinyl chloride resin composition was prepared, and the resulting soft vinyl chloride resin was obtained. A vinyl chloride sheet was prepared from the composition and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

[Comparative Example 1]
The same procedure as in Example 1 was conducted except that epoxy 4 was used in place of epoxy 1, the moldability was measured, a soft vinyl chloride resin composition was subsequently prepared, and the resulting soft vinyl chloride resin was obtained. A vinyl chloride sheet was prepared from the composition and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

[Comparative Example 2]
The same procedure as in Example 1 was conducted except that epoxy 5 was used in place of epoxy 1, the moldability was measured, a soft vinyl chloride resin composition was subsequently prepared, and the resulting soft vinyl chloride resin was obtained. A vinyl chloride sheet was prepared from the composition and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

[Comparative Example 3]
The same procedure as in Example 1 was conducted except that epoxy 6 was used in place of epoxy 1, the moldability was measured, a soft vinyl chloride resin composition was prepared, and the resulting soft vinyl chloride resin was obtained. A vinyl chloride sheet was prepared from the composition and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

[Comparative Example 4]
Except that di-2-ethylhexyl phthalate (manufactured by Shin Nippon Rika Co., Ltd., Sunsocizer DOP) was used in place of epoxy 1, the processability was measured in the same manner as in Example 1, followed by soft chlorination. A vinyl resin composition was prepared, a vinyl chloride sheet was prepared from the obtained soft 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 5]
Except for using diisononyl phthalate (manufactured by Shin Nippon Rika Co., Ltd., Sansosizer DINP) instead of epoxy 1, the same process as in Example 1 was carried out to measure the moldability, followed by a soft vinyl chloride resin. A composition was prepared, a vinyl chloride sheet was prepared from the obtained soft 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 6]
Except for using commercially available tri-2-ethylhexyl trimellitic acid (TOTM) instead of epoxy 1, the same procedure as in Example 1 was performed to measure the molding processability, and then a soft vinyl chloride resin composition was prepared. Then, a vinyl chloride sheet was produced from the obtained soft 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 shown in Table 1, the most frequently used phthalic acid diester (Comparative Examples 4 and 5) is obtained by using 4,5-epoxycyclohexanedicarboxylic acid diester of the present invention (Examples 1 to 3) as a plasticizer. It can be seen that the heat resistance, in particular, the heat coloring property, can be greatly improved while maintaining the same moldability, flexibility and cold resistance as compared with the case where is used. Furthermore, compared with trimellitic acid ester (Comparative Example 6) often used as a heat-resistant plasticizer, although it is slightly inferior in volatility, it is greatly improved in heat-resistant colorability, and has excellent moldability. The usefulness is clear considering flexibility and cold resistance. Further, from the results in Table 1, the conventional 4,5-epoxycyclohexanedicarboxylic acid diester (Comparative Example 1) was obtained by using the 4,5-epoxycyclohexanedicarboxylic acid diester of the present invention (Examples 1 and 3) as a plasticizer. It can be seen that the cold resistance and the heat resistance are greatly improved while maintaining the same moldability and flexibility as compared with the case of using a). Furthermore, the effect is clear even when compared to the case of using 4,5-epoxycyclohexanedicarboxylic acid diester (Comparative Examples 2 and 3) outside the scope of the present invention. Similarly, when the 4,5-epoxycyclohexanedicarboxylic acid diester (Example 2) of the present invention is used as a plasticizer, it exhibits molding processability equal to or higher than that of a phthalic acid diester, which is a general-purpose plasticizer, and is also resistant to cold. It can be seen that the heat resistance is further improved, and it is particularly useful when used in a harsher environment.

  The 4,5-epoxycyclohexanedicarboxylic acid diester of the present invention is excellent in plasticization efficiency and flexibility, and further has a significantly improved cold resistance and volatilization resistance compared to conventional plasticizers for vinyl chloride resins. Molded products obtained from a soft vinyl chloride resin composition containing the plasticizer can be used as a vinyl chloride resin molded product corresponding to heat and cold resistance requirements, which are becoming increasingly severe in recent years, and epoxy resins. The vinyl chloride resin moldings used for applications such as outdoor use for a long period of time, such as wire coating applications and automotive parts applications, general film sheets (laminates, packaging, vehicles, miscellaneous goods, etc.) Etc.) Applications, agricultural film applications, leather applications, compound applications, flooring applications, wallpaper applications, footwear applications, sealing materials applications, textile applications, hose applications, gas Tsu door applications, building materials applications, coating applications, adhesive applications, paste applications, it is very useful in medical applications.

Claims (13)

The ratio (molar ratio) of linear alkyl groups to the total amount of alkyl groups comprising 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester represented by the following general formula (1) and constituting the dicarboxylic acid diester ) Is 50 to 99%, a plasticizer for vinyl chloride resin.
(In formula, R1 and R2 are the same or different, and represent a C7-C13 linear or branched alkyl group.) The plasticizer for a vinyl chloride resin according to claim 1, wherein the alkyl group has 8 to 12 carbon atoms. The alkyl group is mainly composed of an alkyl group 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 is 10 to 25/35 to 50/30 to The plasticizer for vinyl chloride resin according to claim 1 or 2, which is in the range of 45. The plasticizer for vinyl chloride resins according to claim 1 or 2, wherein the alkyl group contains 90% or more (molar ratio) of a C9 alkyl group. The plasticizer for a vinyl chloride resin according to any one of claims 1 to 4, 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 5, wherein a ratio of the linear alkyl group in the alkyl group is 60 to 95%. The plasticizer for a vinyl chloride resin according to claim 6, wherein a ratio of the linear alkyl group in the alkyl group is 70 to 95%. The vinyl chloride resin according to any one of claims 1 to 7, wherein 4,5-epoxycyclohexane-1,2-dicarboxylic acid diester is obtained by epoxidation of 4-cyclohexene-1,2-dicarboxylic acid diester. Plasticizer for use. The 4-cyclohexene-1,2-dicarboxylic acid diester obtained by esterification of 4-cyclohexene-1,2-dicarboxylic acid or an acid anhydride thereof and a saturated aliphatic alcohol having 7 to 13 carbon atoms The saturated aliphatic alcohol is mainly composed of a saturated aliphatic alcohol having 9 to 11 carbon atoms, and the linear ratio (molar ratio) of the saturated aliphatic alcohol is 50 to 95%. The plasticizer for vinyl chloride resin as described. A soft vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer for vinyl chloride resin according to any one of claims 1 to 9. The soft vinyl chloride resin composition according to claim 10, wherein the content of the plasticizer for vinyl chloride resin is 20 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. The soft vinyl chloride resin composition according to claim 11, wherein the content of the plasticizer for vinyl chloride resin is 30 to 150 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. A vinyl chloride-based molded article obtained from the soft vinyl chloride-based resin composition according to any one of claims 10 to 12.