JP6520570B2 - Plasticizer for vinyl chloride resin containing 1,2-cyclohexanedicarboxylic acid diester - Google Patents

Description

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

The vinyl chloride resin is added with a plasticizer for the purpose of imparting various performances including flexibility and lowering the processing temperature at the time of forming processing such as extrusion and calendering, and facilitating the forming processing. It is often used as a vinyl chloride resin composition.

As a function required for a plasticizer used for such a vinyl chloride resin composition, various performances such as flexibility, cold resistance, heat resistance, electrical properties, etc. when the composition is used as a raw material and formed into a molded article To give or exert As plasticizers for such vinyl chloride resin compositions, for example, plasticizers for phthalate ester vinyl chloride represented by di 2-ethylhexyl phthalate (DOP) and diisononyl phthalate (DINP) are widely used. Are used.

However, in recent years, due to the fact that reproductive toxicity is observed when a large amount of DOP is administered to rodents while the safety against chemical substances has been raised, infants are mainly used in Japan, the US and Europe according to the precautionary principle. The use of phthalic acid ester compounds such as DOP is restricted as an object of protection, and nonphthalic acid ester plasticizers are desired in the market also in the field of plasticizers.

To date, tributyl acetyl citrate (hereinafter referred to as "ATBC"), di 2-ethylhexyl adipate (hereinafter referred to as "DOA"), tri 2-ethyl trimellitate as non-phthalate ester plasticizers 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. The heat resistance is largely lacking. Moreover, TOTM has heat resistance equal to or higher than that of phthalate ester, and is expected as a heat-resistant good plasticizer that can substitute for phthalate ester plasticizer, but phthalate ester Compared to the above, it is not flexible enough and has limitations on its use. Therefore, it has not been possible to completely replace phthalic acid ester plasticizers with non-phthalic acid ester plasticizers.

Under such circumstances, in recent years, alicyclic dicarboxylic acid diester based plasticizers represented by diisononyl 1,2-cyclohexanedicarboxylate (hereinafter referred to as “DINCH”) have flexibility close to phthalic acid ester based plasticizers. It has attracted attention as a non-phthalic acid ester plasticizer having heat resistance (volatilization resistance) and cold resistance, and having a good balance (Patent Document 4).

On the other hand, in recent years, the demand for cold resistance and heat resistance has become increasingly severe in wire coating applications and so on, and cases where conventional non-phthalate plasticizers can not be handled by DINCH are increasing, satisfying the above requirements It has been awaited to develop non-phthalic acid ester plasticizers that are more similar, that is, more improved in cold resistance and heat resistance.

JP, 2000-226482, A Unexamined-Japanese-Patent No. 2002-194159 JP, 2013-147520, A Japanese Patent Publication No. 2001-526252

The objective of the present invention is a plasticizer for vinyl chloride resin of 1,2-cyclohexanedicarboxylic acid diester which can solve the above-mentioned problems, that is, it is excellent in cold resistance and heat resistance and is excellent in flexibility, and its plasticizer It is an object of the present invention to provide a vinyl chloride resin composition containing

In the previous invention (Japanese Patent Application No. 2015-51854), the present inventors are a mixture of 1,2-cyclohexanedicarboxylic acid or its anhydride and an aliphatic saturated alcohol mainly composed of a C9 aliphatic saturated alcohol. And a plasticizer for a vinyl chloride resin containing a 1,2-cyclohexanedicarboxylic acid diester obtained by esterification reaction with the compound of the formula (I) having good performance as an inherent plasticizer, that is, good plasticizing performance and flexibility, and It has been reported that it is excellent in heat resistance and cold resistance, but as described above, there has been a need to further improve the heat resistance in some applications while the flow of resource saving has been increasingly accelerated.

Therefore, in view of the present situation, the present inventors have intensively studied to solve the above-mentioned problems, and as a result, 1,2-cyclohexanedicarboxylic acid diester having a specific structure is a compound 1,2-of the invention described above. The inventors have found that further improvement in heat resistance is possible without deteriorating the performance of cyclohexanedicarboxylic acid diester as a plasticizer and the cold resistance, and the present invention has been completed.

That is, the present invention provides the following novel plasticizer for vinyl chloride resin and a vinyl chloride resin composition containing the same.

[Item 1] A 1,2-cyclohexanedicarboxylic acid diester represented by the following general formula (1), wherein R ¹ and R ² are 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 the alkyl group having 10 carbon atoms to the alkyl group having 11 carbon atoms is in the range of 8-28 / 32 to 52/28 to 48, and relative to the total amount of alkyl groups constituting R ¹ and R ² A plasticizer for a vinyl chloride resin, wherein the proportion (molar ratio) of linear alkyl groups is 50 to 99%.

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

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

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

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

[Item 5] The plasticizer for a vinyl chloride resin according to Item 4, wherein the proportion of the linear alkyl group in the alkyl group is 60 to 95%.

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

[Item 7] A method for producing 1,2-cyclohexanedicarboxylic acid diester for use in the plasticizer for a vinyl chloride resin according to any one of items 1 to 6, comprising: The ratio (molar ratio) of cyclohexanedicarboxylic acid or its anhydride and a saturated aliphatic alcohol having 9 to 11 carbon atoms, wherein each alcohol having 9 to 10, 11 carbon atoms accounts for 10 to 25/35 to 50 / An esterification reaction is carried out with a mixture of saturated aliphatic alcohols in the range of 30 to 45 and in which the ratio (molar ratio) of linear saturated aliphatic alcohols in the saturated aliphatic alcohols is 50 to 99%. A process for producing 1,2-cyclohexanedicarboxylic acid diester characterized in that

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

[Item 9] A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer for a vinyl chloride resin according to any one of [Item 1] to [Item 6].

[Item 10] A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to [Item 9].

The plasticizer for vinyl chloride resin of the present invention can greatly improve the heat resistance, that is, the volatilization resistance while maintaining good plasticizing performance, flexibility, and excellent cold resistance, and it is becoming more and more severe in recent years. Can be used in various applications as a plasticizer that can meet the heat resistance requirements. Moreover, the vinyl chloride resin composition which can respond to the request | requirement of resource saving etc. in recent years can be obtained by including the plasticizer for vinyl chloride resin.

<Plasticizer for vinyl chloride resin>
The plasticizer for vinyl chloride-based resin of the present invention is characterized by comprising 1,2-cyclohexanedicarboxylic 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 each represents a linear or branched alkyl group, mainly composed of an alkyl group having 9 to 11 carbon atoms, an alkyl group having 9 carbon atoms / carbon The ratio (molar ratio) of the alkyl group of the number 10 / the alkyl group having 11 carbons 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 group represented by R ¹ and R ² is 50 to 99%, preferably 55 to 35, preferably in the range of 24/36 to 48/32 to 44. It is 95%, more preferably 60 to 95%, particularly preferably 70 to 95%. Satisfying such a ratio means that the plasticizer for a vinyl chloride resin of the present invention consists of a mixture of 1,2-cyclohexanedicarboxylic acid diester represented by the general formula (1), and the ratio is The total amount of alkyl groups in the whole mixture is defined as a premise. The alkyl group represented by R ¹ and R ² is preferably selected from the range of 7 to 13 carbon atoms from the viewpoint of the effect of the present invention.

The 1,2-cyclohexanedicarboxylic acid diester (hereinafter referred to as "the ester") according to the present invention is not limited by any particular manufacturing method, as long as it satisfies the performance as a plasticizer. For example, 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, in the absence of a catalyst or in the presence of a catalyst.

[A mixture of saturated aliphatic alcohol]
The saturated aliphatic alcohol which is an alcohol component used for the esterification reaction mainly comprises 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 having 11 carbon atoms The ratio (molar ratio) of the groups is in the range of 8-28 / 32 to 52/28 to 48, preferably 10 to 26/34 to 50/30 to 46, more preferably 12 to 24/36 to 48/32 to 44 It is a mixture of saturated aliphatic alcohols. The term "mainly" means that the ratio (molar ratio) of the saturated aliphatic alcohol having 9 to 11 carbon atoms to the entire saturated aliphatic alcohol is 90% or more, preferably 95% or more. The said saturated aliphatic alcohol is a raw material alcohol used as the alkyl group which comprises 1, 2- cyclohexane dicarboxylic acid diester shown by said General formula (1), ie, the said description becomes synonymous with description of this alkyl group.

Further, in the mixture of saturated aliphatic alcohols, the ratio (linear ratio, molar ratio) of linear saturated aliphatic alcohols in the saturated aliphatic alcohols is 50 to 99%, preferably 55 to 95%. It is more preferably 60 to 95%, particularly preferably 70 to 95%.

As details of the embodiment of the mixture of saturated aliphatic alcohols used in the present invention, the mixture of saturated aliphatic alcohols is a mixture of mainly saturated aliphatic alcohols having 9 to 11 carbon atoms, and further, 9, 9, 10, 11 carbon atoms The ratio (molar ratio) of each alcohol in the range of 8 to 28/32 to 52/28 to 48, preferably 10 to 26/34 to 50/30 to 46, more preferably 12 to 24/36 to 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 45. The aspect etc. which are 95% are recommended.

The ratio of the linear saturated aliphatic alcohol in the mixture of saturated aliphatic alcohols is 50% or more, and the ratio (molar ratio) of each alcohol having 9, 10 and 11 carbon atoms is 10 to 25 / When it is in the range of 35 to 50/30 to 45, the heat resistance, which is the object of the present invention, can be greatly improved while maintaining the effect of good or excellent flexibility and cold resistance.

The ratio (molar ratio) of the alcohol having 9 to 11 carbon atoms and having 9 to 10 carbon atoms and having 10 to 11 carbon atoms in the range of 10 to 25/35 to 50/30 to 45 is mainly used in the present invention. A mixture of a saturated aliphatic alcohol which is a saturated aliphatic alcohol which is 50% to 99% of a ratio (molar ratio) of a linear saturated aliphatic alcohol is (1) 1-octene, 1-nonene, Comprising a step of producing an aldehyde having 9 to 11 carbon atoms by a hydroformylation reaction of 1-decene, carbon monoxide and hydrogen, and (2) a step of hydrogenating an aldehyde having 9 to 11 carbon atoms to reduce 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 le.

The hydroformylation reaction of the step (1) has, for example, 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, for example, 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 from Shell Chemicals.

[Esterification reaction]
The esterification reaction according to the present invention means an esterification reaction of the above-mentioned alcohol component with 1,2-cyclohexanedicarboxylic acid or its anhydride, and when carrying out the esterification reaction, the alcohol component is, for example, 1 Preferably, it is 2.00 mol to 5.00 mol, more preferably 2.01 mol to 3.00 mol, in particular 2.02 mol to 2.50 mol, per 1 mol of 2-cyclohexanedicarboxylic acid or its anhydride. It is recommended to use moles.

When a catalyst is used in the esterification reaction, examples of the catalyst include mineral acids, organic acids, Lewis acids and the like. More specifically, examples of mineral acids include sulfuric acid, hydrochloric acid and phosphoric acid, and examples of organic acids include p-toluenesulfonic acid and methanesulfonic acid. Examples of Lewis acids include aluminum derivatives and tin derivatives. A titanium derivative, a lead derivative, a zinc derivative etc. are illustrated and it is possible to use together these 1 type (s) or 2 or more types.

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 thereof is, for example, preferably 0.01% by weight to 5.0% by weight, more preferably 0.02% by weight to 4.0% by weight, based on the total weight of the acid component and the alcohol component which are ester synthesis raw materials. It is recommended to use wt%, in particular 0.03 wt% to 3.0 wt%.

The esterification temperature is, for example, 100 ° C. to 230 ° C. The reaction is usually completed in 3 hours to 30 hours.

1,2-Cyclohexanedicarboxylic acid anhydride, which is the acid component of the raw material of this ester, is usually a cyclohexene dicarboxylic acid anhydride obtained by subjecting maleic anhydride and 1,3-butadiene to a usual Diels-Alder reaction. Can be obtained by hydrogenating

In esterification, it is possible to use a water entrainer such as benzene, toluene, xylene, cyclohexane and the like to promote distillation of water produced by the reaction.

In addition, when oxygenated organic compounds such as oxides, peroxides and carbonyl compounds are generated due to oxidation degradation of raw materials, formed esters and organic solvents (water entrainer) at the time of esterification reaction, heat resistance, weather resistance, etc. are adversely affected. Therefore, it is desirable to carry out the reaction under normal pressure or reduced pressure in an inert gas atmosphere such as nitrogen gas or under an inert gas flow, in the system. After completion of the esterification reaction, it is recommended to distill off excess raw material under reduced pressure or under normal pressure.

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

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, diatomaceous earth and the like. They can be used alone or in combination of two or more.

The purification treatment after esterification may be carried out at normal temperature, but can also be carried out 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-mentioned ester with 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 vinyl chloride, and the production method thereof is carried out by a conventionally known polymerization method, and general-purpose chloride In the case of vinyl resin, a method of suspension polymerization in the presence of an oil-soluble polymerization catalyst may be mentioned, and in the case of vinyl chloride paste resin, a method of emulsion polymerization in an aqueous medium in the presence of a water-soluble polymerization catalyst may be mentioned. The polymerization degree of these vinyl chloride resins is usually 300 to 5,000, preferably 400 to 3,500, and more preferably 700 to 3,000. If the degree of polymerization is too low, the heat resistance and the like decrease, and if it is too high, the moldability tends to decrease.

In the case of the copolymer, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-docene C2-C30 α-olefins such as tridecene and 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, alkyl vinyl ether and the like Vinyl monomers, multifunctional monomers such as diallyl phthalate and copolymers of these mixtures with vinyl chloride monomers, ethylene-acrylic acid ester copolymers such as ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid ester co Polymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene 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 methyl methacrylate and graft copolymers obtained by grafting a vinyl chloride monomer to a mixture thereof.

[Vinyl chloride resin composition]
The content of the present ester in the vinyl chloride resin composition is appropriately selected according to the application, but is usually 1 to 100 parts by weight, preferably 5 to 100 parts by weight with respect 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 is more than 100 parts by weight, the bleeding to the surface of the molded article is severe, which is not preferable in either case. However, when a filler etc. are added with respect to said vinyl chloride-type resin composition, in order for a filler itself to oil-absorb, the said plasticizer can be mix | blended exceeding said range. For example, when 100 parts by weight of calcium carbonate is blended as a filler with respect to 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 as long as the effects of the present invention are exhibited. Also, known flame retardants, stabilizers, stabilizing aids, coloring agents, processing aids, fillers, antioxidants (anti-aging agents), UV absorbers, which are usually used for plastics if necessary 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 can be exhibited.

Other plasticizers and additives other than the above-mentioned ester may be blended together with the ester in one kind or in combination of two or more kinds.

Examples of known plasticizers that can be used in combination with this ester include benzoic acid esters such as diethylene glycol dibenzoate, dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), and diisononyl phthalate (DINP) And phthalic acid such as diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), bis (2-ethylhexyl) terephthalate (DOTP), and bis (2-ethylhexyl) isophthalate (DOIP) Aliphatic di-esters such as esters, di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), diisononyl sebacate (DINS) Basic acid S Trimellitic esters such as tri-2-ethylhexyl trimellitate (TOTM), triisononyl trimellitate (TINTM), triisodecyl trimellitate (TIDTM), tetra-2-ethylhexyl pyromellitate (TOPM), etc. Of 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, epoxidized linseed oil, etc., 4, 5-epoxy-1, 2-cyclohexanedicarboxylic acid di-2- Such as ethyl hexyl ester Alicyclic dibasic acid esters such as xyesters, hexahydrophthalic acid diisononyl ester (DINCH), 4-cyclohexene-1,2-dicarboxylic acid di-2-ethylhexyl, etc., dicapric acid-1,4-butanediol, etc. Fatty acid glycol esters of tributyl acetyl citrate (ATBC), trihexyl acetyl citrate (ATHC), citric acid esters such as triethylhexyl acetyl citrate (ATEHC), butyryl citrate (BTHC), isosorbide diesters, paraffin wax And chlorinated paraffins obtained by chlorinating n-paraffins, chlorinated fatty acid esters such as chlorinated stearic acid esters, higher fatty acid esters such as butyl oleate, and the like. When mix | blending the plasticizer which can be used together, the compounding quantity is recommended about 1 to 100 parts by weight with respect to 100 parts by weight of vinyl chloride resin.

As flame retardants, inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, zinc borate, cresyl diphenyl phosphate, tris chloroethyl phosphate, tris chloro propyl phosphate, tris dichloro propyl phosphate, etc. Examples thereof include phosphorus compounds and halogen compounds such as chlorinated paraffin. Moreover, when mix | blending a flame retardant, about 0.1-20 parts weight is recommended about the compounding quantity of the flame retardant with respect to 100 weight part of vinyl chloride-type resin.

As a stabilizer, 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 thereof include metal soap compounds such as zinc, dimethyltin bis-2-ethylhexyl thioglycolate, dibutyltin maleate, organic tin compounds such as dibutyltin bisbutyl maleate and dibutyltin dilaurate, and an antimony mercapto compound. When a stabilizer is blended, the blending amount of the stabilizer is preferably about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

Stabilization aids include phosphite compounds such as triphenyl phosphite, monooctyl diphenyl phosphite and tridecyl phosphite, beta diketone compounds such as acetylacetone and benzoylacetone, glycerin, sorbitol, pentaerythritol and polyethylene glycol Examples thereof include polyol compounds, perchlorate compounds such as barium perchlorate and sodium perchlorate, hydrotalcite compounds and zeolites. When a stabilizing aid is blended, the blending amount of the stabilizing aid is preferably about 0.1 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

Examples of the colorant include carbon black, lead sulfide, white carbon, titanium white, lithopone, iron oxide, antimony sulfide, chromium yellow, chromium green, cobalt blue, molybdenum orange and the like. When a coloring agent is blended, the blending amount of the coloring agent is preferably about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

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

Fillers include calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, metal oxides such as ferrite, glass, fibers and powders such as carbon and metal, glass spheres, graphite, aluminum hydroxide, barium sulfate, magnesium oxide , Magnesium carbonate, magnesium silicate, calcium silicate and the like. In addition, when a 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 such as 2,6-di-tert-butylphenol, tetrakis [methylene-3- (3,5-tert-butyl-4-hydroxyphenol) propionate] methane, 2-hydroxy-4-methoxybenzophenone and the like Phenolic compounds, alkyl disulfides, thiodipropionic acid esters, sulfur compounds such as benzothiazole, trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) And phosphoric acid compounds such as phosphites, and organometallic compounds such as zinc dialkyl dithiophosphates and zinc diaryl dithiophosphates. Moreover, when mix | blending antioxidant, about 0.2-20 weight part is recommended about the compounding quantity of antioxidant with respect to 100 weight part of vinyl chloride-type resin.

UV 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, Other than benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, cyanoacrylate compounds and the like are exemplified. When an ultraviolet absorber is blended, the blending amount of the ultraviolet absorber is preferably about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

Examples of light stabilizers based on hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1 2,2,2,6,6-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, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester of decanedioic acid and 1,1-dimethylethyl Reaction product of hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidino Ester mixtures of fatty acid and higher fatty acids, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6- Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 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. In addition, when a light stabilizer is blended, the blending amount of the light stabilizer per 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, higher fatty acid wax and the like. When a lubricant is blended, the blending amount of the lubricant relative to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

As antistatic agents, anionic antistatic agents of alkyl sulfonate type, alkyl ether carboxylic acid type or dialkyl sulfosuccinate type, nonionic antistatic agents such as polyethylene glycol derivative, sorbitan derivative, diethanolamine derivative, alkylamido amine type, alkyl Examples thereof include quaternary ammonium salts such as dimethyl benzyl type, cationic antistatic agents such as organic acid salts or hydrochlorides of alkyl pyridinium type, and amphoteric antistatic agents such as alkyl betaine type and alkyl imidazoline type. When an antistatic agent is blended, the blending amount of the antistatic agent is preferably about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

The vinyl chloride resin composition of the present invention comprises the present ester, vinyl chloride resin and, if necessary, other known plasticizers and various additives, for example, handling mixing, pony mixer, butterfly mixer, planetary mixer, dissolver, Stirring and mixing can be performed by a stirring / mixing machine such as a twin-screw mixer, three-roll mill, mortar mixer, Henschel mixer, Banbury mixer, ribbon blender, etc. to obtain a mixed powder of the vinyl chloride resin composition.

In addition, the ester, vinyl chloride resin and other known plasticizers and various additives as required, for example, conical twin screw extruder, parallel twin screw extruder, single screw extruder, co-kneader type kneader, roll It is also possible to obtain a pelletized vinyl chloride resin composition by melt mixing using a kneader such as a kneader.

Furthermore, the ester, vinyl chloride paste resin and other known plasticizers and various additives as required, for example, pony mixer, butterfly mixer, planetary mixer, ribbon blender, kneader, dissolver, biaxial mixer, Henschel mixer, It can be uniformly mixed by a mixer such as a triple roll mill, and if necessary, degassed under reduced pressure to obtain a paste-like vinyl chloride resin composition.

[Vinyl chloride resin molded product]
The vinyl chloride resin composition (compounded powder or pellet) according to the present invention can be subjected to conventionally known methods such as vacuum molding, compression molding, extrusion molding, injection molding, calendar molding, press molding, blow molding and powder molding. It can be molded into a desired shape by melt molding processing using

On the other hand, the vinyl chloride resin composition in the form of paste is spread coating, dip coating, spray coating, paper casting, extrusion coating, gravure printing, screen printing, slush molding, rotational molding, casting, dip molding, etc. It can be molded into a desired shape by molding using a conventionally known method.

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

The thus obtained molded articles are pipes such as water pipes, fittings for pipes, mosses such as rain gutters, window frame siding, flat plates, corrugated sheets, automobile underbody coats, instrument panels, consoles, door sheets , Automotive materials such as under carpet, trunk sheet, door trims, various leathers, decorative sheets, films for agriculture, films for food packaging, electric wire coatings, various foamed products, hoses, medical tubes, tubes for food, for refrigerators Gaskets, packings, wallpaper, flooring, boots, curtains, soles, gloves, waterproofing boards, toys, decorative boards, blood bags, infusion bags, tarpaulins, mats, waterproof sheets, civil engineering sheets, roofing, tarpaulins , Insulating sheets, industrial tapes, glass films, erasers, etc.

EXAMPLES The present invention will be described in more detail by way of the following examples, but the present invention is not limited by 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 to linear alkyl group The carbon number of alkyl group in the plasticizer used in the examples and comparative examples of the present invention and the ratio of linear alkyl group were used for the production. The composition in the raw material alcohol was measured by gas chromatography (hereinafter abbreviated as GC), and the result was taken as the ratio of the number of carbon atoms of the alkyl group in the plasticizer to the linear alkyl group. The measuring method of the raw material alcohol by said GC is as follows.
<< Measurement conditions of GC >>
Model: Gas chromatograph GC-17A (made by Shimadzu Corporation)
Detector: FID
Column: Capillary column ZB-1 30 m
Column temperature: raised from 60 ° C to 290 ° C. Heating rate: 13 ° C / min Carrier gas: Helium sample: 50% acetone solution Injection amount: 1μl
Quantitative determination: Quantitative determination using n-propyl benzoate as an internal standard substance.
In selecting the internal standard substance, it was confirmed in advance that n-propyl benzoate as a raw material alcohol was below the detection limit by GC.
In the esterification reaction described above, there is no difference in the reactivity due to the structure of the raw material alcohol within the scope of the present invention, and there is no difference in the compositional ratio in the raw material alcohol used and the compositional ratio of the alkyl group in this ester Has confirmed in advance.

(2) Evaluation of physical properties of ester The ester obtained in the following production example was analyzed by the following method.
Ester value: Measured in accordance with JIS K-0070 (1992).
Acid value: Measured in accordance with JIS K-0070 (1992).
Color number: The Hazen unit color number was determined according to JIS K-0071 (Hazen) (1998).

(3) Preparation of vinyl chloride sheet (tensile property, cold resistance, heat resistance test sheet)
To 100 parts by weight of a vinyl chloride resin having a polymerization degree of 1050 or 2500, calcium stearate (manufactured by Nacalai Tesque Inc.) and zinc stearate (manufactured by Nacalai Tesque Inc.) as stabilizers were 0.3 and 0.2, 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. The obtained resin composition is melt-kneaded at 160 to 166 ° C. for 4 minutes using a 5 × 12 inch double roll and a vinyl chloride resin having a polymerization degree of 1050, and a vinyl chloride resin having a polymerization degree of 2500 is obtained When used, the mixture was melt-kneaded at 180 to 186 ° C. for 5 minutes to prepare a roll sheet. Subsequently, press molding is performed at 162 to 168 ° C. for 10 minutes when a vinyl chloride resin having a polymerization degree of 1050 is used, and at 167 to 173 ° C. for 10 minutes if a vinyl chloride resin having a polymerization degree of 2500 is used. A 1 mm press sheet was prepared.

[Physical evaluation of resin]
(4) Tensile properties: 100% modulus, breaking strength and breaking elongation of the pressed sheet were measured in accordance with JIS K-6723 (1995). The smaller the 100% modulus value, the better the flexibility, and the breaking strength and the breaking elongation are indicators of the practical strength of the material. Generally, the larger the value, the more practical strength. It can be said that it is excellent.

(5) Cold resistance: Measured according to JIS K-6773 (1999) using a Crushberg tester. The lower the flexible temperature (° C.), the better the cold resistance. The term "soft temperature" as used herein refers to a temperature at a low temperature limit at which a predetermined torsional rigidity (3.17 × 10 ³ kg / cm ² ) is indicated in the measurement.

(6) Heat resistance: Based on the evaluation of volatilization loss and sheet coloring.
a) Volatilization loss: The weight change of the sheet after heating the roll sheet at 170 ° C. for 60 minutes and 120 minutes in a gear oven was measured, and the volatilization loss (%) was calculated according to the following equation.
The smaller the volatility loss value, the higher the heat resistance.
Volatilization loss (%) = ((weight before test-weight after test) / weight before test) x 100
b) Sheet coloring: The degree of coloring after heating the roll sheet at 170 ° C. for 30 minutes for 60 minutes in a gear oven was visually evaluated in six steps.
:: no coloration, :: slightly colored, △: slightly colored,
△: coloring, ×: strong coloring, ××: remarkable coloring

Production Example 1
In a 2 L four-necked flask equipped with a thermometer, a decanter, a stirring blade, and a reflux condenser, the ratio of 77.0 g (0.5 mol) of 1,2-cyclohexanedicarboxylic acid anhydride and having 9/10 carbon atoms is C. 9 to 11 mixed saturated aliphatic alcohol (manufactured by Shell Chemicals: Neodol 911) 192 g (1.2 mol) having an overall linear ratio of 84%, and 19/43/38, and esterification 5.0 g of p-toluenesulfonic acid was added as a catalyst, and the esterification reaction was carried out at a reaction temperature of 140 ° C. The reaction was carried out until the acid value of the reaction solution reached 0.5 mg KOH / g while refluxing the alcohol under reduced pressure and removing generated water out of the system. After completion of the reaction, unreacted alcohol is distilled out of the system under reduced pressure, followed by neutralization, washing with water and dehydration according to a conventional method to obtain the desired 1,2-cyclohexanedicarboxylic acid diester (hereinafter referred to as "ester 1"). ) I obtained 228 g.
The obtained ester 1 had an ester value of 245 mg KOH / g, an acid value of 0.01 mg KOH / g, and a color number of 15.

Production Example 2
11. Instead of 192 g of a mixed saturated aliphatic alcohol having 9 to 11 carbon atoms (Neodol 911), a linear saturated aliphatic alcohol having 9 carbon atoms, 87.2% by weight, and a branched saturated aliphatic alcohol having 9 carbon atoms. It is carried out in the same manner as in Production Example 1 except that 173 g (1.2 mol) of mixed saturated aliphatic alcohol containing 7% by weight (manufactured by Shell Chemicals: Lineeball 9) is added, and 1,2-cyclohexanedicarboxylic acid diester ( Hereinafter, it called "ester 2." 212g was obtained.
The obtained ester 2 had an ester value of 262 mg KOH / g, an acid value of 0.01 mg KOH / g, and a color number of 10.

Example 1
As described in the above-mentioned "(3) Preparation of vinyl chloride sheet", a vinyl chloride resin having a degree of polymerization of 1050 (straight, trade name "Zest 1000 Z", manufactured by Shin-ichi Shiori PVC Co., Ltd.) using ester 1 as a plasticizer The vinyl chloride resin composition based on was prepared, and the vinyl chloride sheet was produced from the obtained vinyl chloride resin composition, and the tension test, the cold resistance test, and the heat resistance test were done. The obtained results are shown in Table 1.

Example 2
The procedure is carried out in the same manner as in Example 1 except that a vinyl chloride resin having a degree of polymerization of 2500 (Straight, trade name "Zest 2500 Z" manufactured by Shin-ichi Daiichi Vinyl Co., Ltd.) is used instead of the vinyl chloride resin having a degree of polymerization 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 conducted. The obtained results are summarized in Table 1.

Comparative Example 1
The same procedure as in Example 1 is carried out except using ester 2 in place of ester 1 to make a vinyl chloride resin composition, and then a vinyl chloride sheet is produced from the obtained vinyl chloride resin composition to conduct a tensile test, cold resistance The heat resistance test and heat resistance test were conducted. The obtained results are summarized in Table 1.

Comparative Example 2
The same procedure as in Example 1 was carried out except that diisononyl 1,2-cyclohexanedicarboxylate (hexamoll DINCH, manufactured by BASF Corp.) was used instead of ester 1 to prepare a vinyl chloride resin composition, and then the obtained chloride was obtained. A vinyl chloride sheet was prepared from the vinyl resin composition, and a tensile test, a cold resistance test and a heat resistance test were conducted. The obtained results are summarized in Table 1.

Comparative Example 3
The same procedure as in Example 2 was carried out except that diisononyl 1,2-cyclohexanedicarboxylate (hexamoll DINCH, manufactured by BASF Corp.) was used instead of ester 1 to prepare a vinyl chloride resin composition, and then the obtained chloride was obtained. A vinyl chloride sheet was prepared from the vinyl resin composition, and a tensile test, a cold resistance test and a heat resistance test were conducted. The obtained results 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 .: Sanso Cizer DOP) was used instead of ester 1. A vinyl chloride sheet was prepared from the vinyl chloride resin composition, and a tensile test, a cold resistance test and a heat resistance test were conducted. The obtained results are summarized in Table 1.

From the results of Table 1, the vinyl chloride resin compositions (Examples 1 and 2) in which the 1,2-cyclohexanedicarboxylic acid diester of the present invention is clearly blended as a plasticizer have a resin composition in which a conventionally known plasticizer is blended. It can be seen that the flexibility is good and the cold resistance and the heat resistance are very excellent as compared with the products (Comparative Examples 2 to 4). Moreover, compared with the resin composition (comparative example 1) which mix | blended 1, 2- cyclohexanedicarboxylic acid diester outside the scope of the present invention as a plasticizer, while maintaining the effect of good or outstanding pliability and cold resistance. It can be seen that the heat resistance is further greatly improved.

The 1,2-cyclohexanedicarboxylic acid diester of the present invention can be used as a plasticizer for vinyl chloride resins having excellent cold resistance and heat resistance and good flexibility, and a vinyl chloride resin containing the plasticizer Molded products obtained from the composition are used for wire coating applications requiring high cold resistance, heat resistance and flexibility, automotive applications, general film sheets (lamination, packaging, vehicles, sundries, etc.) applications, agriculture Film applications, leather applications, compound applications, flooring applications, wallpaper applications, footwear applications, sealing applications, fiber applications, hose applications, gasket applications, building material applications, paint applications, adhesive applications, paste applications, medical applications, etc. Useful for

Claims (9)

It consists of a 1, 2- cyclohexanedicarboxylic acid diester shown by following General formula (1), and the alkyl group which comprises this diester is mainly comprised from a C9-C11 alkyl group, a C9 alkyl group / carbon number The ratio (molar ratio) of 10 alkyl groups / alkyl groups having 11 carbon atoms is in the range of 8 to 28/32 to 52/28 to 48, and linear to the total amount of alkyl groups constituting the dicarboxylic acid diester The ratio (molar ratio) of the alkyl group of these is 50 to 99%, The plasticizer for vinyl chloride resin characterized by the above-mentioned.

(Wherein, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group)   The plasticizer for vinyl chloride resins 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.   The plasticizer for vinyl chloride resins according to claim 1 or 2, wherein the proportion of linear alkyl groups in the alkyl group is 55 to 95%.   The plasticizer for vinyl chloride resins according to claim 3, wherein the proportion of linear alkyl groups in the alkyl group is 60 to 95%.   The plasticizer for vinyl chloride resins according to claim 4, wherein the proportion of linear alkyl groups in the alkyl group is 70 to 95%.   A method for producing 1,2-cyclohexanedicarboxylic acid diester for use in a plasticizer for a vinyl chloride resin according to any one of claims 1 to 5, comprising: 1,2-cyclohexanedicarboxylic acid or an anhydride thereof And a ratio (molar ratio) of a C 9-11 saturated aliphatic alcohol as a main component and a C 9, 10, 11 alcohol ratio of 10 to 25/35 to 50/30 to 45, And a process for producing 1,2-cyclohexanedicarboxylic acid diester, which comprises an esterification reaction of the saturated aliphatic alcohol with a mixture of saturated aliphatic alcohols having a linear ratio (molar ratio) of 50 to 99%.   The mixture of saturated aliphatic alcohols comprises (1) 1-octene, 1-nonene, 1-decene, a step of producing an aldehyde having 9 to 11 carbon atoms by hydroformylation reaction of carbon monoxide and hydrogen, and (2) The method according to claim 6, which is obtained by a method comprising the step of hydrogenating an aldehyde having 9 to 11 carbon atoms and reducing it to an alcohol.   A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer for a vinyl chloride resin according to any one of claims 1 to 5.   A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to claim 8.