JP2019059888A - Plasticizer for vinyl chloride resin comprising isophthalic acid diester - Google Patents

Abstract

To provide a plasticizer for a vinyl chloride-based resin which has good compatibility with a vinyl chloride-based resin, excellent transfer resistance or bleed-out resistance and extremely excellent heat resistance.SOLUTION: There is provided a plasticizer for a vinyl chloride-based resin composition and its molded body which have no problems caused by the transfer and bleed-out of a plasticizer and has extremely excellent cold resistance and heat resistance by finding out that an isophthalic acid diester having a specific structure has excellent compatibility with a vinyl chloride-based resin, has no problems such as transfer or bleed-out and has extremely excellent cold resistance and heat resistance and using the isophthalic acid diester as a plasticizer for a vinyl chloride-based resin.SELECTED DRAWING: None

Description

  The present invention is a novel plasticizer for vinyl chloride resin, which is very excellent in heat resistance, good in compatibility with vinyl chloride resin, and excellent in migration resistance and bleed out resistance, and contains the same. In particular, a plasticizer for vinyl chloride resin composed of isophthalic acid diester having a specific structure and an excellent heat resistance containing the same, and resistance to The present invention relates to a vinyl chloride resin composition excellent in migration.

  A vinyl chloride resin imparts various performances including flexibility, and a plasticizer is added for the purpose of 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 the performance required for a plasticizer used for such a vinyl chloride resin composition, there are various properties 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. As a typical plasticizer used for such a vinyl chloride resin composition, a phthalic acid ester represented by di 2-ethylhexyl phthalate (hereinafter referred to as "DOP") (in the present invention, phthalic acid) Higher alkyl esters of polybasic acids such as 1,2-benzenedicarboxylic acid (hereinafter referred to as "phthalic acid"), adipic acid esters and trimellitic acid esters are known, and may be used alone or in combination of two or more. Is used in combination. Until now, phthalate ester plasticizers have often been used mainly in terms of price and performance balance. However, in recent years, environmental regulations and voluntary regulations such as the REACH regulation and the RoHS directive have been strengthened for phthalate esters including Europe, and alternative non-phthalate plasticizers are desired in the market.

  Under such circumstances, plasticizers other than phthalate esters conventionally known so far, for example, tributyl acetyl citrate (hereinafter referred to as "ATBC") and di 2-ethylhexyl adipate (hereinafter referred to as "DOA") ) And tri-ethylhexyl trimellitate (hereinafter referred to as “TOTM”) have been investigated to replace phthalate plasticizers with plasticizers. When compared with esters, ATBC has a poor heat resistance, DOA has excellent cold resistance, but has poor compatibility, and TOTM has a problem that it has good heat resistance but poor plasticization efficiency. At present, plasticizers alone have not been able to replace phthalate ester plasticizers.

  In recent years, isophthalic acid esters such as di 2-ethylhexyl isophthalate (hereinafter referred to as "DOIP") structurally closest to phthalic acid esters and terephthalols such as di 2-ethylhexyl terephthalate (hereinafter referred to as "DOTP") Studies are also in progress to use acid esters as alternative plasticizers for phthalic acid ester plasticizers such as the above-mentioned DOP. Among them, isophthalic acid esters represented by DOIP have properties close to those of phthalic acid esters, and are attracting attention as alternative plasticizers for phthalic acid ester plasticizers (for example, Patent Documents 1 to 4) .

  On the other hand, in automotive applications and wire applications, the demand for heat resistance and cold resistance is becoming increasingly severe for the purpose of thinning and the like. The same applies to isophthalic acid esters, and conventional DOIPs are not necessarily satisfactory, and improvements in heat resistance and cold resistance are required. For example, isononyl alcohol having a long alkyl chain length is used as a raw material Investigation of ester is underway. Similarly, the influence of the branched structure of the alkyl chain is also studied, and the use of a straight chain alcohol such as normal octyl alcohol as a raw material to improve heat resistance has also been reported (Patent Document 5). However, in the case of esters using isononyl alcohol, the requirements for cold resistance and heat resistance, which are becoming more and more severe, are not necessarily satisfied, and in the case of esters using linear alcohols such as normal octyl alcohol. There is a concern that the compatibility with the vinyl chloride resin tends to be lowered, and not only the molding processability is lowered but also the bleed out resistance and the migration resistance are lowered. In particular, the reduction in migration resistance may cause not only the performance deterioration of the vinyl chloride resin itself but also the performance deterioration of the resin to which the plasticizer has migrated, which has been a major obstacle to practical use. Therefore, development of an isophthalic acid ester plasticizer which has good compatibility with a vinyl chloride resin, has no concern about deterioration in migration resistance and the like and satisfies severe requirements such as heat resistance has been desired.

JP 2012-089287 A JP 2012-255104 A JP-A-2017-506216 JP-A-2017-509592 JP, 2014-098135, A

  The object of the present invention is to solve the above problems, has good compatibility with vinyl chloride resin, and is good in migration resistance and bleed out resistance, in particular migration resistance, and heat resistance. It is an object of the present invention to provide a very excellent plasticizer for vinyl chloride resin comprising a diester of isophthalic acid and a vinyl chloride resin composition excellent in heat resistance and good migration resistance comprising the same. .

  As a result of intensive studies to solve the above problems in view of the present situation, the present inventors have found that isophthalic acid diester having a specific structure has good compatibility with vinyl chloride resins. The inventors have found that the plasticizer is a plasticizer for vinyl chloride resins which exhibits excellent migration resistance and bleed-out resistance and is extremely excellent in cold resistance and heat resistance, particularly heat resistance, and has completed the present invention.

  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] An isophthalic acid diester represented by the following general formula (1), wherein the alkyl group constituting the diester is mainly composed of an alkyl group having 9 carbon atoms, and a linear alkyl group relative to the total amount of the alkyl group The plasticizer for vinyl chloride resin, characterized in that the ratio (molar ratio) of 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 proportion of the linear alkyl group in the alkyl group is 55 to 95%.

[Item 3] The plasticizer for a vinyl chloride resin according to Item 2, wherein the proportion of the linear alkyl group in the alkyl group is 60 to 95%.

[Item 4] A method for producing an isophthalic acid diester for use in the plasticizer for a vinyl chloride resin according to any one of [Item 1] to [Item 3], which is isophthalic acid or its dimethyl ester, and carbon Carrying out an esterification reaction or a transesterification reaction with a saturated aliphatic alcohol containing a saturated aliphatic alcohol of the number 9 as a main component and a proportion (molar ratio) of a linear saturated aliphatic alcohol being 50 to 99% Process for producing isophthalic acid diester characterized by the present invention.

[Item 5] The step of producing an aldehyde having 9 carbon atoms by (1) 1-octene, hydroformylation reaction of carbon monoxide and hydrogen, and (2) hydrogenation of an aldehyde having 9 carbon atoms, by the saturated aliphatic alcohol. The production method according to Item 4, which is obtained by a method comprising the step of reducing to alcohol.

[Item 6] The method according to Item 5, wherein the proportion of the linear alkyl group in the alkyl group is 55 to 95%.

[Item 7] The method according to Item 6, wherein the proportion of linear alkyl groups in the alkyl group is 60 to 95%.

[Item 8] A vinyl chloride resin, and the isophthalic acid diester according to any one of [Item 1] to [Item 3] as a plasticizer, or the production according to any of [Item 4] to [Item 7]. A vinyl chloride resin composition comprising the isophthalic acid diester produced by the method.

[Item 9] The vinyl chloride resin composition according to [Item 8], wherein the content of the isophthalic acid diester is 10 to 150 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

[Item 10] The vinyl chloride resin composition according to [Item 9], wherein the content of the isophthalic acid diester is 20 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

[Item 11] A vinyl chloride resin molded article, which is a molded product of the vinyl chloride resin composition according to any one of [Item 8] to [Item 10].

  The plasticizer for vinyl chloride resins of the present invention can be used as a plasticizer having good cold resistance and flexibility, which is the inherent performance of the plasticizer, and very excellent heat resistance. In addition, the plasticizer for vinyl chloride resin of the present invention has good compatibility with vinyl chloride resin, is also excellent in migration resistance and bleed out resistance, and can be used in a wide range of applications. Therefore, the vinyl chloride resin composition containing the plasticizer for vinyl chloride resin of the present invention and the molded article thereof have excellent heat resistance without any problems such as performance degradation due to migration of plasticizer and bleed out. Because of its properties, it is very useful as a vinyl chloride resin composition for covering electric wires, for automobiles, such as interior materials, for flooring, for various medical treatments, etc., and as industrial sheet materials.

<Plasticizer for vinyl chloride resin>
The plasticizer for vinyl chloride resin of the present invention is characterized by being essentially composed of an isophthalic 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, which is mainly composed of an alkyl group having 9 carbon atoms, and is linear relative to the total amount of the alkyl group The ratio (molar ratio) of the alkyl group is 50 to 99%, preferably 55 to 95%, more preferably 60 to 95%.

  The isophthalic acid diester (hereinafter referred to as "the ester") according to the present invention is not particularly limited by the method for producing the same as long as the effects of the present invention are not impaired. In a conventional manner, preferably under an inert gas atmosphere such as nitrogen, in the absence of a catalyst or in the presence of a catalyst, and easily obtained by an esterification reaction or a transesterification reaction.

[Alcohol component]
The alcohol component used for the esterification reaction or transesterification reaction is composed of a saturated aliphatic alcohol (hereinafter sometimes simply referred to as "saturated aliphatic alcohol") mainly composed of a saturated aliphatic alcohol having 9 carbon atoms, 50 to 99 mol%, preferably 60 to 95 mol%, more preferably 70 to 90 mol% of a linear saturated aliphatic alcohol having a carbon number of 9 to 50 mol% in the alcohol component, and 1 to 50 mol %, Preferably 5 to 40 mol%, more preferably 10 to 30 mol%, of a branched saturated aliphatic alcohol having 9 carbon atoms such as 2-methyloctanol. When the content of the linear saturated aliphatic alcohol having 9 carbon atoms is less than 50 mol%, cold resistance and heat resistance tend to be poor and flexibility tends to decrease, and when it exceeds 99 mol%, vinyl chloride type The compatibility with the resin tends to decrease, and there is a concern that the physical properties may be reduced due to migration of the plasticizer and bleeding out, which is not preferable. In addition, the said saturated aliphatic alcohol is a raw material alcohol used as the alkyl group which comprises the isophthalic-acid diester shown by said General formula (1), ie, the said description becomes synonymous with description of this alkyl group.

  Further, the saturated aliphatic alcohol used in the present invention produces (1) α-olefin having 1-octene as a main component, and aldehyde having 9 carbon atoms as a main component by hydroformylation reaction of carbon monoxide and hydrogen. It can manufacture by the manufacturing process which comprises the process and the process of hydrogenating the aldehyde which has (2) C9 as a main component, and reduce | restoring to alcohol.

  The hydroformylation reaction which is the above-mentioned step (1) has, for example, mainly 9 carbon atoms by reacting an α-olefin mainly composed of 1-octene, carbon monoxide and hydrogen in the presence of a cobalt catalyst or a rhodium catalyst. It is possible to produce an aldehyde as a component.

  The hydrogenation in the step (2) is reduced to an alcohol by hydrogenating an aldehyde containing 9 carbons as a main component under hydrogen pressure in the presence of a noble metal catalyst such as, for example, a nickel catalyst or a palladium catalyst. be able to. In addition, a reduction method using a reagent is also exemplified.

  Specific examples of the saturated aliphatic alcohol mainly composed of a saturated aliphatic alcohol having 9 carbon atoms obtained by the above-mentioned production process include about 70% or more of linear nonanol and about 30% or less of branched one. Examples thereof include Lineeball 9 (trade name, Shell Chemicals Co., Ltd.), which is a mixture of nonanol.

[Acid component]
The acid component used for the esterification reaction or transesterification reaction is isophthalic acid or dimethyl isophthalic acid, and is not particularly limited, and those produced by known methods, those available as commercial products, reagents, etc. are used. it can.

  Moreover, although the said dimethyl isophthalate is preferable as an acid component of transesterification, in addition, the lower alkyl ester (for example, carbon number 2 or 3) of isophthalic acid can be used equally.

[Esterification reaction]
The esterification reaction according to the present invention means an esterification reaction of the alcohol component and isophthalic acid which is an acid component, and when the esterification reaction is carried out, the alcohol component is, for example, 1 mol of isophthalic acid. Preferably, it is recommended to use 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.

  When a catalyst is used in the esterification reaction, examples of the catalyst include mineral acids, organic acids or Lewis acids. More specifically, examples of mineral acids include sulfuric acid, hydrochloric acid and phosphoric acid, examples of organic acids include p-toluenesulfonic acid and methanesulfonic acid, and examples of Lewis acids include aluminum derivatives, tin derivatives and titanium. The derivatives, lead derivatives and zinc derivatives are exemplified, and one or more of them can be used in combination.

  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 to 5.0% by weight, more preferably 0.02 to 4.0% by weight, particularly preferably 0.01 to 5.0% 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 0.03 to 3.0% by weight.

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

[Ester exchange reaction]
The transesterification according to the present invention means transesterification of the alcohol component and dimethyl isophthalate which is an acid component, and when the transesterification is carried out, the alcohol component is, for example, 1 mol of dimethyl isophthalate. Preferably, it is recommended to use 2.00 to 5.00 mol, more preferably 2.01 to 3.00 mol, especially 2.02 to 2.50 mol.

  When a catalyst is used for transesterification reaction, Lewis acids or alkali metals are exemplified as the catalyst. More specifically, examples of Lewis acids include aluminum derivatives, tin derivatives, titanium derivatives, lead derivatives and zinc derivatives, and examples of alkali metals include sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide and the like. It is possible to use one or more of these in combination.

  Among them, tetraalkyl titanate having 3 to 8 carbon atoms, titanium oxide, titanium hydroxide, sodium alkoxide having 1 to 4 carbon atoms, sodium hydroxide, fatty acid tin having 3 to 12 carbon atoms, tin oxide, tin hydroxide, oxide Particularly preferred are zinc, zinc hydroxide, lead oxide, lead hydroxide, aluminum oxide and aluminum hydroxide. The amount thereof is, for example, preferably 0.01 to 5.0% by weight, more preferably 0.02 to 4.0% by weight, particularly preferably 0.01 to 5.0% 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 0.03 to 3.0% by weight.

  The temperature of the transesterification is, for example, 100 to 230 ° C. and the reaction is usually completed in 3 to 30 hours.

  In the esterification reaction or transesterification reaction, it is possible to use an entrainer or entrainer such as benzene, toluene, xylene, cyclohexane or the like to accelerate the distillation of water or methanol produced by the reaction.

  In addition, when oxygenated organic compounds such as oxides, peroxides and carbonyl compounds are produced by oxidation degradation of raw materials, formed ester and entrainer (entrainer) at the time of esterification reaction or transesterification reaction, heat resistance, weather resistance etc. Adversely affect. In order to suppress the adverse effect and from the viewpoint of safety, 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 or transesterification reaction, the excess raw material is usually distilled off under reduced pressure or under normal pressure.

  The reaction crude of the above ester is usually purified by subsequent workup. For example, treatment methods employed in this technical field such as catalyst inactivation treatment (neutralization treatment, base treatment, acid treatment, etc.), water washing treatment, liquid-liquid extraction, distillation (pressure reduction, dehydration treatment), adsorption purification treatment, etc. Can be purified alone or in combination.

  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. They can be used alone or in combination of two or more.

  Examples of the adsorbent used for adsorption purification 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 above treatment may be carried out at normal temperature, but can also be carried out under normal pressure or reduced pressure by heating to about 40 to 95 ° C.

<Vinyl chloride resin composition>
The vinyl chloride resin composition of the present invention is obtained by blending the above-mentioned ester as a plasticizer with a vinyl chloride resin.

[Vinyl chloride resin]
The vinyl chloride-based 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. In the case of a resin, a method of suspension polymerization in the presence of an oil-soluble polymerization catalyst may be mentioned, and in the case of a 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 150 parts by weight, preferably 10 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. It is 150 parts by weight, more preferably 20 to 100 parts by weight, still more preferably 5 to 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 150 parts by weight, the bleeding to the surface of the molded article is severe and it is not preferable in any 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.

  The vinyl chloride resin composition can be used in combination with the ester and other known plasticizers, depending on the purpose of use of the vinyl chloride resin molded article. In addition, 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 Additives such as antistatic agents can be blended.

  The plasticizers and additives other than the above-mentioned ester may be blended together with the present ester singly or in appropriate combination of two or more.

  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) Phthalate esters such as diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), terephthalic acid esters such as bis (2-ethylhexyl) terephthalate (DOTP), bis isophthalic acid Isophthalic acid esters other than this ester such as (2-ethylhexyl) (DOIP), di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), sebacic acid di-2- Ethyl hexyl DOS), Aliphatic dibasic acid esters such as diisononyl sebacate (DINS), Tri-2-ethylhexyl trimellitate (TOTM), Triisononyl trimellitate (TINTM), Trimellist such as triisodecyl trimellitate (TIDTM) Acid esters, pyromellitic acid esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM), tri-2-ethylhexyl phosphate (TOP), phosphoric acid esters such as tricresyl phosphate (TCP), pentaerythritol, etc. Alkyl esters of polyhydric alcohols, polyesters having a molecular weight of 800 to 4000 synthesized by polyesterifying dibasic acids such as adipic acid and glycols, epoxidized soybean oil such as epoxidized soybean oil, epoxidized linseed oil, hexacarboxylic acid Hydrophal Alicyclic dibasic acids such as diisononyl ester (DINCH), fatty acid glycol esters such as dicapric acid 1.4-butanediol, tributyl acetyl citrate (ATBC), chlorinated chlorinated paraffin wax and n-paraffin Examples thereof include paraffins, chlorinated fatty acid esters such as chlorinated stearic acid esters, and higher fatty acid esters such as butyl oleate. The blending amount of the plasticizer is about 1 to 100 parts by weight.

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

  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. Further, the blending amount of the stabilizer with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 20 parts by weight.

  Stabilization aids include phosphite compounds such as triphenyl phosphite, monooctyl diphenyl phosphite 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. Further, the blending amount of the stabilizing aid is 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. Further, the blending amount of the coloring agent is 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 amides, ethylenebisstearic acid amides, butyl stearate, calcium stearate and the like. Moreover, the compounding quantity of the processing aid with respect to 100 parts by weight of vinyl chloride resin is about 0.1 to 20 parts by weight.

  As the filler, metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, ferrite, etc., fibers and powders of glass, carbon, metal etc., glass spheres, graphite, aluminum hydroxide, barium sulfate, oxide Magnesium, magnesium carbonate, magnesium silicate, calcium silicate and the like are exemplified. In addition, the compounding amount of the filler is about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

  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, the compounding quantity of the antioxidant with respect to 100 weight part of vinyl chloride type resin is about 0.2-20 weight part.

  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. Further, the blending amount of the ultraviolet light absorber is 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. Further, the compounding amount of the light stabilizer is about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

  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. Further, the compounding amount of the lubricant is about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

  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. The amount of the antistatic agent is 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 plasticizer for vinyl chloride resin of the present invention, a vinyl chloride resin, and, if necessary, the above known plasticizer and various additives, for example, pony mixer, butterfly Agitation mixers such as mixers, planetary mixers, dissolvers, twin screw mixers, three-roll mills, mortar mixers, Henschel mixers, Banbury mixers, ribbon blenders, etc .; Conical twin screw extruder, parallel twin screw extruder; single screw extruder, Stir mixing or melt mixing is performed by a kneader such as a co-kneader type kneader or a roll kneader to obtain a powder, pellet or paste 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 paste-like vinyl chloride resin composition is molded into a desired shape by molding and processing using a conventionally known method such as spread molding, dipping molding, gravure molding, slush molding, screen processing and the like. Can.

  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.

  In particular, since the molded body is excellent in high heat resistance and cold resistance while maintaining good moldability and flexibility, the electric wire / cable which is placed in high temperature and low temperature harsh environments outdoors etc. It is suitable as a coating material.

  In addition, the molded body is excellent in bleed-out resistance while maintaining high heat resistance and cold resistance, so it is placed not only at high temperature and low temperature but also in a more severe environment such as high humidity, environmental regulations, etc. It is suitable for industrial material sheets such as more severe wall and floor materials and waterproof sheets.

  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 Linear Alkyl Group in Alkyl Group The ratio of linear alkyl group in the alkyl group in the plasticizer used in the examples and comparative examples of the present invention is the same as that in the raw material alcohol used for the production. The composition was measured by gas chromatography (hereinafter abbreviated as GC), and the result was 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 DB-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
Determination: It quantified using 1-hexanol as an internal standard substance.
In selecting the internal standard substance, it was previously confirmed that 1-hexanol as a raw material alcohol was below the detection limit by GC.
In the above-mentioned esterification reaction and transesterification reaction, within the scope of the present invention, there is no difference in reactivity due to the structure of the raw material alcohol, and the difference between the composition ratio in the raw material alcohol used and the composition ratio of the alkyl group in this ester I have confirmed in advance that there is no.

(2) Physical Property Evaluation 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: Measured according to JIS K-0071 (Hazen) (1998) to obtain the Hazen unit color number.

(3) Preparation of vinyl chloride sheet 100 parts by weight of vinyl chloride resin (straight, degree of polymerization 1050, trade name "Zest 1000 Z", manufactured by Shin-ichi Daiichi PVC Co., Ltd.), calcium stearate as a stabilizer (Nacalai Tesque Inc.) 0.3 and 0.2 parts by weight of zinc stearate (manufactured by Nacalai Tesque, Inc.) and mixed with stirring using a mortar mixer, and then 50 parts by weight of a plasticizer is added and handled until uniform It mixed and was set as the vinyl chloride resin composition. The resin composition was melt-kneaded for 4 minutes at 160 ° C. using a 5 × 12 inch two-roll mill to form a roll sheet. Subsequently, press molding was performed at 162 ° C. for 10 minutes to prepare a press sheet having a thickness of about 1 mm.

[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 roll sheet was measured after heating the roll sheet at 170 ° C. for 60 minutes and 120 minutes in a gear oven, and the weight reduction rate (%) was calculated. The smaller the value, the better the heat resistance.
Weight loss rate (%) = ((weight before test-weight after test) / weight before test) x 100
b) Sheet coloring: The strength of the degree of coloring after heating the roll sheet at 170 ° C. for 30 minutes in a gear oven was visually evaluated in four steps.
◎: no coloration, :: slightly colored, Δ: colored, ×: strongly colored.

(7) Bleed-out resistance:
A test piece (25 mm × 60 mm × 1 mm) cut out from the press sheet was hung under the environment of 70 ° C. 90% RH (Relative Humidity), and after 1 week each, the sheet surface was visually observed and evaluated according to the following criteria ,
:: Good (no bleed)
○: Slightly good (Bleeding is slightly recognized but there is no problem in practical use)
:: Slightly defective (some bleeding is observed, and there is a problem in practical use)
X: Bad (with bleed)

Production Example 1
A 1-liter four-necked flask equipped with a thermometer, a decanter, a stirring blade, and a reflux condenser, 83.1 g (0.5 mol) of isophthalic acid, and a linear saturated aliphatic alcohol having 9 carbon atoms as the raw material alcohol 88 .75 g (1.2 mol) of an aliphatic saturated alcohol containing 11.1 mol% of a branched saturated aliphatic alcohol having 5 mol% and 9 carbon atoms (manufactured by Shell Chemicals, product name: Lineeball 9), and an ester An esterification reaction was carried out by adding 0.1 g of tetraisopropyl titanate as a conversion catalyst and setting the reaction temperature to 185.degree. The reaction was carried out until the acid value of the reaction solution reached 0.5 KOHmg / 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 188 g of the desired isophthalic acid diester (hereinafter referred to as "ester 1"). .
The obtained ester 1 had an ester value of 266 mg KOH / g, an acid value of 0.01 mg KOH / g, and a color number of 10.

Production Example 2
N-nonyl alcohol (reagent, 100% linear ratio) 163 g (1.133 mol) and isononyl alcohol (commercially available, linear chain instead of 173 g of saturated aliphatic alcohol (manufactured by Shell Chemicals, product name: Lineeball 9) The same procedure as in Production Example 1 was carried out except that 10 g (0.067 mol) of 10% was added, to obtain 190 g of an isophthalic acid diester (hereinafter referred to as "ester 2").
The obtained ester 2 had an ester value of 266 mg KOH / g, an acid value of 0.01 mg KOH / g, and a color number of 10.

[Production Example 3]
Production Example 1 except that 115 g (0.8 mol) of n-nonyl alcohol and 58 g (0.4 mol) of isononyl alcohol are added instead of 173 g of saturated aliphatic alcohol (manufactured by Shell Chemicals, product name: Lineeball 9) In the same manner as in the above, 192 g of isophthalic acid diester (hereinafter referred to as "ester 3") was obtained.
The obtained ester 3 had an ester value of 267 mg KOH / g, an acid value of 0.02 mg KOH / g, and a color number of 10.

Production Example 4
Production Example 1 except that 77 g (0.533 mol) of n-nonyl alcohol and 96 g (0.667 mol) of isononyl alcohol are added instead of 173 g of aliphatic saturated alcohol (manufactured by Shell Chemicals, product name: Lineeball 9) In the same manner as in the above, 180 g of isophthalic acid diester (hereinafter referred to as "ester 4") was obtained.
The obtained ester 4 had an ester value of 267 mg KOH / g, an acid value of 0.03 mg KOH / g, and a color number of 10.

Production Example 5
It is carried out in the same manner as in Production Example 1 except that 156 g (1.2 mol) of 2-ethylhexanol (commercially available product) is added instead of 173 g of aliphatic saturated alcohol (manufactured by Shell Chemicals, product name: Lineeball 9), 179 g of isophthalic acid diester (hereinafter referred to as "ester 5") were obtained.
The obtained ester 5 had an ester value of 285 mg KOH / g, an acid value of 0.03 mg KOH / g, and a color number of 20.

Production Example 6
It is carried out in the same manner as in Production Example 1 except that 173 g (1.2 mol) of n-nonanol is added instead of 173 g of aliphatic saturated alcohol (manufactured by Shell Chemicals, product name: Lineeball 9), and isophthalic acid diester , "Ester 6".
The obtained ester 6 had an ester value of 266 mg KOH / g, an acid value of 0.04 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 a vinyl chloride sheet was produced from the obtained vinyl chloride resin, and a tensile test, a cold resistance test, a heat resistance test and a bleed out test were conducted. The obtained results are summarized in Table 1.

Example 2
A vinyl chloride sheet is produced in the same manner as in Example 1 except that the ester 2 obtained in Production Example 2 is used instead of the ester 1, and a tensile test, a cold resistance test, a heat resistance test and a bleed out are performed. The sex test was done. The obtained results are summarized in Table 1.

[Example 3]
A vinyl chloride sheet is prepared in the same manner as in Example 1 except that the ester 3 obtained in Production Example 3 is used instead of the ester 1, and a tensile test, a cold resistance test, a heat resistance test and a bleed out are performed. The sex test was done. The obtained results are summarized in Table 1.

Example 4
A vinyl chloride sheet is prepared in the same manner as in Example 1 except that the ester 4 obtained in Production Example 4 is used instead of the ester 1, and a tensile test, a cold resistance test, a heat resistance test and a bleed out are performed. The sex test was done. The obtained results are summarized in Table 1.

Comparative Example 1
A vinyl chloride sheet is prepared in the same manner as in Example 1 except that the ester 5 obtained in Production Example 5 is used instead of the ester 1, and a tensile test, a cold resistance test, a heat resistance test and a bleed out are performed. The sex test was done. The obtained results are summarized in Table 1.

Comparative Example 2
A vinyl chloride sheet is prepared in the same manner as in Example 1 except that the ester 6 obtained in Production Example 6 is used instead of the ester 1, and a tensile test, a cold resistance test, a heat resistance test and a bleed out are performed. The sex test was done. The obtained results are summarized in Table 1.

Comparative Example 3
A vinyl chloride sheet was prepared in the same manner as in Example 1 except that a commercially available DOP was used instead of the ester 1, and a tensile test, a cold resistance test, a heat resistance test and a bleed out test were conducted. The obtained results are summarized in Table 1.

Comparative Example 4
A vinyl chloride sheet is produced in the same manner as in Example 1 except that commercially available diisononyl phthalate (hereinafter referred to as "DINP") is used instead of ester 1, and a tensile test, a cold resistance test, a heat resistance test And a bleed-out resistance test. The obtained results are summarized in Table 1.

  From the results of Table 1, molded articles (Examples 1 to 5) obtained from the vinyl chloride resin composition using the isophthalic acid diester according to the present invention as a plasticizer, used general-purpose phthalic esters such as DOP and DINP. Compared with the molded articles used (Comparative Examples 3 and 4) and the molded articles using a conventionally known isophthalic acid ester such as DOIP (Comparative Example 1), the heat resistance, cold resistance, particularly heat resistance is very high. It is clear that it is excellent. Moreover, the isophthalic acid diester of the present invention does not have any reduction in the bleed out resistance which was a problem when using isophthalic acid ester (comparative example 2) which is said to have good heat resistance and cold resistance. It is clearly shown.

  The isophthalic acid diester according to the present invention is very excellent in cold resistance and heat resistance, has good compatibility with a vinyl chloride resin, and is also excellent in bleed out resistance and migration resistance. The vinyl chloride resin composition and its molded product using the plasticizer are extremely excellent in heat resistance and cold resistance, and cause deterioration in performance and troubles due to migration and bleeding out of the plasticizer. As coverings for electric wires and cables, various automobile members such as interior materials, various medical materials such as bags and tubes, and sheet materials for various industries such as agriculture and civil engineering and construction, etc. It is useful.

Claims (7)

It consists of an isophthalic acid diester shown by following General formula (1), The alkyl group which comprises this diester is mainly comprised from a C9 alkyl group, The ratio (mol of the linear alkyl group to the whole quantity of this alkyl group) Ratio is 50 to 99%.
(Wherein, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group having 7 to 11 carbon atoms.) The plasticizer for vinyl chloride resins according to claim 1, wherein the proportion of linear alkyl groups in the alkyl group is 55 to 95%. The plasticizer for vinyl chloride resins according to claim 2, wherein the proportion of linear alkyl groups in the alkyl group is 60 to 95%. A method for producing an isophthalic acid diester for use in a plasticizer for a vinyl chloride resin according to any one of claims 1 to 3, which is isophthalic acid or its dimethyl ester, and a saturated aliphatic alcohol having 9 carbon atoms. Production of an isophthalic acid diester characterized by esterification reaction or transesterification reaction with a saturated aliphatic alcohol having a proportion (molar ratio) of a linear saturated aliphatic alcohol of 50 to 99 as a main component Method. A process of producing an aldehyde having 9 carbons as a main component by the hydroformylation reaction of (1) 1-octene, an α-olefin, the carbon monoxide and hydrogen; 5. The method according to claim 4, which is obtained by a method comprising the step of hydrogenating an aldehyde containing carbon atoms 9 as a main component to reduce it to an alcohol. It is characterized by containing a vinyl chloride resin and the isophthalic acid diester according to any one of claims 1 to 3 as a plasticizer, or the isophthalic acid diester produced by the production method according to claim 4 or 5. Vinyl chloride resin composition. A vinyl chloride resin molded article, which is a molded article of the vinyl chloride resin composition according to claim 6.