JP2017200976A - Method for improving thermostable colorability of vinyl chloride resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for improving thermostable coloration while maintaining excellent flexibility and cold resistance in a vinyl chloride resin, especially in a medical material, a vinyl chloride resin composition with the thermostable coloration improved by the method, a vinyl chloride resin molding made of the same with lowered thermal coloration, a medical material composed of the molding, and a plasticizer composition being a raw material thereof and effective to improve thermostable colorability.SOLUTION: By blending a plasticizer composition including trimellitic acid triester of a specific structure and 4-cyclohexene-1,2-dicarboxylic acid diester of a specific structure into a vinyl chloride resin as a plasticizer, thermostable colorability, which has been a problem, can be improved as well as excellent flexibility, cold resistance and thermostability are achieved.SELECTED DRAWING: None

Description

  The present invention relates to a method for suppressing coloration of a vinyl chloride resin molded body, and more specifically, as a plasticizer, a plasticizer comprising trimellitic acid triester having a specific structure and 4-cyclohexene-1,2-dicarboxylic acid diester. The present invention relates to a method for suppressing coloring, particularly thermal coloring, of a vinyl chloride resin molded article by using a composition.

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

  The performance required for the plasticizer used in such a vinyl chloride resin composition includes various properties such as flexibility, cold resistance, heat resistance, and electrical characteristics when the composition is used as a raw material. As typical plasticizers used in such vinyl chloride resin compositions, higher alkyl esters of polybasic acids such as phthalic acid esters, adipic acid esters and trimellitic acid esters are known, either alone or Used in combination of two or more. Up to now, phthalates have been mainly used in terms of price and performance balance, but trimellitic esters are often used in applications that require heat resistance that cannot be handled by phthalates. (Patent Documents 1 to 5).

  As described above, the vinyl chloride resin has various characteristics from its unique structure and is widely used, but the colorability resulting from the structure, particularly the colorability during heating, is a major issue. Often used with a stabilizer or the like added. In addition, in the case of a soft material with a large amount of plasticizer added, it is known that coloring can be suppressed by using an ester plasticizer such as trimellitic acid or cyclohexene dicarboxylic acid depending on the type of plasticizer to be added. Yes.

  However, in recent years, the required performance has become increasingly severe in various fields, and the same applies to heat-resistant colorability. For example, in the field of automotive interior materials, there is a demand for materials that do not change their appearance for a long time even under harsh conditions such as in hot weather, and in the field of medical materials, the contents have become more visible than the current state of frequent medical accidents. Therefore, a material with little coloring due to heating or the like is required (Patent Documents 6 to 10).

Japanese Patent Laying-Open No. 2015-74709 Japanese Patent Laid-Open No. 2003-165881 JP 2006-239026 A JP2012-081247A JP 60-115640 A JP 2012-81247 A Japanese Patent Laid-Open No. 08-024329 Japanese Patent Laid-Open No. 08-176383 Japanese Patent Laid-Open No. 56-061448 Japanese Patent Laid-Open No. 02-222436

  An object of the present invention is to provide a method that satisfies the above-described requirements, that is, a method for improving heat-resistant coloring while maintaining the excellent flexibility, cold resistance, and heat resistance inherent in the vinyl chloride resin. .

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have combined the trimellitic acid triester having a specific structure with 4-cyclohexene-1,2-dicarboxylic acid diester, but the reason is not clear. The present inventors have found that an effect of improving heat-resistant colorability, which was not obtained with each ester, can be obtained, and the present invention has been completed.

  Also, a vinyl chloride resin containing a trimellitic acid triester plasticizer, which has been a problem in the past, by using 4-cyclohexene-1,2-dicarboxylic acid diester having a specific structure in the course of the above study. It has been found that improvements can also be made regarding the processability of the composition.

  That is, the present invention provides a plasticizer composition, a vinyl chloride resin composition containing the plasticizer composition, a vinyl chloride resin molded article comprising the plasticizer composition, a heat resistant coloring improvement method, and a processability improvement method. It is to provide.

[Item 1] A plasticizer composition for a vinyl chloride resin comprising (A) trimellitic acid triester and (B) 4-cyclohexene-1,2-dicarboxylic acid diester,
Component (A) is trimellitic acid triester represented by the following general formula (1):
And,
A plasticizer composition for a vinyl chloride resin, wherein the component (B) is 4-cyclohexene-1,2-dicarboxylic acid diester represented by the following general formula (2).
[Wherein R ¹ , R ² and R ³ are the same or different and are each a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a straight chain having 7 to 13 carbon atoms. Or branched chain saturated aliphatic alcohol. ]
[Wherein, R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is linear or branched having 7 to 13 carbon atoms. It is a chain saturated aliphatic alcohol. ]

[Claim 2] The plasticizer composition according to [Claim 1], wherein the ratio (weight ratio) of the component (A) to the component (B) is in the range of 95/5 to 30/70.

[Claim 3] The plasticizer composition according to [Claim 2], wherein the ratio (weight ratio) of the component (A) to the component (B) is in the range of 90/10 to 40/60.

[Claim 4] The plasticizer composition according to [Claim 3], wherein the ratio (weight ratio) of the component (A) to the component (B) is in the range of 80/20 to 50/50.

[Item 5] The saturated aliphatic alcohol in the general formula (1) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 9% or more by weight. [Claim 1]-containing a saturated aliphatic alcohol having a chain shape and a branched saturated aliphatic alcohol having 9 or less carbon atoms and having a carbon number of not more than 40% by weight, and the linear ratio of the saturated aliphatic alcohol being 60% or more. The plasticizer composition according to any one of [Item 4].

[Claim 6] Any one of [Claim 1] to [Claim 5], wherein the saturated aliphatic alcohol in the general formula (2) is a linear or branched saturated aliphatic alcohol having mainly 8 carbon atoms. Plasticizer composition.

[Claim 7] The plasticizer composition according to [Claim 6], wherein the saturated aliphatic alcohol in the general formula (2) is a linear or branched saturated aliphatic alcohol having 8 carbon atoms.

CLAIM | ITEM 8 The plasticizer composition as described in [Claim 7] whose saturated aliphatic alcohol in General formula (2) is 2-ethylhexanol.

[Section 9] The saturated aliphatic alcohol in the general formula (2) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 9% or more by weight. [Claim 1]-containing a saturated aliphatic alcohol having a chain shape and a branched saturated aliphatic alcohol having 9 or less carbon atoms and having a carbon number of not more than 40% by weight, and the linear ratio of the saturated aliphatic alcohol being 60% or more. The plasticizer composition according to any one of [5].

[Item 10] The saturated aliphatic alcohol in the general formula (2) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 9 wt% or more. [Claim 9] containing a saturated aliphatic alcohol having a chain shape and a branched saturated aliphatic alcohol having 9 or less carbon atoms and having a carbon number of 9 or less, and the saturated aliphatic alcohol has a linear ratio of 70% or more. The plasticizer composition as described.

[Item 11] The saturated aliphatic alcohol in the general formula (2) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the content in the saturated aliphatic alcohol is 9 to 9 carbon atoms of 75 to 98% by weight or more. It contains a linear saturated aliphatic alcohol and a branched saturated aliphatic alcohol having 9 to 9 carbon atoms and having a carbon number of 2 to 25% by weight, and the linear ratio of the saturated aliphatic alcohol is 75 to 98% or more. The plasticizer composition according to [Item 10].

[Claim 12] The plasticizer composition according to any one of [Claim 1] to [Claim 11], wherein the vinyl chloride resin is a vinyl chloride resin for medical materials.

[Item 13] A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer composition according to any one of [Item 1] to [Item 12].

[Item 14] The vinyl chloride resin according to Item 13, wherein the content of the plasticizer composition in the vinyl chloride resin composition is 20 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. Composition.

[Item 15] The vinyl chloride resin according to Item 14, wherein the content of the plasticizer composition in the vinyl chloride resin composition is 30 to 150 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. Composition.

[Item 16] A vinyl chloride resin molded article using the vinyl chloride resin composition according to any one of [Item 13] to [Item 15] as a raw material.

[Item 17] A medical material comprising the vinyl chloride resin molded article according to Item 16.

[Item 18] The medical material according to [Item 17], wherein the medical material is a medical tube.

[Item 19] A method for improving the heat resistant colorability of a vinyl chloride resin molded article,
For vinyl chloride resin comprising (A) trimellitic acid triester represented by the following general formula (1) and (B) 4-cyclohexene-1,2-dicarboxylic acid diester represented by the following general formula (2) The plasticizer composition is used as a plasticizer for a vinyl chloride resin that is a raw material resin of a vinyl chloride resin molded article.
[Wherein R ¹ , R ² and R ³ are the same or different and are each a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a straight chain having 7 to 13 carbon atoms. Or branched chain saturated aliphatic alcohol. ]
[Wherein, R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is linear or branched having 7 to 13 carbon atoms. It is a chain saturated aliphatic alcohol. ]

[Item 20] A method for improving the processability of a vinyl chloride resin composition comprising a trimellitic acid triester plasticizer,
In addition to trimellitic acid triester, a plasticizer composition for vinyl chloride resin comprising 4-cyclohexene-1,2-dicarboxylic acid diester represented by the following general formula (2) is used for vinyl chloride resin: A method characterized by being used as a plasticizer.
[Wherein, R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a linear or branched chain having 8 carbon atoms. Is a saturated fatty alcohol. ]

  The plasticizer composition for vinyl chloride resin of the present invention is a plasticizer for vinyl chloride resin that has good flexibility, cold resistance, and heat resistance, and can improve the heat resistance coloring property that has been a problem. Can be used. In addition, by including the plasticizer for vinyl chloride resin, the vinyl chloride resin composition has excellent flexibility, cold resistance and heat resistance, and further improved heat resistance coloring property, that is, extremely excellent durability. And a molded product thereof can be obtained, and can be suitably used as a medical material (especially a medical tube) requiring particularly high heat-resistant coloring. In addition, when 4-cyclohexene-1,2-dicarboxylic acid diester having a specific structure is used, processability can be improved, and further practicality is expected.

<Plasticizer composition for vinyl chloride resin>
The plasticizer composition for vinyl chloride resin of the present invention comprises (A) trimellitic acid triester represented by the following general formula (1) and (B) 4-cyclohexene- represented by the following general formula (2). It is characterized by comprising 1,2-dicarboxylic acid diester.
[Wherein R ¹ , R ² and R ³ are the same or different and are each a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a straight chain having 7 to 13 carbon atoms. Or branched chain saturated aliphatic alcohol. ]
[Wherein, R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is linear or branched having 7 to 13 carbon atoms. It is a chain saturated aliphatic alcohol. ]

  In the present invention, the plasticizer composition includes not only those preliminarily mixed but also a plasticizer component including the component (A) and the component (B) blended in the vinyl chloride resin at the same time.

  As a preferred embodiment of the trimellitic acid triester of the component (A) (hereinafter referred to as “the present ester compound 1”), a saturated aliphatic alcohol that defines the residue in the general formula (1) is carbon The aspect which is a linear or branched saturated aliphatic alcohol of several 7-13, preferably 8-11 is mentioned. Among these, as a more preferable embodiment, the Hoiwa aliphatic alcohol that defines the residue is (i) a linear or branched chain mainly composed of a saturated aliphatic alcohol having 8 or 9 carbon atoms. A saturated aliphatic alcohol, (ii) a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the content in the saturated aliphatic alcohol defining the residue is 9 carbon atoms having 60% by weight or more Linear saturated fatty alcohol and 40% by weight or less of a branched saturated aliphatic alcohol having 9 carbon atoms, and the linear ratio of the saturated aliphatic alcohol defining the residue is 60 % (Iii) a mixture of saturated aliphatic alcohols having mainly 9 to 11 carbon atoms, and the ratio (molar ratio) of each alcohol having 9, 10, and 11 carbon atoms is 10 to 25/35 to 50 / A range of 30 to 45, One linear rate of saturated fatty alcohols of the residues defining is recommended like manner is 55% or more.

  The ester compound 1 is not particularly limited by its production method as long as it satisfies the object performance of the present invention. For example, trimellitic acid or an anhydride thereof and a saturated aliphatic alcohol having a specific structure. Can be easily obtained by esterification 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. Further, depending on the type of saturated aliphatic alcohol, after esterification with a lower alcohol having about 1 to 6 carbon atoms in advance, the saturated aliphatic alcohol is added, and according to a conventional method, preferably in an inert gas atmosphere such as nitrogen It can also be easily obtained by transesterification in the absence of a catalyst or in the presence of a catalyst.

  As a preferred embodiment of the 4-cyclohexene-1,2-dicarboxylic acid diester compound (hereinafter referred to as “the present ester compound 2”) as the component (B), the residue in the general formula (2) is defined. An embodiment in which the saturated aliphatic alcohol is a linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms, preferably 8 to 11 carbon atoms.

  Among these, as a more preferable embodiment, the saturated aliphatic alcohol that defines the residue is (i) a linear or branched saturated aliphatic alcohol mainly composed of a saturated aliphatic alcohol having 9 carbon atoms. An embodiment which is an alcohol; (ii) a linear chain having 9 carbon atoms, the main component of which is a saturated aliphatic alcohol having 9 carbon atoms, and the content in the saturated aliphatic alcohol defining the residue is 60% by weight or more Of the saturated aliphatic alcohol and the branched saturated aliphatic alcohol having 9 or less carbon atoms and 40% by weight or less, and the linear ratio of the saturated aliphatic alcohol defining the residue is 60% or more Embodiment (iii) is a mixture of mainly saturated aliphatic alcohols having 9 to 11 carbon atoms, and the ratio (molar ratio) of each alcohol having 9, 10, and 11 carbon atoms is 10-25 / 35-50 / 30-45 And the residue is Straight ratio of saturated fatty alcohols are constant is recommended like manner is 55% or more.

  Further, regarding the processability improving method described in [Item 20] above, from the viewpoint of improving the processability of trimellitic acid ester plasticizers such as the present ester compound 1, etc., as a more preferred embodiment, An embodiment in which the saturated aliphatic alcohol that defines the residue in Formula (2) is a linear or branched saturated aliphatic alcohol mainly composed of a saturated aliphatic alcohol having 8 carbon atoms.

  The ester compound 2 is not particularly limited by its production method as long as it satisfies the object performance of the present invention. For example, it is specified as 4-cyclohexene-1,2-dicarboxylic acid or an anhydride thereof. It can be easily obtained by esterification with a saturated aliphatic alcohol having the following structure 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. Further, depending on the type of saturated aliphatic alcohol, after esterification with a lower alcohol having about 1 to 6 carbon atoms in advance, the saturated aliphatic alcohol is added, and according to a conventional method, preferably in an inert gas atmosphere such as nitrogen It can also be easily obtained by transesterification in the absence of a catalyst or in the presence of a catalyst.

  The ratio (weight ratio) of the component (A) to the component (B) is preferably (A) / (B) = 95/5 to 30/70, more preferably 90/10 to 40/60, particularly preferably. 80/20 to 50/50 is recommended. When the ratio of the component (A) to the component (B) is within the above range, the effect of combining the component (A) and the component (B), that is, the effect of improving the heat-resistant coloring property can be expressed more preferentially. Can do.

[Saturated fatty alcohol]
The saturated aliphatic alcohol used as a raw material for the ester compound 1 and the ester compound 2 is a linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms, preferably 8 to 11 carbon atoms. When a saturated aliphatic alcohol having a carbon number of less than 7 is included, the performance such as volatility tends to decrease, and when a saturated aliphatic alcohol having a carbon number of more than 13 is included, the performance such as flexibility is decreased. There is a tendency and neither is preferable.

  More specifically, for example, the saturated aliphatic alcohol includes (i) a linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms, and a saturated aliphatic alcohol having 9 carbon atoms. The saturated aliphatic alcohol as a main component, the ratio of the saturated aliphatic alcohol having 9 carbon atoms as the main component in the linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms, Preferably 60% by weight or more (60-100% by weight), more preferably 70% by weight or more (70-100% by weight), particularly preferably 80% by weight or more (80-100% by weight), (Ii) mainly composed of a linear or branched saturated aliphatic alcohol having 9 to 11 carbon atoms, a saturated aliphatic alcohol having 9 carbon atoms / saturated aliphatic alcohol having 10 carbon atoms / saturated fat having 11 carbon atoms. Ratio of family alcohol (molar ratio) is a form etc. are recommended saturated aliphatic alcohols in the range of 10 to 25 / 35-50 / 30-45.

  When improvement in processability is also required, the saturated aliphatic alcohol used as a raw material for the ester compound 2 is a linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms, An embodiment that is a saturated aliphatic alcohol mainly composed of a saturated aliphatic alcohol having 8 carbon atoms is recommended.

  The “main component” means that the ratio in the saturated aliphatic alcohol is 60% or more, preferably 70% or more, more preferably 80% or more. This means that the ratio of the saturated aliphatic alcohol is 90% or more, preferably 95% or more.

  In the case of the recommended aspect of (i) or (ii), the saturated aliphatic alcohol according to the present invention preferably has a linear chain ratio of the saturated aliphatic alcohol of preferably 55% or more, more preferably A range of 60% or more, more preferably 70% or more, particularly preferably 75 to 98% is recommended.

  The content of the linear saturated aliphatic alcohol having 9 carbon atoms in the saturated aliphatic alcohol in the recommended embodiment of (i) above is preferably 60 wt% or more in the saturated aliphatic alcohol. A range of 70% by weight or more, particularly preferably in the range of 75 to 98% by weight is recommended, and a branched saturated aliphatic alcohol having 9 carbon atoms in a saturated aliphatic alcohol (for example, 2-methyloctanol) The content of is preferably 40% by weight or less, more preferably 30% by weight or less, and particularly preferably 2 to 25% by weight.

  As the details of the embodiment of the linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms, as the first preferred embodiment, the saturated aliphatic alcohol is a saturated aliphatic alcohol having 9 carbon atoms. It is a main component (preferably 60% by weight or more), and its content in a linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms is a straight chain having 9 carbon atoms having a content of 60% by weight or more. The linear chain ratio of a saturated aliphatic alcohol containing a saturated aliphatic alcohol and a branched saturated aliphatic alcohol having 9 to 9 carbon atoms and having a carbon number of 9 to 13 and having a carbon number of 7 to 13 60% or more. In a more preferred embodiment, the linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms (preferably 70% by weight or more), and 7 carbon atoms. -13 linear or branched saturated aliphatic alcohols having a content of 70% by weight or more of C9 linear saturated aliphatic alcohols and 30% by weight or less of 9 branched carbons In which the linear chain ratio of the linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms is 70% or more is recommended. The linear or branched saturated aliphatic alcohol having a number of 7 to 13 is composed mainly of a saturated aliphatic alcohol having a carbon number of 9 (preferably 80% by weight or more), In branched saturated aliphatic alcohol A linear saturated aliphatic alcohol having 9 to 9 carbon atoms and a branched saturated aliphatic alcohol having 9 to 9 carbon atoms and 7 to 13 carbon atoms. An embodiment in which the straight chain ratio of the linear or branched saturated aliphatic alcohol is 75 to 98% is recommended.

  As the details of the embodiment of the linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms, as a second preferred embodiment, the saturated aliphatic alcohol is mainly a saturated fat having 9 to 11 carbon atoms. Is a mixture of aliphatic alcohols, and the ratio of each alcohol having 9, 10, and 11 carbon atoms is in the range of 10-25 / 35-50 / 30-45, and the linear ratio of the saturated aliphatic alcohol is 55 %, More preferably 60% or more, still more preferably 70% or more, and particularly preferably 75 to 98% is recommended.

  As the details of the embodiment of the linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms, as a third preferred embodiment, the saturated aliphatic alcohol is mainly a linear or branched carbon having 8 or 13 carbon atoms. Embodiments that are branched saturated fatty alcohols are recommended.

  From the viewpoint of performance such as cold resistance and heat resistance, if the straight chain ratio of the saturated aliphatic alcohol is 55% or more, the performance such as cold resistance and heat resistance is preferentially maintained, and for the purposes of the present invention. It is possible to improve certain color resistance. In addition, even if the linearity ratio is in the above range, sufficient performance as the object of the present invention can be obtained, but the linearity ratio is 55% or more, preferably 60% or more, more preferably 70% or more, and particularly preferably 75 to By making it within the range of 98%, not only cold resistance and heat resistance are improved, but also mixing with vinyl chloride resin becomes easier, and as a result, better performance is obtained with respect to tensile properties such as tensile elongation. There is a tendency to be easily.

  From the viewpoint of improving processability, etc., the saturated aliphatic alcohol used as a raw material of the ester compound 2 has about 8 carbon atoms, while maintaining other performances, the processability can be improved. The coloration resistance that is possible and the object of the present invention can also be improved.

  In the present specification and claims, the linear ratio of a linear or branched saturated aliphatic alcohol having 7 to 13 carbon atoms is the ratio (weight) of the linear alcohol in the saturated aliphatic alcohol. Specifically, it can be determined by a method of analysis by gas chromatography.

  Specific examples (commercially available) of saturated aliphatic alcohols mainly composed of the above-mentioned saturated aliphatic alcohol having 9 carbon atoms include linear nonanol of about 80% by weight or more and branched chain of about 20% by weight or less. Linenball 9 (trade name) made by Shell Chemicals, which is a mixture of nonanol, and Oxea, which is a mixture of about 90% by weight or more of linear nonanol and about 10% by weight or less of branched nonanol. n-Nonanol etc. are mentioned. Moreover, as a specific example (commercial product) of saturated aliphatic alcohol which is a mixture of saturated aliphatic alcohol mainly having 9 to 11 carbon atoms, linear or branched nonanol, decanol and undecanol are each 18% by weight, Line ball 911 (trade name) manufactured by Shell Chemicals Co., Ltd. containing 42% by weight and 38% by weight is included.

  Examples of the saturated aliphatic alcohol having 7 to 13 carbon atoms used in the present invention include (1) an α-olefin having 6 to 12 carbon atoms, and an aldehyde having 7 to 13 carbon atoms by hydroformylation reaction of carbon monoxide and hydrogen. It can be produced by a production method comprising a production step and (2) a step of hydrogenating an aldehyde having 7 to 13 carbon atoms to reduce it to an alcohol.

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

  The hydrogenation in the step (2) can be reduced to an alcohol by hydrogenating an aldehyde having 9 carbon atoms under hydrogen pressure in the presence of a noble metal catalyst such as a nickel catalyst or a palladium catalyst.

[Esterification reaction]
In the production of the ester compound 1, when the esterification reaction between the saturated aliphatic alcohol and trimellitic acid or anhydride thereof is performed, the saturated aliphatic alcohol is, for example, 1 mol of trimellitic acid or anhydride thereof. It is recommended to use 3.05 to 4.00 moles, more preferably 3.10 to 3.80 moles, especially 3.15 to 3.60 moles. In the production of the ester compound 2, when the esterification of the saturated aliphatic alcohol with 4-cyclohexene-1,2-dicarboxylic acid or its anhydride is performed, the saturated aliphatic alcohol is, for example, 4-cyclohexene- Preferably it is 2.05 mol-4.00 mol with respect to 1 mol of 1, 2- dicarboxylic acid or its anhydride, More preferably, it is 2.10 mol-3.00 mol, Most preferably, it is 2.15 mol-2 It is recommended to use 50 moles.

  Examples of the catalyst used in the esterification reaction include mineral acids, organic acids, Lewis acids and the like. More specifically, examples of the mineral acid include sulfuric acid, hydrochloric acid, and phosphoric acid, examples of the organic acid include p-toluenesulfonic acid and methanesulfonic acid, and examples of the Lewis acid include aluminum derivatives, tin derivatives, Titanium derivatives, lead derivatives, zinc derivatives and the like are exemplified, and these can be used alone or in combination of two or more.

  Among them, p-toluenesulfonic acid, tetraalkyl titanate having 3 to 8 carbon atoms, titanium oxide, titanium hydroxide, fatty acid tin having 3 to 12 carbon atoms, tin oxide, tin hydroxide, zinc oxide, zinc hydroxide, Lead oxide, lead hydroxide, aluminum oxide and aluminum hydroxide are particularly preferred. The amount used is, for example, preferably 0.01 to 5.0% by weight, more preferably 0.02 to 4.0% by weight, based on the total weight of the acid component and alcohol component that are the raw materials for the synthesis of the ester compound. In particular, it is recommended to use 0.03 to 3.0% by weight.

  Examples of the esterification temperature include 100 ° C. to 230 ° C. Usually, the esterification reaction is completed in 3 to 30 hours.

  There are no particular restrictions on trimellitic acid or its anhydride, which is a raw material of the present ester compound 1, and 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, which is a raw material of the present ester compound 2. What was manufactured, a commercial item, what can be obtained with a reagent, etc. can be used. For example, as a raw material of the present ester compound 2, Rikacid TH (trade name, Shin Nippon Rika Co., Ltd.) is exemplified as a commercial product. 4-Cyclohexene-1,2-dicarboxylic acid anhydride is usually obtained by Diels-Alder reaction of maleic anhydride and 1,3-butadiene. From the viewpoint of esterification reaction, it is recommended to use trimellitic anhydride for the present ester compound 1 and 4-cyclohexene-1,2-dicarboxylic anhydride for the present ester compound 2 as raw materials. Is done.

  In the esterification reaction, a water entraining agent such as benzene, toluene, xylene, cyclohexane or the like can be used in order to promote distillation of water generated by the reaction.

  Also, when oxygenated organic compounds such as oxides, peroxides, and carbonyl compounds are produced by oxidative degradation of raw materials, generated esters, and organic solvents (water entraining agents) during the esterification reaction, heat resistance, weather resistance, etc. are adversely affected. Therefore, it is desirable to carry out the esterification reaction under normal pressure or reduced pressure in an inert gas atmosphere such as nitrogen gas or in an inert gas stream. After completion of the esterification reaction, it is recommended that excess raw materials be distilled off under reduced pressure or normal pressure.

  The present ester compound 1 and the present ester compound 2 obtained by the esterification reaction are subsequently subjected to base treatment (neutralization treatment), water washing treatment, liquid-liquid extraction, distillation (decompression, dehydration treatment), adsorption purification as necessary. You may refine | purify by a process 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 purification include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, and diatomaceous earth. They can be used alone or in combination of two or more.

  Although the said process may be performed at normal temperature, it can also be performed by heating to about 40-90 degreeC.

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

  Although the said process may be performed at normal temperature, it can also be performed by heating to about 40-100 degreeC.

<Vinyl chloride resin composition>
The vinyl chloride resin composition of the present invention comprises a plasticizer composition (hereinafter referred to as “the present plasticizer”) comprising the component (A) and the component (B) (that is, the present ester compound 1 and the present ester compound 2 described above). It is obtained by blending a “composition”) with a vinyl chloride resin.

  In addition, as above-mentioned, this plasticizer composition is not only what mixed the component (A) and the component (B) previously, but the component (A) and component (B) mix | blended with a vinyl chloride resin simultaneously. Is meant to be included. That is, as a method of blending with the vinyl chloride resin, the component (A) and the component (B) may be mixed in advance, and then blended with the vinyl chloride resin. Alternatively, the component (A) and the component (B ) May be blended with the vinyl chloride resin at the same time.

[Vinyl chloride resin]
The vinyl chloride resin used in the present invention is a homopolymer of vinyl chloride or vinylidene chloride and a copolymer of vinyl chloride or vinylidene chloride, and the production method thereof is carried out by a conventionally known polymerization method. For example, in the case of a general-purpose vinyl chloride resin, a method of suspension polymerization in the presence of an oil-soluble polymerization catalyst can be used. For vinyl chloride paste resin, a method of emulsion polymerization in the presence of a water-soluble polymerization catalyst in an aqueous medium can be used. The degree of polymerization of these vinyl chloride resins is usually 300 to 5000, preferably 400 to 3500, and more preferably 700 to 3000. If the degree of polymerization is too low, heat resistance and the like are lowered, and if it is too high, moldability tends to be lowered.

  In the case of a copolymer, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- C2-C30 α-olefins such as tridecene, 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, alkyl vinyl ether, etc. Copolymers of vinyl compounds, polyfunctional monomers such as diallyl phthalate, and mixtures thereof with vinyl chloride monomers, ethylene-acrylate copolymers such as ethylene-ethyl acrylate copolymers, ethylene-methacrylate esters Polymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene Butyl rubber, crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile- (α-methyl) styrene copolymer (ABS), styrene-butadiene copolymer, polyethylene, polymethyl methacrylate And a graft copolymer obtained by grafting a vinyl chloride monomer onto a mixture thereof.

[Soft vinyl chloride resin composition]
The content of the plasticizer composition in the vinyl chloride resin composition according to the present invention is appropriately selected according to its use, but is preferably 1 to 200 weights with respect to 100 parts by weight of the vinyl chloride resin. Part, more preferably 20 to 150 parts by weight, still more preferably 30 to 120 parts by weight. If it is 1 part by weight or more, it can contribute to plasticization at the time of processing, and further to improve the plasticity of the obtained molded product. If it is 20 parts by weight or more, even in applications where flexibility is required. Sufficient flexibility can be obtained, and in applications where further flexibility is required, flexibility can be imparted by appropriately adjusting the blending amount. Even in applications where there is a concern about bleeding on the surface of the molded product, the amount of 200 parts by weight or less can be preferably used without concern. However, when adding a filler etc. with respect to said vinyl chloride resin composition, since the filler itself absorbs oil, the said plasticizer may be mix | blended exceeding said range. For example, when 100 parts by weight of calcium carbonate is added as a filler to 100 parts by weight of the vinyl chloride resin, the plasticizer may be added up to about 500 parts by weight.

  In the vinyl chloride resin composition according to the present invention, other known plasticizers can be used in combination with the plasticizer composition. If necessary, stabilizers, stabilizing aids, antioxidants (anti-aging agents), UV absorbers, light stabilizers such as hindered amines, flame retardants, colorants, processing aids, fillers, lubricants or In many cases, additives such as antistatic agents are appropriately blended and used.

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

  As other plasticizers that can be used in combination with the plasticizer composition, known plasticizers conventionally used in this technical field can be used, for example, benzoic acid esters such as diethylene glycol dibenzoate, phthalic acid, and the like. Phthalic acid esters such as di-2-ethylhexyl (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), isophthalic acid esters such as di-2-ethylhexyl isophthalate (DOIP), di-terephthalic acid Terephthalic acid esters such as 2-ethylhexyl, 1,2-cyclohexanedicarboxylic acid diisononyl (DINCH), alicyclic dibasic acid esters such as tetrahydrophthalic acid ester outside the scope of the present invention, di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), a Aliphatic dibasic acid esters such as diisodecyl pinate (DIDA), di-2-ethylhexyl sebacate (DOS), diisononyl sebacate (DINS), trimellitic acid esters, pyromellitic acid tetra Pyromellitic esters such as 2-ethylhexyl (TOPM), phosphoric esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP), alkyl esters of polyhydric alcohols such as pentaerythritol , Polyesters having a molecular weight of 800 to 4000 synthesized by polyesterification of dibasic acid such as adipic acid and glycol, epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, 4,5-epoxy-1, 2-Cyclohexanedicarboxylic acid di-2-ethylhexyl ester Epoxy esters, fatty acid glycol esters such as dicapric acid-1,4-butanediol, acetyl tributyl citrate (ATBC), acetyl citrate trihexyl (ATHC), acetyl citrate triethylhexyl (ATEHC), butyryl citrate trihexyl Citric acid esters such as (BTHC), isosorbide diesters, chlorinated paraffins chlorinated paraffin wax and n-paraffin, chlorinated fatty acid esters such as chlorinated stearic acid esters, higher fatty acid esters such as butyl oleate Examples are shown. When blending other plasticizers that can be used in combination, the blending amount is appropriately selected within a range not impairing the effect of the plasticizer according to the present invention, and is usually 1 to 100 weights per 100 parts by weight of the vinyl chloride resin. About 1 part is recommended.

  Incorporating a stabilizer is an effective method for improving coloring resistance, which is an object of the present invention. Stabilizers that can be used in combination with the plasticizer composition include epoxy compounds such as epoxidized soybean oil, lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, Metal soap compounds such as organic acid compounds including metals such as barium ricinoleate, barium stearate, zinc octylate, zinc laurate, zinc ricinoleate, zinc stearate, barium-zinc stearate, barium-zinc laurate, ricinol Metal soap compounds such as organic acid compounds containing complex metals such as barium-zinc acid, barium-zinc octylate, calcium-zinc stearate, calcium-zinc laurate, calcium-ricinoleate-zinc, calcium octylate-zinc, dimethyl Tin bis-2-ethylhexyl thioglycolate, dibutyltin maleate, dibutyltin bis-butyl maleate, organic tin compounds such as dibutyltin dilaurate, antimony mercaptan Tide compounds, etc. are exemplified. The said stabilizer can be mix | blended individually or in combination. When the stabilizer is blended, the blending amount is appropriately selected within a range not impairing the effect of the plasticizer composition according to the present invention, and usually 0.1 to 100 parts by weight of the vinyl chloride resin. About 20 parts by weight is recommended.

  In addition, the addition of a stabilizing aid as shown below is also effective as a method for making the improvement of the coloration resistance, which is the object of the present invention, more effective. As the stabilizing aid, phosphite compounds such as triphenyl phosphite, monooctyl diphenyl phosphite, tridecyl phosphite, beta diketone compounds such as acetylacetone and benzoylacetone, glycerin, sorbitol, pentaerythritol, polyethylene glycol, etc. Polyol compounds, perchlorate compounds such as barium perchlorate and sodium perchlorate, hydrotalcite compounds, zeolites and the like. When the stabilizing aid is blended, the blending amount is appropriately selected within a range not impairing the effect of the stabilizer according to the present invention, and usually 0.1 to 20 with respect to 100 parts by weight of the vinyl chloride resin. About parts by weight are recommended.

  In addition, blending an antioxidant, an ultraviolet absorber antioxidant, a light stabilizer, and the like is also effective as a method for making the improvement of the color resistance, which is the object of the present invention, more effective. Antioxidants include 2,6-di-tert-butylphenol, tetrakis [methylene-3- (3,5-tert-butyl-4-hydroxyphenol) propionate] methane, 2-hydroxy-4-methoxybenzophenone, and the like. Sulfur compounds such as phenolic compounds, alkyl disulfides, thiodipropionic esters, benzothiazoles, trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) ) Phosphinic compounds such as phosphites, organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. Moreover, when mix | blending antioxidant, about 0.2-20 weight part of the compounding quantity of antioxidant with respect to 100 weight part of vinyl chloride resin is recommended.

  Examples of ultraviolet absorbers include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate, benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-methoxybenzophenone, 5- In addition to benzotriazole compounds such as methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, cyanoacrylate compounds are exemplified. When the ultraviolet absorber is blended, the blending amount of the ultraviolet absorber with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

  Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1 , 2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1- Dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester and 1,1-dimethylethyl Reaction product of hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidino And higher fatty acid ester mixtures, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6- Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, poly [ {(6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidyl) Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}}, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6) -Tetramethyl- Polycondensate of 4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, N, N ′, N ″, N ′ ″ − Tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1 10-diamine, etc. When a light stabilizer is blended, the blending amount of the light stabilizer with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

  Flame retardants include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, zinc borate, cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, trisdichloropropyl phosphate, etc. Illustrative are halogen compounds such as phosphorus compounds and chlorinated paraffins. When the flame retardant is blended, the blending amount of the flame retardant with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 20 parts by weight.

  Examples of the colorant include carbon black, lead sulfide, white carbon, titanium white, lithopone, benigara, antimony sulfide, chrome yellow, chrome green, cobalt blue, and molybdenum orange. When blending a colorant, the blending amount of the colorant with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 1 to 100 parts by weight.

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

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

  Examples of the lubricant include silicone, liquid paraffin, baraffin wax, fatty acid metal salts such as metal stearate and metal laurate, fatty acid amides, fatty acid wax, and higher fatty acid wax. When a lubricant is blended, the blending amount of the lubricant with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

  Antistatic agents include alkyl sulfonate type, alkyl ether carboxylic acid type or dialkyl sulfosuccinate type anionic antistatic agents, non-ionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, diethanolamine derivatives, alkylamidoamine type, alkyl Examples include quaternary ammonium salts such as dimethylbenzyl type, cationic antistatic agents such as alkylpyridinium type organic acid salts or hydrochlorides, amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. When the antistatic agent is blended, the blending amount of the antistatic agent with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

  The vinyl chloride resin composition of the present invention is obtained by stirring and mixing the plasticizer composition, the vinyl chloride resin and various additives as required, for example, with a stirrer such as a mortar mixer, a Henschel mixer, a Banbury mixer, or a ribbon blender. It is possible to obtain a mixed powder of the vinyl chloride resin composition.

  In addition, the plasticizer composition, vinyl chloride resin and various additives as required, such as conical twin screw extruder, parallel twin screw extruder, single screw extruder, Kneader type kneader, roll kneader, etc. A pellet-like vinyl chloride resin composition can also be obtained by melt molding with a kneader.

  In addition, the plasticizer composition, the vinyl chloride paste resin, and various additives as required, such as pony mixer, butterfly mixer, planetary mixer, ribbon blender, kneader, dissolver, twin screw mixer, Henschel mixer, three roll mill It is possible to obtain a paste-like vinyl chloride resin composition by uniformly mixing with a mixer such as the like and defoaming under reduced pressure as necessary.

[Vinyl chloride resin molding]
Conventional methods such as vacuum molding, compression molding, extrusion molding, injection molding, calendar molding, press molding, blow molding, powder molding, etc., for the vinyl chloride resin composition (forms such as blended powder and pellets) according to the present invention It can be formed into a desired shape by melt molding using a known method.

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

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

  The molded body thus obtained includes medical materials such as medical tubes, blood bags, infusion bags, automobile underbody coats, instrument panels, consoles, door seats, under carpets, trunk seats, door trims, etc. Especially useful for medical materials. In addition to the above, pipes such as water pipes, pipe fittings, rain gutters, window frame siding, flat plates, corrugated plates, various leathers, decorative sheets, agricultural films, food packaging Film, wire coating, various foam products, hoses, food tubes, refrigerator gaskets, packings, wallpaper, flooring, boots, curtains, shoe soles, gloves, waterstops, toys, decorative boards, tarpaulins, mats, It can be usefully used for water shielding sheets, civil engineering sheets, roofing, waterproof sheets, insulating sheets, industrial tapes, glass films, erasers, and the like.

  In particular, in the medical material application, for example, tubes such as chest tube, dialysis tube, artificial respiration tube, endotracheal tube, respiratory tube, nutrition tube, extension tube, urinary catheter, suction catheter, intravenous catheter, Gastrointestinal catheters and other catheters, blood bags, infusion bags, drug solution bags, drain bags and other bags, blood component separators, hemodialysis circuits, peritoneal dialysis circuits, cardiopulmonary circuits and other circuit equipment members, connecting members, branches It can be used for connector members such as valves, speed control members, infusion sets, blood transfusion sets, intravenous injection sets, cardiopulmonary bypass, surgical gloves, pharmaceutical packaging materials, medical films, sanitary materials, respiratory masks, etc. Very useful.

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

(1) Ratio of carbon number of saturated aliphatic alcohol to linear saturated aliphatic alcohol In the present ester compound 1 and the present ester compound 2 used in the examples and comparative examples of the present invention, the general formula (1) and the general formula The carbon number of the saturated aliphatic alcohol that defines the residue in (2) and the ratio of the linear saturated aliphatic alcohol are determined by gas chromatography (hereinafter abbreviated as GC) of the composition in the raw material alcohol used in the production. The measurement result was defined as the ratio of the number of carbon atoms of the saturated aliphatic alcohol and the linear saturated aliphatic alcohol in these compounds. The measuring method of the raw material alcohol by GC is as follows.
<< GC measurement conditions >>
Model: Gas chromatograph GC-17A (manufactured by Shimadzu Corporation)
Detector: FID
Column: Capillary column ZB-1 30m
Column temperature: raised from 60 ° C to 290 ° C. Temperature increase rate = 13 ° C./min Carrier gas: helium Sample: 50% acetone solution Injection volume: 1 μl
Quantification: Quantification was performed using n-propyl benzoate as an internal standard substance.
In selecting the internal standard substance, it was confirmed in advance that n-propyl benzoate was less than the detection limit by GC in the raw material alcohol.
In the above esterification reaction, there is no difference in reactivity depending on the structure of the raw alcohol within the scope of the present invention, and the composition ratio in the raw alcohol used and the residues of the ester compound 1 and the ester compound 2 are defined. It has been confirmed in advance that there is no difference in the composition ratio of the saturated aliphatic alcohol.

(2) Physical property evaluation of this ester compound 1 and this ester compound 2 The ester compound obtained by the following manufacture example analyzed by the following method.
Ester value: Measured according to JIS K-0070 (1992).
Acid value: measured in accordance with JIS K-0070 (1992).
Iodine value: measured according to JIS K-0070 (1992).
Hue: Measured according to JIS K-0071 (1998) to determine the Hazen unit color number.

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

(4) Production of vinyl chloride sheet 100 parts by weight of vinyl chloride resin (straight, degree of polymerization 1050, trade name “Zest1000Z”, manufactured by Shin Daiichi PVC Co., Ltd.), calcium stearate (Nacalai Tesque (Nacalai Tesque) Co.) and zinc stearate (Nacalai Tesque Co., Ltd.) in an amount of 0.3 and 0.2 parts by weight respectively, and after stirring and mixing with a mortar mixer, the plasticizer composition according to the present invention, that is, (A ) Trimellitic acid triester and (B) 4-cyclohexene-1,2-dicarboxylic acid diester are added in a total of 50 parts by weight in the ratios shown in Table 1, and are mixed and mixed until uniform. did. This resin composition was melt-kneaded at 160 to 166 ° C. for 4 minutes using a 5 × 12 inch double roll to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168 ° C. for 10 minutes to produce a press sheet having a thickness of about 1 mm.

[Evaluation of physical properties of vinyl chloride resin moldings]
(5) Tensile properties: Based on JIS K-6723 (1995), 100% modulus, breaking strength and breaking elongation of the press sheet were measured. The smaller the value of 100% modulus, the better the flexibility, and the breaking strength and breaking elongation are measures of practical strength of the material. Generally, the larger the value, the more practical the strength. It can be said that it is excellent.

(6) Cold resistance: The flexible temperature (° C.) of the press sheet was measured according to JIS K-6773 (1999) using a crashberg tester. The lower the softening temperature (° C), the better the cold resistance. The flexible temperature here refers to a temperature at a low temperature limit indicating a predetermined torsional rigidity (3.17 × 10 3 kg / cm 2) in the measurement.

(7) Heat resistance (volatility, colorability): Depends on loss of volatility after heating and evaluation of sheet coloring.
a) Volatilization loss: The change in weight of the sheet after heating the roll sheet for 60 minutes at 170 ° C. for 120 minutes in a gear oven was measured, and the volatilization loss (%) was calculated according to the following formula.
The smaller the value of volatilization loss, the higher the heat resistance.
Volatilization loss (%) = ((weight before test−weight after test) / weight before test) × 100
b) Sheet coloring: The degree of coloring after heating a roll sheet at 170 ° C. for 30 minutes, 60 minutes, and 90 minutes in a gear oven was visually evaluated in four stages.
A: No coloring, B: Slight coloring, B: Coloring, X: Strong coloring

[Production Example 1]
In a 1 L four-necked flask equipped with a thermometer, decanter, stirring blade, and reflux condenser, 96 g (0.5 mol) trimellitic anhydride (commercially available product for industry), linear saturated fat having 9 carbon atoms 260 g of saturated aliphatic alcohol (linear ratio: 87%, manufactured by Shell Chemicals: Lineball 9) containing 85.1% by weight of aromatic alcohol and 11.7% by weight of branched saturated aliphatic alcohol having 9 carbon atoms (1 .8 mol) and 0.3 g of tetraisopropyl titanate as an esterification catalyst were added, and the reaction temperature was 190 ° C. to carry out the esterification reaction. The reaction was continued until the acid value of the reaction solution reached 0.5 mgKOH / g while the generated water was removed from the system by refluxing the alcohol under reduced pressure. After completion of the reaction, unreacted alcohol was distilled out of the system under reduced pressure, and then neutralized, washed with water and dehydrated according to a conventional method to obtain 245 g of the desired trimellitic acid triester (hereinafter referred to as “ester 1”). Obtained.
The obtained ester 1 had an ester value of 285 mgKOH / g, an acid value of 0.01 mgKOH / g, and a color number of 20.

[Production Example 2]
Trimellitic acid triester (hereinafter referred to as ester 2) was carried out in the same manner as in Production Example 1 except that 234 g of 2-ethylhexyl alcohol was added instead of 260 g of aliphatic saturated alcohol (manufactured by Shell Chemicals: Lineball 9). ) 219 g was obtained.
The obtained ester 2 had an ester value of 309 mgKOH / g, an acid value of 0.04 mgKOH / g, and a color number of 20.

[Production Example 3]
In a 2 L four-necked flask equipped with a thermometer, a decanter, a stirring blade, and a reflux condenser, 182.6 g of 4-cyclohexene-1,2-dicarboxylic anhydride (1.2 mol, manufactured by Shin Nippon Rika Co., Ltd.): Ricacid TH), 374 g (2.9 mol) of 2-ethylhexyl alcohol, and 0.24 g of tetraisopropyl titanate as an esterification catalyst were added, and the esterification reaction was carried out at a reaction temperature of 200 ° C. The reaction was continued until the acid value of the reaction solution reached 0.5 mgKOH / g while the generated water was removed from the system by refluxing the alcohol under reduced pressure. After completion of the reaction, unreacted alcohol was distilled off under reduced pressure, and neutralized, washed with water and dehydrated according to a conventional method to obtain the desired 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter referred to as “ester 3”). 269 g was obtained.
The obtained ester 3 had an ester value of 283 mgKOH / g, an acid value of 0.01 mgKOH / g, and a hue of 10.

[Example 1]
Trimellitic acid triester (ester 1) obtained in Production Example 1 and 4-cyclohexene-1,2-dicarboxylic acid obtained in Production Example 3 in accordance with the method described in “(3) Production of Vinyl Chloride Sheet” above. A vinyl chloride resin composition is prepared using a plasticizer composition in which an acid diester (ester 3) is blended at a ratio of 80/20, and a vinyl chloride sheet is prepared from the obtained vinyl chloride resin composition and pulled. A test, a cold resistance test, a heat resistance test, and a gelation temperature test were performed. The results obtained are summarized in Table 1.

[Example 2]
A vinyl chloride resin composition was prepared in the same manner as in Example 1 except that the ratio of ester 1 and ester 3 was changed to 70/30, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition. A tensile test, a cold resistance test, a heat resistance test, and a gelation test were performed. The results obtained are summarized in Table 1.

[Example 3]
A vinyl chloride resin composition was prepared in the same manner as in Example 1 except that the ratio of the ester 1 and the ester 3 was changed to 60/40, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition. A tensile test, a cold resistance test, a heat resistance test, and a gelation test were performed. The results obtained are summarized in Table 1.

[Example 4]
A vinyl chloride resin composition was prepared in the same manner as in Example 1 except that the ratio of ester 1 and ester 3 was changed to 50/50, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition. A tensile test, a cold resistance test, a heat resistance test, and a gelation test were performed. The results obtained are summarized in Table 1.

[Example 5]
According to the method described in “(3) Preparation of vinyl chloride sheet” instead of ester 1, the same procedure as in Example 2 was performed except that trimellitic acid triester (ester 2) obtained in Production Example 2 was used. Then, a vinyl chloride resin composition was prepared, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and a tensile test, a cold resistance test, a heat resistance test, and a gelation test were performed. The results obtained are summarized in Table 1.

[Example 6]
According to the method described in “(3) Preparation of vinyl chloride sheet” instead of ester 1, the same procedure as in Example 4 was conducted except that trimellitic acid triester (ester 2) obtained in Production Example 2 was used. Then, a vinyl chloride resin composition was prepared, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and a tensile test, a cold resistance test, a heat resistance test, and a gelation test were performed. The results obtained are summarized in Table 1.

[Comparative Example 1]
According to the method described in “(3) Production of vinyl chloride sheet” above, a vinyl chloride resin composition was prepared using only the trimellitic acid triester (ester 1) obtained in Production Example 1. A vinyl chloride sheet was prepared from the vinyl chloride resin composition and subjected to a tensile test, a cold resistance test, a heat resistance test, and a gelation test. The results obtained are summarized in Table 1.

[Comparative Example 2]
According to the method described in “(3) Production of vinyl chloride sheet” above, a vinyl chloride resin composition was prepared using only the trimellitic acid triester (ester 2) obtained in Production Example 2. A vinyl chloride sheet was prepared from the vinyl chloride resin composition and subjected to a tensile test, a cold resistance test, a heat resistance test, and a gelation test. The results obtained are summarized in Table 1.

[Comparative Example 3]
In accordance with the method described in “(3) Production of vinyl chloride sheet” above, a vinyl chloride resin composition was prepared using only 4-cyclohexene-1,2-dicarboxylic acid diester (ester 3) obtained in Production Example 3. A vinyl chloride sheet was prepared from the vinyl chloride resin composition prepared and subjected to a tensile test, a cold resistance test, a heat resistance test, and a gelation test. The results obtained are summarized in Table 1.

  From the results of Table 1, when a component (A) and a component (B) are blended singly by blending a plasticizer composition in which the component (A) and the component (B) are combined as a plasticizer (comparative example) 1 to 3), the thermal coloring is reduced, and it is apparent that the heat resistant coloring property can be improved by using the plasticizer composition of the present invention. Further, by adding the component (B) of the present invention to the component (A), the gelation temperature is reduced as compared with the case where the component (A) is blended alone (Comparative Examples 1 and 2). The improvement effect of workability by adding the component (B) to the present invention is confirmed.

  The plasticizer composition for vinyl chloride resin of the present invention has various uses as a plasticizer for vinyl chloride resin, which has good flexibility, cold resistance, heat resistance, and improved heat resistance coloring, which has been a problem. Can be used in In addition, by including the plasticizer for vinyl chloride resin, the vinyl chloride resin has good flexibility and cold resistance, excellent heat resistance, and further improved heat coloring resistance, that is, extremely excellent durability. A resin composition and a molded body thereof can be obtained, and are extremely useful as a medical material (particularly a medical tube) requiring particularly high durability. Also, in applications other than medical materials, for example, various leathers, decorative sheets, agricultural films, food packaging films, electric wire coatings, various foamed products, hoses, food tubes, refrigerator gaskets, packings, wallpaper, Floor materials, boots, curtains, shoe soles, gloves, water blocking boards, toys, decorative boards, blood bags, infusion bags, tarpaulins, mats, waterproof sheets, civil engineering sheets, roofing, waterproof sheets, insulating sheets, industrial tapes It can also be used effectively in applications such as glass film and eraser.

Claims (13)

A plasticizer composition for a vinyl chloride resin comprising (A) trimellitic acid triester and (B) 4-cyclohexene-1,2-dicarboxylic acid diester,
Component (A) is trimellitic acid triester represented by the following general formula (1):
And,
A plasticizer composition for a vinyl chloride resin, wherein the component (B) is 4-cyclohexene-1,2-dicarboxylic acid diester represented by the following general formula (2).
[Wherein R ¹ , R ² and R ³ are the same or different and are each a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a straight chain having 7 to 13 carbon atoms. Or branched chain saturated aliphatic alcohol. ]
[Wherein, R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is linear or branched having 7 to 13 carbon atoms. It is a chain saturated aliphatic alcohol. ] The plasticizer composition according to claim 1, wherein the ratio (weight ratio) of the component (A) to the component (B) is in the range of 95/5 to 30/70. The plasticizer composition of Claim 2 whose ratio (weight ratio) of a component (A) and a component (B) is the range of 90 / 10-40 / 60. The saturated aliphatic alcohol in the general formula (1) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 9 wt% or more. The aromatic alcohol and the branched saturated aliphatic alcohol having 9 or less carbon atoms of 40% by weight or less, and the linear ratio of the saturated aliphatic alcohol is 60% or more. The plasticizer composition as described. The plasticizer composition according to any one of claims 1 to 4, wherein the saturated aliphatic alcohol in the general formula (2) is mainly a saturated aliphatic alcohol having 8 carbon atoms. The plasticizer composition according to any one of claims 1 to 5, wherein the vinyl chloride resin is a vinyl chloride resin for medical materials. A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer composition according to claim 1. The vinyl chloride resin composition according to claim 7, wherein the content of the plasticizer composition in the vinyl chloride resin composition is 20 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. A vinyl chloride resin molded article using the vinyl chloride resin composition according to claim 7 or 8 as a raw material. A medical material comprising the vinyl chloride resin molded article according to claim 9. The medical material according to claim 10, wherein the medical material is a medical tube. A method for improving the heat resistant colorability of a vinyl chloride resin molded article,
For vinyl chloride resin comprising (A) trimellitic acid triester represented by the following general formula (1) and (B) 4-cyclohexene-1,2-dicarboxylic acid diester represented by the following general formula (2) The plasticizer composition is used as a plasticizer for a vinyl chloride resin that is a raw material resin of a vinyl chloride resin molded article.
[Wherein R ¹ , R ² and R ³ are the same or different and are each a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a straight chain having 7 to 13 carbon atoms. Or branched chain saturated aliphatic alcohol. ]
[Wherein, R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is linear or branched having 7 to 13 carbon atoms. It is a chain saturated aliphatic alcohol. ] A method for improving the moldability of a vinyl chloride resin composition containing a trimellitic acid triester plasticizer,
In addition to trimellitic acid triester, a plasticizer composition for vinyl chloride resin comprising 4-cyclohexene-1,2-dicarboxylic acid diester represented by the following general formula (2) is used for vinyl chloride resin: A method characterized by being used as a plasticizer.
[Wherein, R ⁴ and R ⁵ are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a linear or branched chain having 8 carbon atoms. Is a saturated fatty alcohol. ]