JP6694136B2 - Plasticizer composition for vinyl chloride resin having excellent coloring resistance - Google Patents

Description

  The present invention relates to a vinyl chloride resin plasticizer having excellent durability, and a vinyl chloride resin composition containing the same, and more specifically, containing a specific trimellitic acid triester and a specific epoxy compound. A plasticizer for a vinyl chloride resin, which has excellent cold resistance, volatility resistance, and greatly improved durability such as amine coloring resistance and heat coloring resistance, and an automobile member containing the plasticizer. It relates to a suitable vinyl chloride resin composition.

  Various interior materials are used in the interior of automobiles to improve the riding comfort. Usually, an automobile interior material is composed of a skin layer for giving a soft feel or the like (feel), a high-grade feel, and an aesthetic appearance or the like, and a base material layer for retaining the structure. Furthermore, in order to give a softer feeling to the skin layer, a foam layer such as urethane is often used as a lining.

  As the skin layer, a polyvinyl chloride resin, a thermoplastic elastomer, or a polyolefin foam such as polyethylene is used. Among them, polyvinyl chloride resin is widely used because it can give various tactile sensations ranging from semi-hard to soft depending on the amount of plasticizer compounded, and because it has excellent moldability and designability. There is.

  As the plasticizer, relatively inexpensive diisononyl phthalate (hereinafter referred to as "DINP") and diisodecyl phthalate (hereinafter referred to as "DIDP") phthalate diester-based plasticizers are also used. However, for members that become hot in the hot weather such as instrument panels, trimellitic acid such as tri-2-ethylhexyl trimellitate (hereinafter referred to as “TOTM”), which has more excellent heat resistance, particularly volatility resistance, is used. A triester-based plasticizer is widely used (Patent Document 1).

  As a recent tendency, demands for weight reduction and durability are becoming strict for all automobile members, and improvement in performance is also desired for individual members such as automobile interior materials. Specifically, there is a problem of deterioration due to heat and light under hot weather, that is, deterioration of performance due to volatilization of plasticizers and other additives, deterioration of physical properties and coloring due to heat and light peculiar to vinyl chloride resin, and volatile components. Further improvement has been desired with respect to the problem of fogging of windshields, that is, the problem of fogging, and the problem of destruction due to reduced flexibility in cold regions.

  Under such circumstances, the present inventors have found that the plasticizer made of trimellitic acid triester having a specific structure / composition has cold resistance as compared with the conventionally used trimellitic acid triester such as TOTM. It has been proposed that volatile resistance and flexibility can be improved (Patent Document 2).

  However, when used as a laminate with polyurethane foam to give a softer feeling as described above, the vinyl chloride resin interior material skin of the amine compound used as a catalyst when forming the polyurethane foam molded article The deterioration and coloring due to the heat and light peculiar to the vinyl chloride resin caused by the desorption of hydrogen chloride due to the decomposition of the vinyl chloride resin in the molecule, which is accelerated with the migration of the vinyl chloride resin (Patent Document 3), The present situation is that the deterioration of coloring and the like cannot be sufficiently suppressed even by the method, and further improvement is desired.

  Therefore, for the purpose of preventing deterioration, coloration, and deterioration of the vinyl chloride resin molded product promoted by this amine compound, that is, in order to improve amine resistance, sodium perchlorate, barium perchlorate, perchloric acid treatment A method of incorporating a perchloric acid compound such as hydrotalcite into a vinyl chloride resin composition is used (Patent Documents 4 and 5).

  However, even with a vinyl chloride resin composition containing a perchloric acid compound, its deterioration rate is remarkable under summer climatic conditions in which the vehicle interior temperature reaches 100 ° C., and the amine resistance improving effect of the perchloric acid compound is increased. Was not sufficient (Patent Documents 6 and 7). In addition, perchlorates, which are also used in explosives and explosives, are dangerous substances defined by the Fire Service Act Class 1 (oxidizing solids) and always have the risk of causing an explosion or fire due to friction or impact. There is. In addition, water pollution due to perchlorate has been reported in at least 20 states in the United States, and the California Toxic Substances Control Agency (DTSC) has established regulations regarding the handling of perchlorate. There are many safety and environmental concerns regarding the use of chloric acid compounds. From the above, there is a demand for a vinyl chloride resin composition or an automobile interior material, which does not use a perchloric acid compound and is excellent in amine resistance and suitable for automobile members and the like.

International publication WO2005 / 033197 JP, 2014-189688, A International publication WO2012 / 020618 JP-A-59-184240 JP, 7-173354, A JP-A-6-198825 JP-A-7-228615

  In view of the above situation, the object of the present invention is to color the vinyl chloride resin molded article (particularly in automobile interior materials) without impairing the physical properties such as cold resistance and volatility. (Coloring due to the influence of amine derived from laminated polyurethane), a vinyl chloride resin composition in which the coloring of a vinyl chloride resin is suppressed, a vinyl chloride resin molded product comprising the composition, and An object of the present invention is to provide an automobile interior material composed of the molded product, and a plasticizer composition effective in suppressing coloring of the vinyl chloride resin.

  As described above, the present inventors have found that a plasticizer made of trimellitic acid triester having a specific structure / composition has cold resistance as compared with the conventionally used trimellitic acid triester such as TOTM. It was found that the coloring resistance can be improved by further blending a specific antioxidant (Patent Document 2, Japanese Patent Application No. 2015-20870, Japanese Patent Application No. 2015-203311). ..

  The present inventors, based on the research and studies so far, as a result of further intensive studies to solve the above problems, trimellitic acid triester of a specific structure and at least one in the molecule having a specific structure By blending a plasticizer composition containing an epoxy compound having an ester group into a vinyl chloride resin as a plasticizer, the flexibility and cold resistance are good, and the heat resistance such as volatility is excellent, and the problem It was found that the above-mentioned coloring property, particularly the amine coloring property due to the influence of amine, was remarkably improved, and the present invention was completed.

  That is, the present invention provides a plasticizer composition shown below, a vinyl chloride resin composition containing the plasticizer composition, a vinyl chloride resin molded article and an automobile interior material comprising the same, and a method for suppressing amine coloring. To do.

[Item 1] A plasticizer composition for a vinyl chloride resin, comprising (A) trimellitic acid triester and (B) an epoxy compound having at least one ester group in the molecule,
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 an epoxy compound having a molecular weight of 300 to 1200 and an oxirane oxygen concentration of 2 to 13%.
[Wherein, R ¹ , R ² and R ³ 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 straight chain having 8 to 11 carbon atoms. Alternatively, it is a branched saturated aliphatic alcohol. ]

[Item 2] The plasticizer composition according to item 1, wherein the ratio (weight ratio) of the component (A) to the component (B) is 80/20 to 30/70.

[Item 3] The plasticizer composition according to item 2, wherein the ratio (weight ratio) of the component (A) to the component (B) is 70/30 to 40/60.

[Item 4] In any one of [Item 1] to [Item 3], the component (B) is an epoxy compound represented by the following general formula (2) and / or an epoxy compound represented by the general formula (3). The plasticizer composition described.
[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 has a linear or branched chain having 8 to 18 carbon atoms. It is a chain saturated aliphatic alcohol. ]
[Wherein, R ⁶ and R ⁸ are the same or different and each represent a linear or branched alkylene group having 8 to 12 carbon atoms, and R ⁷ and R ⁹ are the same or different, Each represents a linear or branched alkyl group having 6 to 8 carbon atoms. ]

[Item 5] The plasticizer composition according to item 4, wherein the saturated aliphatic alcohol in the general formula (2) is a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms.

[Item 6] The saturated aliphatic alcohol in the general formula (2) contains a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the content in the saturated aliphatic alcohol is 60% by weight or more and a straight chain having 9 carbon atoms. A saturated aliphatic alcohol in the form of a chain and a branched saturated aliphatic alcohol having 9 or less carbon atoms in an amount of 40% by weight or less, and the linear ratio of the saturated aliphatic alcohol is 60% or more. The plasticizer composition described.

[Item 7] The saturated aliphatic alcohol in the general formula (2) contains a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 70% by weight or more and a straight chain having 9 carbon atoms. [Claim 6], which contains a saturated aliphatic alcohol in the form of a chain and a branched saturated aliphatic alcohol having a carbon number of 9 and which is 30% by weight or less, and has a linearity of 70%. Plasticizer composition.

[Item 8] The saturated aliphatic alcohol in the general formula (2) contains a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 75 to 98% by weight. It contains a chain-like saturated aliphatic alcohol and 2 to 25% by weight of a branched chain saturated aliphatic alcohol having 9 carbon atoms, and the linear ratio of the saturated aliphatic alcohol is 75 to 98% or more. Item 7] The plasticizer composition according to Item 7.

[Item 9] The saturated aliphatic alcohol in the general formula (2) contains a saturated aliphatic alcohol having 9 to 11 carbon atoms as a main component, and the ratio of each saturated aliphatic alcohol having 9, 10 and 11 carbon atoms is 10 to 25. / 35-55 / 30-45, and the linear ratio of the saturated aliphatic alcohol is 55% or more, [Paragraph 4].

[Item 10] The plasticizer composition according to item 4, wherein the component (B) is an epoxy compound represented by the general formula (3).

[Item 11] The plasticizer composition according to any one of [Item 4] to [Item 10], wherein the alkylene group in the general formula (3) has 8 carbon atoms, and the alkyl group has 8 carbon atoms. object.

[Item 12] The saturated aliphatic alcohol in the general formula (1) contains a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the content of the saturated aliphatic alcohol is 60% by weight or more and a straight chain having 9 carbon atoms. A saturated aliphatic alcohol in the form of a chain and a branched saturated aliphatic alcohol having a carbon number of 9 and containing 40% by weight or less, and the linear ratio of the saturated aliphatic alcohol is 60% or more, [Claim 1] to The plasticizer composition according to any one of [Item 11].

[Item 13] The saturated aliphatic alcohol in the general formula (1) contains a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 70% by weight or more and is a straight chain having 9 carbon atoms. A saturated aliphatic alcohol in the form of a chain and a branched saturated aliphatic alcohol having a carbon number of 9 and containing 30% by weight or less, and the linear rate of the saturated aliphatic alcohol is 70% or more. The plasticizer composition described.

[Item 14] The saturated aliphatic alcohol in the general formula (1) contains a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 75 to 98% by weight. [Claim 13], which contains a chain-like saturated aliphatic alcohol and 2 to 25% by weight of a branched chain saturated aliphatic alcohol, and has a linearity of 75 to 98%. Plasticizer composition.

[Item 15] The saturated aliphatic alcohol in the general formula (1) contains a saturated aliphatic alcohol having 9 to 11 carbon atoms as a main component, and a ratio (molar ratio) of each saturated aliphatic alcohol having 9 to 10 carbon atoms. Is in the range of 10 to 25/35 to 55/30 to 45, and the linear ratio of the saturated aliphatic alcohol is 55% or more.

[Item 16] The plasticizer composition according to any one of [Item 1] to [Item 15], wherein the vinyl chloride resin is a vinyl chloride resin for automobile interior materials.

[Item 17] The vinyl chloride resin for an automobile interior material is a raw material resin for a vinyl chloride resin molding used in an automobile interior material composed of a laminate of a polyurethane molding and a vinyl chloride resin molding. The plasticizer composition according to item [16].

[Item 18] A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer composition according to any one of [Item 1] to [Item 15].

[Item 19] The vinyl chloride resin composition according to [Item 18], further containing one or more fatty acid metal salts selected from the group consisting of fatty acid calcium salts, fatty acid zinc salts, and fatty acid barium.

[Item 20] The vinyl chloride resin composition according to [Item 18] or [Item 19], which is for an automobile interior material.

[Item 21] The vinyl chloride-based resin composition according to [Item 20], which is for an automobile interior material and is composed of a laminate of a polyurethane molded product and a vinyl chloride-based resin molded product.

[Item 22] According to [Item 18] to [Item 21], 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. The vinyl chloride resin composition according to any one of claims.

[Item 23] The vinyl chloride resin according to [Item 22], 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. Resin composition.

[Item 24] A vinyl chloride resin molded product using the vinyl chloride resin composition according to any one of [Item 18], [Item 19], [Item 22] or [Item 23] as a raw material.

[Item 25] The vinyl chloride-based resin molded product according to [Item 24], which is for an automobile interior material.

[Item 26] The vinyl chloride-based resin molded product according to [Item 25], which is for an automobile interior material and is composed of a laminate of a polyurethane molded product and a vinyl chloride-based resin molded product.

[Item 27] An automobile interior material comprising the vinyl chloride resin molded product according to [Item 25].

[Item 28] The automobile interior material according to [Item 27], which is laminated with a polyurethane molded article.

[Item 29] A method for suppressing coloring of an automobile interior material comprising a laminate of a polyurethane molded product and a vinyl chloride resin molded product,
At least one (A) trimellitic acid triester represented by the following general formula (1) and (B) a molecular weight of 300 to 1200, and an oxirane oxygen concentration of 2 to 13% are present in the molecule. A method for suppressing coloration, which comprises using a plasticizer composition containing an epoxy compound having an ester group as a plasticizer for a vinyl chloride resin that is a raw material for a vinyl chloride resin molded body.
[Wherein R ¹ , R ² and R ³ 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 straight chain having 8 to 11 carbon atoms. Of branched or branched saturated aliphatic alcohols is the main component. ]

  The plasticizer composition for vinyl chloride resin of the present invention has good flexibility and cold resistance, is excellent in heat resistance such as volatility, and has a problem of heat coloring resistance, particularly amine coloring due to the influence of amine. Can be used as a plasticizer for vinyl chloride-based resins. Further, by containing the plasticizer for the vinyl chloride resin, the flexibility and cold resistance are good, the heat resistance such as volatility is excellent, and further the heat coloring resistance, particularly the amine resistance coloring is improved, That is, a vinyl chloride resin composition having excellent durability and a molded product thereof can be obtained and can be suitably used as an automobile member (particularly an automobile interior material) which requires particularly high durability.

<Plasticizer composition for vinyl chloride resin>
The plasticizer composition for vinyl chloride-based resins of the present invention comprises (A) a trimellitic acid triester represented by the following general formula (1), and (B) a molecular weight in the range of 300 to 1200, and its oxirane oxygen concentration. Is characterized by comprising an epoxy compound having at least one ester group in the molecule in the range of 2 to 13%.
[In the formula, R ¹ , R ² and R ³ 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 straight chain having 8 to 11 carbon atoms. Alternatively, it is a branched saturated aliphatic alcohol. ]
In the present application, the plasticizer composition includes not only a premixed composition but also a plasticizer component in the case where the combination is simultaneously mixed with a vinyl chloride resin.

  In a preferred embodiment of the trimellitic acid triester of the component (A) (hereinafter, referred to as “the present ester compound 1”), the saturated aliphatic alcohol defining the residue in the general formula (1) is carbon. It is a linear or branched saturated aliphatic alcohol of the number 8 to 11, and the ratio (weight ratio) of the linear saturated aliphatic alcohol to the total amount of saturated aliphatic alcohol defining the residue. Is 55% or more. In a further preferred embodiment, the saturated aliphatic alcohol defining the residue is (i) a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the saturated aliphatic alcohol defining the residue is It contains a straight chain saturated aliphatic alcohol having a carbon number of 9 and having a content of 60% by weight or more and a branched saturated aliphatic alcohol having a carbon number of 9 and having a content of 40% by weight or less, and the residue is defined. The linearity of the saturated aliphatic alcohol is 60% or more, (ii) a mixture of saturated aliphatic alcohols having 9 to 11 carbon atoms, and the ratio of each alcohol having 9 to 10 carbon atoms (mol It is recommended that the ratio) is in the range of 10 to 25/35 to 50/30 to 45, and the linear ratio of the saturated aliphatic alcohol defining the residue is 55% or more.

  The ester compound 1 is not particularly limited as long as it satisfies the performance of the object of the present invention, and is not particularly limited by its production method. For example, trimellitic acid or its anhydride and a saturated aliphatic alcohol having a specific structure. Can be easily obtained by esterification according to a conventional method, preferably in an atmosphere of an inert gas such as nitrogen, with or without a catalyst. In addition, depending on the type of the 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 atmosphere of an inert gas 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 component (B) epoxy compound (hereinafter referred to as “the present epoxy compound 1”) has at least one ester group in the molecule from the viewpoint of compatibility with the present ester compound 1 and the vinyl chloride resin. From the viewpoint of volatility, etc., the molecular weight is in the range of 300 to 1200, preferably in the range of 400 to 1000, and from the viewpoint of amine resistance, etc., the oxirane oxygen concentration is in the range of 2 to 13%, Epoxy compounds preferably in the range of 2.5 to 12% are recommended. Further, the epoxy compound is preferably an epoxy compound represented by the following general formula (2) (hereinafter referred to as "present epoxy compound 2") or an epoxy compound represented by the following general formula (3) (hereinafter referred to as "present" It is recommended that the present epoxy compound 3 is particularly preferable, and the present epoxy compounds 1 to 3 can be used alone or in combination of two or more.
[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 to 11 carbon atoms. It is a saturated aliphatic alcohol. ]
[Wherein, R ⁶ and R ⁸ are the same or different and each represent a linear or branched alkylene group having 8 to 12 carbon atoms, and R ⁷ and R ⁹ are the same or different, It represents a linear or branched alkyl group having 6 to 8 carbon atoms. ]

  Further, as the present epoxy compound 1, in addition to the present epoxy compound 2 and the present epoxy compound 3, an epoxidized product of a natural unsaturated fatty acid glyceride and the like can be preferably used. Specifically, for example, epoxidized soybean oil, epoxidized linseed oil, epoxidized rapeseed oil, epoxidized tall oil, epoxidized cottonseed oil, epoxidized palm oil, epoxidized coconut oil, epoxidized castor oil, epoxidized sunflower oil, epoxy Corn oil, epoxidized safflower oil, epoxidized cutting oil, epoxidized canola oil, epoxidized olive oil, epoxidized sesame oil, epoxidized rice bran oil, epoxidized safflower oil, epoxidized beef tallow, epoxidized fish oil, etc. Of these, epoxidized soybean oil, epoxidized linseed oil, and the like can be given as preferable specific examples.

  When the epoxy compound 1 does not have at least one ester group in the molecule, the compatibility with the vinyl chloride resin is remarkably reduced, causing poor dispersion in the resin, resulting in sufficient heat resistance and heat discoloration resistance. Not only is it difficult to improve, but it is also likely to cause surface stains due to bleeding and the like, which is not preferable. When the molecular weight is less than 300, the volatility becomes large, which results in a decrease in the fogging resistance and the like. On the other hand, when the molecular weight exceeds 1200, the compatibility with the vinyl chloride resin decreases, and Both are not preferable because they tend to cause poor dispersion and stains on the surface of the molded product due to bleeding. Further, when the oxirane oxygen concentration is less than 2%, the above-mentioned heat-resistant coloring property, that is, the amine coloring property is not sufficiently improved, and the effect of suppressing the deterioration of the functions and designability of the resin and the molded product by the amine compound is sufficient. If the oxirane oxygen concentration exceeds 13%, the compatibility with the vinyl chloride resin decreases, and it is likely to cause poor dispersion in the resin and stains on the surface of the molded product due to bleeding. ..

  The epoxy compound 1 is not particularly limited by its production method as long as it satisfies the above-mentioned performance aimed at by the present invention. For example, a predetermined acid component and an alcohol component are preferably used according to a conventional method. Can be easily obtained by esterification in the presence of a catalyst or a catalyst in an atmosphere of an inert gas such as nitrogen, and epoxidizing the obtained ester compound (intermediate raw material) under predetermined conditions. Here, the above-mentioned predetermined acid component and alcohol component, both components, or one of the components includes a component having at least one carbon double bond that does not exhibit aromaticity in the molecule, and those components are included. By esterifying, it is possible to obtain an ester compound (intermediate raw material) having at least one carbon double bond that does not exhibit aromaticity in the molecule. Further, as the ester compound having at least one carbon double bond that does not exhibit aromaticity in the molecule, a fat or oil composed of natural unsaturated fatty acid glyceride can be used as it is.

  Specific examples of oils and fats composed of glycerides of natural unsaturated fatty acids include soybean oil, linseed oil, rapeseed oil, tall oil, cottonseed oil, palm oil, coconut oil, castor oil, sunflower oil, corn oil, and safflower. Examples thereof include oil, cutting oil, canola oil, olive oil, sesame oil, rice bran oil, safflower oil, beef tallow, and fish oil. Among them, soybean oil, flaxseed oil and the like can be preferably used.

  In a preferred embodiment of the present epoxy compound 2, the saturated aliphatic alcohol defining the residue in the general formula (2) is a linear or branched saturated aliphatic alcohol having 8 to 18 carbon atoms, preferably 8 to 11 carbon atoms. An embodiment is an aliphatic alcohol in which the ratio (weight ratio) of the linear saturated aliphatic alcohol is 55% or more with respect to the total amount of the saturated aliphatic alcohol defining the residue. In a further preferred embodiment, the saturated aliphatic alcohol defining the residue is (i) a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the saturated aliphatic alcohol defining the residue is It contains a straight chain saturated aliphatic alcohol having a carbon number of 9 and having a content of 60% by weight or more and a branched saturated aliphatic alcohol having a carbon number of 9 and having a content of 40% by weight or less, and the residue is defined. The linearity of the saturated aliphatic alcohol is 60% or more, (ii) a mixture of saturated aliphatic alcohols having 9 to 11 carbon atoms, and the proportion of each alcohol having 9, 10 and 11 carbon atoms ( (Molar ratio) is in the range of 10 to 25/35 to 50/30 to 45, and the linear ratio of the saturated aliphatic alcohol defining the residue is 55% or more. ..

  The present epoxy compound 2 is not particularly limited by its production method as long as it satisfies the objective performance of the present invention, but is specified as, for example, 4-cyclohexene-1,2-dicarboxylic acid or its anhydride. It can be easily obtained by subjecting a saturated aliphatic alcohol having the structure of 1 to an esterification reaction and epoxidizing the obtained 4-cyclohexene-1,2-dicarboxylic acid diester (intermediate raw material) under predetermined conditions. In addition, after 4-cyclohexene-1,2-dicarboxylic acid or its anhydride is epoxidized, the obtained 4,5-epoxycyclohexane-1,2-dicarboxylic acid or its anhydride and a saturated aliphatic alcohol having a specific structure are used. Can also be obtained by a method of esterification. Further, depending on the type of the saturated aliphatic alcohol, there is also a method in which after the esterification with a lower alcohol having about 1 to 6 carbon atoms in advance, the saturated aliphatic alcohol is added and a transesterification reaction is performed. From the viewpoint of practicality such as simplicity, the method of epoxidizing after esterification is most preferable.

In a preferred embodiment of the present epoxy compound 3, the alkylene groups represented by R ⁶ and R ⁸ in the general formula (3) are the same or different and each has a linear or branched chain having 8 to 12 carbon atoms. Examples include an alkylene group, and the alkyl groups represented by R ⁷ and R ⁹ are the same or different and each is a linear or branched alkyl group having 6 to 8 carbon atoms. In a further preferred embodiment, the alkylene group represented by R ⁶ and R ⁸ is a linear or branched alkylene group having 8 carbon atoms, and the alkyl group represented by R ⁷ and R ⁹ is a carbon atom. Examples thereof include an alkyl group of the number 8.

  The epoxy compound 3 is not particularly limited as long as it satisfies the objective performance of the present invention by the production method thereof, but is specified as, for example, 4-cyclohexene-1,2-dicarboxylic acid or an anhydride thereof. It is easily obtained by subjecting the unsaturated aliphatic alcohol having the structure of (4) to an esterification reaction and epoxidizing the obtained 4-cyclohexene-1,2-dicarboxylic acid diester (intermediate raw material) under predetermined conditions. Also, after epoxidizing 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, the obtained 4,5-epoxycyclohexane-1,2-dicarboxylic acid or its anhydride and an epoxidized saturated fat of a specific structure It can also be obtained by a method of esterifying a group alcohol. Further, depending on the type of the unsaturated aliphatic alcohol, there is also a method in which after the esterification with a lower alcohol having about 1 to 6 carbon atoms in advance, the unsaturated aliphatic alcohol is added and the ester exchange reaction is performed. From the viewpoint of practicality such as simplicity, the method of epoxidizing after esterification is most preferable.

  It is recommended that the ratio (weight ratio) of the component (A) to the component (B) is preferably 80/20 to 30/70, more preferably 70/30 to 40/60. If the ratio of the component (B) to the total amount of the component (A) and the component (B) is 20% by weight or more, a more advantageous effect of improving the amine colorability can be obtained, and if it is 70% by weight or less, the cold resistance can be improved. It is preferable since the risk of deterioration of the surface and stains on the surface due to bleeding can be significantly reduced.

[Saturated fatty alcohol]
The saturated aliphatic alcohol used as a raw material of the present ester compound 1 is a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms. When the saturated aliphatic alcohol having less than 8 carbon atoms is contained, the performance such as volatility tends to be deteriorated, and when the saturated aliphatic alcohol having more than 11 carbon atoms is contained, the performance such as flexibility is deteriorated. There is a tendency, and neither is preferable.

  More specifically, the saturated aliphatic alcohol is (i) a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms, and a saturated aliphatic alcohol having 9 carbon atoms is a main component. The saturated aliphatic alcohol having 9 carbon atoms, which is the main component thereof, is contained in the linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms. 60% by weight or more (60 to 100% by weight), more preferably 70% by weight or more (70 to 100% by weight), and particularly preferably 80% by weight or more (80 to 100% by weight), (ii) ) Mainly composed of a linear or branched saturated aliphatic alcohol having 9 to 11 carbon atoms, and a saturated aliphatic alcohol having 9 carbon atoms / a saturated aliphatic alcohol having 10 carbon atoms / a saturated aliphatic alcohol having 11 carbon atoms. Ratio of Le (molar ratio) and a saturated aliphatic alcohol is in the range of 10 to 25/35 to 50/30 to 45 is recommended. The term "mainly" means that the ratio of the saturated aliphatic alcohol having 9 to 11 carbon atoms in the saturated aliphatic alcohol is 90% or more, preferably 95% or more.

  Further, the saturated aliphatic alcohol according to the present invention, including the recommended modes of (i) and (ii), has a linearity ratio of the saturated aliphatic alcohol of preferably 55% or more, more preferably 60%. % Or more, more preferably 70% or more, particularly preferably 75 to 98% is recommended.

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

  As the details of the embodiment of the straight-chain or branched-chain saturated aliphatic alcohol having 8 to 11 carbon atoms, as a 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 8 to 11 carbon atoms is 60% by weight or more and is a linear chain having 9 carbon atoms. It contains a saturated aliphatic alcohol and 40% by weight or less of a branched saturated aliphatic alcohol having 9 carbon atoms, and has a linear ratio of a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms. It is 60% or more. In a more preferred embodiment, the straight-chain or branched-chain saturated aliphatic alcohol having 8 to 11 carbon atoms contains a saturated aliphatic alcohol having 9 carbon atoms as a main component (preferably 70% by weight or more), and has 8 carbon atoms. Content in the linear or branched saturated aliphatic alcohol of 1 to 11 of 70% by weight or more and a linear saturated aliphatic alcohol of 9 carbon atoms and 30% by weight or less of a branched chain of 9 carbon atoms Of the saturated aliphatic alcohol and the linear ratio of the linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms is 70% or more is recommended, and a particularly preferable embodiment is carbon. The linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms is a saturated aliphatic alcohol having 9 carbon atoms as the main component (preferably 80% by weight or more), and the linear or branched aliphatic alcohol having 8 to 11 carbon atoms or In a branched saturated aliphatic alcohol It contains a linear saturated aliphatic alcohol having 9 to 9 carbon atoms and a branched saturated aliphatic alcohol having 9 to 9 carbon atoms in an amount of 75 to 98% by weight, and having 8 to 11 carbon atoms. It is recommended that the linear or branched saturated aliphatic alcohol has a linear ratio of 75 to 98%.

  As a detail of the embodiment of the linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms, as a second preferred embodiment, the saturated aliphatic alcohol is mainly saturated aliphatic alcohol having 9 to 11 carbon atoms. It is a mixture of group alcohols, and the ratio of each alcohol having 9, 10, and 11 carbon atoms is in the range of 10 to 25/35 to 50/30 to 45, and the linear ratio of the saturated aliphatic alcohol is 55. % Or more, more preferably 60% or more, further preferably 70% or more, and particularly preferably 75 to 98%.

  From the viewpoint of the effect of the present invention, if the linear ratio of the saturated aliphatic alcohol is 55% or more, it is possible to predominantly maintain performance such as cold resistance and heat resistance. Further, even if the linearity is in the above range, sufficient performance which is the object of the present invention can be obtained, but the linearity is further 55% or more, preferably 60% or more, more preferably 70% or more, particularly preferably 75- By setting the range to 98%, not only cold resistance and heat resistance are further improved, but also mixing with a vinyl chloride resin becomes easier, and as a result, better performance is obtained with respect to tensile properties such as tensile elongation. It tends to be easily damaged.

  On the other hand, the saturated aliphatic alcohol used as a raw material of the present epoxy compound 2 is a linear or branched saturated aliphatic alcohol having 8 to 18 carbon atoms, preferably 8 to 11 carbon atoms. When a saturated aliphatic alcohol having less than 8 carbon atoms is contained, performance such as volatility tends to be deteriorated, which is not preferable. Further, when the carbon number is 18 or less, there is no problem in compatibility with the resin and the like, and it is possible to stably exhibit a good coloring prevention effect. Further, when the number of carbon atoms is 11 or less, a better coloring preventing effect tends to be easily obtained, which is preferable.

  More specifically, the saturated aliphatic alcohol is (i) a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms, and a saturated aliphatic alcohol having 9 carbon atoms is a main component. The saturated aliphatic alcohol having 9 carbon atoms, which is the main component thereof, is contained in the linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms. 60% by weight or more (60 to 100% by weight), more preferably 70% by weight or more (70 to 100% by weight), and particularly preferably 80% by weight or more (80 to 100% by weight), (ii) ) Mainly composed of a linear or branched saturated aliphatic alcohol having 9 to 11 carbon atoms, and a saturated aliphatic alcohol having 9 carbon atoms / a saturated aliphatic alcohol having 10 carbon atoms / a saturated aliphatic alcohol having 11 carbon atoms. Ratio of Le (molar ratio) and a saturated aliphatic alcohol is in the range of 10 to 25/35 to 50/30 to 45 is recommended. The term "mainly" means that the ratio of the saturated aliphatic alcohol having 9 to 11 carbon atoms in the saturated aliphatic alcohol is 90% or more, preferably 95% or more.

  Further, the saturated aliphatic alcohol according to the present invention, including the recommended modes of (i) and (ii), has a linearity ratio of the saturated aliphatic alcohol of preferably 55% or more, more preferably 60%. % Or more, more preferably 70% or more, particularly preferably 75 to 98% is recommended.

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

  As the details of the embodiment of the straight-chain or branched-chain saturated aliphatic alcohol having 8 to 11 carbon atoms, as a 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 8 to 11 carbon atoms is 60% by weight or more and is a linear chain having 9 carbon atoms. It contains a saturated aliphatic alcohol and 40% by weight or less of a branched saturated aliphatic alcohol having 9 carbon atoms, and has a linear ratio of a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms. It is 60% or more. In a more preferred embodiment, the straight-chain or branched-chain saturated aliphatic alcohol having 8 to 11 carbon atoms contains a saturated aliphatic alcohol having 9 carbon atoms as a main component (preferably 70% by weight or more), and has 8 carbon atoms. Content in the linear or branched saturated aliphatic alcohol of 1 to 11 of 70% by weight or more and a linear saturated aliphatic alcohol of 9 carbon atoms and 30% by weight or less of a branched chain of 9 carbon atoms Of the saturated aliphatic alcohol and the linear ratio of the linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms is 70% or more is recommended, and a particularly preferable embodiment is carbon. The linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms is a saturated aliphatic alcohol having 9 carbon atoms as the main component (preferably 80% by weight or more), and the linear or branched aliphatic alcohol having 8 to 11 carbon atoms or In a branched saturated aliphatic alcohol It contains a linear saturated aliphatic alcohol having 9 to 9 carbon atoms and a branched saturated aliphatic alcohol having 9 to 9 carbon atoms in an amount of 75 to 98% by weight, and having 8 to 11 carbon atoms. It is recommended that the linear or branched saturated aliphatic alcohol has a linear ratio of 75 to 98%.

  As a detail of the embodiment of the linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms, as a second preferred embodiment, the saturated aliphatic alcohol is mainly saturated aliphatic alcohol having 9 to 11 carbon atoms. It is a mixture of group alcohols, and the ratio of each alcohol having 9, 10, and 11 carbon atoms is in the range of 10 to 25/35 to 50/30 to 45, and the linear ratio of the saturated aliphatic alcohol is 55. % Or more, more preferably 60% or more, further preferably 70% or more, and particularly preferably 75 to 98%.

  From the viewpoint of the effect of the present invention, when the linear ratio of the saturated aliphatic alcohol is 55% or more, the coloring resistance, which is the object of the present invention, can be obtained while predominantly maintaining performance such as cold resistance and heat resistance. It is possible to improve. Further, even if the linearity is in the above range, sufficient performance which is the object of the present invention can be obtained, but the linearity is further 55% or more, preferably 60% or more, more preferably 70% or more, particularly preferably 75- By setting the range to 98%, not only cold resistance and heat resistance are further improved, but also mixing with a vinyl chloride resin becomes easier, and as a result, better performance is obtained with respect to tensile properties such as tensile elongation. It tends to be easily damaged.

  In the present specification and claims, the linearity ratio of a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms means the proportion of the linear alcohol in the saturated aliphatic alcohol (weight. Ratio), which can be specifically determined by a method of analyzing by gas chromatography.

  Specific examples (commercially available products) of the saturated aliphatic alcohol containing the saturated aliphatic alcohol having 9 carbon atoms as a main component include about 80% by weight or more of linear nonanol and about 20% by weight or less of branched chain. Of Renebol 9 (trade name) manufactured by Shell Chemicals Co., which is a mixture of nonanol, and Oxea manufactured by Oxea, which is a mixture of about 90% by weight or more of a linear nonanol and about 10% by weight or less of a branched chain nonanol. Examples include n-Nonanol and the like. Further, as specific examples (commercially available products) of saturated aliphatic alcohols which are mainly mixtures of saturated aliphatic alcohols having 9 to 11 carbon atoms, linear or branched nonanol, decanol and undecanol are each 18% by weight, Examples include Lineball 911 (trade name) manufactured by Shell Chemicals, which contains 42% by weight and 38% by weight.

  Examples of the saturated aliphatic alcohol having 8 to 11 carbon atoms used in the present invention include (1) α-olefin having 7 to 10 carbon atoms and aldehyde having 8 to 11 carbon atoms by hydroformylation reaction of carbon monoxide and hydrogen. It can be manufactured by a manufacturing method including a manufacturing step and a step of (2) hydrogenating an aldehyde having 8 to 11 carbon atoms to reduce it to an alcohol.

  In the hydroformylation reaction of 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.

[Unsaturated aliphatic alcohol]
The unsaturated aliphatic alcohol used as a raw material of the present epoxy compound 3 is an unsaturated aliphatic alcohol having 16 to 22 carbon atoms represented by the following general formula (4).
[In the formula, R ¹⁰ represents a linear or branched alkyl group having 6 to 8 carbon atoms, and R ¹¹ represents a linear or branched alkylene group having 8 to 12 carbon atoms. Represent ]

  As details of the embodiment of the unsaturated aliphatic alcohol, an unsaturated aliphatic alcohol in which the alkyl group of the general formula (4) has 6 carbon atoms and the alkylene group has 8 carbon atoms, and the carbon of the alkyl group An unsaturated aliphatic alcohol having 8 alkylene groups and 8 carbon atoms, an unsaturated aliphatic alcohol having 8 alkyl groups and 12 alkylene groups, and the like Among them, preferred examples include unsaturated alcohols having an alkyl group having 8 carbon atoms and an alkylene group having 8 carbon atoms.

  Specific examples of the unsaturated aliphatic alcohol having 16 to 22 carbon atoms include palmitolyl alcohol having 16 carbon atoms, oleyl alcohol having 18 carbon atoms, and erucyl alcohol having 22 carbon atoms, and among them, preferable specific examples. An example is C18 oleyl alcohol.

  Hereinafter, an example of the production method and conditions of the present ester compound 1, the present epoxy compound 1 and the like according to the present invention will be described. However, as described above, the present invention is not limited as long as the desired performance can be obtained. A commercial product having the structure of the present ester compound 1 or the present epoxy compound 1 may be used as it is as the component (A) or the component (B) according to the present invention without depending on the production method and conditions.

[Esterification reaction]
In the production of the present ester compound 1, in the esterification reaction of the saturated aliphatic alcohol with trimellitic acid or its anhydride, the saturated aliphatic alcohol is, for example, 1 mol of trimellitic acid or its anhydride. 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 respective ester compounds which are intermediate raw materials of the present epoxy compound 2 and the present epoxy compound 3, the saturated aliphatic alcohol or unsaturated aliphatic alcohol and 4-cyclohexene-1,2-dicarboxylic acid or the In carrying out esterification with an anhydride, the saturated aliphatic alcohol or unsaturated aliphatic alcohol is, for example, preferably 2.00 mol per 1 mol of 4-cyclohexene-1,2-dicarboxylic acid or its anhydride. ~ 5.00 mol, more preferably 2.01 mol to 3.00 mol, particularly preferably 2.02 mol to 2.50 mol is recommended.

  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, phosphoric acid, etc., examples of the organic acid include p-toluenesulfonic acid, methanesulfonic acid, etc., and examples of the Lewis acid include an aluminum derivative, a tin derivative, Titanium derivatives, lead derivatives, zinc derivatives and the like are exemplified, and it is possible to use one kind or a proper combination of two or more kinds thereof.

  Among them, p-toluene sulfonic 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 preferable. 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 the alcohol component, which are raw materials for synthesizing the ester compound. It is recommended to use, in particular, 0.03 to 3.0% by weight.

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

  The trimellitic acid or its anhydride, which is the raw material of the present ester compound 1, and the 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, which is the raw material of the present epoxy compound 2 and the present epoxy compound 3, are not particularly limited. Those manufactured by known methods, those commercially available, those available as reagents, etc. can be used. For example, as raw materials of the present epoxy compound 2 and the present epoxy compound 3, commercially available products such as RIKACID TH (trade name, Shin Nippon Rika Co., Ltd.) are exemplified. 4-Cyclohexene-1,2-dicarboxylic acid anhydride is usually obtained by the Diels-Alder reaction of maleic anhydride and 1,3-butadiene. From the viewpoint of the esterification reaction, trimellitic anhydride is used for the present ester compound 1, and 4-cyclohexene-1,2-dicarboxylic acid anhydride is used for the present epoxy compound 2 and the present epoxy compound 3 as raw materials, respectively. Recommended to use.

  In the esterification reaction, it is possible to use a water entraining agent such as benzene, toluene, xylene and cyclohexane in order to accelerate the distillation of water produced by the reaction.

  In addition, when oxygen-containing organic compounds such as oxides, peroxides and carbonyl compounds are generated due to oxidative deterioration of raw materials, produced ester and organic solvent (water entraining agent) during esterification reaction, heat resistance and weather resistance are adversely affected. Therefore, it is desirable to carry out the esterification reaction in the system under an atmosphere of an inert gas such as nitrogen gas or under an inert gas stream under normal pressure or reduced pressure. After completion of the esterification reaction, it is recommended to distill off excess starting materials under reduced pressure or normal pressure.

  The present ester compound 1 obtained by the above esterification reaction and the respective ester compounds which are intermediate raw materials of the present epoxy compound 2 and the present epoxy compound 3 are continuously subjected to a base treatment (neutralization treatment) → washing treatment, if necessary, It may be purified by liquid-liquid extraction, distillation (reduced pressure, dehydration treatment), adsorption purification treatment, or the like.

  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 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 kinds.

  The above treatment may be performed at room temperature, but may also be performed by heating to about 40 to 90 ° C.

[Epoxidation reaction]
The epoxidation reaction according to the present invention means an epoxidation reaction of a carbon double bond (unsaturated bond) which does not exhibit aromaticity in a molecule in order to obtain the present epoxy compound 1. It can be easily carried out by using a well-known epoxidation reaction described in Organic Synthetic Chemistry, Vol. 23, No. 7, pages 612 to 619 (1985). For example, (i) a method of using an organic peracid such as peracetic acid or formic acid as an epoxidizing agent, and (ii) a method of using hydrogen peroxide as an epoxidizing agent are mentioned. The target site of the epoxidation reaction in the present invention is the double bond of the cyclohexene ring site or the double bond of the alkenyl site derived from unsaturated aliphatic alcohol or unsaturated fatty acid.

  More specifically, in the case of the method (i), for example, peracetic acid obtained by reacting hydrogen peroxide with acetic anhydride or acetic acid with a strong acid such as sulfuric acid as a catalyst is used as an intermediate raw material of the present epoxy compound 1. In addition to the ester compound, the mixture is stirred at 20 to 30 ° C. for several hours, then the temperature is gradually raised, and after reaching 50 to 60 ° C., the temperature is maintained for 2 to 3 hours to complete the reaction. You can Other than the above, as the organic peracid, monoperphthalic acid, permethacrylbenzoic acid, pertrifluoroacetic acid and the like can be used.

  In the case of the method (ii), for example, epoxidation can be performed by reacting with an ester compound which is an intermediate raw material of the present epoxy compound 1 in the coexistence of an oxygen carrier such as formic acid and a strong acid catalyst such as sulfuric acid. More specifically, acetic acid or formic acid is used in a small amount of 0.5 mol or less and sulfuric acid is used as a catalyst in a small amount of 0.05 mol or less with respect to 1 mol of hydrogen peroxide, and the temperature is 40 to 70 ° C. for 2 to 15 hours. By holding and reacting, the ester compound, which is an intermediate raw material of the present epoxy compound 1, can be easily epoxidized. In addition to the above, phosphoric acid, hydrochloric acid, nitric acid, boric acid, or salts thereof are well known as the above-mentioned catalyst, and sulfonic acid-type strongly acidic cation exchange resin and aluminum oxide are also effective.

  The present epoxy compound 1 obtained by the above-mentioned epoxidation method may be subsequently purified, if necessary, by liquid-liquid extraction, vacuum distillation, adsorption purification or the like.

  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 kinds.

  The above treatment may be performed at room temperature, but may also be performed by heating to about 40 to 100 ° C.

<Vinyl chloride resin composition>
The vinyl chloride resin composition of the present invention comprises a component (A) and a component (B) (that is, a plasticizer composition containing the ester compound 1 and the epoxy compound 1 described above (hereinafter referred to as “the plasticizer composition”). It is obtained by blending a "substance") with a vinyl chloride resin.
In addition, as described above, the present plasticizer composition is meant to include not only a mixture of the component (A) and the component (B) in advance, but also a combination in the case of simultaneously mixing with the vinyl chloride resin. Is. Therefore, as a method of blending with the vinyl chloride resin, the components (A) and (B) may be mixed in advance and then blended with the vinyl chloride resin, or the components (A) and (B) may be blended. ) May be simultaneously added to the vinyl chloride resin.

[Vinyl chloride resin]
The vinyl chloride resin used in the present invention is a homopolymer of vinyl chloride or vinylidene chloride and a copolymer of vinyl chloride or vinylidene chloride, and the production method thereof is a conventionally known polymerization method. For example, in the case of a general-purpose vinyl chloride resin, a method of carrying out suspension polymerization in the presence of an oil-soluble polymerization catalyst can be mentioned. For the vinyl chloride paste resin, a method of emulsion polymerization in an aqueous medium in the presence of a water-soluble polymerization catalyst 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 will decrease, and if it is too high, moldability will tend to decrease.

  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 and 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, alkyl vinyl ethers, etc. Vinyl compounds, copolymers of polyfunctional monomers such as diallyl phthalate and mixtures thereof with vinyl chloride monomers, ethylene-acrylic acid ester copolymers such as ethylene-ethyl acrylate copolymers, ethylene-methacrylic acid ester copolymers Polymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene Butyl rubber, cross-linked 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.

[Vinyl chloride resin composition]
The plasticizer composition has an effect as a plasticizer and an effect as a stabilizer, as described above for the effect of the present invention. The content of the present plasticizer composition in the vinyl chloride resin composition of the present invention is appropriately selected depending on its application and expected effect, for example, when the effect as a stabilizer is mainly desired. The effect is exerted more predominantly from a relatively small content, specifically, 1 to 200 parts by weight, and more preferably 5 to 150 parts by weight, based on 100 parts by weight of the vinyl chloride resin. When the range is recommended and the effect as a plasticizer is mainly desired, the effect is more dominantly exerted from a content slightly higher than the above content, specifically, preferably 20 to 200 parts by weight, Preferably 30 to 150 parts by weight are recommended.

  That is, when the content is 100 parts by weight or more based on 100 parts by weight of the vinyl chloride resin, the effect of the present plasticizer composition as a stabilizer can be sufficiently exerted, and 200 parts by weight or less. In this case, there is no concern about bleeding on the surface of the molded product and it can be used with confidence. Further, when the effect as a plasticizer is mainly desired, if the content is 20 parts by weight or more based on 100 parts by weight of the vinyl chloride resin, sufficient flexibility corresponding to the purpose of use can be more predominantly obtained. .. Further, when it is mainly desired to improve the amine coloration resistance as an effect as a stabilizer, the content is preferably 20 parts by weight or more based on 100 parts by weight of the vinyl chloride resin, It is more preferably 150 parts by weight.

[Stabilizer]
When the present plasticizer composition is mainly desired to have an effect as a stabilizer, the combined use of other stabilizers is an effective method for exerting the effect further. As stabilizers that can be used in combination with the present plasticizer composition, lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, octyl acid. Metal soap compounds such as organic acid compounds containing metals such as zinc, zinc laurate, zinc ricinoleate and zinc stearate, barium-zinc stearate, barium laurate-zinc, barium ricinoleate-zinc, barium octylate-zinc , A metal soap compound such as an organic acid compound containing a complex metal such as calcium-zinc stearate, calcium laurate-zinc, calcium ricinoleate-zinc, and calcium octylate-dimethyltin bis-2-ethylhexyl thiogly Rate, dibutyltin maleate, dibutyltin bis-butyl maleate, organic tin compounds such as dibutyltin dilaurate, antimony mercaptan Tide compounds, epoxy compounds and the like other than the epoxy compound 1 is exemplified. Among them, the combined use of the above metal soap compounds is particularly preferable because it exhibits the effect of amplifying the stabilizing effect of the present plasticizer composition by a synergistic effect. Preferred metal soap compounds include, for example, fatty acid calcium salts, fatty acid zinc salts, and fatty acid magnesium salts, and particularly preferred metal soap compounds include fatty acid calcium salts and fatty acid zinc salts, which may be used alone or in combination. can do. When the other stabilizer that can be used in combination is blended, the blending amount is appropriately selected within a range that does not impair the effects of the stabilizer according to the present invention, and is usually 0 with respect to 100 parts by weight of the vinyl chloride resin. 1 to 20 parts by weight is recommended.

  Other known plasticizers may be used in combination with the present plasticizer composition in the vinyl chloride resin composition according to the present invention. In addition, if necessary, stabilizers, antioxidants (aging inhibitors), ultraviolet absorbers, light stabilizers such as hindered amines, flame retardants, colorants, processing aids, fillers, lubricants or antistatic agents. It is often used by appropriately mixing the additive of.

  Other than the above plasticizer composition, other plasticizers and other additives may be blended alone or in combination with the present plasticizer composition.

  As the other plasticizer that can be used in combination with the present plasticizer composition, known plasticizers conventionally used in the present technical field can be used, and examples thereof include benzoic acid esters such as diethylene glycol dibenzoate, phthalic acid. Dibutyl (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), bis (2-terephthalate) Phthalates such as ethylhexyl) (DOTP) and bis (2-ethylhexyl) isophthalate (DOIP), tetrahydrophthalates such as 4-cyclohexene-1,2-dicarboxylic acid bis (2-ethylhexyl) (DOTH) , Di-2-ethylhexyl adipate (DOA) Aliphatic dibasic acid esters such as diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), diisononyl sebacate (DINS), trimellitic acid outside the scope of the present invention 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 polyesterification of dibasic acids such as adipic acid and glycols, epoxidized esters outside the scope of the present invention, alicyclic compounds such as DINCH Dibasic acid esters, dicapric acid-1,4- Fatty acid glycol esters such as butanediol, acetyl tributyl citrate (ATBC), acetyl citrate trihexyl (ATHC), acetyl citrate triethylhexyl (ATEHC), butyryl citrate trihexyl (BTHC) and other citrate esters, isosorbide diesters Examples thereof include chlorinated paraffins obtained by chlorinating paraffin wax and n-paraffin, chlorinated fatty acid esters such as chlorinated stearic acid esters, and higher fatty acid esters such as butyl oleate. When blending the other plasticizer which can be used in combination, the blending amount is appropriately selected within a range that does not impair the effect of the plasticizer according to the present invention, and is usually 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. Some copies are recommended.

  The component (A) and the component (B) that compose the present plasticizer composition according to the present invention, and the above-mentioned plasticizer that can be used in combination may be added separately to the vinyl chloride resin, but after mixing in advance. The method of adding to vinyl chloride resin is more preferable. By mixing in advance, the compatibility with the resin is not good, that is, the compatibilization of the plasticizer with poor plasticization efficiency to the resin, that is, the improvement of the plasticization efficiency, and further, when the content is small, The uniformity of a small amount of components in the resin can be maintained, and as a result, there is less concern that the stabilizing effects such as the heat-resistant coloring property and the amine coloring resistance improving effect of the present invention will be uneven.

  Further, the combined use of the following stabilizing aids is also effective as a method for making the effect of the present plasticizer composition more effective. As the stabilizing aid, phosphite compounds such as triphenyl phosphite, monooctyl diphenyl phosphite and tridecyl phosphite, beta diketone compounds such as acetylacetone and benzoylacetone, glycerin, sorbitol, pentaerythritol, polyethylene glycol and the like. Examples thereof include polyol compounds, barium perchlorates, perchlorate compounds such as sodium perchlorate, hydrotalcite compounds, and zeolites. When the stabilizing aid is blended, the blending amount is appropriately selected within a range that does not impair the effects of the stabilizer according to the present invention, and is usually 0.1 to 20 with respect to 100 parts by weight of the vinyl chloride resin. About parts by weight is recommended.

  Further, the combined use of an antioxidant, an ultraviolet absorber antioxidant, a light stabilizer and the like is also effective as a method for making the effect of the present plasticizer composition more effective. Examples of the antioxidant include 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, thiodipropionates, sulfur compounds such as benzothiazole, trisnonylphenylphosphite, diphenylisodecylphosphite, triphenylphosphite, tris (2,4-di-tert-butylphenyl) ) Phosphate-based compounds such as phosphite, and organic metal-based compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. When an antioxidant is blended, it is recommended that the amount of the antioxidant be 0.2 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin.

  Examples of the ultraviolet absorber 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- Examples thereof include benzotriazole-based compounds such as methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, and cyanoacrylate-based compounds. When blending the ultraviolet absorber, it is recommended that the blending amount of the ultraviolet absorber be about 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin.

  Examples of the hindered amine-based light stabilizer 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 ester mixture of higher fatty acid, 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- A polycondensation product 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 compounding a light stabilizer, it is recommended that the compounding amount of the light stabilizer be about 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

  As the flame retardant, aluminum hydroxide, antimony trioxide, magnesium hydroxide, inorganic compounds such as zinc borate, cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, trisdichloropropyl phosphate, etc. Examples include phosphorus compounds and halogen compounds such as chlorinated paraffin. When blending the flame retardant, it is recommended that the blending amount of the flame retardant be 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, safflower, antimony sulfide, chrome yellow, chrome green, cobalt blue, molybdenum orange and the like. When the colorant is blended, it is recommended that the blending amount of the colorant be about 1 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin.

  Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylenebisstearic acid amide, butyl stearate, and calcium stearate. When a processing aid is added, it is recommended that the amount of the processing aid be 0.1 to 20 parts by weight per 100 parts by weight of the vinyl chloride resin.

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

  Examples of the lubricant include silicone, liquid paraffin, paraffin wax, fatty acid metal salts such as metal stearate and metal laurate, fatty acid amides, fatty acid wax, and higher fatty acid wax. When compounding the lubricant, it is recommended that the compounding amount of the lubricant is about 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin.

  As the antistatic agent, alkylsulfonate type, alkyl ether carboxylic acid type or dialkylsulfosuccinate type anionic antistatic agents, nonionic 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, and amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. When blending the antistatic agent, it is recommended that the blending amount of the antistatic agent be 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, the present plasticizer composition, vinyl chloride resin and various additives as necessary, for example, by stirring and mixing with a stirrer such as mortar mixer, Henschel mixer, Banbury mixer, ribbon blender. The mixed powder of the vinyl chloride resin composition can be obtained.

  Further, the present plasticizer composition, vinyl chloride resin and various additives as necessary, such as a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, a kneader type kneader, a roll kneader A pelletized vinyl chloride resin composition can also be obtained by melt-molding with a kneader.

  Further, the present plasticizer composition, vinyl chloride-based paste resin and various additives as necessary, for example, pony mixer, butterfly mixer, planetary mixer, ribbon blender, kneader, dissolver, twin screw mixer, Henschel mixer, three roll mill. It is also possible to obtain a paste-like vinyl chloride resin composition by uniformly mixing with a mixer such as the above and performing defoaming treatment under reduced pressure if necessary.

[Vinyl chloride resin molding]
Conventionally known methods such as vacuum molding, compression molding, extrusion molding, injection molding, calender molding, press molding, blow molding, and powder molding of the vinyl chloride resin composition (compounded powder or pellet) according to the present invention. It is possible to form into a desired shape by melt-forming using.

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

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

  Molded articles thus obtained are instrument panels, door trims, console boxes, glove boxes, pillar trims, dashboards, trunk trims, seats, ceiling materials, AT shifts, armrests, floor carpets, wire harnesses, various malls, sashes, It can be effectively used as an automobile interior material or an automobile exterior material such as a sealing material, a weather strip, a gasket and an undercoat material, and in particular, the above-mentioned automobile interior material laminated with polyurethane, for example, an instrument panel, a door trim, a seat. Very useful as sheets and ceiling materials.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The abbreviations of the compounds in Examples and Comparative Examples and the measurement of each property 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 epoxy compound 2 used in Examples and Comparative Examples of the present invention, the general formula (1) and the general formula The carbon number of the saturated aliphatic alcohol defining 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 for the production. The measurement result was used as the ratio of the number of carbon atoms of the saturated aliphatic alcohol and the linear saturated aliphatic alcohol in the compounds. The method for measuring the raw material alcohol by the 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: increased from 60 ° C to 290 ° C. Temperature rising rate = 13 ° C./min Carrier gas: Helium sample: 50% acetone solution injection amount: 1 μl
Quantification: Quantification was performed using n-propyl benzoate as an internal standard substance.
In selecting the internal standard substance, it was previously confirmed that n-propyl benzoate in the raw material alcohol was below the detection limit by GC.
In the above-mentioned esterification reaction, there is no difference in reactivity depending on the structure of the raw material alcohol within the scope of the present invention, and the composition ratio in the used raw material alcohol and the residues of the present ester compound 1 and the present epoxy compound 2 are defined. It has been confirmed in advance that there is no difference in the composition ratio of the saturated aliphatic alcohol used. The above confirmation also means that there is no difference in the composition ratio of the saturated aliphatic alcohol defining the residue of the present epoxy compound 2 and the composition ratio of the alkyl moiety of the ester compound as an intermediate raw material of the present epoxy compound 2. To do.

(2) Evaluation of Physical Properties of Present Ester Compound 1 and Present Epoxy Compound 1 The ester compounds and epoxy compounds obtained in the following production examples were analyzed by the following methods.
Ester value: Measured according to JIS K-0070 (1992).
Acid value: Measured according to JIS K-0070 (1992).
Iodine value: Measured according to JIS K-0070 (1992).
Oxirane oxygen: It was measured according to the standard oil and fat analysis test method 2.3.7.1-2013 “Oxirane oxygen determination method (1)”.
Hue: Measured according to JIS K-0071 (1998) to determine the Hazen unit color number.

(3) Preparation 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.) was added with calcium stearate (Nacalai Tesque ( Co., Ltd.) and zinc stearate (manufactured by Nacalai Tesque Co., Ltd.) in an amount of 0.1 and 0.1 parts by weight, respectively, and mixed with stirring with a mortar mixer, and then the plasticizer composition of the present invention, that is, (A). A total of 50 parts by weight of trimellitic acid triester and (B) epoxy compound were added at a ratio shown in Table 1, and the resulting mixture was handled and mixed until it became uniform to obtain a vinyl chloride resin composition. This resin composition was melt-kneaded for 4 minutes at 160 to 166 ° C. using a 5 × 12 inch two-roll to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168 ° C. for 10 minutes to prepare a press sheet having a thickness of about 1 mm.

[Evaluation of physical properties of resin]
(4) Tensile properties: The 100% modulus, breaking strength and breaking elongation of the press sheet were measured according to JIS K-6723 (1995). The smaller the value of 100% modulus is, the better the flexibility is, and the breaking strength and the elongation at break are indicators of the practical strength of the material. Generally, the larger the value is, the practical strength is. Can be said to be excellent.

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

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

(7) Amine coloring resistance: A DOP solution (amine: N, N, N ', N) prepared by cutting a press sheet into a size of 3.5 cm x 2 cm and adjusting the amine concentration to 0.1% by weight. 0.02-mL of'-tetramethyl-1,6-diaminohexane) was applied, and a press sheet of the same type and the same size was further stacked thereon, and heated in a gear oven at 100 ° C for 100 hours and 200 hours. After the heating, the degree of coloring of the sheet was visually observed, and the amine coloring resistance was evaluated based on the degree of coloring on a 6-point scale. It is shown that the less the coloring of the sheet is, the more excellent the amine coloring resistance is, and that the discoloration of the vinyl chloride resin caused by the contact with the polyurethane-based molded body is less likely to occur.
Amine color resistance:
Excellent (no coloration) A>B>C>D>E> F Poor (strong coloration)

[Production Example 1]
In a 1 L four-necked flask equipped with a thermometer, a decanter, stirring blades, and a reflux condenser, 96 g (0.5 mol) of trimellitic anhydride (commercial commercial product), a linear saturated fat having 9 carbon atoms 260 g (1.8 mol) of saturated aliphatic alcohol (Shell Chemicals: Lineball 9) containing 85.1% by weight of group alcohol and 11.7% by weight of branched saturated aliphatic alcohol having 9 carbon atoms, and ester 0.3 g of tetraisopropyl titanate was added as an esterification catalyst, and the esterification reaction was carried out at a reaction temperature of 190 ° C. The reaction was performed until the acid value of the reaction solution reached 0.5 mgKOH / g while refluxing the alcohol under reduced pressure to remove the produced water out of the system. After completion of the reaction, unreacted alcohol was distilled out of the system under reduced pressure, followed by neutralization, washing with water and dehydration according to a conventional method to obtain 245 g of a desired trimellitic acid triester (hereinafter referred to as "ester 1"). Obtained.
The ester 1 thus obtained 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 an aliphatic saturated alcohol (Line Chemical 9 manufactured by Shell Chemicals). ) 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]
Trimellitic acid triester (hereinafter referred to as "ester 3") was carried out in the same manner as in Production Example 1 except that 234 g of n-octyl alcohol was added instead of 260 g of saturated aliphatic alcohol (Line Chemical 9 manufactured by Shell Chemicals). .) 220 g was obtained.
The ester 3 thus obtained had an ester value of 308 mgKOH / g, an acid value of 0.05 mgKOH / g, and a color number of 20.

[Production Example 4]
238 g of trimellitic acid triester (hereinafter referred to as "ester 4") in the same manner as in Production Example 1 except that 260 g of isononyl alcohol was added instead of 260 g of saturated aliphatic alcohol (Line Chemical 9 manufactured by Shell Chemicals). Got
The obtained ester 4 had an ester value of 284 mgKOH / g, an acid value of 0.06 mgKOH / g, and a color number of 20.

[Production Example 5]
Trimellitic acid triester (hereinafter referred to as "ester 5") was carried out in the same manner as in Production Example 1 except that 284 g of isodecyl alcohol was added instead of 260 g of saturated aliphatic alcohol (Line Chemical 9 manufactured by Shell Chemicals). ) 252 g were obtained.
The ester 5 thus obtained had an ester value of 265 mgKOH / g, an acid value of 0.05 mgKOH / g, and a color number of 20.

[Production Example 6]
Esterification process In a 2 L four-necked flask equipped with a thermometer, a decanter, a stirring blade, and a reflux condenser, 182.6 g (1.2 mol, Shin Nippon Rika Co., Ltd.) of 4-cyclohexene-1,2-dicarboxylic acid anhydride was added. ) Manufactured by Rikacid TH), a saturated aliphatic alcohol containing 85.1% by weight of a linear saturated aliphatic alcohol having 9 carbon atoms and 11.7% by weight of a branched saturated aliphatic alcohol having 9 carbon atoms (shell). 416 g (2.9 mol) of Lineball 9 manufactured by Chemicals Co., Ltd. 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 performed until the acid value of the reaction solution reached 0.5 mgKOH / g while refluxing the alcohol under reduced pressure to remove the produced water out of the system. After completion of the reaction, the unreacted alcohol is distilled out of the system under reduced pressure, followed by neutralization, washing with water and dehydration according to a conventional method to obtain the desired 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter, referred to as “ester 6 ) Was obtained.
The ester 6 thus obtained had an ester value of 254 mgKOH / g, an acid value of 0.04 mgKOH / g, and a color number of 15.

Epoxidation step Next, in a 1 L four-necked flask equipped with an upper thermometer, stirring blades, and a condenser tube, 423 g (1.0 mol) of the ester 6 obtained in the above esterification reaction was charged, and the temperature was adjusted to 60 to 70 ° C. The temperature was raised. After the temperature was raised, 76.6 g (1.35 mol) of 60% hydrogen peroxide solution, 18.3 g (0.30 mol) of 76% formic acid, and 1.47 g (0.01 mol) of 75% phosphoric acid were used for 15 hours. It dripped slowly over minutes. After the completion of the dropping, the temperature was maintained for 4 hours, and the reaction was completed by aging. After completion of the reaction, the aqueous phase was removed to the outside of the system, followed by washing with water and dehydration according to a conventional method to obtain 397 g of a desired 4,5-epoxycyclohexanedicarboxylic acid diester (hereinafter referred to as "epoxy 1").
The epoxy 1 thus obtained had an ester value of 256 mgKOH / g, an acid value of 0.06 mgKOH / g, an iodine value of 2.5 gI2 / 100 g, an oxirane oxygen of 3.5% and a color number of 10.

[Production Example 7]
Esterification process In a 2 L four-necked flask equipped with a thermometer, a decanter, a stirring blade, and a reflux condenser, 182.6 g (1.2 mol, Shin Nippon Rika Co., Ltd.) of 4-cyclohexene-1,2-dicarboxylic acid anhydride was added. ) Manufactured by Rikacid TH), 778 g (2.9 mol) of oleyl alcohol, 40 g of xylene as a water entraining agent, 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 carried out until the acid value of the reaction solution reached 0.5 mgKOH / g while refluxing xylene and alcohol under reduced pressure to remove the produced water out of the system. After completion of the reaction, xylene and unreacted alcohol are distilled out of the system under reduced pressure, followed by neutralization, washing with water and dehydration according to a conventional method to obtain the desired 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter, referred to as " This is referred to as "ester 7").
The ester 7 thus obtained had an ester value of 164 mgKOH / g, an acid value of 0.05 mgKOH / g and a color number of 90.

Epoxidation step Next, in a 2 L four-necked flask equipped with an upper thermometer, stirring blades, and a cooling tube, 671 g (1.0 mol) of the ester 7 obtained in the above esterification reaction was charged, and the temperature was adjusted to 60 to 70 ° C. The temperature was raised. After the temperature was raised, 229.5 g (4.05 mol) of 60% hydrogen peroxide solution, 36.3 g (0.60 mol) of 76% formic acid, and 1.47 g (0.01 mol) of 75% phosphoric acid were taken over 3 hours. And dripped slowly. After the completion of the dropping, the temperature was maintained for 5 hours to complete the reaction by aging. After completion of the reaction, the aqueous phase was removed to the outside of the system, followed by washing with water and dehydration according to a conventional method to obtain 624 g of a desired 4,5-epoxycyclohexanedicarboxylic acid diester (hereinafter referred to as "epoxy 2").
The obtained epoxy 2 had an ester value: 163 mgKOH / g, an acid value: 0.33 mgKOH / g, an iodine value: 2.6 gI2 / 100 g, an oxirane oxygen: 5.6%, and a color number: 30.

[Example 1]
According to the method described in "(3) Preparation of vinyl chloride sheet" above, the trimellitic acid triester (ester 1) obtained in Production Example 1 and the epoxycyclohexanedicarboxylic acid diester (epoxy 1) were mixed at a ratio of 40/60. A vinyl chloride resin composition is prepared using the blended plasticizer composition, and a vinyl chloride sheet is prepared from the obtained vinyl chloride resin composition to perform a tensile test, a cold resistance test, a heat resistance test, and an amine resistance. A coloring test was conducted. The obtained results are summarized in Table 1.

[Example 2]
A vinyl chloride resin composition was prepared in the same manner as in Example 1 except that Epoxy 2 was used instead of Epoxy 1 and the ratio of Ester 1 to Epoxy 2 was changed to 50/50. A vinyl chloride sheet was prepared from the vinyl resin composition and subjected to a tensile test, a cold resistance test, a heat resistance test, and an amine coloration resistance test. The obtained results are summarized in Table 1.

[Example 3]
A vinyl chloride resin composition was prepared in the same manner as in Example 2 except that the ratio of the ester 1 to the epoxy 2 was changed to 60/40, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition. It was produced and subjected to a tensile test, a cold resistance test, a heat resistance test, and an amine coloration resistance test. The obtained results are summarized in Table 1.

[Example 4]
A vinyl chloride resin composition was prepared in the same manner as in Example 2 except that the ratio of the ester 1 to the epoxy 2 was changed to 70/30, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition. It was produced and subjected to a tensile test, a cold resistance test, a heat resistance test, and an amine coloration resistance test. The obtained results are summarized in Table 1.

[Example 5]
A vinyl chloride resin composition was prepared in the same manner as in Example 2 except that ester 2 was used instead of ester 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and stretched. A test, a cold resistance test, a heat resistance test, and an amine coloration resistance test were conducted. The obtained results are summarized in Table 1.

[Example 6]
A vinyl chloride resin composition was prepared in the same manner as in Example 2 except that ester 3 was used instead of ester 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and stretched. A test, a cold resistance test, a heat resistance test, and an amine coloration resistance test were conducted. The obtained results are summarized in Table 1.

[Example 7]
A vinyl chloride resin composition was prepared in the same manner as in Example 2 except that ester 4 was used instead of ester 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and stretched. A test, a cold resistance test, a heat resistance test, and an amine coloration resistance test were conducted. The obtained results are summarized in Table 1.

[Example 8]
A vinyl chloride resin composition was prepared in the same manner as in Example 2 except that ester 5 was used instead of ester 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and stretched. A test, a cold resistance test, a heat resistance test, and an amine coloration resistance test were conducted. The obtained results are summarized in Table 1.

[Example 9]
A vinyl chloride resin composition was prepared in the same manner as in Example 2 except that a commercially available epoxidized soybean oil (ESBO) (manufactured by Shin Nippon Rika Co., Ltd., Sanso Sizer E-2000H) was used instead of Epoxy 2. Was prepared, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and subjected to a tensile test, a cold resistance test, a heat resistance test, and an amine coloration resistance test. The obtained results are summarized in Table 1.

[Example 10]
A vinyl chloride resin composition was prepared in the same manner as in Example 5 except that a commercially available epoxidized soybean oil (ESBO) (manufactured by Shin Nippon Rika Co., Ltd., Sanso Sizer E-2000H) was used instead of Epoxy 2. Was prepared, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and subjected to a tensile test, a cold resistance test, a heat resistance test, and an amine coloration resistance test. The obtained results are summarized in Table 1.

[Comparative Example 1]
A vinyl chloride resin composition other than the present invention was prepared in the same manner as in Example 1 except that the compounding amount of the ester 1 was changed to 50 parts by weight without adding the epoxy compound as the component (B). A vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and subjected to a tensile test, a cold resistance test, a heat resistance test, and an amine color resistance test. The obtained results are summarized in Table 1.

[Comparative example 2]
Example 1 except that the compounding amount of the ester 1 was changed to 50 parts by weight, the epoxy compound of the component (B) was not added, and 1 part by weight of sodium perchlorate which was a perchloric acid compound was added instead. In the same manner, a vinyl chloride resin composition other than the present invention is prepared, and a vinyl chloride sheet is prepared from the obtained vinyl chloride resin composition to perform a tensile test, a cold resistance test, a heat resistance test, and a resistance test. An amine colorability test was conducted. The obtained results are summarized in Table 1.

  From the results in Table 1, by adding the epoxy compound which is the component (B) of the present invention, the heat coloring resistance, particularly the amine coloring resistance, is greatly improved as compared with the system not containing the same (Comparative Example 1). You can see that it is done. Among them, in the system (Examples 2 to 8) containing the epoxy compound represented by the general formula (3) as the component (B) and the system (Example 1) containing the epoxy compound represented by the general formula (2), The effect was more prominent, and the effect was most prominent especially in the system containing the epoxy compound represented by the general formula (3). Further, even when compared with the system (Comparative Example 2) in which a perchlorate is conventionally used, the epoxy compound of the present invention has the same or higher effect on the improvement of amine color resistance. It turns out that In addition, from the results in Table 1, by using the ester compound represented by the general formula (1) of the present invention as the component (A), the plasticizer composition of the present invention can be used in, for example, instrument panels that are particularly demanding. It can be seen that it has excellent cold resistance and volatility resistance, which is not a problem even when used for automobile interior materials.

  The plasticizer composition for vinyl chloride resin of the present invention has good flexibility and cold resistance, is excellent in heat resistance such as volatility, and has a problem of heat coloring resistance, particularly amine coloring due to the influence of amine. It can be used in various applications as a plasticizer for vinyl chloride-based resins. Further, by containing the plasticizer for the vinyl chloride resin, the flexibility and cold resistance are good, the heat resistance such as volatility is excellent, and further the heat coloring resistance, particularly the amine resistance coloring is improved, That is, a vinyl chloride resin composition having excellent durability and a molded article thereof can be obtained, and an automobile member (particularly an automobile interior material) that requires particularly high durability, for example, an instrument panel, a door trim, a console box, Glove box, pillar trim, dashboard, trunk trim, seat, ceiling material, rear tray, airbag cover, armrest, headrest, meter cover, crash pad, floor carpet wire harness, various malls, sash, sealing material, weather strip, gasket. , Interior materials such as undercoat materials and automobiles It can be effectively used as Paneling is very useful in the automotive interior material which is laminated with inter alia polyurethane. Also, in applications other than automobiles, for example, various leathers, decorative sheets, agricultural films, food packaging films, wire coatings, various foam products, hoses, medical tubes, food tubes, refrigerator gaskets, packings, Wallpaper, flooring, boots, curtains, shoe soles, gloves, waterstops, toys, decorative plates, blood bags, infusion bags, tarpaulins, mats, water barrier sheets, civil engineering sheets, roofing, tarpaulins, insulating sheets, industrial It can also be effectively used for applications such as tapes, glass films and erasers.

Claims (12)

A plasticizer composition for a vinyl chloride resin, comprising (A) trimellitic acid triester and (B) an epoxy compound represented by the following general formula (2) and / or an epoxy compound represented by the general formula (3) . And
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 an epoxy compound having a molecular weight of 300 to 1200 and an oxirane oxygen concentration of 2 to 13%.
[Wherein R ¹ , R ² and R ³ 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 straight chain having 8 to 11 carbon atoms. It is a saturated aliphatic alcohol in the form of a branched or branched chain. ]
[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 has a linear or branched chain having 8 to 18 carbon atoms. It is a chain saturated aliphatic alcohol. ]
[Wherein, R ⁶ and R ⁸ are the same or different and each represent a linear or branched alkylene group having 8 to 12 carbon atoms, and R ⁷ and R ⁹ are the same or different, Each represents a linear or branched alkyl group having 6 to 8 carbon atoms. ] The plasticizer composition according to claim 1, wherein the ratio (weight ratio) of the component (A) and the component (B) is in the range of 80/20 to 30/70. The plasticizer composition according to claim 1 or 2 , wherein the saturated aliphatic alcohol in the general formula (2) is a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms. The saturated aliphatic alcohol in the general formula (2) contains a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 60% by weight or more and a linear saturated fatty acid having 9 carbon atoms. The plasticizer composition according to claim 3, which contains an aromatic alcohol and 40% by weight or less of a branched saturated aliphatic alcohol having 9 carbon atoms, and a linearity of the saturated aliphatic alcohol is 60% or more. object. The plasticizer composition according to any one of claims 1 to 4 , wherein the alkylene group in the general formula (3) has 8 carbon atoms, and the alkyl group has 8 carbon atoms. The saturated aliphatic alcohol in the general formula (1) contains a saturated aliphatic alcohol having 9 carbon atoms as a main component, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 60% by weight or more and a linear saturated fatty acid having 9 carbon atoms. Any of claims 1 to 5 , which contains a group alcohol and 40% by weight or less of a branched-chain saturated aliphatic alcohol having 9 carbon atoms, and a linear rate of the saturated aliphatic alcohol is 60% or more. A plasticizer composition according to claim 1. The plasticizer composition according to any one of claims 1 to 6 , wherein the vinyl chloride resin is a vinyl chloride resin for automobile interior materials. Vinyl chloride resin for the automotive interior material is a raw material resin of the vinyl chloride resin molded body used in automobile interior material made of a laminate of a polyurethane molded article with vinyl chloride resin molded product according to claim 7 The plasticizer composition described in 1. Comprising a plasticizer composition according to any one vinyl chloride-based resin according to claim 1 to 6, a vinyl chloride resin composition. The vinyl chloride resin composition according to claim 9 , 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 product, which is obtained by using the vinyl chloride resin composition according to claim 9 or 10 as a raw material. An automobile interior material comprising the vinyl chloride resin molded product according to claim 11 .