JP2017165793A - Plasticizer composition for vinyl chloride resin excellent in discoloration resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for suppressing coloration, especially, coloration due to an influence of amine derived from laminated polyurethane without impairing other physical properties such as cold resistance and volatilization resistance in a vinyl chloride resin, especially, in an automobile interior material, and to provide a vinyl chloride resin composition in which coloration is suppressed by the method, a vinyl chloride resin molding formed from the same, an automobile interior material formed from the molded material, and a plasticizer composition which is a raw material of the automobile interior material and has an effect for suppressing coloration.SOLUTION: A plasticizer composition containing an epoxy compound having at least one ester group in phthalic acid diester having a specific structure and a molecule having a specific structure is blended with a vinyl chloride resin as a plasticizer, and thereby flexibility and cold resistance are excellent, heat resistance such as volatilization resistance is excellent, and colorability, especially, amine colorability by an influence of amine is remarkably improved.SELECTED DRAWING: None

Description

  The present invention relates to a plasticizer for vinyl chloride resin having excellent durability, and a vinyl chloride resin composition containing the plasticizer. Specifically, it comprises a specific phthalic diester and a specific epoxy compound. Suitable for plasticizers for vinyl chloride resins that have excellent cold resistance and volatile resistance, and have greatly improved durability such as amine coloration resistance and heat resistance coloration, and automobile members containing the plasticizer. The present invention relates to a vinyl chloride resin composition.

  In automobiles, lightweight and easy-to-process plastics are used as various components. Among these, polyvinyl chloride resin is excellent in processability and can exhibit various physical properties by blending with a plasticizer, etc. Furthermore, it is most widely used as an automobile member from the viewpoint of flame retardancy. It is one of the plastics.

  Various interior materials are used in the interior of automobiles to improve ride comfort. Usually, automotive interior materials are composed of a skin layer for providing a touch (feel) such as a soft feeling, a high-class feeling, and a design such as aesthetics, and a base material layer for maintaining the structure. Furthermore, in order to give a soft feeling to the skin layer, it is often used by lining a foam layer such as urethane.

  As the skin layer, thermoplastic elastomer and polyolefin foams such as polyethylene are used, but as described above, polyvinyl chloride resin gives various feels from semi-rigid to soft depending on the amount of plasticizer. It is most widely used because it is easy to mold and has excellent design.

  As the plasticizer, phthalate diester plasticizers typified by diisononyl phthalate (hereinafter referred to as “DINP”) and diisodecyl phthalate (hereinafter referred to as “DIDP”) are inexpensive and good. It is most commonly used because of its performance.

  As a recent trend, demands for weight reduction and durability have become stricter for automobile members in general, and it is desired to improve the performance of individual members such as automobile interior materials. Specifically, there is a problem of deterioration due to heat and light under hot weather, that is, performance deterioration due to volatilization of plasticizers and other additives, physical property deterioration and coloring problems due to heat and light peculiar to vinyl chloride resins, and volatile components. Further improvement has been desired with respect to the fogging of the windshield, etc. caused by fogging, that is, the problem of fogging, and the problem of breakage due to reduced flexibility in cold regions.

  Under such circumstances, the present inventors have found that a plasticizer comprising a phthalic acid diester having a specific structure / composition is more resistant to cold and volatilization than conventional phthalic acid diesters such as DINP. And proposed that the flexibility can be improved (Patent Document 1).

  However, when used as a laminate with foamed polyurethane to give a soft feeling as described above, the vinyl chloride resin interior material skin of the amine compound used as a catalyst during the formation of the polyurethane foamed molded product Deterioration and coloring due to heat and light peculiar to vinyl chloride resin due to desorption of hydrogen chloride due to intramolecular decomposition of the vinyl chloride resin promoted with the transition of the resin (Patent Document 2) Even the method has not been able to sufficiently suppress the deterioration such as coloring, and further improvement is desired.

  Therefore, sodium perchlorate, barium perchlorate, perchloric acid treatment is performed for the purpose of preventing deterioration, coloring, and alteration of the vinyl chloride resin molded body promoted by the amine compound, that is, to improve amine resistance. A method of blending a perchloric acid compound such as hydrotalcite into a vinyl chloride resin composition is employed (Patent Documents 3 and 4).

  However, even with vinyl chloride resin compositions containing perchloric acid compounds, the deterioration rate is remarkable in summer climatic conditions where the in-vehicle temperature reaches as high as 100 ° C. However, it was not sufficient (Patent Documents 5 and 6). In addition, perchlorates used in explosives and explosives are dangerous materials as 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. Yes. In addition, perchlorate water pollution has been reported in at least 20 states in the United States, and the California Department of Hazardous Substances Control (DTSC) has established regulations regarding the handling of perchlorate. There are many concerns about the use of chloric acid compounds in terms of safety and environment. From the above, a vinyl chloride resin composition or an automobile interior material suitable for an automobile member having excellent amine resistance and not using a perchloric acid compound is desired.

JP 2012-7184 A International Publication WO2012 / 020618 JP 59-184240 A JP-A-7-173354 JP-A-6-198825 Japanese Patent Laid-Open No. 7-228615

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

  As a result of intensive studies to solve the above problems, the present inventors have determined that a plasticizer comprising a phthalic diester having a specific structure and an epoxy compound having at least one ester group in the molecule having a specific structure By blending the composition into a vinyl chloride resin as a plasticizer, flexibility and cold resistance are excellent, heat resistance such as volatility is excellent, and coloring, which is a problem, particularly amines due to the influence of amines The present inventors have found that the colorability is remarkably improved and have completed the present invention.

  That is, the present invention provides the following plasticizer composition, 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) a phthalic acid diester and (B) an epoxy compound having at least one ester group in the molecule,
Component (A) is a phthalic acid diester 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 and R ² are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is linear or branched having 8 to 11 carbon atoms. It is a chain saturated aliphatic alcohol. ]

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

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

[Claim 4] In any one of [Claim 1] to [Claim 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 as described.
[Wherein R ³ and R ⁴ are the same or different and are each a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is linear or branched having 8 to 11 carbon atoms. It is a chain saturated aliphatic alcohol. ]
[Wherein, R ⁵ and R ⁷ are the same or different and each represents a linear or branched alkylene group having 8 to 12 carbon atoms, and R ⁶ and R ⁸ are the same or different, Each represents a linear or branched alkyl group having 6 to 8 carbon atoms. ]

[Item 5] The saturated aliphatic alcohol in the general formula (2) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 9 linear carbon atoms having a weight of 60% by weight or more. [Claim 4] comprising a saturated aliphatic alcohol in the form of a chain and a branched saturated aliphatic alcohol having 9 or less carbon atoms of 40% by weight or less, and the linear ratio of the saturated aliphatic alcohol is 60% or more. The plasticizer composition as described.

[Section 6] The saturated aliphatic alcohol in the general formula (2) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 9% or more by weight. [Item 5], wherein the saturated aliphatic alcohol has a linear chain ratio of 70%, and the saturated aliphatic alcohol has 30% by weight or less and a branched saturated aliphatic alcohol having 9 carbon atoms. Plasticizer composition.

[Item 7] The saturated aliphatic alcohol in the general formula (2) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the content in the saturated aliphatic alcohol is 75 to 98% by weight. A chain saturated aliphatic alcohol and 2 to 25% by weight of a branched saturated aliphatic alcohol having 9 carbon atoms, and the linear ratio of the saturated aliphatic alcohol is 75 to 98% or more. Item 6. A plasticizer composition according to item 6.

[Section 8] The saturated aliphatic alcohol in the general formula (2) is mainly composed of a saturated aliphatic alcohol having 9 to 11 carbon atoms, and the ratio of each saturated aliphatic alcohol having 9, 10, and 11 carbon atoms is 10 to 25. The plasticizer composition according to [Item 4], which is in the range of / 35 to 55/30 to 45, and the linear ratio of the saturated aliphatic alcohol is 55% or more.

[Item 9] The plasticizer composition according to Item 4, wherein the component (B) is an epoxy compound represented by the general formula (3).

[Claim 10] The plasticizer composition according to any one of [Claim 4] to [Claim 9], wherein the alkylene group in General Formula (3) has 8 carbon atoms and the alkyl group has 8 carbon atoms. object.

[Item 11] The saturated aliphatic alcohol in the general formula (1) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 9 linear carbon atoms having a weight of 60% by weight or more. [Claim 1]-containing a saturated aliphatic alcohol having a chain shape and a branched saturated aliphatic alcohol having 9 or less carbon atoms and having a carbon number of not more than 40% by weight, and the linear ratio of the saturated aliphatic alcohol being 60% or more. [10] The plasticizer composition according to any one of [10].

[Section 12] The saturated aliphatic alcohol in the general formula (1) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 9% or more by weight. [Item 11], wherein the saturated aliphatic alcohol is in the form of a branched saturated aliphatic alcohol having 9 carbon atoms or less and 30% by weight or less, and the linear ratio of the saturated aliphatic alcohol is 70% or more. The plasticizer composition as described.

[Item 13] The saturated aliphatic alcohol in the general formula (1) is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms, and the content in the saturated aliphatic alcohol is 75 to 98% by weight. [Item 12], which contains a linear saturated aliphatic alcohol and 2 to 25% by weight of a branched saturated aliphatic alcohol, and the linear ratio of the saturated aliphatic alcohol is 75 to 98%. Plasticizer composition.

[Item 14] The saturated aliphatic alcohol in the general formula (1) is mainly composed of a saturated aliphatic alcohol having 9 to 11 carbon atoms, and the ratio of each saturated aliphatic alcohol having 9, 10, and 11 carbon atoms is 10 to 25. The plasticizer composition according to [Item 12], which is in the range of / 35 to 55/30 to 45, and the linear ratio of the saturated aliphatic alcohol is 55% or more.

[Item 15] The plasticizer composition according to any one of Items 1 to 14, wherein the vinyl chloride resin is an automobile interior material.

[Item 16] The plasticizer composition according to Item 15, wherein the automobile interior material is laminated with a polyurethane molded body.

[Item 17] A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer composition according to any one of [Item 1] to [Item 14].

[Item 18] The vinyl chloride resin composition according to Item 17, further comprising a fatty acid calcium salt and / or a fatty acid zinc salt.

[Item 19] The vinyl chloride resin composition according to [Item 17] or [Item 18], which is used for automobile interior materials.

[Claim 20] The vinyl chloride resin composition according to [Claim 19], which is for an automobile interior material laminated with a polyurethane molded body.

[Claim 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, according to [Claim 17] to [Claim 20]. The vinyl chloride resin composition according to any one of the above.

[Claim 22] The vinyl chloride resin according to [Claim 21], 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 23] A vinyl chloride-based resin molded article using the vinyl chloride-based resin composition according to any one of [Item 17], [Item 18], [Item 21], or [Item 22] as a raw material.

[Claim 24] The vinyl chloride resin molded article according to [Claim 23], which is for automobile interior materials.

[Item 25] The vinyl chloride resin molded product according to [Item 24], which is used for automobile interior materials laminated with a polyurethane molded product.

[Item 26] An automobile interior material comprising the vinyl chloride resin molded article according to Item 24.

[Item 27] The automobile interior material according to Item 26, which is laminated with a polyurethane molded body.

[Item 28] 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,
(A) a phthalic acid diester represented by the following general formula (1) and (B) a molecular weight in the range of 300 to 1200, and an oxirane oxygen concentration in the range of 2 to 13%, and at least one ester group in the molecule A method for suppressing coloration, comprising using a plasticizer composition comprising an epoxy compound having a vinyl chloride resin as a raw material resin of a vinyl chloride resin molded body as a plasticizer.
[Wherein, R ¹ and R ² are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is linear or branched having 8 to 11 carbon atoms. A chain saturated aliphatic alcohol is the main component. ]

The plasticizer composition for vinyl chloride resin of the present invention has good flexibility and cold resistance, excellent heat resistance such as volatility, and heat resistance coloring, which is a problem, particularly amines due to the influence of amines. It can be used as a plasticizer for vinyl chloride resins with improved coloring. Moreover, by including 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 coloring resistance 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) that requires particularly high durability.

<Plasticizer composition for vinyl chloride resin>
The plasticizer composition for vinyl chloride resin of the present invention is (A) a phthalic acid diester represented by the following general formula (1) and (B) a molecular weight in the range of 300 to 1200, and further its oxirane oxygen concentration is It is characterized by comprising an epoxy compound having at least one ester group in the molecule in the range of 2 to 13%.
[Wherein, R ¹ and R ² are the same or different and are each a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a linear or branched chain having 8 to 11 carbon atoms. In the form of saturated fatty alcohol. ]

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

  As a preferred embodiment of the component (A) phthalic acid diester (hereinafter referred to as “the present ester compound 1”), the saturated aliphatic alcohol that defines the residue in the general formula (1) has 8 carbon atoms. The ratio (weight ratio) of the linear saturated aliphatic alcohol to the total saturated aliphatic alcohol that defines the residue thereof is 60 to 11 linear or branched saturated aliphatic alcohols. The aspect which is% or more is mentioned. In a more preferred embodiment, the saturated aliphatic alcohol that defines the residue comprises (i) a saturated aliphatic alcohol having 9 carbon atoms as a main component, and in the saturated aliphatic alcohol that defines the residue. A linear saturated aliphatic alcohol having 9 carbon atoms with a content of 60% by weight or more and a branched saturated aliphatic alcohol having 9 carbon atoms with a content of 40% by weight or less, and defining the residue An embodiment in which the straight chain ratio of the saturated aliphatic alcohol is 60% or more, (ii) a mixture of mainly saturated aliphatic alcohols having 9 to 11 carbon atoms, and the ratio (moles) of each alcohol having 9, 10 and 11 carbon atoms Ratio) is in the range of 10 to 25/35 to 50/30 to 45, and an aspect in which the linear ratio of the saturated aliphatic alcohol defining the residue is 55% or more is recommended.

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

The epoxy compound of component (B) (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. In addition, from the viewpoint of volatility resistance and the like, 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 and the like, the oxirane oxygen concentration is in the range of 2 to 13%. Epoxy compounds preferably in the range of 2.5-12% are recommended.
Further, the epoxy compound is preferably an epoxy compound represented by the following general formula (2) (hereinafter referred to as “the present epoxy compound 2”) or an epoxy compound represented by the following general formula (3) (hereinafter referred to as “the present”). It is recommended that the epoxy compound 3 is particularly preferably the epoxy compound 3, and the epoxy compounds 1 to 3 may be used alone or in combination of two or more.
[Wherein R ³ and R ⁴ are the same or different and are each a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is a linear or branched chain having 8 to 11 carbon atoms. In the form of saturated fatty alcohol. ]
[Wherein, R ⁵ and R ⁶ are the same or different and each represents a linear or branched alkylene group having 8 to 12 carbon atoms, and R ⁶ and R ⁸ are the same or different, A linear or branched alkyl group having 6 to 8 carbon atoms is represented. ]

  Moreover, as this epoxy compound 1, besides the said epoxy compound 2 and this epoxy compound 3, the epoxidized material of a natural unsaturated fatty acid glyceride, etc. can be used conveniently. 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 beech oil, epoxidized beef tallow, epoxidized fish oil, etc. Among them, preferred specific examples include epoxidized soybean oil and epoxidized linseed oil.

  In this epoxy compound 1, when no ester group is present in the molecule, the compatibility with the vinyl chloride resin is remarkably lowered, resulting in poor dispersion in the resin, and sufficient heat resistance and coloration resistance. Not only is it difficult to improve, but it also tends to cause surface contamination due to bleeding or the like, which is not preferable. When the molecular weight is less than 300, the volatility increases, resulting in a decrease in fogging resistance and the like. On the other hand, when the molecular weight exceeds 1200, the compatibility with the vinyl chloride resin decreases, This is likely to cause the surface of the molded product to become dirty due to poor dispersion or bleed. In addition, when the oxirane oxygen concentration is less than 2%, the above-mentioned heat-resistant colorability, that is, the amine colorability is not sufficiently improved, and the effect of suppressing the deterioration of the function and designability of the resin and the molded body by the amine compound is sufficient. When the oxirane oxygen concentration exceeds 13%, the compatibility with the vinyl chloride resin is lowered, and it tends to cause poor dispersion in the resin and contamination of the surface of the molded product due to bleeding. .

  The present epoxy compound 1 is not particularly limited by its production method as long as it satisfies the above-mentioned performance intended 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 an inert gas atmosphere such as nitrogen in the absence of a catalyst or in the presence of a catalyst, and epoxidizing the resulting ester compound (intermediate raw material) under predetermined conditions. Here, the above-mentioned predetermined acid component and alcohol component, both components, or any one component includes a component having one or more carbon double bonds not showing aromaticity in the molecule, and these components By esterifying, an ester compound (intermediate raw material) having one or more carbon double bonds that do not exhibit aromaticity in the molecule can be obtained. Further, as an ester compound having one or more carbon double bonds that do not exhibit aromaticity in the molecule, fats and oils composed of natural unsaturated fatty acid glycerides can be used as they are.

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

  As a preferred embodiment of the present epoxy compound 2, the saturated aliphatic alcohol that defines the residue in the general formula (2) is a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms. The ratio (weight ratio) of linear saturated aliphatic alcohol is 60% or more with respect to the total amount of saturated aliphatic alcohol defining the residue. In a more preferred embodiment, the saturated aliphatic alcohol that defines the residue comprises (i) a saturated aliphatic alcohol having 9 carbon atoms as a main component, and in the saturated aliphatic alcohol that defines the residue. A linear saturated aliphatic alcohol having 9 carbon atoms with a content of 60% by weight or more and a branched saturated aliphatic alcohol having 9 carbon atoms with a content of 40% by weight or less, and defining the residue A mode in which the straight chain ratio of the saturated aliphatic alcohol is 60% or more, (ii) a mixture of mainly saturated aliphatic alcohols having 9 to 11 carbon atoms, and the proportion of each alcohol having 9, 10, and 11 carbon atoms ( The molar ratio is in the range of 10-25 / 35-50 / 30-45, and the saturated aliphatic alcohol that defines the residue has a linear ratio of 55% or more. .

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

As a preferred embodiment of the present epoxy compound 3, the alkylene groups represented by R ⁵ and R ⁷ in the general formula (3) are the same or different and each has a linear or branched chain structure having 8 to 12 carbon atoms. an alkylene group, and the alkyl group represented by R ⁶ and R ⁸ are the same or different and each include embodiments a linear or branched alkyl group having 6 to 8 carbon atoms. In a more preferred embodiment, the alkylene group represented by R ⁵ and R ⁷ is a linear or branched alkylene group having 8 carbon atoms, and the alkyl group represented by R ⁶ and R ⁸ is carbon. The aspect etc. which are the alkyl group of several 8 are mentioned.

  The epoxy compound 3 is not particularly limited by its production method as long as it satisfies the object performance of the present invention. For example, it is specified as 4-cyclohexene-1,2-dicarboxylic acid or an anhydride thereof. It is easily obtained by esterifying the unsaturated aliphatic alcohol having the structure of ## STR4 ## and epoxidizing the obtained 4-cyclohexene-1,2-dicarboxylic acid diester (intermediate raw material) under predetermined conditions. In addition, after epoxidizing 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, the resulting 4,5-epoxycyclohexane-1,2-dicarboxylic acid or its anhydride and an epoxidized saturated fat having a specific structure It can also be obtained by esterifying a group alcohol. Furthermore, depending on the type of the unsaturated aliphatic alcohol, there is 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 obtained by transesterification. From the viewpoint of practicality such as simplicity, the method of epoxidation 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 amine coloration improving effect can be obtained, and if it is 70% by weight or less, the cold resistance is improved. Concerns that cause surface contamination and the like due to lowering and bleeding are significantly reduced, which is preferable.

[Saturated fatty alcohol]
The saturated aliphatic alcohol used as a raw material for the ester compound 1 and the epoxy compound 2 is a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms. When a saturated aliphatic alcohol having a carbon number of less than 8 is included, the performance such as volatility tends to decrease, and when a saturated aliphatic alcohol having a carbon number of more than 11 is included, the performance such as flexibility is decreased. 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, the main component being a saturated aliphatic alcohol having 9 carbon atoms. In the linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms, the ratio of the saturated aliphatic alcohol having 9 carbon atoms as the main component is preferably A saturated aliphatic alcohol that is 60% by weight or more (60-100% by weight), more preferably 70% by weight or more (70-100% by weight), particularly preferably 80% by weight or more (80-100% by weight), (ii ) It is mainly composed of a linear or branched saturated aliphatic alcohol having 9 to 11 carbon atoms, and is a saturated aliphatic alcohol having 9 carbon atoms / saturated aliphatic alcohol having 10 carbon atoms / 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 “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.

  In addition, the saturated aliphatic alcohol according to the present invention includes the recommended aspects of (i) and (ii) above, and the linear ratio of the saturated aliphatic alcohol is preferably 55% or more, more preferably 60%. % Or more, more preferably 70% or more, particularly preferably in the range of 75 to 98%.

  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. %, Particularly preferably in the range of 75 to 98% by weight, and the content of the branched saturated aliphatic alcohol having 9 carbon atoms (for example, 2-methyloctanol and the like) in the saturated aliphatic alcohol 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 linear or branched 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 a straight chain having 9 carbon atoms having a content of 60% by weight or more. The linear chain ratio of the saturated aliphatic alcohol containing a saturated aliphatic alcohol and a branched saturated aliphatic alcohol having 9 to 9 carbon atoms and having a carbon number of 9 to 11 and having 8 to 11 carbon atoms 60% or more. As a more preferred embodiment, the linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms (preferably 70% by weight or more), and has 8 carbon atoms. -11 linear or branched saturated aliphatic alcohols having a content of 70% by weight or more of C9 linear saturated aliphatic alcohols and 30% by weight or less of C9 branched chains In which the linear chain ratio of the linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms is 70% or more is recommended. The linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms mainly comprises a saturated aliphatic alcohol having 9 carbon atoms (preferably 80% by weight or more), In branched saturated aliphatic alcohol A linear saturated aliphatic alcohol having 9 to 9 carbon atoms and a branched saturated aliphatic alcohol having 9 to 9 carbon atoms and having a content of 75 to 98% by weight, and 8 to 11 carbon atoms. An embodiment in which the straight chain ratio of the linear or branched saturated aliphatic alcohol is 75 to 98% is recommended.

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

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

  In the present specification and claims, the straight chain ratio of a linear or branched saturated aliphatic alcohol having 8 to 11 carbon atoms is the ratio (weight) of the linear alcohol in the saturated aliphatic alcohol. Specifically, it can be determined by a method of analysis by gas chromatography.

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

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

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

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

[Unsaturated aliphatic alcohol]
Moreover, the unsaturated aliphatic alcohol used as a raw material of this epoxy compound 3 is a C16-C22 unsaturated aliphatic alcohol shown by following General formula (4).
[Wherein, R ⁹ represents a linear or branched alkyl group having 6 to 8 carbon atoms, and R ¹⁰ represents a linear or branched alkylene group having 8 to 12 carbon atoms. Represent. ]

  As the details of the embodiment of the unsaturated aliphatic alcohol, the 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, the carbon of the alkyl group An unsaturated aliphatic alcohol having 8 carbon atoms and an alkylene group having 8 carbon atoms, an unsaturated aliphatic alcohol having an alkyl group having 8 carbon atoms and an alkylene group having 12 carbon atoms, and the like Among them, a preferable embodiment includes an unsaturated alcohol in which the alkyl group has 8 carbon atoms and the alkylene group has 8 carbon atoms.

  Specific examples of the unsaturated aliphatic alcohol having 16 to 22 carbon atoms include palmitoleyl alcohol having 16 carbon atoms, oleyl alcohol having 18 carbon atoms, and erucyl alcohol having 22 carbon atoms. An example is oleyl alcohol having 18 carbon atoms.

  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 below. As described above, the present invention can be used as long as the intended performance is obtained. It does not depend on a manufacturing method and conditions, Furthermore, the commercial item which has the structure of this ester compound 1 or this epoxy compound 1 can also be used as it is as a component (A) or a component (B) based on this invention.

[Esterification reaction]
In the production of the present ester compound 1, when the esterification reaction between the saturated aliphatic alcohol and phthalic acid or its anhydride is performed, the saturated aliphatic alcohol is preferably used, for example, with respect to 1 mol of phthalic acid or its anhydride. It is recommended to use 2.00 to 5.00 mol, more preferably 2.01 to 3.00 mol, especially 2.02 to 2.50 mol. Further, 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 its In the esterification with an anhydride, the saturated aliphatic alcohol or unsaturated aliphatic alcohol is preferably 2.00 mol per mol of 4-cyclohexene-1,2-dicarboxylic acid or anhydride thereof, for example. It is recommended to use ˜5.00 mol, more preferably 2.01 mol to 3.00 mol, particularly preferably 2.02 mol to 2.50 mol.

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

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

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

  There are no particular restrictions on phthalic acid or its anhydride, which is a raw material of the ester compound 1, and 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, which is a raw material of the epoxy compound 2 and the epoxy compound 3. A product manufactured by a known method, a commercially available product, a product available as a reagent, or the like can be used. For example, as a raw material of the present epoxy compound 2 and the present epoxy compound 3, Rikacid TH (trade name, Shin Nippon Rika Co., Ltd.) is exemplified as a commercial product. 4-Cyclohexene-1,2-dicarboxylic acid anhydride is usually obtained by Diels-Alder reaction of maleic anhydride and 1,3-butadiene. From the viewpoint of esterification reaction, phthalic anhydride is used as the raw material for the ester compound 1, and 4-cyclohexene-1,2-dicarboxylic anhydride is used as the raw material for the epoxy compound 2 and the epoxy compound 3, respectively. It is recommended to do.

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

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

  The ester compound 1 obtained by the esterification reaction and the ester compounds that are intermediate raw materials of the epoxy compound 2 and the epoxy compound 3 are subsequently subjected to base treatment (neutralization treatment), water washing treatment, You may refine | purify by liquid-liquid extraction, distillation (reduced pressure, dehydration process), adsorption purification process, etc.

  The base used for the base treatment is not particularly limited as long as it is a basic compound, and examples thereof include sodium hydroxide and sodium carbonate.

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

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

[Epoxidation reaction]
The epoxidation reaction according to the present invention means an epoxidation reaction of a carbon double bond (unsaturated bond) that does not exhibit aromaticity and exists in the molecule in order to obtain the 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, 612-619 (1985). Examples include (i) a method using an organic peracid such as peracetic acid or performic acid as the epoxidizing agent, and (ii) a method using hydrogen peroxide as the epoxidizing agent. The target site of the epoxidation reaction in the present invention is a double bond of a cyclohexene ring site or a double bond of an alkenyl site derived from an unsaturated aliphatic alcohol or an unsaturated fatty acid.

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

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

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

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

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

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

  In addition, as above-mentioned, this plasticizer composition is not only what mixed the component (A) and the component (B) previously, but the component (A) and component (B) mix | blended with a vinyl chloride resin simultaneously. Therefore, as a method of blending into the vinyl chloride resin, the component (A) and the component (B) may be mixed in advance, and then blended into the vinyl chloride resin. Moreover, you may mix | blend a component (A) and a component (B) with a vinyl chloride resin simultaneously.

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

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

[Vinyl chloride resin composition]
The plasticizer composition has an effect as a plasticizer as well as an effect as a stabilizer, as has been described so far. The content of the plasticizer composition in the vinyl chloride resin composition of the present invention is appropriately selected according to its use and expected effects. For example, when the effect is mainly desired as a stabilizer. The effect is exerted more preferentially from a relatively small amount of content, specifically, preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. The range is recommended, and when the effect as a plasticizer is mainly desired, the effect is exhibited more significantly from a slightly higher content than the above content, specifically preferably 20 to 200 parts by weight, more 30 to 150 parts by weight are recommended.

  That is, if the content relative to 100 parts by weight of the vinyl chloride resin is 1 part by weight or more, the effect as a stabilizer of the plasticizer composition can be sufficiently exerted, and if it is 200 parts by weight or less. If it is used, it can be used safely without fear of bleeding on the surface of the molded product. Moreover, when the effect as a plasticizer is mainly desired, if the content with respect to 100 parts by weight of the vinyl chloride resin is 20 parts by weight or more, sufficient flexibility according to the purpose of use can be obtained more preferentially. . Further, when the effect of improving the above-mentioned amine coloration resistance is mainly desired as a stabilizer, the content with respect to 100 parts by weight of the vinyl chloride resin is preferably 20 parts by weight or more, 150 parts by weight is more preferable.

[Stabilizer]
When an effect as a stabilizer is mainly desired for the plasticizer composition, it is an effective method for further exerting the effect to use other stabilizers in combination. Stabilizers that can be used in combination with this plasticizer composition include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, octylic acid Metal soap compounds such as organic acid compounds containing metals such as zinc, zinc laurate, zinc ricinoleate, zinc stearate, barium stearate-zinc, barium laurate-zinc, barium zinc ricinoleate, barium octylate-zinc , Metal soap compounds such as organic acid compounds containing composite metals such as calcium stearate-zinc, calcium laurate-zinc, calcium ricinoleate-zinc, calcium octylate-zinc, dimethyltin bis-2-ethylhexylthioglycol 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 these, the combined use of the metal soap compound is particularly preferable because it shows the effect of amplifying the stabilizing effect of the plasticizer composition by a synergistic effect. Particularly preferred metal soap compounds include, for example, fatty acid calcium salts and fatty acid zinc salts, which can be used alone or in combination. When the other stabilizer that can be used in combination is blended, the blending amount is appropriately selected within a range not impairing the effect of the stabilizer according to the present invention, and is usually 0 with respect to 100 parts by weight of the vinyl chloride resin. About 1 to 20 parts by weight is recommended.

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

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

  As other plasticizers that can be used in combination with the present plasticizer composition, known plasticizers conventionally used in this technical field can be used, for example, benzoic acid esters such as diethylene glycol dibenzoate, and the present invention. Phthalates outside the range, isophthalic acid esters such as di-2-ethylhexyl isophthalate (DOIP), terephthalic acid esters such as di-2-ethylhexyl terephthalate, bis (4-cyclohexene-1,2-dicarboxylate ( Tetrahydrophthalic acid esters such as 2-ethylhexyl) (DOTH), di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS) , Fats such as diisononyl sebacate (DINS) Group dibasic acid esters, trimellitic acid tri-2-ethylhexyl (TOTM), trimellitic acid tri-n-octyl (nTOTM), etc., pyromellitic acid tetra-2-ethylhexyl (TOPM) 2 bases such as pyromellitic acid esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP), alkyl esters of polyhydric alcohols such as pentaerythritol, and adipic acid Polyesters having a molecular weight of 800 to 4000 synthesized by polyesterification of acid and glycol, epoxidized esters outside the scope of the present invention, alicyclic dibasic esters such as DINCH, dicapric acid-1,4-butane Fatty acid glycol esters such as diol, tribute acetyl citrate Chlorination of citrates such as (ATBC), trihexyl acetyl citrate (ATHC), triethylhexyl acetyl citrate (ATEHC), trihexyl butyl citrate (BTHC), isosorbide diesters, paraffin wax and n-paraffin Examples include paraffins, chlorinated fatty acid esters such as chlorinated stearic acid esters, and higher fatty acid esters such as butyl oleate. When blending other plasticizers that can be used in combination, the blending amount is appropriately selected within a range not impairing the effect of the plasticizer according to the present invention, and is usually 1 to 100 weights per 100 parts by weight of the vinyl chloride resin. About 1 part is recommended.

  In addition, although the component (A) and component (B) which comprise this plasticizer composition which concerns on this invention, and also the said plasticizer which can be used together together may be added separately to a vinyl chloride resin, after mixing beforehand A method of adding to a vinyl chloride resin is more preferable. By mixing in advance, the compatibility with the resin is not good, i.e., the plasticizer with poor plasticization efficiency is compatible with the resin, i.e. the plasticization efficiency is improved. Uniformity in the resin of a small amount of components can be maintained, and as a result, there is less concern that unevenness of the stabilizing effect such as the improvement effect of heat resistance coloration and amine coloration resistance of the present invention will occur.

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

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

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

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

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

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

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

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

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

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

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

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

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

[Vinyl chloride resin molding]
Conventionally known methods such as vacuum molding, compression molding, extrusion molding, injection molding, calendar molding, press molding, blow molding, powder molding, etc., for the vinyl chloride resin composition (mixed powder or pellets) according to the present invention Can be molded into a desired shape.

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

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

  The molded body thus obtained is instrument panel, door trim, console box, glove box, pillar trim, dashboard, trunk trim, seat seat, ceiling material, AT shift, armrest, floor carpet, wire harness, various moldings, sash, It can be used effectively as automotive interior materials and automotive exterior materials such as sealing materials, weather strips, gaskets, undercoat materials, etc. Above all automotive interior materials laminated with polyurethane, such as door trims, trunk trims, ceiling materials It is very useful as such.

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

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

(2) Physical property evaluation of this ester compound 1 and this epoxy compound 1 The ester compound and epoxy compound obtained by the following manufacture example analyzed by the following method.
Ester value: Measured according to JIS K-0070 (1992).
Acid value: measured in accordance with JIS K-0070 (1992).
Iodine value: measured according to JIS K-0070 (1992).
Oxirane Oxygen: Measured according to the standard oil and fat analysis test method 2.3.7.1-2013 “oxirane oxygen determination method (1)”.
Hue: Measured according to JIS K-0071 (1998) to determine the Hazen unit color number.

(3) Production of vinyl chloride sheet 100 parts by weight of vinyl chloride resin (straight, degree of polymerization 1050, trade name “Zest1000Z”, manufactured by Shin Daiichi PVC Co., Ltd.), calcium stearate (Nacalai Tesque (Nacalai Tesque) Co., Ltd.) and zinc stearate (manufactured by Nacalai Tesque Co., Ltd.) in 0.1 and 0.1 parts by weight, respectively, and after stirring and mixing with a mortar mixer, A total of 50 parts by weight of phthalic acid diester and (B) epoxy compound were added in the proportions shown in Table 1, and the mixture was handled and mixed until uniform to obtain a vinyl chloride resin composition. This resin composition was melt-kneaded at 160 to 166 ° C. for 4 minutes using a 5 × 12 inch double roll to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168 ° C. for 10 minutes to produce a press sheet having a thickness of about 1 mm.

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

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

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

(7) Amine coloring resistance: DOP solution prepared by cutting a press sheet into a size of 3.5 cm × 2 cm and adjusting the amine concentration to 0.1% by weight (amine: N, N, N ′, N '-Tetramethyl-1,6-diaminohexane) 0.02 mL 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 heating, the degree of coloration of the sheet was visually observed, and the amine coloration resistance was evaluated in four stages from the degree of coloration. The less the sheet is colored, the better the resistance to amine coloring, and the less discoloration of the vinyl chloride resin caused by contact with the polyurethane molded product.
Amine coloring resistance: ◎: No coloring, ○: Slightly colored, △: Colored, ×: Strong coloring

[Production Example 1]
In a 1 L four-necked flask equipped with a thermometer, decanter, stirring blade and reflux condenser, 74.1 g (0.5 mol) of phthalic anhydride (commercially available product for industry), linear saturated with 9 carbon atoms 173.1 g (1.2 moles) of a saturated aliphatic alcohol (Shell Chemicals: Lineball 9) containing 85.1% by weight of aliphatic alcohol and 11.7% by weight of a branched saturated aliphatic alcohol having 9 carbon atoms. And 0.1 g of tetraisopropyl titanate as an esterification catalyst was added, and the esterification reaction was carried out at a reaction temperature of 190 ° C. The reaction was continued until the acid value of the reaction solution reached 0.5 mgKOH / g while the generated water was removed from the system by refluxing the alcohol under reduced pressure. After completion of the reaction, unreacted alcohol was distilled out of the system under reduced pressure, and then neutralized, washed with water and dehydrated according to a conventional method to obtain 178 g of the desired phthalic acid diester (hereinafter referred to as “ester 1”). .
The obtained ester 1 had an ester value of 267 mgKOH / g, an acid value of 0.03 mgKOH / g, and a color number of 10.

[Production Example 2]
In place of 173.1 g of aliphatic saturated alcohol (manufactured by Shell Chemicals: Lineball 9), the ratio of carbon number 9/10/11 is 19/43/38, and the total linearity is 84%. This was carried out in the same manner as in Production Example 1 except that 193 g of a saturated aliphatic alcohol of -11 (manufactured by Shell Chemicals: Lineball 911) was added to obtain 181 g of phthalic acid diester (hereinafter referred to as “ester 2”).
The obtained ester 2 had an ester value of 250 mgKOH / g, an acid value of 0.02 mgKOH / g, and a color number of 10.
[Production Example 3]
To a 2 L four-necked flask equipped with an esterification process thermometer, decanter, stirring blade, and reflux condenser, 182.6 g of 4-cyclohexene-1,2-dicarboxylic anhydride (1.2 mol, Shin Nippon Rika Co., Ltd.) Sliced fatty alcohol (shell) containing 95.1% by weight of a linear saturated aliphatic alcohol having 9 carbon atoms and 11.7% by weight of a branched saturated aliphatic alcohol having 9 carbon atoms. Chemicals Co., Ltd .: 416 g (2.9 mol) of lineball 9) and 0.24 g of tetraisopropyl titanate as an esterification catalyst were added, and the esterification reaction was carried out at a reaction temperature of 200 ° C. The reaction was continued until the acid value of the reaction solution reached 0.5 mgKOH / g while the generated water was removed from the system by refluxing the alcohol under reduced pressure. After completion of the reaction, unreacted alcohol was distilled off under reduced pressure, and neutralized, washed with water and dehydrated according to a conventional method to obtain the desired 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter referred to as “ester 3”). 449 g was obtained.
The obtained ester 3 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, 423 g (1.0 mol) of the ester 3 obtained by the above esterification reaction was charged into a 1 L four-necked flask equipped with an upper thermometer, a stirring blade, and a cooling tube, and the temperature was adjusted to 60 to 70 ° C. The temperature rose. After raising the temperature, 76.6 g (1.35 mol) of 60% hydrogen peroxide, 18.3 g (0.30 mol) of 76% formic acid, and 1.47 g (0.01 mol) of 75% phosphoric acid were added for 15 hours. It was slowly added dropwise over a period of minutes. After completion of the dropwise addition, the temperature was further maintained for 4 hours, and the reaction was completed by aging. After completion of the reaction, the aqueous phase was removed out of the system, and then washed and dehydrated according to a conventional method to obtain 397 g of the desired 4,5-epoxycyclohexanedicarboxylic acid diester (hereinafter referred to as “epoxy 1”).
The obtained epoxy 1 had an ester value of 256 mg KOH / g, an acid value of 0.06 mg KOH / g, an iodine value of 2.5 g I 2/100 g, an oxirane oxygen of 3.5%, and a color number of 10.

[Production Example 4]
To a 2 L four-necked flask equipped with an esterification process thermometer, decanter, stirring blade, and reflux condenser, 182.6 g of 4-cyclohexene-1,2-dicarboxylic anhydride (1.2 mol, Shin Nippon Rika Co., Ltd.) ): Ricacid TH), 778 g (2.9 mol) of oleyl alcohol, 40 g of xylene as a water entrainer, 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 were distilled out of the system under reduced pressure, and then neutralized, washed with water and dehydrated according to a conventional method to obtain the desired 4-cyclohexene-1,2-dicarboxylic acid diester (hereinafter, “ 684 g of ester 4 ”.
The obtained ester 4 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, 671 g (1.0 mol) of the ester 4 obtained by the above esterification reaction was charged into a 2 L four-necked flask equipped with an upper thermometer, a stirring blade, and a cooling tube, and the temperature was adjusted to 60 to 70 ° C. The temperature rose. After the temperature rise, 229.5 g (4.05 mol) of 60% aqueous hydrogen peroxide, 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 slowly dropped. After completion of the dropwise addition, the temperature was further maintained for 5 hours, and the reaction was completed by aging. After completion of the reaction, the aqueous phase was removed out of the system, and then washed with water and dehydrated according to a conventional method to obtain 624 g of the desired 4,5-epoxycyclohexanedicarboxylic acid diester (hereinafter referred to as “epoxy 2”).
The obtained epoxy 2 had an ester value of 163 mg KOH / g, an acid value of 0.33 mg KOH / g, an iodine value of 2.6 g I 2/100 g, an oxirane oxygen of 5.6%, and a color number of 30.

[Example 1]
In accordance with the method described in “(3) Production of vinyl chloride sheet”, the phthalic acid diester (ester 1) obtained in Production Example 1 and the epoxycyclohexanedicarboxylic acid diester (epoxy 1) were blended at a ratio of 50/50. A vinyl chloride resin composition is prepared using a plasticizer composition, a vinyl chloride sheet is prepared from the obtained vinyl chloride resin composition, and a tensile test, a cold resistance test, a heat resistance test, and an amine coloring resistance are prepared. A test was conducted. The results obtained are summarized in Table 1.

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

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

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

[Example 5]
A vinyl chloride resin composition was carried out in the same manner as in Example 2 except that commercially available epoxidized soybean oil (ESBO) (manufactured by Shin Nippon Rika Co., Ltd., Sansosizer E-2000H) was used instead of Epoxy 2. A vinyl chloride sheet was prepared from the resulting 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 results obtained are summarized in Table 1.

[Example 6]
A vinyl chloride resin composition was prepared in the same manner as in Example 5 except that epoxy 2 was used in place of epoxy 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition. A test, a cold resistance test, a heat resistance test, and an amine coloring resistance test were performed. The results obtained are summarized in Table 1.

[Example 7]
A vinyl chloride resin composition was prepared in the same manner as in Example 6 except that the ratio of ester 1 and epoxy 2 was changed to 60/40, and a vinyl chloride sheet was prepared from the resulting vinyl chloride resin composition. A tensile test, a cold resistance test, a heat resistance test, and an amine coloring resistance test were performed. The results obtained are summarized in Table 1.

[Example 8]
A vinyl chloride resin composition was prepared in the same manner as in Example 6 except that the ratio of the ester 1 and the epoxy 2 was changed to 70/30. A vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition. A tensile test, a cold resistance test, a heat resistance test, and an amine coloring resistance test were performed. The results obtained 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 plasticizer DOP was used instead of the ester 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition. Then, a tensile test, a cold resistance test, a heat resistance test, and an amine coloring resistance test were performed. The results obtained are summarized in Table 1.

[Example 10]
A vinyl chloride resin composition was prepared in the same manner as in Example 2 except that the commercially available plasticizer DINP was used instead of the ester 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition. Then, a tensile test, a cold resistance test, a heat resistance test, and an amine coloring resistance test were performed. The results obtained are summarized in Table 1.

[Example 11]
A vinyl chloride resin composition was prepared in the same manner as in Example 2 except that a commercially available plasticizer DIDP was used instead of the ester 1, and a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition. Then, a tensile test, a cold resistance test, a heat resistance test, and an amine coloring resistance test were performed. The results obtained are summarized in Table 1.

[Comparative Example 1]
The same procedure as in Example 1 was carried out without adding the component (B) epoxy compound to prepare a vinyl chloride resin composition outside the present invention, and a vinyl chloride sheet was prepared from the resulting vinyl chloride resin composition. A tensile test, a cold resistance test, a heat resistance test, and an amine coloring resistance test were performed. The results obtained are summarized in Table 1.

[Comparative Example 2]
The same procedure as in Example 1 was carried out without adding the component (B) epoxy compound to prepare a vinyl chloride resin composition outside the present invention, and a vinyl chloride sheet was prepared from the resulting vinyl chloride resin composition. A tensile test, a cold resistance test, a heat resistance test, and an amine coloring resistance test were performed. The results obtained are summarized in Table 1.

  From the results shown in Table 1, heat-resistant coloring properties, particularly amine-coloring resistance, are greatly improved by blending the epoxy compound which is the component (B) of the present invention, as compared with the unblended system (Comparative Example 1). You can see that Among them, as a component (B), a system (Examples 2-3 and 6-11) in which an epoxy compound represented by the general formula (3) is blended and a system (Example) in which an epoxy compound represented by the general formula (2) is blended. In 1), the effect is more prominent, and the effect is most prominent in the system in which the epoxy compound represented by the general formula (3) is blended. Further, from the results shown 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 for automobiles such as demanding automobile interior materials. It can be seen that when used as a member, it has sufficient cold resistance and volatility resistance.

  The plasticizer composition for vinyl chloride resin of the present invention has good flexibility and cold resistance, excellent heat resistance such as volatilization resistance, and heat resistance coloring which has been a problem, especially amine coloring due to the influence of amine It can be used in various applications as an improved plasticizer for vinyl chloride resins. Moreover, by including 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 coloring resistance is improved, That is, a vinyl chloride resin composition having excellent durability and a molded product thereof can be obtained, and automotive parts (particularly automotive interior materials) that require particularly high durability, such as instrument panels, door trims, console boxes, Glove box, pillar trim, dashboard, trunk trim, seat seat, ceiling material, rear tray, airbag cover, armrest, headrest, meter cover, crash pad, floor carpet wire harness, various moldings, sash, sealing material, weather strip, gasket Automotive 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, electric wire coatings, various foamed products, hoses, medical tubes, food tubes, refrigerator gaskets, packings, Wallpaper, flooring, boots, curtains, shoe soles, gloves, waterproofing boards, toys, decorative boards, blood bags, infusion bags, tarpaulins, mats, waterproof sheets, civil engineering sheets, roofing, tarpaulins, insulating sheets, industrial It can also be used effectively in applications such as tape, glass film, and eraser.

Claims (15)

A plasticizer composition for vinyl chloride resin comprising (A) phthalic acid diester and (B) an epoxy compound having at least one ester group in the molecule,
Component (A) is a phthalic acid diester 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 and R ² are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is linear or branched having 8 to 11 carbon atoms. It is a chain saturated aliphatic alcohol. ] The plasticizer composition according to claim 1, wherein the ratio (weight ratio) of the component (A) to the component (B) is in the range of 80/20 to 30/70. The plasticizer composition according to claim 1 or 2, wherein 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).

[Wherein R ³ and R ⁴ are the same or different and are each a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is linear or branched having 8 to 11 carbon atoms. It is a chain saturated aliphatic alcohol. ]

[Wherein, R ⁵ and R ⁷ are the same or different and each represents a linear or branched alkylene group having 8 to 12 carbon atoms, and R ⁶ and R ⁸ are the same or different, Each represents a linear or branched alkyl group having 6 to 8 carbon atoms. ] The saturated aliphatic alcohol in the general formula (2) is composed of 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 having 9 carbon atoms is 60% by weight or more. 4. The plasticizer composition according to claim 3, comprising an aliphatic alcohol and a branched saturated aliphatic alcohol having 9 or less carbon atoms and having a carbon number of 40% or less, and wherein the linear ratio of the saturated aliphatic alcohol is 60% or more. object. The plasticizer composition according to claim 3 or 4, wherein the alkylene group in General Formula (3) has 8 carbon atoms and the alkyl group has 8 carbon atoms. The saturated aliphatic alcohol in the general formula (1) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the content of the saturated aliphatic alcohol in the saturated aliphatic alcohol is 9 wt% or more. The aromatic alcohol and the branched saturated aliphatic alcohol having 9 or less carbon atoms of 40% by weight or less, and the linear ratio of the saturated aliphatic alcohol is 60% or more. The plasticizer composition as described. The saturated aliphatic alcohol in the general formula (1) is composed of 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 9 wt% or more. The plasticizer composition according to claim 6, comprising an aliphatic alcohol and a branched saturated aliphatic alcohol having 9 or less carbon atoms and having a carbon number of 9 or less, and the linear ratio of the saturated aliphatic alcohol is 70% or more. object. The saturated aliphatic alcohol in the general formula (1) is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms, and the saturated saturated aliphatic alcohol has a content of 75 to 98% by weight and has 9 to 9% by weight of linear saturated alcohol. The plasticizer composition according to claim 7, wherein the plasticizer composition contains an aliphatic alcohol and 2 to 25% by weight of a branched saturated aliphatic alcohol, and the linear ratio of the saturated aliphatic alcohol is 75 to 98%. . The plasticizer composition according to any one of claims 1 to 8, wherein the vinyl chloride resin is a vinyl chloride resin for automobile interior materials. The vinyl chloride resin for automobile interior material is a raw material resin of a vinyl chloride resin molded body used in an automobile interior material comprising a laminate of a polyurethane molded body and a vinyl chloride resin molded body. The plasticizer composition described in 1. A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer composition according to claim 1. The vinyl chloride resin composition according to claim 11, wherein the content of the plasticizer composition in the vinyl chloride resin composition is 20 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. A vinyl chloride resin molded article using the vinyl chloride resin composition according to claim 11 or 12 as a raw material. An automobile interior material comprising the vinyl chloride resin molded body according to claim 13. A method for suppressing coloration of an automobile interior material comprising a laminate of a polyurethane molded body and a vinyl chloride resin molded body,
(A) a phthalic acid diester represented by the following general formula (1) and (B) a molecular weight in the range of 300 to 1200, and an oxirane oxygen concentration in the range of 2 to 13%, and at least one ester group in the molecule A method for suppressing coloration, which comprises using a plasticizer composition comprising an epoxy compound having a vinyl chloride resin as a raw material resin for a vinyl chloride resin molded article.

[Wherein, R ¹ and R ² are the same or different and each is a residue obtained by removing a hydroxyl group from a saturated aliphatic alcohol, and the saturated aliphatic alcohol is linear or branched having 8 to 11 carbon atoms. It is a chain saturated aliphatic alcohol. ]