Plasticizer for halogen-based resins

Abstract

To provide a plasticizer which imparts excellent plasticity and low-temperature flexibility to a halogen-based resin.SOLUTION: The plasticizer for a halogen-based resin comprises a compound represented by formula (I). (In the formula (I), at least one of R1 and R2 is a group represented by the formula (II). (In the formula (II), m and n are each an integer of 2 or more, and the sum of m and n is 7 or more and 9 or less.). *Represents a bonding position with an oxygen atom in General Formula (I). ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a plasticizer for halogen-based resins, a halogen-based resin composition containing the same, and a method for producing the plasticizer for halogen-based resins. [Background technology]

[0002] Halogen-containing resins such as polyvinyl chloride (PVC) are important general-purpose polymers used in a variety of fields, including home interiors such as wallpaper, general-purpose products such as toys, and automotive materials such as sealants. When a halogen-based resin is used, for example, a resin powder of the halogen-based resin is blended with a plasticizer, a diluent, a viscosity reducer, a filler such as calcium carbonate, a pigment, a flame retardant, a foaming agent, a stabilizer, an antioxidant, etc. to prepare a halogen-based resin composition.

[0003] Patent Document 1 describes furandicarboxylic acid C as a plasticizer that is blended to improve the processability and texture of halogen-based resins. 11 ~C 13 -dialkyl esters are disclosed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2014-506618 Summary of the Invention [Problem to be solved by the invention]

[0005] In Patent Document 1, C of furandicarboxylic acid 11 ~C 13 The present invention discloses dialkyl esters and mixtures thereof. However, although these compounds and mixtures have a plasticizing effect on plastics, the plasticizing effect is not sufficient. In addition, there is also a problem with low-temperature flexibility, which is the ability to maintain flexibility even at low temperatures. The present invention relates to a plasticizer for halogen-based resins that imparts excellent plasticity and low-temperature flexibility to halogen-based resins, a halogen-based resin composition containing the same, and a method for producing the plasticizer for halogen-based resins. [Means for solving the problem]

[0006] The present inventors have found that a furandicarboxylic acid diester having a structure derived from a branched alcohol having a specific structure can solve the above problems. That is, the present invention relates to the following [1] to

[16] . [1] A plasticizer for halogen-based resins, comprising a compound represented by the following general formula (I): [ka] (In general formula (I), R 1 and R 2 At least one of the groups is a hydrocarbon group represented by the following general formula (II): [ka] (In the general formula (II), m and n are each an integer of 2 or more, and the sum of m and n is 7 or more and 9 or less. In addition, R 1 and R 2 In the formula (I), m and n may be the same or different. * indicates the bonding position with the oxygen atom in the formula (I). [2] The plasticizer for halogen-based resins according to [1], wherein in the general formula (II), m is n+2. [3] The plasticizer for halogen-based resins according to [2], wherein n is 3. [4] In the general formula (I), R 1 and R 2 and (3) a compound in which both of the above are hydrocarbon groups represented by the general formula (II). [5] In the general formula (I), R 1 and R 2 The plasticizer for halogen-based resins according to [4], wherein the groups represented by the following formula (I) are the same hydrocarbon group. [6] In the general formula (I), R 1 and R 2 and R 1 and R 2 The plasticizer for halogen-based resins according to any one of [1] to [4], comprising a compound in which one of the following is a hydrocarbon group represented by the general formula (II) and the other is a hydrocarbon group other than the hydrocarbon group represented by the general formula (II). [7] The plasticizer for halogen-based resins according to [6], wherein the hydrocarbon group other than the hydrocarbon group represented by the general formula (II) is a linear hydrocarbon group having 5 to 7 carbon atoms. [8] The plasticizer for halogen-based resins according to [6], wherein the hydrocarbon group represented by the general formula (II) is a 2-butyl-1-n-octyl group, and the hydrocarbon group other than the hydrocarbon group represented by the general formula (II) is an n-hexyl group. [9] In the plasticizer for halogen-based resins comprising the compound represented by the general formula (I), R of the compound represented by the general formula (I) 1 and R 2 and (ii) are hydrocarbon groups represented by the general formula (II), the content of which is 90% by mass or more and less than 100% by mass.

[10] A plasticizer composition for halogen-based resins, comprising the plasticizer for halogen-based resins according to any one of [1] to [9] above.

[11] A halogen-based resin composition containing the plasticizer for halogen-based resins according to any one of [1] to [9] above and a halogen-based resin.

[12] A method for producing a plasticizer for halogen-based resins, which comprises a compound represented by the following general formula (I), the method comprising a step of reacting a raw material alcohol containing a compound represented by the following general formula (III) with a furandicarboxylic acid compound: [ka] (In the general formula (III), m and n are each an integer of 2 or more, and the sum of m and n is 7 or more and 9 or less. In addition, R 1 and R 2In the formula, m and n may be the same or different. [ka] (In general formula (I), R 1 and R 2 At least one of the groups is a hydrocarbon group represented by the following general formula (II): [ka] (In general formula (II), m and n have the same meanings as m and n in general formula (III). * indicates the bonding position with the oxygen atom in general formula (I).)

[13] The method for producing a plasticizer for halogen-based resins according to

[12] , wherein the compound represented by general formula (III) is 2-butyl-1-n-octanol.

[14] Use of a compound represented by the following general formula (I) as a plasticizer for halogen-based resins: [ka] (In general formula (I), R 1 and R 2 At least one of the groups is a hydrocarbon group represented by the following general formula (II): [ka] (In the general formula (II), m and n are each an integer of 2 or more, and the sum of m and n is 7 or more and 9 or less. In addition, R 1 and R 2 In the formula (I), m and n may be the same or different. * indicates the bonding position with the oxygen atom in the formula (I).

[15] A method for improving the low-temperature flexibility of a halogen-containing resin composition by using a compound represented by the following general formula (I): [ka] (In general formula (I), R 1 and R 2 At least one of the groups is a hydrocarbon group represented by the following general formula (II): [ka] (In the general formula (II), m and n are each an integer of 2 or more, and the sum of m and n is 7 or more and 9 or less. In addition, R 1 and R 2 In the formula (I), m and n may be the same or different. * indicates the bonding position with the oxygen atom in the formula (I).

[16] Use of a compound represented by the following general formula (I) as a plasticizer for improving the low-temperature flexibility of a halogen-containing resin composition: [ka] (In general formula (I), R 1 and R 2 At least one of the groups is a hydrocarbon group represented by the following general formula (II): [ka] (In the general formula (II), m and n are each an integer of 2 or more, and the sum of m and n is 7 or more and 9 or less. In addition, R 1 and R 2 In the formula (I), m and n may be the same or different. * indicates the bonding position with the oxygen atom in the formula (I).

[17] A plasticizer for improving the low-temperature flexibility of a halogen-containing resin composition, which is a compound represented by the following general formula (I): [ka] (In general formula (I), R 1 and R 2 At least one of the groups is a hydrocarbon group represented by the following general formula (II): [ka] (In the general formula (II), m and n are each an integer of 2 or more, and the sum of m and n is 7 or more and 9 or less. In addition, R 1 and R 2In the formula (I), m and n may be the same or different. * indicates the bonding position with the oxygen atom in the formula (I). [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a plasticizer for halogen-based resins that imparts excellent plasticity and low-temperature flexibility to halogen-based resins. DETAILED DESCRIPTION OF THE INVENTION

[0008] The plasticizer for halogen-containing resins of the present invention is a 2,5-furandicarboxylic acid diester in which at least one alcohol residue of the 2,5-furandicarboxylic acid diester has a structure derived from a specific branched alcohol.

[0009] The halogen-based resin composition containing the plasticizer for halogen-based resins of the present invention has excellent plasticity and low-temperature flexibility. The reason for this effect is not clear, but is thought to be as follows. The plasticizer for halogen-based resins of the present invention is composed of a compound represented by general formula (I), and it is believed that compatibility with halogen-based resins is improved because at least one of the alcohol residues of the two ester moieties of 2,5-furandicarboxylic acid diester has a structure represented by general formula (II). As a result, it is believed that the plasticizer for halogen-based resins of the present invention disperses in a balanced manner in the halogen-based resin, thereby imparting excellent plasticity to the halogen-based resin. Furthermore, since the structure of the hydrocarbon group represented by general formula (II) is branched at the β-position of the oxygen atom in general formula (I) and the branched hydrocarbon group has 3 or more carbon atoms, the structure becomes more likely to entangle with the polymer chain of the halogen-based resin, and this ease of entanglement acts to prevent the polymer chains of the halogen-based resin from approaching each other. Therefore, when the plasticizer for halogen-based resins of the present invention is blended with a halogen-based resin, it is thought that excellent low-temperature flexibility can be imparted to the halogen-based resin. In the present invention, furandicarboxylic acid and furandicarboxylic acid diester mean 2,5-furandicarboxylic acid and 2,5-furandicarboxylic acid diester unless otherwise specified.

[0010] [Plasticizer for halogen-based resins] The plasticizer for halogen-based resins of the present invention is composed of a compound represented by the following general formula (I), and contains one or more compounds represented by general formula (I). Hereinafter, when the plasticizer for halogen-based resins of the present invention is mainly described, it will be referred to as a plasticizer for halogen-based resins composed of a compound represented by general formula (I), and when the individual compounds contained in the plasticizer for halogen-based resins composed of a compound represented by general formula (I) are mainly described, it will be referred to as a compound represented by general formula (I).

[0011] [ka]

[0012] In general formula (I), R 1 and R 2 At least one of the groups is a hydrocarbon group represented by the following general formula (II).

[0013] [ka]

[0014] In general formula (II), m and n are each an integer of 2 or more, and the sum of m and n is 7 or more and 9 or less. 1 and R 2 In the formula (I), m and n may be the same or different. * indicates the bonding position to the oxygen atom in the formula (I). From the viewpoint of enhancing the plasticizing effect and low-temperature flexibility of the halogen-based resin, it is preferable that m is n+2, and it is more preferable that m is 5 and n is 3. In addition, from the viewpoint of enhancing the plasticizing effect and low-temperature flexibility of halogen-based resins, R 1 and R 2 It is preferable that the groups represented by the following formula (I) are the same hydrocarbon group. Furthermore, from the viewpoint of enhancing the plasticizing effect and low-temperature flexibility of halogen-based resins, R 1 and R 2 It is preferable that both of the groups represented by the following formula (II) are hydrocarbon groups represented by the above formula (II). Furthermore, from the viewpoint of enhancing the plasticizing effect and low-temperature flexibility of halogen-based resins, R 1 and R 2 and a compound (hereinafter sometimes referred to as Compound A) in which both of the groups represented by R 1 and R 2 and a compound (hereinafter sometimes referred to as compound B) in which one of the above is a hydrocarbon group represented by general formula (II) and the other is a hydrocarbon group other than the hydrocarbon group represented by general formula (II).

[0015] R 1 and R 2 Examples of the hydrocarbon group represented by general formula (II) as the aryl group include a 2-butyl-n-heptyl group, a 2-pentyl-n-heptyl group, a 2-hexyl-n-heptyl group, a 2-propyl-n-octyl group, a 2-butyl-n-octyl group, a 2-pentyl-n-octyl group, a 2-propyl-n-nonyl group, a 2-butyl-n-nonyl group, and a 2-propyl-n-decyl group. Among them, R 1 and R 2 From the viewpoint of ensuring that the furandicarboxylic acid diester represented by general formula (I) exhibits excellent compatibility with halogen-based resins, is preferably a group selected from 2-pentyl-n-heptyl group, 2-hexyl-n-heptyl group, 2-butyl-n-octyl group, 2-pentyl-n-octyl group, 2-propyl-n-nonyl group, 2-butyl-n-nonyl group, and 2-propyl-n-decyl group, and more preferably 2-butyl-n-octyl group.

[0016] R 1 and R 2When one of the groups is a hydrocarbon group other than the hydrocarbon group represented by general formula (II), preferred groups include linear hydrocarbon groups having 5 to 7 carbon atoms, linear hydrocarbon groups having 8 to 13 carbon atoms, branched hydrocarbon groups having 10 to 13 carbon atoms and having a branch at a position other than the β-position of the oxygen atom in general formula (I), hydrocarbon groups in which the sum of m and n in general formula (II) is 10 or more, and hydrocarbon groups in which the sum of m and n in general formula (II) is 4 to 6.

[0017] Examples of the straight-chain hydrocarbon group having 5 to 7 carbon atoms include an n-pentyl group, an n-hexyl group, and an n-heptyl group. Examples of the linear hydrocarbon group having 8 to 13 carbon atoms include an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, and an n-tridecyl group. Suitable examples of the branched hydrocarbon group having 10 to 13 carbon atoms and having a branch at a position other than the β-position of the oxygen atom in general formula (I) include an isodecyl group, an isoundecyl group, an isododecyl group, and an isotridecyl group. In the general formula (II), suitable examples of the hydrocarbon group in which the sum of m and n is 10 or more include a 2-hexyl-n-decyl group, a 2-heptyl-n-undecyl group, and a 2-octyl-n-dodecyl group. In the general formula (II), a suitable example of the hydrocarbon group in which the sum of m and n is 4 or more and 6 or less is a 2-propyl-n-heptyl group. Among these, straight-chain hydrocarbon groups having 5 to 7 carbon atoms, branched hydrocarbon groups having 10 to 13 carbon atoms and having a branch at a position other than the β-position of the oxygen atom in general formula (I), and hydrocarbon groups in which the sum of m and n in general formula (II) is 10 or more are more preferred, straight-chain hydrocarbon groups having 5 to 7 carbon atoms and branched hydrocarbon groups having 10 to 13 carbon atoms and having a branch at a position other than the β-position of the oxygen atom in general formula (I) are even more preferred, and straight-chain hydrocarbon groups having 5 to 7 carbon atoms are even more preferred.

[0018] Among the compounds represented by general formula (I), R 1 and R 2However, the compound (compound A) having a hydrocarbon group represented by the above general formula (II) is preferably one or more selected from bis(2-butyl-n-heptyl) furandicarboxylate, bis(2-pentyl-n-heptyl) furandicarboxylate, bis(2-hexyl-n-heptyl) furandicarboxylate, bis(2-butyl-n-octyl) furandicarboxylate, bis(2-propyl-n-octyl) furandicarboxylate, bis(2-pentyl-n-octyl) furandicarboxylate, bis(2-propyl-n-nonyl) furandicarboxylate, bis(2-butyl-n-nonyl) furandicarboxylate, and bis(2-propyl-n-decyl) furandicarboxylate, and more preferably bis(2-butyl-n-octyl) furandicarboxylate. Among the compounds represented by general formula (I), R 1 and R 2 The compound (compound B) in which one of the groups is a hydrocarbon group represented by general formula (II) above and the other is a hydrocarbon group other than the hydrocarbon group represented by general formula (II) is preferably one or more selected from furandicarboxylic acid (2-pentyl-n-heptyl) (hexyl), furandicarboxylic acid (2-butyl-n-octyl) (hexyl), furandicarboxylic acid (2-butyl-n-octyl) (isotridecyl), and furandicarboxylic acid (2-propyl-n-nonyl) (hexyl), more preferably one or more selected from furandicarboxylic acid (2-butyl-n-octyl) (isotridecyl) and furandicarboxylic acid (2-butyl-n-octyl) (hexyl), and even more preferably furandicarboxylic acid (2-butyl-n-octyl) (hexyl).

[0019] In the plasticizer for halogen-based resins comprising the compound represented by general formula (I), R 1 and R 2 are hydrocarbon groups represented by the above general formula (II) (compound A), and compounds represented by the general formula (I) 1 and R 2In order to enhance the plasticizing effect and low-temperature flexibility of the halogen-based resin, it is preferable to contain a compound (compound B) in which one of the hydrocarbon groups is a hydrocarbon group represented by the above general formula (II) and the other is a hydrocarbon group other than the hydrocarbon group represented by the general formula (II). As the hydrocarbon group other than the hydrocarbon group represented by the general formula (II), a linear hydrocarbon group having 5 to 7 carbon atoms is preferred. From the viewpoint of further enhancing the plasticizing effect and low-temperature flexibility of halogen-based resins, the content of the compound A in the plasticizer for halogen-based resins, which is composed of a compound represented by general formula (I), is preferably 10% by mass or more, more preferably 25% by mass or more, even more preferably 50% by mass or more, still more preferably 75% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 97% by mass or more, and also preferably less than 100% by mass, more preferably 99% by mass or less. From the viewpoint of further enhancing the plasticizing effect and low-temperature flexibility of halogen-based resins, the content of the compound B in the plasticizer for halogen-based resins, which is composed of a compound represented by general formula (I), is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and is preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 16% by mass or less, still more preferably 12% by mass or less, still more preferably 10% by mass or less, still more preferably 6% by mass or less, and still more preferably 4% by mass or less. From the viewpoint of further enhancing the plasticizing effect and low-temperature flexibility of halogen-based resins, the content of bis(2-butyl-n-octyl)furandicarboxylic acid in the plasticizer for halogen-based resins consisting of a compound represented by general formula (I) is preferably 10% by mass or more, more preferably 25% by mass or more, even more preferably 50% by mass or more, still more preferably 75% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 97% by mass or more, and also preferably less than 100% by mass, more preferably 99% by mass or less. From the viewpoint of further enhancing the plasticizing effect and low-temperature flexibility of halogen-based resins, the content of furandicarboxylic acid (2-butyl-n-octyl) (hexyl) in the plasticizer for halogen-based resins consisting of a compound represented by general formula (I) is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and is preferably 20% by mass or less, more preferably 16% by mass or less, still more preferably 12% by mass or less, still more preferably 10% by mass or less, still more preferably 6% by mass or less, and still more preferably 4% by mass or less.

[0020] [Method for producing a plasticizer for halogen-based resins comprising a compound represented by general formula (I)] A method for producing a plasticizer for halogen-based resins comprising a compound represented by general formula (I), i.e., a method for producing a compound represented by general formula (I), includes a step of reacting a raw material alcohol containing a compound represented by the following general formula (III) with a furandicarboxylic acid compound.

[0021] [ka]

[0022] In general formula (III), m and n are each an integer of 2 or more, and the sum of m and n is 7 or more and 9 or less. 1 and R 2 In the formula, m and n may be the same or different.

[0023] Examples of furandicarboxylic acid compounds include furandicarboxylic acid and a diester of furandicarboxylic acid and a lower alcohol. That is, a method for producing a plasticizer for halogen-based resins comprising a compound represented by general formula (I) preferably includes an esterification reaction between furandicarboxylic acid and a raw material alcohol containing a compound represented by general formula (III) (hereinafter also referred to as "reaction A"), or a transesterification reaction between a diester of furandicarboxylic acid and a lower alcohol and the raw material alcohol (hereinafter also referred to as "reaction B").

[0024] Examples of the compound represented by general formula (III) include 2-propyl-1-n-heptanol, 2-butyl-1-n-heptanol, 2-pentyl-1-n-heptanol, 2-hexyl-1-n-heptanol, 2-propyl-1-n-octanol, 2-butyl-1-n-octanol, 2-pentyl-1-n-octanol, 2-propyl-1-n-nonanol, 2-butyl-1-n-nonanol, and 2-propyl-1-n-decanol. Among these, from the viewpoint of obtaining a method for producing a plasticizer for halogen-based resins comprising the compound represented by general formula (I), which enhances the plasticizing effect and low-temperature flexibility of halogen-based resins, the compound represented by general formula (III) is preferably 2-butyl-1-n-octanol. The compound represented by the general formula (III) can be produced by a Guerbet reaction or a mixed Guerbet reaction.

[0025] The content of the compound represented by general formula (III) relative to the total amount of raw material alcohol is preferably 30 mol% or more, more preferably 50 mol% or more, even more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and still more preferably substantially 100 mol%. The content of the compound represented by general formula (III) relative to the total amount of raw material alcohol being substantially 100 mol% means that in addition to the compound represented by general formula (III) intended to be used as the raw material alcohol, it is acceptable to contain compounds that may be unintentionally mixed in.

[0026] The content of 2-butyl-1-n-octanol relative to the total amount of raw material alcohols is preferably 30 mol% or more, more preferably 50 mol% or more, even more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and still more preferably substantially 100 mol%. The content of 2-butyl-1-n-octanol relative to the total amount of raw material alcohols being substantially 100 mol% means that in addition to 2-butyl-1-n-octanol, which is intentionally used as the raw material alcohol, compounds that may be unintentionally mixed in are allowed to be contained.

[0027] Examples of alcohols other than the compound represented by general formula (III) relative to the total amount of raw material alcohols include linear alkyl alcohols having 5 to 7 carbon atoms, linear alkyl alcohols having 8 to 13 carbon atoms, alkyl alcohols having 10 to 13 carbon atoms and having a branch at a position other than the β-position of the hydroxyl group, and alcohols in which the sum of m and n in general formula (III) is 10 or more.

[0028] Examples of the linear alkyl alcohol having 5 to 7 carbon atoms include n-pentanol, n-hexanol, and n-heptanol. Examples of the linear alkyl alcohol having 8 to 13 carbon atoms include n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, and n-tridecanol. Suitable examples of alkyl alcohols having 10 to 13 carbon atoms and having a branch at a position other than the β-position of the hydroxyl group include isodecanol, isoundecanol, isododecanol, and isotridecanol. In the general formula (III), suitable examples of the alcohol in which the sum of m and n is 10 or more include 2-hexyl-1-n-decanol, 2-heptyl-1-n-undecanol, and 2-octyl-1-n-dodecanol. In the general formula (III), a suitable example of the hydrocarbon group in which the sum of m and n is 4 or more and 6 or less is 2-propyl-1-n-heptanol. Among these, linear alkyl alcohols having 5 to 7 carbon atoms, branched alkyl alcohols having 10 to 13 carbon atoms and having a branch at a position other than the β-position of the hydroxyl group, and alcohols in which the sum of m and n in general formula (III) is 10 or more are more preferred, linear alkyl alcohols having 5 to 7 carbon atoms and alkyl alcohols having 10 to 13 carbon atoms and having a branch at a position other than the β-position of the hydroxyl group are even more preferred, and linear alkyl alcohols having 5 to 7 carbon atoms are even more preferred.

[0029] When the raw material alcohol contains an alcohol other than the compound represented by general formula (III), a composition containing a plasticizer for halogenated resins consisting of a compound represented by general formula (I) and a furandicarboxylic acid diester other than the compound represented by general formula (I) is produced by reaction A or reaction B. This composition corresponds to the plasticizer composition for halogenated resins described below, which contains a plasticizer for halogenated resins consisting of a compound represented by general formula (I) and a furandicarboxylic acid diester other than the compound represented by general formula (I). Furthermore, when one or more compounds selected from phthalic acid, aliphatic dibasic acids, and their diesters with lower alcohols, trimellitic acid and its triesters with lower alcohols, and pyromellitic acid and its tetraesters with lower alcohols are used in addition to a furandicarboxylic acid compound, a composition containing a plasticizer for halogenated resins consisting of a compound represented by general formula (I) and a compound commonly used as a plasticizer for halogenated resins is produced by reaction A or reaction B. This composition corresponds to a plasticizer composition for halogenated resins containing a plasticizer for halogenated resins consisting of a compound represented by general formula (I) and a compound commonly used as a plasticizer for halogenated resins, as described below.

[0030] In Reaction A, the amount of the raw material alcohol charged at the start of the esterification reaction is preferably in excess of the stoichiometric amount of furandicarboxylic acid. The stoichiometric amount of the raw material alcohol charged in the esterification reaction is the theoretical ratio for producing a furandicarboxylic acid diester, and is twice the molar amount of the furandicarboxylic acid compound used. That is, in reaction A, the amount of the raw material alcohol charged is preferably 2.0 times by mole or more, more preferably 2.1 times by mole or more, and even more preferably 2.2 times by mole or more, relative to 1 mole of furandicarboxylic acid, from the viewpoint of promoting the reaction and completing the reaction, and is preferably 3.0 times by mole or less, more preferably 2.7 times by mole or less, and even more preferably 2.5 times by mole or less, from the viewpoint of production efficiency. It is preferable to reduce the water content of the raw material alcohol as much as possible.

[0031] In the reaction A, a known esterification catalyst having esterification ability can be used. Suitable examples of the esterification catalyst include one or more selected from tin compounds such as tin tetraethylate, butyltin maleate, dimethyltin oxide, monobutyltin oxide, dibutyltin oxide, and dioctyltin oxide, titanium compounds such as titanium tetraisopropoxide, and zinc compounds such as zinc acetate. Among these, from the viewpoint of productivity, titanium compounds are preferred, and one or more selected from titanium tetraisopropoxide, titanium tetra-n-butoxide, and titanium tetra-2-ethylhexyloxide are preferred.

[0032] When an esterification catalyst is used in Reaction A, the amount of the catalyst used varies depending on the type of catalyst, but from the viewpoint of fully exerting catalytic activity, the amount is preferably 0.01 part by mass or more, more preferably 0.015 part by mass or more, and even more preferably 0.02 part by mass or more, relative to 100 parts by mass of the total amount of furandicarboxylic acid and the raw material alcohol supplied to the reactor; and from the viewpoint of catalyst addition efficiency, the amount is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less.

[0033] In reaction A, the esterification reaction can be carried out under reflux of the raw material alcohol using a known reaction apparatus equipped with equipment capable of refluxing the raw material alcohol. The reaction temperature for Reaction A is preferably 100° C. or higher, more preferably 130° C. or higher, and even more preferably 150° C. or higher from the viewpoint of reactivity, and is preferably 280° C. or lower, more preferably 260° C. or lower, and even more preferably 240° C. or lower from the viewpoint of yield. When the reaction temperature is 100° C. or higher, the reaction proceeds quickly, and when the reaction temperature is 280° C. or lower, the production of reaction by-products can be suppressed. The reaction pressure of Reaction A is preferably 13.3 kPa or more and 101.3 kPa or less in absolute pressure. The reaction pressure is preferably adjusted to a pressure at which the reaction mixture is maintained in a boiling state, and more preferably adjusted to a pressure at which by-product water can be removed from the system. From the viewpoint of yield, the reaction time of Reaction A is preferably 1 hour or longer, more preferably 2 hours or longer. If the reaction time is sufficient, the load on the separation step of unreacted furandicarboxylic acid and the reaction intermediate furandicarboxylic acid monoester is reduced. On the other hand, from the viewpoint of suppressing the formation of by-products, the reaction time is preferably 24 hours or shorter, more preferably 10 hours or shorter.

[0034] In Reaction A, under the above reaction conditions, it is preferable to remove the water produced from the reaction system, increase the reaction rate to nearly 100%, separate the excess raw material alcohol, and then perform post-treatment by a known method such as alkali washing, water washing, adsorption of impurities, or distillation to obtain the furandicarboxylic acid diester represented by general formula (I).

[0035] In reaction B, the amount of the raw material alcohol charged at the start of the esterification reaction is preferably in excess of the stoichiometric amount of the diester of furandicarboxylic acid and a lower alcohol. In reaction B, the preferred range of the amount of the raw material alcohol charged per mole of the diester of furandicarboxylic acid and a lower alcohol is the same as the range specified for reaction A above.

[0036] In reaction B, for example, alkali metals, alkaline earth metals, and their hydrides and hydroxides (hereinafter also referred to as "metal compounds") can be used to activate the raw material alcohol. From the viewpoint of safety, it is preferable to use hydroxides of alkali metals and alkaline earth metals, more preferably lithium hydroxide, magnesium hydroxide, and calcium hydroxide, and even more preferably lithium hydroxide, sodium hydroxide, and potassium hydroxide.

[0037] The amount of the metal compound used for activating the raw material alcohols is, relative to 100 parts by mass of the total amount of the raw material alcohols supplied to the reactor, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, from the viewpoint of reactivity; and is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 60 parts by mass or less, from the viewpoint of production efficiency.

[0038] The reaction temperature of Reaction B is preferably 20°C or higher, more preferably 30°C or higher, and even more preferably 50°C or higher, from the viewpoint of reactivity, and is preferably 120°C or lower, more preferably 100°C or lower, and even more preferably 80°C or lower, from the viewpoint of production efficiency. The reaction pressure for reaction B is not particularly limited, but is preferably atmospheric pressure. The reaction time for Reaction B is preferably 1 hour or longer, more preferably 2 hours or longer, from the viewpoint of yield, while it is preferably 24 hours or shorter, more preferably 10 hours or shorter, from the viewpoint of suppressing by-products.

[0039] [Plasticizer composition for halogen-based resins] The plasticizer composition for halogen-based resins of the present invention contains a plasticizer for halogen-based resins comprising a compound represented by the above general formula (I). The plasticizer composition for halogen-based resins of the present invention may contain a plasticizer for halogen-based resins comprising a compound represented by the above general formula (I), and at least one selected from plasticizers other than the plasticizer for halogen-based resins comprising a compound represented by the general formula (I), and additives.

[0040] Examples of plasticizers other than the halogen-based resin plasticizer composed of the compound represented by general formula (I) that may be contained in the halogen-based resin plasticizer composition of the present invention include compounds commonly used as plasticizers for halogen-based resins. Specific examples include furandicarboxylic acid diesters other than the compound represented by general formula (I), phthalic acid plasticizers, trimellitic acid plasticizers, aliphatic dibasic acid plasticizers, epoxy plasticizers, pyromellitic acid ester plasticizers, phosphate ester plasticizers, ether ester plasticizers, and polyester plasticizers. In the halogen-based resin plasticizer composition of the present invention, the plasticizers other than the halogen-based resin plasticizer composed of the compound represented by general formula (I) may be used alone or in combination of two or more.

[0041] Examples of additives that may be contained in the plasticizer composition for halogen-based resins of the present invention include additives generally contained in halogen-based resin compositions, such as inorganic fillers, stabilizers, processing aids, colorants, antioxidants, ultraviolet absorbers, antistatic agents, and lubricants, which will be described later.

[0042] In the plasticizer composition for halogen-based resins of the present invention, the content of the plasticizer for halogen-based resins consisting of a compound represented by general formula (I) relative to the total of the plasticizer for halogen-based resins consisting of a compound represented by general formula (I) and plasticizers other than the plasticizer for halogen-based resins consisting of a compound represented by general formula (I) is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, still more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 100% by mass, from the viewpoint of improving the plasticity and low-temperature flexibility of the halogen-based resin. Furthermore, in the plasticizer composition for halogen-based resins of the present invention, the content of the plasticizer for halogen-based resins comprising the compound represented by general formula (I) is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, still more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably less than 100% by mass, from the viewpoint of enhancing the plasticity and low-temperature flexibility of the halogen-based resin.

[0043] From the viewpoint of further enhancing the plasticity and low-temperature flexibility of a halogen-based resin, in the plasticizer composition for halogen-based resins of the present invention, the ratio of R of the compound represented by the general formula (I) to the total of a plasticizer for halogen-based resins comprising a compound represented by the general formula (I) and a plasticizer other than the plasticizer for halogen-based resins comprising a compound represented by the general formula (I) is 1 and R 2 and (II) are hydrocarbon groups represented by the general formula (II), the content of which is preferably 5% by mass or more, more preferably 25% by mass or more, even more preferably 50% by mass or more, even more preferably 75% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and is preferably less than 100% by mass, and more preferably 99% by mass or less. From the viewpoint of further enhancing the plasticity and low-temperature flexibility of a halogen-based resin, in the plasticizer composition for halogen-based resins of the present invention, when a plasticizer for halogen-based resins comprising a compound represented by general formula (I) and a plasticizer other than the plasticizer for halogen-based resins comprising a compound represented by general formula (I) are contained, the content of bis(2-butyl-n-octyl furandicarboxylate) is preferably 5% by mass or more, more preferably 25% by mass or more, even more preferably 50% by mass or more, even more preferably 75% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and preferably less than 100% by mass, and more preferably 99% by mass or less. Furthermore, from the viewpoint of further enhancing the plasticity and low-temperature flexibility of the halogen-based resin, the content of bis(2-butyl-n-octyl)furandicarboxylic acid in the plasticizer composition for halogen-based resins of the present invention is preferably 5% by mass or more, more preferably 25% by mass or more, even more preferably 50% by mass or more, even more preferably 75% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and preferably less than 100% by mass, and more preferably 99% by mass or less. Furthermore, from the viewpoint of further enhancing the plasticity and low-temperature flexibility of the halogen-based resin, the content of furandicarboxylic acid (2-butyl-n-octyl) (hexyl) in the plasticizer composition for halogen-based resin of the present invention is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and is preferably 20% by mass or less, more preferably 16% by mass or less, still more preferably 12% by mass or less, still more preferably 10% by mass or less, still more preferably 6% by mass or less, and still more preferably 4% by mass or less.

[0044] [Halogen-based resin composition] The halogen-based resin composition of the present invention contains a halogen-based resin plasticizer comprising a compound represented by the general formula (I) above, and a halogen-based resin. The halogen-based resin composition of the present invention may contain a halogen-based resin and a plasticizer composition for halogen-based resins containing a halogen-based resin plasticizer comprising a compound represented by the general formula (I) above.

[0045] [Halogen-based resin] In the present invention, the term "halogen-based resin" refers to a homopolymer or copolymer of a halogen-containing monomer, or a polymer modified with a halogen. Examples of halogen-based resins include vinyl chloride resins such as vinyl chloride resin, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, and polyurethane-grafted polyvinyl chloride copolymer, vinylidene chloride resin, chlorinated polyethylene, chlorinated polypropylene, chlorosulfonated polyethylene, and chloroprene rubber, which are readily available. Examples of halogen-based resins include vinyl chloride resin, vinylidene chloride resin, and chloroprene rubber, which are flexible. The halogen-based resin composition of the present invention preferably contains at least one selected from vinyl chloride resin, vinylidene chloride resin, and chloroprene rubber.

[0046] (Vinyl chloride resin) Examples of vinyl chloride resins include vinyl chloride homopolymers (vinyl chloride resins), copolymers of vinyl chloride with monomers copolymerizable with vinyl chloride (hereinafter also referred to as "vinyl chloride copolymers"), and graft copolymers in which vinyl chloride is graft-copolymerized onto polymers other than the vinyl chloride copolymers. The monomer copolymerizable with vinyl chloride may be any monomer having a reactive double bond in the molecule from the viewpoint of increasing the plasticity and low-temperature flexibility of the halogen-based resin, and preferred examples thereof include α-olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and phenyl (meth)acrylate; aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. Furthermore, the copolymer other than vinyl chloride in the graft copolymer obtained by graft copolymerization of vinyl chloride may be any copolymer that can be graft copolymerized with vinyl chloride, and preferred examples thereof include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, acrylonitrile-butadiene copolymer, polyurethane, etc.

[0047] The content of the halogen-based resin plasticizer comprising the compound represented by general formula (I) in the halogen-based resin composition of the present invention is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, relative to 100 parts by mass of the halogen-based resin, from the viewpoint of imparting plasticity to the halogen-based resin composition, and is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less, from the viewpoint of suppressing bleeding of the halogen-based resin plasticizer from the halogen-based resin composition.

[0048] The content of bis(2-butyl-n-octyl)furandicarboxylic acid in the halogen-based resin composition of the present invention is preferably 3 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, per 100 parts by mass of the halogen-based resin, from the viewpoint of imparting plasticity to the halogen-based resin composition, and is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less, from the viewpoint of suppressing bleeding of the plasticizer for halogen-based resin from the halogen-based resin composition.

[0049] The content of furandicarboxylic acid (2-butyl-n-octyl) (hexyl) in the halogen-based resin composition of the present invention is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of the halogen-based resin, from the viewpoint of imparting plasticity to the halogen-based resin composition, and is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, from the viewpoint of suppressing bleeding of the halogen-based resin plasticizer from the halogen-based resin composition.

[0050] The content of the halogen-based resin plasticizer consisting of the compound represented by general formula (I) in the halogen-based resin composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of imparting plasticity to the halogen-based resin composition, and is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less, from the viewpoint of suppressing bleeding of the halogen-based resin plasticizer from the halogen-based resin composition.

[0051] The content of bis(2-butyl-n-octyl)furandicarboxylic acid in the halogen-based resin composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and still more preferably 20% by mass or more, from the viewpoint of imparting plasticity to the halogen-based resin composition, and is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less, from the viewpoint of suppressing bleeding of the plasticizer for halogen-based resins from the halogen-based resin composition.

[0052] The content of furandicarboxylic acid (2-butyl-n-octyl) (hexyl) in the halogen-based resin composition of the present invention is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of imparting plasticity to the halogen-based resin composition, and is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, and even more preferably 3% by mass or less, from the viewpoint of suppressing bleeding of the halogen-based resin plasticizer from the halogen-based resin composition.

[0053] [Additives] The halogen-based resin composition of the present invention may contain additives such as inorganic fillers, stabilizers, processing aids, colorants, antioxidants, ultraviolet absorbers, antistatic agents, and lubricants, as necessary, within the range that does not impair the effects of the present invention.

[0054] Examples of inorganic fillers include calcium carbonate, talc, calcium silicate, alumina, etc. One type of inorganic filler may be used alone, or two or more types may be mixed and used. From the viewpoint of economy, the inorganic filler preferably includes calcium carbonate.

[0055] When the halogen-based resin composition of the present invention contains an inorganic filler, the content of the inorganic filler is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and preferably 150 parts by mass or less, more preferably 140 parts by mass or less, even more preferably 130 parts by mass or less, per 100 parts by mass of the halogen-based resin.

[0056] Examples of stabilizers include metal soap compounds such as lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octoate, zinc laurate, zinc ricinoleate, and zinc stearate, organotin compounds such as dimethyltin bis-2-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutylmaleate, and dibutyltin dilaurate, and antimony mercaptide compounds. When the halogen-based resin composition of the present invention contains a stabilizer, the content of the stabilizer is preferably 0.1 to 20 parts by mass per 100 parts by mass of the halogen-based resin.

[0057] Examples of processing aids include liquid paraffin, polyethylene wax, stearic acid, stearamide, ethylene bisstearamide, butyl stearate, calcium stearate, etc. When the halogen-based resin composition of the present invention contains a processing aid, the content of the processing aid is preferably 0.1 to 20 parts by mass per 100 parts by mass of the halogen-based resin.

[0058] Examples of coloring agents include carbon black, lead sulfide, white carbon, titanium white, lithopone, red iron oxide, antimony sulfide, chrome yellow, chrome green, cobalt blue, molybdenum orange, etc. When the halogen-based resin composition of the present invention contains a coloring agent, the content of the coloring agent is preferably 1 to 100 parts by mass per 100 parts by mass of the halogen-based resin.

[0059] Examples of antioxidants include phenolic antioxidants such as 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol)propionate]methane, and 2-hydroxy-4-methoxybenzophenone; sulfur compounds such as alkyl disulfides, thiodipropionic acid esters, and benzothiazole; phosphoric acid antioxidants such as trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite; and organometallic antioxidants such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. Among these, phenolic antioxidants are preferred.

[0060] When the halogen-based resin composition of the present invention contains an antioxidant, the content of the antioxidant is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the halogen-based resin.

[0061] Examples of the ultraviolet absorber include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate, benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone, benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, and cyanoacrylate compounds. When the halogen-based resin composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the halogen-based resin.

[0062] Examples of antistatic agents include anionic antistatic agents of the alkyl sulfonate type, alkyl ether carboxylic acid type, or dialkyl sulfosuccinate type, nonionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, and diethanolamine derivatives, cationic antistatic agents such as quaternary ammonium salts of the alkylamidoamine type, alkyldimethylbenzyl type, and alkylpyridinium type organic acid salts or hydrochlorides, and amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. When the halogen-based resin composition of the present invention contains an antistatic agent, the content of the antistatic agent is preferably 0.1 to 10 parts by mass per 100 parts by mass of the halogen-based resin.

[0063] Examples of lubricants include silicone, liquid paraffin, paraffin wax, fatty acids such as stearic acid and lauric acid and their metal salts, fatty acid amides, fatty acid wax, higher fatty acid wax, etc. When the halogen-based resin composition of the present invention contains a lubricant, the content of the lubricant is preferably 0.1 to 10 parts by mass per 100 parts by mass of the halogen-based resin.

[0064] The content of the additives that may be contained in the halogen-based resin composition of the present invention can be regarded as the amount of each component blended as an additive to the halogen-based resin of the present invention.

[0065] [Method of manufacturing halogen-based resin composition] The method for producing a halogen-based resin composition of the present invention preferably includes a step of mixing a halogen-based resin plasticizer comprising a compound represented by general formula (I) or a halogen-based resin plasticizer composition containing a halogen-based resin plasticizer comprising a compound represented by general formula (I), a halogen-based resin, and, if necessary, a plasticizer other than the halogen-based resin plasticizer comprising a compound represented by general formula (I) and various additives. When the halogen-based resin composition contains a plasticizer other than the halogen-based resin plasticizer comprising a compound represented by general formula (I) and various additives, the halogen-based resin, the halogen-based resin plasticizer comprising a compound represented by general formula (I) or the halogen-based resin plasticizer composition containing a halogen-based resin plasticizer comprising a compound represented by general formula (I), and the halogen-based resin, the plasticizer other than the halogen-based resin plasticizer comprising a compound represented by general formula (I) and various additives may be mixed together all at once or sequentially. The halogen-based resin composition can be prepared by mixing a halogen-based resin plasticizer comprising a compound represented by general formula (I) or a halogen-based resin plasticizer composition containing a halogen-based resin plasticizer comprising a compound represented by general formula (I), a halogen-based resin, and, if necessary, a plasticizer other than the halogen-based resin plasticizer comprising a compound represented by general formula (I) and various additives using a mixer such as a mortar mixer, lab mixer, Henschel mixer, Banbury mixer, ribbon blender, etc. Alternatively, the halogen-based resin composition can be prepared in the form of a mixed powder, pellets, or paste by melt molding using a mixer such as a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, a co-kneader mixer, or a roll mixer. The mixing and melt molding conditions may be those used in a normal method for producing a halogen-based resin composition.

[0066] The mixed powder or pellets of the halogen-based resin composition can be molded into a desired shape by known methods such as extrusion molding, injection molding, calendar molding, press molding, blow molding, etc. Furthermore, the paste-like halogen-based resin composition can be molded into a desired shape by known methods such as spread molding, dipping molding, gravure molding, screen processing, etc.

[0067] (Used as a plasticizer for halogen-based resins) As described above, the compound represented by general formula (I) can be used as a plasticizer for halogen-based resins.

[0068] (Method for improving low-temperature flexibility of halogen-based resin composition) The compound represented by general formula (I) can improve the low-temperature flexibility of the halogen-based resin composition.

[0069] The halogen-based resin composition of the present invention is useful as automotive interior decoration agents such as instrument panel skins, leather seats, and wire harnesses; adhesives, sealants, paints, plastisols, foams, synthetic leather, pipes such as water pipes, building materials, wallpaper, flooring, floor covering materials, heat insulation materials, roofing membrane materials, and other residential interior goods; packaging materials such as food packaging films; agricultural materials such as agricultural films; automotive materials such as sealants and undercoats; base protection materials, fabric coating materials, electric wire coating materials, various types of leather, various foam products, general hoses, gaskets, packings, boots, toys, food packaging materials, and medical supplies such as tubes and blood bags. [Example]

[0070] In the following Production Examples, Examples and Comparative Examples, "parts" and "%" are "parts by mass" and "% by mass" unless otherwise specified.

[0071] <Method for measuring saponification value> Measurement was carried out according to the method of JIS K0070-1992.

[0072] <Method for measuring acid value> Measurement was carried out according to the method of JIS K0070-1992.

[0073] <Calculation of the Content of the Plasticizer for Halogen-Based Resins Comprising the Compound Represented by General Formula (I) in the Plasticizer for Halogen-Based Resins and the Plasticizer Composition for Halogen-Based Resins> The content of the plasticizer for halogen-based resins, which is made of a compound represented by general formula (I), in the plasticizer composition was calculated from the charge ratio (molar ratio) of the raw material alcohols, and is shown in Table 1. For example, when the charge ratio of 2-butyl-1-n-octanol and isotridecyl alcohol is A:B, the content of the plasticizer for halogen-based resins, which is made of a compound represented by general formula (I), in the plasticizer composition is calculated as 100×[1−{B / (A+B)} 2 Specifically, in Example 1-2, the content of the halogen-based resin plasticizer comprising the compound represented by general formula (I) in the plasticizer composition is 100×[1−{0.285 / (71.5+28.5)} 2 =91.9%.

[0074] <Method for measuring the content of bis(2-butyl-n-octyl) furandicarboxylate in halogen-based resin plasticizers and halogen-based resin plasticizer compositions> Using n-hexane solutions of a plasticizer for halogenated resins and a plasticizer composition for halogenated resins adjusted to 10% by mass, the content of bis(2-butyl-n-octyl)furandicarboxylate in the plasticizer composition was measured from the ratio of the peak areas in the chromatogram obtained by the following gas chromatography method. In the measurement, the ratio of the peak area of ​​bis(2-butyl-n-octyl)furandicarboxylate to the total area of ​​the furandicarboxylic acid diester peaks, excluding peaks detected in a short time due to n-hexane and unreacted substances, was calculated and used as the content of bis(2-butyl-n-octyl)furandicarboxylate in the plasticizer for halogenated resins and the plasticizer composition for halogenated resins, and is shown in Table 1. In addition, since the relative sensitivity of each component in a furandicarboxylic acid diester mixture in this gas chromatography method is approximately the same, the ratio of the peak area of ​​furandicarboxylic acid bis(2-butyl-n-octyl) to the total area of ​​the furandicarboxylic acid diester peaks in the obtained chromatogram can be considered to be the mass ratio of furandicarboxylic acid bis(2-butyl-n-octyl) in the halogen-based resin plasticizer and the halogen-based resin plasticizer composition.

[0075] The measurement conditions for gas chromatography are shown below. Measurement equipment: Agilent 8890 (gas chromatograph, manufactured by Agilent Technologies, Inc.) Column: DB-1ht (Agilent Technologies) (Length 30m, inner diameter 0.25mm, film thickness 0.10μm) Carrier gas: He (constant flow mode) Split ratio: 50:1 Detector: FID ·Inlet temperature: 330℃ Detector temperature: 330℃ Measurement temperature conditions: 100°C → Heat at 10°C / min → Hold at 350°C for 10 minutes Detection sensitivity: 20Hz Minimum peak width: 0.01 min Injection volume: 1 μL (split method)

[0076] [Production of plasticizer for halogen-based resin and plasticizer composition for halogen-based resin] Example 1-1 (Production of Plasticizer 1) A 1 L four-neck flask was charged with 120.0 g (0.76 mol) of 2,5-furandicarboxylic acid (V&V Pharma Industries), 341.7 g (1.83 mol, 2.4 mol amount per 1 mol of furandicarboxylic acid) of 2-butyl-1-n-octanol (Tokyo Chemical Industry Co., Ltd.), and 0.23 g of titanium tetraisopropoxide (Fujifilm Wako Pure Chemical Industries, Ltd.), and the mixture was heated to 230°C and then maintained at this temperature for 6.0 hours to carry out a reaction while distilling off water. After the reaction was completed, the mixture was cooled to 90°C, 10.0 g of distilled water was added, and the mixture was stirred for 90 minutes. The mixture was then dehydrated at 90°C and an absolute pressure of 26 kPa for 90 minutes, and then the excess 2-butyl-1-n-octanol was distilled off at 220°C and an absolute pressure of 0.4 kPa. The mixture was then cooled to 90°C, 2.0 g of activated alumina (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 60 minutes. The mixture was then filtered using Radiolite #700 (manufactured by Showa Chemical Industry Co., Ltd.) to obtain 2,5-furandicarboxylic acid di(2-butyl-1-n-octyl) as plasticizer 1. The resulting plasticizer 1 had a saponification value of 228.1 mg KOH / g and an acid value of 0.11 mg KOH / g.

[0077] Examples 1-2 to 1-4 and Comparative Example 1-1 (Production of Plasticizer Compositions 2 to 4 and Plasticizer C1) Plasticizer compositions 2 to 4 and plasticizer C1 were produced in the same manner as in Example 1-1, except that the raw material alcohol and raw material carboxylic acid, and their amounts, were changed as shown in Table 1. The saponification values ​​and acid values ​​of the obtained plasticizer compositions 2 to 4 and plasticizer C1 are shown in Table 1. The isotridecyl alcohol used was Marlipal O13 Alcohol (trade name) manufactured by Sasol.

[0078] Examples 1-5 (Production of Plasticizer Composition 5) Plasticizer composition 5 was obtained by mixing plasticizer 1 and plasticizer C1 prepared in Example 1-1 and Comparative Example 1-1 above at a mass ratio of 1:1.

[0079] [Table 1]

[0080] Examples 1-6 and 1-7 and Comparative Example 1-1 (Preparation of Plasticizer Compositions 6 and 7 and Plasticizer C2) Plasticizer compositions 6 and 7 and plasticizer C1 were produced in the same manner as in Example 1-1, except that the raw material alcohol and raw material carboxylic acid, and their amounts, were changed as shown in Table 2. The saponification values ​​and acid values ​​of the obtained plasticizer compositions 6 and 7 and plasticizer C2 are shown in Table 2.

[0081] [Table 2]

[0082] <Production of unformed vinyl chloride resin sheets> Example 2-1 100 g of vinyl chloride resin (average degree of polymerization 1400, manufactured by Shin-Dai-Ichi Vinyl Corporation, product name: ZEST1400) was mixed with 60.0 g of plasticizer 1, 2 g of a Ca / Mg / Zn-based stabilizer for polyvinyl chloride (manufactured by ADEKA Corporation, product name: ADK STAB RUP-103), and 0.5 g of a lubricant (manufactured by Kao Corporation, product name: LUNAC S-70V) using a stirring rod at room temperature. The mixture was then kneaded at 17 rpm and 170°C using a 4-inch open-roll kneader (manufactured by Nishimura Machinery Co., Ltd.) to gel it, and kneading was continued for 10 minutes after gelation to obtain an unformed vinyl chloride resin sheet as a halogen-based resin composition.

[0083] <Production of vinyl chloride resin molded sheets> The vinyl chloride resin unformed sheet produced above was preheated at 170° C. for 6 minutes and then pressed at a pressure of 20 MPa for 2 minutes to obtain a vinyl chloride resin formed sheet having a thickness of 1.0 mm as a halogen-based resin composition.

[0084] (1) Evaluation of tensile properties Dumbbell-shaped No. 3 test specimens were punched out from the vinyl chloride resin molded sheet prepared above. The stress at 200% elongation (M200, units: MPa) and the elongation at break (EB, units: %) were measured using a tensile tester (Shimadzu Corporation, product name: Autograph AGS-X) in accordance with JIS K6251 under an atmosphere of 23°C and 50% humidity, with an initial gauge length of 20 mm and a tensile speed of 200 mm / min. A smaller M200 indicates better plasticity, and a larger elongation at break indicates better plasticity. The results are shown in Table 3. (2) Evaluation of low-temperature flexibility The vinyl chloride resin molded sheet produced above was subjected to a low-temperature flexibility test using a "Crashberg flexibility temperature tester" (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) according to the method specified in JIS K 6745. The obtained flexibility temperature Tf value (unit: °C) was used as an index for evaluating the low-temperature flexibility of the halogen-based resin composition. The lower the value, the better the low-temperature flexibility. The results are shown in Table 3.

[0085] Examples 2-2 to 2-5 and Comparative Example 2-1 Vinyl chloride resin molded sheets were obtained as halogen-based resin compositions in the same manner as in Example 2-1, except that plasticizer 1 was replaced with plasticizer compositions 2 to 5 or plasticizer C1 as shown in Table 3. The resulting vinyl chloride resin molded sheets were evaluated for tensile properties and low-temperature flexibility in the same manner as in Example 2-1. The results are shown in Table 3. The content of the halogen-based resin plasticizer consisting of the compound represented by general formula (I) and the content of bis(2-butyl-n-octyl) furandicarboxylate (both in parts by mass) per 100 parts by mass of vinyl chloride resin are calculated values ​​based on the content of the halogen-based resin plasticizer consisting of the compound represented by general formula (I) and the content of bis(2-butyl-n-octyl) furandicarboxylate (both in % by mass) in the plasticizer or plasticizer composition shown in Table 1.

[0086] [Table 3]

[0087] It can be seen from Table 3 that the halogen-based resin compositions of Examples 2-1 to 2-5 are excellent in plasticity and low-temperature flexibility.

[0088] Examples 2-6 and 2-7 and Comparative Example 2-2 A vinyl chloride resin molded sheet was obtained as a halogen-based resin composition in the same manner as in Example 2-1, except that plasticizer 1 was replaced with plasticizer composition 6 or 7 or plasticizer C2 as shown in Table 4. The resulting vinyl chloride resin molded sheet was evaluated for tensile properties and low-temperature flexibility in the same manner as in Example 2-1. The results are shown in Table 4. The content of the halogen-based resin plasticizer consisting of the compound represented by general formula (I) and the content of bis(2-butyl-n-octyl) furandicarboxylate (both in parts by mass) per 100 parts by mass of vinyl chloride resin are calculated based on the content of the halogen-based resin plasticizer consisting of the compound represented by general formula (I) and the content of bis(2-butyl-n-octyl) furandicarboxylate (both in mass%) in the plasticizer or plasticizer composition shown in Table 2.

[0089] [Table 4]

[0090] From Table 4, it can be seen that the halogen-based resin compositions of Examples 2-6 and 2-7 are excellent in plasticity and low-temperature flexibility.

Claims

1. A plasticizer composition for vinyl chloride resins, comprising a plasticizer for vinyl chloride resins comprising a compound represented by the following general formula (I): 【Chemistry 1】 (In general formula (I), R １ and R 2 are hydrocarbon groups represented by the following general formula (II) or hydrocarbon groups other than the hydrocarbon groups represented by the general formula (II), and at least one of R 1 and R 2 is a hydrocarbon group represented by the following general formula (II): 【Chemistry 2】 (In the general formula (II), m and n are each an integer of 2 or more, and the sum of m and n is 7 or more and 9 or less. In addition, R １ and R ２ In the formula (I), m and n may be the same or different. * indicates the bonding position with the oxygen atom in the formula (I).

2. 2. The plasticizer composition for vinyl chloride resins according to claim 1, wherein in said general formula (II), m is n+2.

3. 3. The plasticizer composition for vinyl chloride resins according to claim 2, wherein n is 3.

4. In the general formula (I), R １ and R ２ and (b) a hydrocarbon group represented by general formula (II) above.

5. In the general formula (I), R １ and R ２ and are the same hydrocarbon group.

6. In the general formula (I), R １ and R ２ and R are hydrocarbon groups represented by the general formula (II), and １ and R ２ and the other is a hydrocarbon group other than the hydrocarbon group represented by general formula (II).

7. 7. The plasticizer composition for vinyl chloride resins according to claim 6, wherein the hydrocarbon group other than the hydrocarbon group represented by general formula (II) is a linear hydrocarbon group having 5 to 7 carbon atoms.

8. 7. The plasticizer composition for vinyl chloride resins according to claim 6, wherein the hydrocarbon group represented by general formula (II) is a 2-butyl-n-octyl group, and the hydrocarbon group other than the hydrocarbon group represented by general formula (II) is an n-hexyl group.

9. In the plasticizer for vinyl chloride resins comprising the compound represented by the general formula (I), R of the compound represented by the general formula (I) １ and R ２ and (II) are hydrocarbon groups represented by general formula (II), the content of the compound in which both of the above are hydrocarbon groups represented by general formula (II) is 90% by mass or more and less than 100% by mass.

10. A vinyl chloride resin composition comprising the plasticizer composition for vinyl chloride resins according to any one of claims 1 to 9 and a vinyl chloride resin.

11. A method for producing a plasticizer composition for vinyl chloride resins, which contains a plasticizer for vinyl chloride resins comprising a compound represented by general formula (I) below, the method comprising the step of reacting a raw material alcohol containing a compound represented by general formula (III) below with a furandicarboxylic acid compound: 【Transformation 3】 (In the general formula (III), m and n are each an integer of 2 or more, and the sum of m and n is 7 or more and 9 or less. In addition, R １ and R ２ In the formula, m and n may be the same or different. 【Chemistry 4】 (In general formula (I), R １ and R 2 are hydrocarbon groups represented by the following general formula (II) or hydrocarbon groups other than the hydrocarbon groups represented by the general formula (II), and at least one of R 1 and R 2 is a hydrocarbon group represented by the following general formula (II): 【Transformation 5】 (In general formula (II), m and n have the same meanings as m and n in general formula (III). * indicates the bonding position with the oxygen atom in general formula (I).)

12. The method for producing a plasticizer composition for vinyl chloride resins according to claim 11, wherein the compound represented by general formula (III) is 2-butyl-1-n-octanol.

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