Halogen resin plasticizer

Abstract

The present invention relates to a halogen resin plasticizer that comprises a compound represented by general formula (I). The present invention makes it possible to provide a halogen resin plasticizer that gives halogen resins excellent plasticity and low-temperature flexibility. (In general formula (I), at least one of R1 and R2 is a hydrocarbon group represented by general formula (II).) (In general formula (II), m and n, which may each be the same or different at R1 and R2, are each an integer that is at least 2, the total of m and n is at least 7 but no more than 9, and * indicates the location of the bond to the oxygen atom in general formula (I).)

Description

Plasticizer for halogen-based resins

[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.

[0002] Halogen-based resins such as polyvinyl chloride resin (PVC) are important resins used in a variety of fields as general-purpose polymers. For example, PVC is used in a variety of applications, including home interior items such as wallpaper, general-purpose products such as toys, and automotive materials such as sealants. When using a halogen-based resin, a halogen-based resin composition is prepared by blending, for example, resin powder of the halogen-based resin 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, and the like.

[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.

[0004] Special Publication No. 2014-506618

[0005] In Patent Document 1, C of furandicarboxylic acid １１ ~C １３ -dialkyl esters and mixtures thereof have been disclosed. However, although these compounds and mixtures have a plasticizing effect on plastics, the plasticizing effect is insufficient. Furthermore, there is also a problem with low-temperature flexibility, which allows flexibility to be maintained 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.

[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-mentioned problems. That is, the present invention relates to the following [1] to

[16] . [1] A plasticizer for halogen-containing resins, comprising a compound represented by the following general formula (I): (In general formula (I), R １ and R ２At least one of the groups is a hydrocarbon group represented by the following general formula (II): (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 the formula (1), wherein m is n+2 in the formula (II). [3] The plasticizer for halogen-based resins according to the formula (2), wherein n is 3. [4] In the formula (I), R １ and R ２ [5] The plasticizer for halogen-based resins according to any one of [1] to [3], which contains a compound in which both of R １ and R ２ [6] The plasticizer for halogen-based resins according to [4], wherein the groups represented by R １ and R ２ and R are hydrocarbon groups represented by the general formula (II), and 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 R 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], in which the hydrocarbon group other than the hydrocarbon group represented by the general formula (II) is a straight-chain hydrocarbon group having 5 to 7 carbon atoms. [8] The plasticizer for halogen-based resins according to [6], in which 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] The plasticizer for halogen-based resins comprising the compound represented by the general formula (I), １ and R ２and (b) are hydrocarbon groups represented by 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, comprising 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, 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 furan dicarboxylic acid compound. (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. (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): (In general formula (II), m and n have the same meanings as m and n in general formula (III). * indicates the bonding position to the oxygen atom in general formula (I).)

[13] A 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: (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): (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 to the oxygen atom in general formula (I).

[15] A method for improving the low-temperature flexibility of a halogen-based resin composition using a compound represented by the following general formula (I): (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): (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 wherein m and n may be the same or different. * indicates the bonding position with the oxygen atom in general formula (I).

[16] The plasticizer for halogen-based resins according to

[15] , wherein m is n+2 in general formula (II).

[17] The plasticizer for halogen-based resins according to

[16] , wherein n is 3.

[18] Use of a plasticizer for improving the low-temperature flexibility of a halogen-based resin composition, the plasticizer being a compound represented by the following general formula (I): (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): (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 wherein m and n may be the same or different. * indicates the bonding position with the oxygen atom in general formula (I).

[19] The plasticizer for halogen-based resins according to

[18] , wherein m is n+2 in general formula (II).

[20] The plasticizer for halogen-based resins according to

[19] , wherein n is 3.

[21] A plasticizer for improving low-temperature flexibility of a halogen-based resin composition, which is a compound represented by the following general formula (I): (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): (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).

[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.

[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] Halogen-based resin compositions containing the halogen-based resin plasticizer of the present invention exhibit excellent plasticity and low-temperature flexibility. While the reason for this effect is unclear, it is believed to be as follows: The halogen-based resin plasticizer of the present invention is composed of a compound represented by general formula (I), and compatibility with halogen-based resins is thought to be improved by the fact that at least one of the alcohol residues of the two ester moieties of the 2,5-furandicarboxylic acid diester has a structure represented by general formula (II). As a result, the halogen-based resin plasticizer of the present invention is thought to impart excellent plasticity to halogen-based resins by dispersing in a balanced manner within the halogen-based resin. Furthermore, because the hydrocarbon group structure 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, this structure becomes more likely to entangle with the polymer chains of the halogen-based resin. This entanglement acts to prevent the polymer chains of the halogen-based resin from approaching each other, and therefore, when the halogen-based resin plasticizer of the present invention is blended with the halogen-based resin, it is thought to impart excellent low-temperature flexibility 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 mainly describing the plasticizer for halogen-based resins of the present invention, it will be referred to as a plasticizer for halogen-based resins composed of a compound represented by general formula (I), and when mainly describing the individual compounds contained in the plasticizer for halogen-based resins composed of a compound represented by general formula (I), it will be referred to as a compound represented by general formula (I).

[0011]

[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]

[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 with the oxygen atom in general 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 more preferably m is 5 and n is 3. Furthermore, from the viewpoint of enhancing the plasticizing effect and low-temperature flexibility of the halogen-based resin, R １ and R ２ It is preferable that the groups represented by R １ and R ２ In order to enhance the plasticizing effect and low-temperature flexibility of the halogen-based resin, it is preferable that both of the groups represented by 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 ２and a compound (hereinafter sometimes referred to as 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).

[0015] R １ and R ２ Examples of the hydrocarbon group represented by general formula (II) as R 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. １ and R ２ From the viewpoint of the excellent compatibility of the furandicarboxylic acid diester represented by general formula (I) 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 ２ When 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 from 5 to 7 carbon atoms, linear hydrocarbon groups having from 8 to 13 carbon atoms, branched hydrocarbon groups having from 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 or more and 6 or less.

[0017] Examples of linear hydrocarbon groups having 5 to 7 carbon atoms include n-pentyl, n-hexyl, and n-heptyl. Examples of linear hydrocarbon groups having 8 to 13 carbon atoms include n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, and n-tridecyl. Preferred examples of 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) include isodecyl, isoundecyl, isododecyl, and isotridecyl. Preferred examples of hydrocarbon groups in general formula (II) where the sum of m and n is 10 or greater include 2-hexyl-n-decyl, 2-heptyl-n-undecyl, and 2-octyl-n-dodecyl. Preferred examples of hydrocarbon groups in general formula (II) where the sum of m and n is 4 to 6 include 2-propyl-n-heptyl. Among these, linear hydrocarbon groups having from 5 to 7 carbon atoms, branched hydrocarbon groups having from 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, linear hydrocarbon groups having from 5 to 7 carbon atoms and branched hydrocarbon groups having from 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 linear hydrocarbon groups having from 5 to 7 carbon atoms are even more preferred.

[0018] Among the compounds represented by general formula (I), R １ and R ２is a hydrocarbon group represented by the above general formula (II) (compound A) is preferably one or more selected from furandicarboxylic acid bis(2-butyl-n-heptyl), furandicarboxylic acid bis(2-pentyl-n-heptyl), furandicarboxylic acid bis(2-hexyl-n-heptyl group), furandicarboxylic acid bis(2-butyl-n-octyl), furandicarboxylic acid bis(2-propyl-n-octyl), furandicarboxylic acid bis(2-pentyl-n-octyl), furandicarboxylic acid bis(2-propyl-n-nonyl), furandicarboxylic acid bis(2-butyl-n-nonyl), and furandicarboxylic acid bis(2-propyl-n-decyl), and more preferably furandicarboxylic acid bis(2-butyl-n-octyl). Among the compounds represented by general formula (I), R １ and R ２ and the other is a hydrocarbon group other than the hydrocarbon group represented by general formula (II) (compound B) 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 of the compound represented by general formula (I) １ and R ２ and R are hydrocarbon groups represented by the general formula (II) above (compound A), and R are hydrocarbon groups represented by the general formula (I). １ and R ２and the other is a hydrocarbon group other than the hydrocarbon group represented by general formula (II), the compound (compound B) preferably containing the compound A. The hydrocarbon group other than the hydrocarbon group represented by general formula (II) is preferably a straight-chain hydrocarbon group having 5 to 7 carbon atoms. From the viewpoint of further enhancing the plasticizing effect and low-temperature flexibility of the halogen-based resin, the content of compound A in the plasticizer for halogen-based resins comprising the 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 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 a halogen-based resin, the content of the compound B in the plasticizer for halogen-based resins comprising the 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 comprising the 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, which comprises 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)] The method for producing a plasticizer for halogen-based resins comprising a compound represented by general formula (I), i.e., the method for producing the 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]

[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 the furandicarboxylic acid compound include furandicarboxylic acid or a diester of furandicarboxylic acid and a lower alcohol. That is, the method for producing a plasticizer for halogen-containing 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 compounds 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 a compound represented by general formula (I) that enhances the plasticizing effect and low-temperature flexibility of halogen-based resins, 2-butyl-1-n-octanol is preferred as the compound represented by general formula (III). Compounds represented by 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, it is acceptable to contain compounds that may be unintentionally mixed in.

[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 linear alkyl alcohols having 5 to 7 carbon atoms include n-pentanol, n-hexanol, and n-heptanol. Examples of linear alkyl alcohols 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. Suitable examples of alcohols in which the sum of m and n in general formula (III) is 10 or greater include 2-hexyl-1-n-decanol, 2-heptyl-1-n-undecanol, and 2-octyl-1-n-dodecanol. Suitable examples of hydrocarbon groups in which the sum of m and n in general formula (III) is 4 to 6 include 2-propyl-1-n-heptanol. Among these, linear alkyl alcohols having from 5 to 7 carbon atoms, branched alkyl alcohols having from 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 from 5 to 7 carbon atoms and alkyl alcohols having from 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 from 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), Reaction A or Reaction B produces a composition containing a plasticizer for halogenated resins consisting of the compound represented by general formula (I) and a furandicarboxylic acid diester other than the compound represented by general formula (I). This composition corresponds to the plasticizer composition for halogenated resins, described below, containing a plasticizer for halogenated resins consisting of the 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 triester with lower alcohols, and pyromellitic acid and its tetraester with lower alcohols are used in addition to the furandicarboxylic acid compound, Reaction A or Reaction B produces a composition containing a plasticizer for halogenated resins consisting of the compound represented by general formula (I) and a compound commonly used as a plasticizer for halogenated resins. This composition corresponds to a plasticizer composition for halogen-based resins, which contains a plasticizer for halogen-based resins consisting of a compound represented by general formula (I) described below, and a compound generally used as a plasticizer for halogen-based resins.

[0030] In reaction A, the amount of 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 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 raw material alcohol charged is preferably 2.0 times or more by mole, more preferably 2.1 times or more by mole, and even more preferably 2.2 times or more by mole, relative to 1 mole of furandicarboxylic acid, from the viewpoints of promoting the reaction and completing the reaction, and is preferably 3.0 times or less by mole, more preferably 2.7 times or less by mole, and even more preferably 2.5 times or less by mole, 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 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. From the viewpoint of reactivity, the reaction temperature of 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 yield, the reaction temperature is preferably 280°C or lower, more preferably 260°C or lower, and even more preferably 240°C or lower. A reaction temperature of 100°C or higher allows the reaction to proceed rapidly, while a reaction temperature of 280°C or lower can suppress the production of reaction by-products. The reaction pressure of reaction A is preferably 13.3 kPa or higher and 101.3 kPa or lower 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 to a pressure at which the 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. A sufficient reaction time reduces the load on the separation process of unreacted furandicarboxylic acid and the furandicarboxylic acid monoester, which is a reaction intermediate. On the other hand, from the viewpoint of suppressing the production of by-products, the reaction time is preferably 24 hours or less, more preferably 10 hours or less.

[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, distillation, etc., 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 of reaction B is not particularly limited, but is preferably atmospheric pressure. The reaction time of reaction B is preferably 1 hour or higher, more preferably 2 hours or higher, from the viewpoint of yield. On the other hand, from the viewpoint of suppressing by-products, it is preferably 24 hours or lower, more preferably 10 hours or lower.

[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 a plasticizer for halogen-based resins other than the plasticizer for halogen-based resins comprising a compound represented by the general formula (I), and an additive.

[0040] Examples of plasticizers other than the halogen-based resin plasticizers consisting of the compounds 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 compounds 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 plasticizers consisting of the compounds 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, even 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 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, even 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 improving 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, the plasticizer composition for halogen-based resins of the present invention contains 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), and the ratio of R １ and R ２and (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, still more preferably 75% by mass or more, even more preferably 90% by mass or more, and still 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, still more preferably 75% by mass or more, even more preferably 90% by mass or more, still 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 a 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, still more preferably 75% by mass or more, even more preferably 90% by mass or more, still 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 a halogen-based resin, the content of furandicarboxylic acid (2-butyl-n-octyl) (hexyl) in the plasticizer composition for halogen-based resins 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 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 resins, vinylidene chloride resins, and chloroprene rubber, which are flexible. The halogen-based resin composition of the present invention preferably contains at least one selected from vinyl chloride resins, vinylidene chloride resins, and chloroprene rubber.

[0046] (Vinyl chloride resin) Examples of vinyl chloride resins include vinyl chloride homopolymers (vinyl chloride resins), copolymers of vinyl chloride with a copolymerizable monomer (hereinafter also referred to as "vinyl chloride copolymers"), and graft copolymers in which vinyl chloride is graft-copolymerized onto a polymer other than the vinyl chloride copolymer. The vinyl chloride copolymerizable monomer may be any monomer having a reactive double bond in the molecule, from the viewpoint of enhancing the plasticity and low-temperature flexibility of the halogen-based resin. Examples of preferred monomers 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, and the like.

[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 still 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, 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 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 comprising 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 needed, 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. Of 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 per 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 per 100 parts by mass of the halogen-based resin.

[0062] Examples of the antistatic agent 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 metal salts thereof, 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 for producing 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 by adding them all at once or by sequentially mixing the respective components. 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, a lab mixer, a Henschel mixer, a Banbury mixer, or a ribbon blender to obtain a mixed powder of the halogen-based resin composition. Alternatively, the halogen-based resin composition can be obtained in the form of a mixed powder, pellets, or paste by melt-molding using a kneader such as a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, a co-kneader, or a roll mixer. The mixing and melt-molding conditions may be any conditions commonly used in the production of halogen-based resin compositions.

[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] (Use 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 a halogen-based resin composition.

[0069] The halogen-based resin composition of the present invention is useful as an automotive interior decorative material such as an instrument panel skin, leather seat, or wire harness; an adhesive, a sealant, a paint, a plastisol, a foam, a synthetic leather, a pipe such as a water pipe, a building material, a wallpaper material, a floor material, a floor covering material, a heat insulating material, a roofing membrane material, or other residential interior goods; a packaging material such as a food packaging film; an agricultural material such as an agricultural film; an automotive material such as a sealant or undercoat material; a substrate protective material, a fabric covering material, an electric wire covering material, various leathers, various foam products, general hoses, gaskets, packings, boots, toys, food packaging material, and medical supplies such as tubes and blood bags.

[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 specified in JIS K0070-1992.

[0072] <Method for Measuring Acid Value> The acid value was measured according to the method specified in 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 in the Plasticizer Composition for Halogen-Based Resins> The content of the plasticizer for halogen-based resins comprising the 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 to isotridecyl alcohol is A:B, the content of the plasticizer for halogen-based resins comprising the compound represented by general formula (I) in the plasticizer composition is calculated by 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 a plasticizer for halogen-based resins and a plasticizer composition for halogen-based resins> Using n-hexane solutions of a plasticizer for halogen-based resins and a plasticizer composition for halogen-based 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 a 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 peaks of the furandicarboxylic acid diester, excluding peaks detected in a short time due to n-hexane and unreacted substances, was calculated, and this was taken as the content of bis(2-butyl-n-octyl) furandicarboxylate in the plasticizer for halogen-based resins and the plasticizer composition for halogen-based 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 ​​bis(2-butyl-n-octyl) furandicarboxylic acid in the obtained chromatogram to the total area of ​​the peaks of the furandicarboxylic acid diester can be considered to be the mass ratio of bis(2-butyl-n-octyl) furandicarboxylic acid in the halogen-based resin plasticizer and the halogen-based resin plasticizer composition.

[0075] The measurement conditions for the gas chromatography method are as follows: Measurement apparatus: Agilent 8890 (gas chromatograph, manufactured by Agilent Technologies Inc.) Column: DB-1ht (manufactured by Agilent Technologies Inc.) (length 30 m, inner diameter 0.25 mm, film thickness 0.10 μm) Carrier gas: He (constant flow mode) Split ratio: 50:1 Detector: FID Injection port temperature: 330°C Detector temperature: 330°C Measurement temperature conditions: 100°C → temperature increase at 10°C / min → hold at 350°C for 10 minutes Detection sensitivity: uptake rate, 20 Hz Minimum peak width, 0.01 min Injection volume: 1 μL (split method)

[0076] [Production of Plasticizer for Halogen-Based Resins and Plasticizer Composition for Halogen-Based Resins] Example 1-1 (Production of Plasticizer 1) 120.0 g (0.76 mol) of 2,5-furandicarboxylic acid (V&V Pharma Industries), 341.7 g (1.83 mol, 2.4 mol per 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.) were mixed in a 1 L four-neck flask and heated to 230°C. The mixture was then maintained for 6.0 hours to allow the reaction to proceed while distilling off water. After completion of the reaction, 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 the excess 2-butyl-1-n-octanol was further distilled off at 220°C and an absolute pressure of 0.4 kPa. Thereafter, the mixture was cooled to 90°C, and 2.0 g of activated alumina (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, followed by stirring for 60 minutes, and 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 saponification value of the obtained plasticizer 1 was 228.1 mgKOH / g, and the acid value was 0.11 mgKOH / 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. Note that Marlipal O13 Alcohol (trade name) manufactured by Sasol was used as the isotridecyl alcohol.

[0078] Example 1-5 (Preparation of Plasticizer Composition 5) Plasticizer 1 and plasticizer C1 prepared in Example 1-1 and Comparative Example 1-1 above were mixed in a mass ratio of 1:1 to obtain plasticizer composition 5.

[0079]

[0080] Examples 1-6 and 1-7 and Comparative Example 1-1 (Production 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]

[0082] <Production of vinyl chloride resin unformed sheet> Example 2-1 100 g of vinyl chloride resin (average degree of polymerization 1400, manufactured by Shin-Dai-Ichi Vinyl Corporation, trade 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, trade name: Adekastab RUP-103), and 0.5 g of a lubricant (manufactured by Kao Corporation, trade name: Lunac S-70V) using a stirring rod at room temperature. The mixture was then gelled by kneading at a rotation speed of 17 rpm and 170°C using a 4-inch open roll kneader (manufactured by Nishimura Machinery Co., Ltd.), 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 sheet> The vinyl chloride resin unmolded 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 molded sheet having a thickness of 1.0 mm as a halogen-based resin composition.

[0084] (1) Evaluation of Tensile Properties Test specimens were prepared by punching out a dumbbell-shaped No. 3 specimen from the vinyl chloride resin molded sheet prepared above. Using a tensile tester (Shimadzu Corporation, product name: Autograph AGS-X) in accordance with JIS K6251, the stress at 200% elongation (M200 (unit: MPa)) and the elongation at break (EB: elongation at break (unit: %)) were measured 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 sheets prepared above were subjected to a low-temperature flexibility test using a "Crashberg Flexibility Temperature Tester" (Yasuda Seiki Seisakusho Co., Ltd.) according to the method specified in JIS K 6745. The obtained softening 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 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]

[0087] From Table 3, it can be seen 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: 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 composition 6 or 7 or plasticizer C2 as shown in Table 4. 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 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 % by mass) in the plasticizer or plasticizer composition shown in Table 2.

[0089]

[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 for halogen-based resins, comprising a compound represented by the following general formula (I): (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): (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-containing resins according to claim 1, wherein in said general formula (II), m is n+2.

3. The plasticizer for halogen-containing 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 the general formula (II) above.

5. In the general formula (I), R １ and R ２ The plasticizer for halogen-based resins according to claim 4, wherein 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. The plasticizer for halogen-containing resins according to claim 6, wherein the hydrocarbon group other than the hydrocarbon group represented by general formula (II) is a straight-chain hydrocarbon group having 5 to 7 carbon atoms.

8. The plasticizer for halogen-based 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 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 (b) are hydrocarbon groups represented by general formula (II), the content of which is 90 mass % or more and less than 100 mass %.

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

11. A halogen-based resin composition comprising the plasticizer for halogen-based resins according to any one of claims 1 to 9 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 the step of reacting a raw material alcohol containing a compound represented by the following general formula (III) with a furandicarboxylic acid compound: (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. (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): (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-containing resins according to claim 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: (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): (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, comprising using a compound represented by the following general formula (I): (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): (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. The plasticizer for halogen-containing resins according to claim 15, wherein in the general formula (II), m is n+2.

17. The plasticizer for halogen-containing resins according to claim 16, wherein n is 3.

18. 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: (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): (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).

19. The plasticizer for halogen-containing resins according to claim 18, wherein in the general formula (II), m is n+2.

20. The plasticizer for halogen-containing resins according to claim 19, wherein n is 3.

21. 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): (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): (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).

Images