Carbonate compounds, plasticizers, resin compositions, molded articles, and vehicles

Abstract

To provide novel carbonate compounds. [Solution] A carbonate compound represented by the following general formula (1) is provided. TIFF2026087298000018.tif21139 (In the formula, R1 and R2 may be the same or different from each other, and represent a branched alkyl group having 7 to 12 carbon atoms that may be mediated by an oxygen atom, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms that includes at least one of an aryl group and a cycloalkyl group and may be mediated by an oxygen atom; R3 represents a divalent hydrocarbon group having 4 to 8 carbon atoms that is mediated by an oxygen atom; and m represents 0 to 10. When m is 0, at least one of R1 and R2 is a hydrocarbon group mediated by an oxygen atom, except when both R1 and R2 are phenoxyethyl groups.)

Description

[Technical Field]

[0001] This invention relates to a novel carbonate compound, a plasticizer mainly composed of the same, a resin composition, and a molded article thereof. [Background technology]

[0002] In recent years, from the perspective of environmental protection, there has been a demand for biodegradable resins that decompose naturally after use. Biodegradable resins include aliphatic polyester resins, polyvinyl alcohol resins, and modified starch resins. Aliphatic polyester resins include polybutyl succinate, polyhydroxybutyrate, polylactic acid, and polyglycolic acid. Furthermore, regarding the raw materials for these resins, using plant-derived raw materials rather than petroleum-derived ones has a lower environmental impact.

[0003] From this perspective, biodegradable polyester resins such as polylactic acid resin can be said to be resins with a low environmental impact. Furthermore, because they have a high melting point of around 160-180°C and excellent transparency, they are highly anticipated as materials for packaging and molded products that take advantage of their transparency. However, a drawback of polyester resins is their hardness and brittleness, which stem from the rigidity of their molecular chains, and their applications have been limited in fields where flexibility and impact resistance are required.

[0004] As a way to solve these shortcomings, for example, Patent Document 1 attempts plasticization using ether ester-based plasticizers. However, the plasticizer described in Patent Document 1 exhibits significant bleed-out over time, leading to problems with product contamination. Patent Documents 2, 3, and 4 propose the use of polyethylene glycol dialkyl esters as plasticizers, but while these offer excellent flexibility, they have the drawbacks of high volatility and a tendency to bleed out. Patent Document 5 describes adding crosslinked polycarbonate to polylactic acid to improve brittleness. Patent Document 6 describes adding polyalkylene carbonate, mainly polyethylene carbonate, to polylactic acid to improve flexibility and further enhance gas barrier properties. Patent Document 7 describes adding polyalkylene glycol carbonate, in which terminal hydroxyl groups are encapsulated with linear alkoxy groups, to polylactic acid to improve flexibility and suppress surface bleed-out. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 11-181262 [Patent Document 2] Japanese Patent Application Publication No. 8-199052 [Patent Document 3] Japanese Patent Application Publication No. 8-199053 [Patent Document 4] Japanese Patent Application Publication No. 8-283557 [Patent Document 5] Japanese Patent Application Publication No. 11-140292 [Patent Document 6] Japanese Patent Publication No. 2003-213113 [Patent Document 7] Japanese Patent Publication No. 2006-199799 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, the plasticizers described in Patent Documents 1 to 7 are not sufficient for maintaining the stability of resins. Therefore, there is a strong demand for plasticizers for resins that offer superior resin stability.

[0007] The present invention aims to provide a novel carbonate compound having performance as a plasticizer for resins, particularly polyester resins. Furthermore, the present invention aims to provide a plasticizer mainly composed of such a carbonate compound, and a resin composition containing such a carbonate compound as a plasticizer. [Means for solving the problem]

[0008] The present invention relates, for example, to the following [1] to

[16] . [1] A carbonate compound represented by the following general formula (1). [ka] (In the formula, R1 and R2 may be the same or different from each other, and represent a branched alkyl group having 7 to 12 carbon atoms that may be mediated by an oxygen atom, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms that includes at least one of an aryl group and a cycloalkyl group and may be mediated by an oxygen atom; R3 represents a divalent hydrocarbon group having 4 to 8 carbon atoms that is mediated by an oxygen atom; and m represents 0 to 10. When m is 0, at least one of R1 and R2 is a hydrocarbon group mediated by an oxygen atom, except when both R1 and R2 are phenoxyethyl groups.) [2] The carbonate compound according to [1], in general formula (1), R1 and R2 may be the same or different from each other, and represent a branched alkyl group having 7 to 12 carbon atoms that may be mediated by an oxygen atom, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms that includes at least one of an aryl group and a cycloalkyl group and may be mediated by an oxygen atom. [3] The carbonate compound according to [1] or [2], in general formula (1), R1 and R2 may be the same or different from each other, and represent a branched alkyl group having 7 to 12 carbon atoms mediated by an oxygen atom, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom and include at least one of an aryl group and a cycloalkyl group. [4] A carbonate compound described in any of [1] to [3] that exhibits biodegradability. [5] A plasticizer whose main component is a carbonate compound represented by the following general formula (1). [ka] (In the formula, R1 and R2 may be the same or different from each other, and represent a branched alkyl group having 7 to 12 carbon atoms that may be mediated by an oxygen atom, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms that includes at least one of an aryl group and a cycloalkyl group and may be mediated by an oxygen atom; R3 represents a divalent hydrocarbon group having 4 to 8 carbon atoms that is mediated by an oxygen atom; and m represents 0 to 10. When m is 0, at least one of R1 and R2 is a hydrocarbon group mediated by an oxygen atom, except when both R1 and R2 are phenoxyethyl groups.) [6] A plasticizer comprising the carbonate compound described in [5], wherein in general formula (1), R1 and R2 may be the same or different from each other, and represent a branched alkyl group having 7 to 12 carbon atoms that may be mediated by an oxygen atom, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms that may be mediated by an oxygen atom, comprising at least one of an aryl group and a cycloalkyl group. [7] In general formula (1), R1 and R2 may be the same or different from each other, and represent a branched alkyl group having 7 to 12 carbon atoms with an oxygen atom intervening, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms with an oxygen atom intervening, which contains at least one of an aryl group and a cycloalkyl group, a plasticizer containing the carbonate compound described in [5] or [6] as a main component. [8] A plasticizer containing the carbonate compound described in any one of [5] to [7], in which the carbonate compound represented by general formula (1) exhibits biodegradability, as a main component. [9] A resin composition containing a resin and a carbonate compound represented by the following general formula (1).

Chemical formula

[10] In general formula (1), R1 and R2 may be the same or different from each other, and represent a branched alkyl group having 7 to 12 carbon atoms with an oxygen atom intervening, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms with an oxygen atom intervening, which contains at least one of an aryl group and a cycloalkyl group, a resin composition containing the carbonate compound described in [9] as a plasticizer.

[11] A resin composition comprising the carbonate compound described in [9] or

[10] as a plasticizer, wherein in general formula (1), R1 and R2 may be the same or different from each other, and represent a branched alkyl group having 7 to 12 carbon atoms mediated by an oxygen atom, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms which may be mediated by an oxygen atom and include at least one of an aryl group and a cycloalkyl group.

[12] A resin composition containing a carbonate compound represented by general formula (1) as a plasticizer, which is biodegradable, as described in any of [9] to

[11] .

[13] The resin composition according to any one of [9] to

[12] , wherein the resin is a polyester resin.

[14] The resin composition according to

[13] , wherein the resin is polylactic acid. A molded article comprising the resin composition described in any of

[15] [9] to

[14] . A vehicle equipped with the molded parts described in

[16]

[15] . [Effects of the Invention]

[0009] The present invention can provide a novel carbonate compound that has performance as a plasticizer for resins, particularly polyester resins such as polylactic acid. Furthermore, the present invention can provide a plasticizer for resins mainly composed of such a carbonate compound, and a resin composition containing such a carbonate compound as a plasticizer. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below.

[0011] [Carbonate compounds] The carbonate compound in this invention is a novel compound represented by the following general formula (1). [ka] (In the formula, R1 and R2 may be the same or different from each other, and represent a branched alkyl group having 7 to 12 carbon atoms that may be mediated by an oxygen atom, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms that includes at least one of an aryl group and a cycloalkyl group and may be mediated by an oxygen atom; R3 represents a divalent hydrocarbon group having 4 to 8 carbon atoms that is mediated by an oxygen atom; and m represents 0 to 10. When m is 0, at least one of R1 and R2 is a hydrocarbon group mediated by an oxygen atom, except when both R1 and R2 are phenoxyethyl groups.)

[0012] In the carbonate compound of the present invention, R1 and R2 represent terminal structures extending from the carbonate structure toward the molecular terminals, and R3 represents a structure between carbonate structures. The carbonate compound of the present invention has a carbonate structure (-O-CO-O-) and specific terminal structures, and has a structure mediated by an oxygen atom in a part other than the carbonate structure (at least one of the parts extending from the carbonate structure toward the molecular terminals (R1, R2) and between carbonate structures (R3)). Having such a structure provides excellent transparency and water resistance, and the plasticizer is less prone to bleeding out, when used as a plasticizer for resins.

[0013] One embodiment of R1 and R2 is a branched alkyl group having 7 to 12 carbon atoms, which may be mediated by an oxygen atom. This is either a "branched alkyl group having 7 to 12 carbon atoms not mediated by an oxygen atom" or a "branched alkyl group having 7 to 12 carbon atoms mediated by an oxygen atom." Among these, a "branched alkyl group having 7 to 12 carbon atoms mediated by an oxygen atom" is preferred when a very high level of bleed-out suppression is required. In this specification, "branched alkyl group" does not include cycloalkyl groups.

[0014] Furthermore, the state in which an alkyl group is "interposed by an oxygen atom" refers to a state in which the carbon-carbon bond within the alkyl group is interrupted by an oxygen atom (-carbon-oxygen-carbon-), or a state in which a carbon-oxygen bond exists and that oxygen atom is bonded to another carbon (-carbon-oxygen-).

[0015] As one embodiment of R1 and R2, branched alkyl groups having 7 to 12 carbon atoms that are not interposed by an oxygen atom include, for example, 5-methyl-1-hexyl group, 2-ethyl-1-hexyl group, 2-heptyl group, 3-heptyl group, 2-methyl-1-hexyl group, 2-ethyl-1-pentyl group, 2-octyl group, 3-octyl group, 2-methyl-1-heptyl group, 2-nonyl group, 3-nonyl group, 2-methyl-1-octyl group, 2-ethyl-1-heptyl group, 2- Examples of suitable groups include decyl group, 3-decyl group, 2-methyl-1-nonyl group, and 2-ethyl-1-octyl group. From a manufacturing standpoint, 5-methyl-1-hexyl group, 2-ethyl-1-hexyl group, 2-methyl-1-hexyl group, 2-ethyl-1-pentyl group, and 2-ethyl-1-heptyl group are preferred, 5-methyl-1-hexyl group, 2-ethyl-1-hexyl group, and 2-methyl-1-hexyl group are more preferred, and 2-ethyl-1-hexyl group is particularly preferred.

[0016] As one embodiment of R1 and R2, branched alkyl groups having 7 to 12 carbon atoms interposed by an oxygen atom include, for example, ethylene oxide adducts and propylene oxide adducts of the hydrocarbon group. Examples of ethylene oxide adducts include structures obtained by removing the hydroxyl group from ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoisopropyl ether, diethylene glycol mono-2-ethylhexyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-methoxy-2-butanol, 1-ethoxy-propanol, ethylene glycol mono-t-butyl ether, 1-isopropoxy-2-propanol, etc. However, from a manufacturing standpoint, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoisopropyl ether, and diethylene glycol are preferred. Structures obtained by removing the hydroxyl group from mono-2-ethylhexyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, and ethylene glycol mono-t-butyl ether are preferred, structures obtained by removing the hydroxyl group from ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoisopropyl ether, diethylene glycol mono-2-ethylhexyl ether, and ethylene glycol mono-t-butyl ether are even more preferred, and structures obtained by removing the hydroxyl group from ethylene glycol mono-2-ethylhexyl ether and diethylene glycol mono-2-ethylhexyl ether are particularly preferred.

[0017] One embodiment of R1 and R2 is also a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom, and which includes at least one of an aryl group and a cycloalkyl group. In the phrase "a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom, and which includes at least one of an aryl group and a cycloalkyl group," the number of carbon atoms does not include the number of carbon atoms of the aryl group and the cycloalkyl group. That is, the above group is a group formed by adding at least one of an aryl group and a cycloalkyl group to a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom.

[0018] Examples of the aryl group include aryl groups having 6 to 12 carbon atoms, such as phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, tetramethylphenyl group, and biphenyl group. From a manufacturing standpoint, phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, and tetramethylphenyl group are preferred, phenyl group, tolyl group, and dimethylphenyl group are more preferred, and phenyl group and tolyl group are particularly preferred.

[0019] Examples of the cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclododecyl groups, which are cycloalkyl groups having 3 to 12 carbon atoms. From a manufacturing standpoint, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups are preferred, cyclobutyl, cyclopentyl, and cyclohexyl groups are more preferred, and cyclopentyl and cyclohexyl groups are particularly preferred.

[0020] The aforementioned "linear alkyl group having 1 to 12 carbon atoms or branched alkyl group having 3 to 12 carbon atoms that may be mediated by an oxygen atom" is a "linear alkyl group having 1 to 12 carbon atoms that is not mediated by an oxygen atom," a "branched alkyl group having 3 to 12 carbon atoms that is not mediated by an oxygen atom," a "linear alkyl group having 1 to 12 carbon atoms that is mediated by an oxygen atom," or a "branched alkyl group having 3 to 12 carbon atoms that is mediated by an oxygen atom." When a very high level of bleed-out suppression or a very high level of water resistance is required, the aforementioned "linear alkyl group having 1 to 12 carbon atoms or branched alkyl group having 3 to 12 carbon atoms that may be mediated by an oxygen atom" is preferably a linear alkyl group having 1 to 4 carbon atoms or branched alkyl group having 3 to 12 carbon atoms that may be mediated by an oxygen atom. Furthermore, when an even higher tensile elongation is required for the resulting resin composition, among these, a linear alkyl group having 1 to 4 carbon atoms or branched alkyl group having 3 to 4 carbon atoms that may be mediated by an oxygen atom is more preferable. In addition, when biodegradability is required, or when an extremely high tensile elongation is required for the resulting resin composition, linear alkyl groups having 1 to 2 carbon atoms, which may be interposed by oxygen atoms, are even more preferred among these.

[0021] Examples of the "linear alkyl group having 1 to 12 carbon atoms that is not mediated by an oxygen atom" include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. From a manufacturing standpoint, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups are preferred, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups are more preferred, and methyl, ethyl, propyl, butyl, pentyl, and hexyl groups are particularly preferred.

[0022] Examples of branched alkyl groups in the "branched alkyl groups having 3 to 12 carbon atoms that are not mediated by an oxygen atom" include 5-methyl-1-hexyl group, 2-ethyl-1-hexyl group, 2-heptyl group, 3-heptyl group, 2-methyl-1-hexyl group, 2-ethyl-1-pentyl group, 2-octyl group, 3-octyl group, 2-methyl-1-heptyl group, 2-nonyl group, 3-nonyl group, 2-methyl-1-octyl group, 2-ethyl-1-heptyl group, 2 Examples include -decyl group, 3-decyl group, 2-methyl-1-nonyl group, 2-ethyl-1-octyl group, etc., but from a manufacturing viewpoint, 5-methyl-1-hexyl group, 2-ethyl-1-hexyl group, 2-methyl-1-hexyl group, 2-ethyl-1-pentyl group, and 2-ethyl-1-heptyl group are preferred, 5-methyl-1-hexyl group, 2-ethyl-1-hexyl group, and 2-methyl-1-hexyl group are more preferred, and 2-ethyl-1-hexyl group is particularly preferred.

[0023] Examples of the "linear alkyl group having 1 to 12 carbon atoms interposed by an oxygen atom" include ethylene oxide adducts of the alkyl group and propylene oxide adducts of the alkyl group. Examples of the ethylene oxide adducts of the alkyl group include structures obtained by removing a hydroxyl group from glycol alkyl ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether; and structures obtained by removing one hydroxyl group from glycol compounds such as ethylene glycol, diethylene glycol, and triethylene glycol. However, from a manufacturing standpoint, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether are used. Structures obtained by removing hydroxyl groups from ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether are preferred, structures obtained by removing hydroxyl groups from ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether are particularly preferred.

[0024] Examples of the alkyl group propylene oxide adducts include structures obtained by removing the hydroxyl group from propylene glycol monomethyl ether, propylene glycol monoethyl ether, propingrelicol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether. From a manufacturing standpoint, structures obtained by removing the hydroxyl group from propylene glycol monomethyl ether, propylene glycol monoethyl ether, propingrelicol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether are preferred, structures obtained by removing the hydroxyl group from propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether are even more preferred, and structures obtained by removing the hydroxyl group from propylene glycol monomethyl ether, propylene glycol monoethyl ether, and dipropylene glycol monoethyl ether are particularly preferred.

[0025] Examples of the "branched alkyl group having 3 to 12 carbon atoms interposed by an oxygen atom" include, for example, ethylene oxide adducts of the alkyl group. Examples of ethylene oxide adducts include structures obtained by removing the hydroxyl group from ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoisopropyl ether, diethylene glycol mono-2-ethylhexyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-methoxy-2-butanol, 1-ethoxy-propanol, ethylene glycol mono-t-butyl ether, 1-isopropoxy-2-propanol, etc., but from a manufacturing standpoint, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoisopropyl ether, diethylene glycol Structures obtained by removing the hydroxyl group from mono-2-ethylhexyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, and ethylene glycol mono-t-butyl ether are preferred, structures obtained by removing the hydroxyl group from ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoisopropyl ether, diethylene glycol mono-2-ethylhexyl ether, and ethylene glycol mono-t-butyl ether are even more preferred, and structures obtained by removing the hydroxyl group from ethylene glycol mono-2-ethylhexyl ether and diethylene glycol mono-2-ethylhexyl ether are particularly preferred.

[0026] As one embodiment of R1 and R2, "a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom and include at least one of an aryl group and a cycloalkyl group" is "a linear alkyl group having 1 to 12 carbon atoms that is not mediated by an oxygen atom and includes at least one of an aryl group and a cycloalkyl group", "a branched alkyl group having 3 to 12 carbon atoms that is not mediated by an oxygen atom and includes at least one of an aryl group and a cycloalkyl group", "a linear alkyl group having 1 to 12 carbon atoms that is mediated by an oxygen atom and includes at least one of an aryl group and a cycloalkyl group", or "a branched alkyl group having 3 to 12 carbon atoms that is mediated by an oxygen atom and includes at least one of an aryl group and a cycloalkyl group".

[0027] Examples of the "linear alkyl group having 1 to 12 carbon atoms and not interposed by an oxygen atom, comprising at least one of an aryl group and a cycloalkyl group" include a benzyl group, a phenethyl group, or a structure obtained by removing a hydroxyl group from cyclohexanemethanol. From a manufacturing standpoint, the benzyl group and the phenethyl group are preferred, and the benzyl group is particularly preferred.

[0028] Examples of the "branched alkyl group having 3 to 12 carbon atoms and not interposed by an oxygen atom, comprising at least one of an aryl group and a cycloalkyl group" include structures obtained by removing the hydroxyl group from 1-phenylethanol, 1-phenyl-1-propanol, 1-cyclohexylethanol, and 1-cyclohexyl-1-propanol. From a manufacturing standpoint, structures obtained by removing the hydroxyl group from 1-phenylethanol, 1-phenyl-1-propanol, and 1-cyclohexylethanol are preferred, structures obtained by removing the hydroxyl group from 1-phenylethanol and 1-cyclohexylethanol are even more preferred, and structures obtained by removing the hydroxyl group from 1-phenylethanol are particularly preferred.

[0029] Examples of the aforementioned "linear alkyl group having 1 to 12 carbon atoms, interposed by an oxygen atom, containing at least one of an aryl group and a cycloalkyl group" include structures obtained by removing the hydroxyl group from glycol monobenzyl ether compounds such as ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, and propylene glycol monobenzyl ether; structures obtained by removing the hydroxyl group from glycol monophenyl ether compounds such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, and triethylene glycol monophenyl ether; and structures obtained by removing the hydroxyl group from glycol monocycloalkyl ether compounds such as ethylene glycol monocyclopentyl ether and ethylene glycol monocyclohexyl ether. Among these, a structure obtained by removing the hydroxyl group from a glycol monophenyl ether compound is preferred when a very high level of bleed-out suppression or extremely high water resistance is required. Furthermore, a structure obtained by removing the hydroxyl group from a glycol monobenzyl ether compound is preferred when an extremely low tensile modulus is required for the resulting resin composition.

[0030] As for the "linear alkyl group having 1 to 12 carbon atoms, interposed by an oxygen atom, containing at least one of an aryl group and a cycloalkyl group," from a manufacturing standpoint, structures obtained by removing the hydroxyl group from ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol monophenyl ether, ethylene glycol monocyclopentyl ether, and ethylene glycol monocyclohexyl ether are preferred, structures obtained by removing the hydroxyl group from ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, and ethylene glycol monocyclohexyl ether are even more preferred, and structures obtained by removing the hydroxyl group from ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, and diethylene glycol monobenzyl ether are particularly preferred.

[0031] Examples of the "branched alkyl group having 3 to 12 carbon atoms, interposed by an oxygen atom, comprising at least one of an aryl group and a cycloalkyl group" include 1-phenoxy2-propyl group, 2-phenoxypropyl group, and 2-cyclopentyl-2-methoxyethyl group. From a manufacturing standpoint, 1-phenoxy2-propyl group and 2-phenoxypropyl group are preferred, and 1-phenoxy2-propyl group is particularly preferred.

[0032] It is preferable that R1 and R2 represent branched alkyl groups having 7 to 12 carbon atoms that may be mediated by an oxygen atom, or linear alkyl groups having 1 to 4 carbon atoms or branched alkyl groups having 3 to 12 carbon atoms that may be mediated by an oxygen atom, and include at least one of an aryl group and a cycloalkyl group. It is even more preferable that R1 and R2 represent branched alkyl groups having 7 to 12 carbon atoms that are mediated by an oxygen atom, or linear alkyl groups having 1 to 4 carbon atoms or branched alkyl groups having 3 to 12 carbon atoms that may be mediated by an oxygen atom, and include at least one of an aryl group and a cycloalkyl group.

[0033] R1 and R2 preferably represent branched alkyl groups which may be mediated by an oxygen atom, or alkyl groups which may be mediated by an oxygen atom and contain an aryl group. More preferably, they represent branched alkyl groups which are mediated by an oxygen atom, or alkyl groups which may be mediated by an oxygen atom and contain an aryl group. From the viewpoint of further enhancing the plasticity imparting effect and ease of handling, it is particularly preferable to represent alkyl groups which are mediated by an oxygen atom and contain an aryl group.

[0034] R1 and R2 may be the same or different from each other, but it is preferable that they be the same from a manufacturing standpoint and for ease of handling.

[0035] From the viewpoint of further enhancing the effect of imparting plasticity, it is preferable that at least one of R1 and R2 has a structure mediated by an oxygen atom, and it is even more preferable that both R1 and R2 have a structure mediated by an oxygen atom.

[0036] R3 represents a divalent hydrocarbon group having 4 to 8 carbon atoms mediated by an oxygen atom. The "divalent hydrocarbon group" in the said divalent hydrocarbon group having 4 to 8 carbon atoms mediated by an oxygen atom is a linear, branched, or cyclic divalent hydrocarbon group. These functional groups may contain aromatic groups internally or as side chains.

[0037] Examples of divalent hydrocarbon groups having 4 to 8 carbon atoms, obtained by removing an oxygen atom from R3, include butylene, pentylene, hexylene, 2-butylene, 2-methyl-1,3-butylene, 2,2-dimethylpropylene, 3-methyl-1,5-pentylene, heptylene, octylene, 2-ethyl-1,6-hexylene, cyclohexylene, and 1,4-dimethylcyclohexylene. However, from a manufacturing standpoint, pentylene, hexylene, and 2-butylene groups are examples of divalent hydrocarbon groups. Lenne group, 2-methyl-1,3-butylene group, 2,2-dimethylpropylene group, 3-methyl-1,5-pentylene group, heptylene group, octylene group, and 2-ethyl-1,6-hexylene group are preferred; pentylene group, hexylene group, 2-butylene group, 2-methyl-1,3-butylene group, 2,2-dimethylpropylene group, and 3-methyl-1,5-pentylene group are more preferred; and hexylene group, 2-butylene group, 2-methyl-1,3-butylene group, and 2,2-dimethylpropylene group are particularly preferred.

[0038] Examples of the "divalent hydrocarbon group having 4 to 8 carbon atoms interposed by an oxygen atom" include divalent hydrocarbon groups obtained by removing two hydroxyl groups from diethylene glycol, triethylene glycol, dipropylene glycol, 2,5-dihydroxymethyltetrahydrofuran, etc. However, from a manufacturing standpoint, structures obtained by removing two hydroxyl groups from diethylene glycol, triethylene glycol, and dipropylene glycol are preferred, and structures obtained by removing two hydroxyl groups from triethylene glycol and dipropylene glycol are particularly preferred.

[0039] Examples of the aromatic groups that R3 can contain include phenyl, tolyl, xylyl, mesityl, biphenyl, phenylene, methylphenylene, methylene-phenylene, methylene-phenylene-methylene, dimethylphenylene, methylene-methylphenylene, and biphenylene groups. From a manufacturing standpoint, phenyl, tolyl, dimethylphenyl, trimethylphenyl, and tetramethylphenyl groups are preferred, phenyl, tolyl, and dimethylphenyl groups are more preferred, and phenyl and tolyl groups are particularly preferred.

[0040] In the general formula (1) above, m is between 0 and 10, preferably between 0 and 5, and more preferably between 0 and 3, from the viewpoint of further enhancing the effect of imparting plasticity and improving handling. Furthermore, if an extremely high tensile elongation is required for the resulting resin composition, m is even more preferably 0.5 or higher, particularly preferably 1 or higher, and most preferably 1.5 or higher. Note that if the carbonate compound is a mixture of multiple compounds with different values ​​of m, m represents the average value.

[0041] When m is 0, at least one of R1 and R2 is a hydrocarbon group mediated by an oxygen atom. Also, when m is 0, R1 and R2 cannot both be phenoxyethyl groups. In other words, when m is 0, at least one of R1 and R2 is a group other than a phenoxyethyl group.

[0042] In particular, when m is 0, it is preferable that both R1 and R2 contain a structure mediated by an oxygen atom. Examples include hydrocarbon groups obtained by removing the hydroxyl group from ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol monophenyl ether, triethylene glycol monobenzyl ether, etc. Among these, hydrocarbon groups obtained by removing the hydroxyl group from diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol monophenyl ether, and triethylene glycol monobenzyl ether are preferred.

[0043] The carbonate compounds of general formula (1) in the present invention can be obtained, for example, by reacting a carbonyl compound with a monoalcohol or a diol. Representative examples of each reaction component are shown below.

[0044] [Carbonyl compounds] Carbonyl compounds include diesters of carbonate, halogenated carbonates, and dihalogenated carbonyls, as well as their equivalents.

[0045] Examples of the aforementioned diester carbonates include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, diisopropyl carbonate, ethylene carbonate, propylene carbonate, and diphenyl carbonate. Among these, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and diphenyl carbonate are preferred in terms of ease of raw material availability and reactivity, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate are more preferred, and dimethyl carbonate and diethyl carbonate are particularly preferred.

[0046] Examples of the halogenated carbonate esters include methyl chlorocarbonate, ethyl chlorocarbonate, phenyl chlorocarbonate, 2-ethylhexyl chlorocarbonate, and benzyl chlorocarbonate. Among these, phenyl chlorocarbonate, 2-ethylhexyl chlorocarbonate, and benzyl chlorocarbonate are preferred in terms of reactivity, and 2-ethylhexyl chlorocarbonate and benzyl chlorocarbonate are particularly preferred.

[0047] Examples of the dihalogenated carbonyl include dichlorocarbonyl (phosgene) and dibromocarbonyl, but dichlorocarbonyl is preferred due to its good reactivity.

[0048] [Monoalcohol] The monoalcohol is not particularly limited as long as it can be converted into the carbonate compound of the present invention. Examples include 5-methyl-1-hexanol, 2-ethylhexanol, 2-heptanol, 3-heptanol, 2-methyl-1-hexanol, 2-ethyl-1-pentanol, 2-octanol, 3-octanol, 2-methyl-1-heptanol, 2-nonanol, 3-nonanol, 2-methyl-1-octanol, 2-ethyl-1-heptanol, 2-decanol, 3-decanol, 2-methyl-1-nonanol, 2-ethyl-1-octanol, benzyl alcohol, phenethyl alcohol, etc. Among these, 2-ethylhexanol, benzyl alcohol, and phenethyl alcohol are preferred due to their reactivity and ease of handling.

[0049] Furthermore, ethylene oxide adducts, propylene oxide adducts, etc., of the monoalcohols can also be used. Examples of such adducts include ethylene oxide adducts such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol mono-2-ethylhexyl ether, and triethylene glycol monophenyl ether, and propylene oxide adducts such as propylene glycol monobenzyl ether. Among these, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, and diethylene glycol mono-2-ethylhexyl ether are preferred due to their reactivity and ease of handling.

[0050] [Diol] Examples of the aforementioned diols include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 1,4-dihydroxymethylbenzene, 1,4-dihydroxymethylcyclohexane, 2,2'-oxydiethanol, triethylene glycol, dipropylene glycol, neopentyl glycol, and the like. Among these, diethylene glycol, triethylene glycol, and dipropylene glycol are preferred due to their reactivity and ease of handling.

[0051] [Method for producing carbonate compounds] Examples of methods for producing carbonate compounds in the present invention include the following: When using diester carbonate as a raw material, a monoalcohol and an excess number of diester carbonate relative to the monoalcohol are added to a reactor, and the mixture is reacted at a temperature of 100-130°C, under a nitrogen atmosphere and at atmospheric pressure for 5-10 hours. After that, the diester carbonate in the reactor is removed from the system under reduced pressure, a diol is added, and the mixture is reacted at a temperature of 150-200°C and a pressure of several mmHg for several hours. In the above reaction, it is preferable to remove the by-product alcohol from the system while the reaction is carried out. Furthermore, if the diester carbonate is removed from the system by azeotrope with the by-product alcohol, a larger excess amount of diester carbonate may be added.

[0052] In the above reaction, a catalyst may be present as needed. Preferably used catalysts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates and bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal alkoxides such as sodium methoxide, potassium methoxide, and lithium methoxide; sulfates, phosphates, nitrates, and carboxylates.

[0053] Another method for producing carbonate compounds involves using chlorocarbonate esters as a raw material. This method involves adding a diol, a solvent such as toluene, and a basic compound such as pyridine to neutralize the hydrochloric acid produced as a by-product during the reaction to a reactor. The chlorocarbonate esters are then added dropwise from a dropping funnel under a nitrogen atmosphere and atmospheric pressure, while the reaction is carried out while cooling with ice water to prevent the reaction solution temperature from exceeding 5°C. After that, water is added and the mixture is separated. The extracted organic layer is then dehydrated with a dehydrating agent, and the low-boiling point compounds are removed under reduced pressure. In the above reaction, salt is produced as a by-product in the reactor, which reduces stirring efficiency. Therefore, it is preferable to carry out the reaction while stirring with a device that has strong stirring power.

[0054] The carbonate compound of the present invention preferably exhibits biodegradability. Biodegradability can be evaluated in accordance with OECD 301F.

[0055] The carbonate compound of the present invention preferably has a flash point of 210°C or higher. The method for measuring the flash point is not particularly limited, but examples include the rapid equilibrium method (Seta closed type) of JIS K2265-2:2007 and the Cleveland open type of JIS K2265-4:2007.

[0056] The carbonate compound of the present invention preferably has a dissolution parameter in the range of 8.9 to 12.0, and more preferably in the range of 8.9 to 10.5, according to Fedors estimation, from the viewpoint of further enhancing the effect of imparting plasticity. When the dissolution parameter is within the above range, compatibility with resins can be improved and plasticity can be imparted more effectively.

[0057] The carbon number of the carbonate compound of the present invention is not particularly limited, but from the viewpoint of suitably reducing the tensile modulus of the resulting resin composition, it is preferably 80 or less, more preferably 18 to 60, and even more preferably 20 to 40. Furthermore, if an extremely high tensile elongation is required for the resulting resin composition, the carbon number is particularly preferably 24 or more, and most preferably 26 or more. In the case where the carbonate compound is a mixture of multiple compounds with different carbon numbers, the carbon number represents the average value.

[0058] The carbonate compound of the present invention preferably has a number average molecular weight of 1,000 or less, more preferably 300 to 800, and even more preferably 300 to 500, due to its ease of handling when added to resins as a plasticizer and its biodegradability.

[0059] [Plasticizers primarily composed of carbonate compounds] The present invention also relates to a plasticizer mainly composed of a carbonate compound represented by the following general formula (1). [ka] (In the formula, R1 and R2 may be the same or different from each other, and represent a branched alkyl group having 7 to 12 carbon atoms that may be mediated by an oxygen atom, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms that includes at least one of an aryl group and a cycloalkyl group and may be mediated by an oxygen atom; R3 represents a divalent hydrocarbon group having 4 to 8 carbon atoms that is mediated by an oxygen atom; and m represents 0 to 10. When m is 0, at least one of R1 and R2 is a hydrocarbon group mediated by an oxygen atom, except when both R1 and R2 are phenoxyethyl groups.)

[0060] The resin composition of the present invention provides excellent transparency and water resistance in molded articles, superior surface appearance, and resistance to plasticizer bleed-out.

[0061] The carbonate compound represented by the general formula (1) is the main component of the plasticizer of the present invention, preferably present in an amount of 60-100%, more preferably 70-100%, and particularly preferably 80-100%. The plasticizer may contain multiple types of carbonate compounds represented by the general formula (1).

[0062] Examples of the carbonate compound represented by general formula (1), which is the main component of the plasticizer of the present invention, include those similar to the carbonate compound of the present invention described above, and the preferred embodiments are also the same as the preferred embodiments of the carbonate compound of the present invention described above.

[0063] The plasticizer may contain compounds other than the carbonate compound represented by the general formula (1) above. Such compounds are known plasticizers, including dibasic acid esters, citrate esters, polyalkylene glycol diesters, polyhydric alcohol esters, polyester plasticizers, or polyether ester plasticizers. These may be used individually or in combination of two or more.

[0064] [Resin composition] The present invention further relates to a resin composition comprising a resin (A) and a carbonate compound represented by the general formula (1) described above.

[0065] [resin] The resin used in the present invention is not particularly limited, but examples include polypropylene resins having repeating units derived from propylene, such as propylene homopolymer, propylene-ethylene block copolymer, propylene-1-butene block copolymer, propylene-ethylene-1-butene block copolymer, propylene-ethylene random copolymer, propylene-1-butene random copolymer, propylene-ethylene-1-butene random copolymer, propylene-ethylene random block copolymer, propylene-ethylene-1-butene random block copolymer, propylene-hexene random copolymer, propylene-octene random copolymer, and ethylene-propylene-1-butene copolymer; polyethylene such as low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, and high-density polyethylene; and polyethylene resins having repeating units derived from ethylene, such as ethylene-1-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl alcohol copolymer, and chlorinated polyethylene (polypropylene resins). (Excluding those that fall under the category of resins); polyolefin resins such as polybutene, polyisobutylene, butyl rubber, halogenated butyl rubber, polymethylpentene, and copolymers of cyclic olefins (excluding those that fall under the category of polypropylene resins or polyethylene resins); polyacetal resins such as polyoxymethylene; polylactic acid, polyhydroxypropionic acid, polyhydroxybutyric acid, polycaprolactone, polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, polyhexamethylene succinate, Polyester resins such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene oxalate, polybutylene oxalate, polyhexamethylene oxalate, polyethylene sebacate, polybutylene sebacate, polyhexamethylene oxalate, polybutylene adipate terephthalate, polyethylene terephthalate succinate, 3-hydroxybutyrate-co-3-hydroxyhexanoate polymer, and 3-hydroxybutyrate-co-3-hydroxyvalate polymer;Examples include polyamide resins such as polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, and polyamide 6 / 66; and thermoplastic elastomers such as styrene elastomers, polyolefin elastomers, polyester elastomers, and polyamide elastomers. These resins may be petroleum-derived or plant-derived, and may also be biodegradable.

[0066] Among these, polyester resins are preferred, and aliphatic polyester resins obtained by dehydration polycondensation of hydroxycarboxylic acids or aliphatic polyester resins (including copolymers) obtained by ring-opening polymerization of cyclic lactones; aliphatic polyester resins (including copolymers) obtained by polymerization of aliphatic dicarboxylic acids and aliphatic diols; semi-aromatic polyester resins (including copolymers) obtained by polymerization of aliphatic dicarboxylic acids and aromatic diols, or by reaction of aromatic dicarboxylic acids and aliphatic diols; aromatic polyester resins obtained by reaction of aromatic dicarboxylic acids and aromatic diols are preferred, with aliphatic polyester resins (including copolymers) being particularly preferred from the viewpoint of moldability and compatibility.

[0067] Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, β-hydroxypropionic acid, β-hydroxybutyric acid, hydroxyvaleric acid, hydroxypivalic acid, hydroxycaproic acid, and hydroxydodecanoic acid. If optical isomers exist for these, either the D-form, L-form, or racemic mixture can be used. By reacting these, a resin with the hydroxycarboxylic acid as a repeating unit can be obtained. In addition, the hydroxycarboxylic acid polymer in this invention also includes polymers obtained by transesterification with hydroxycarboxylic acid derivatives (esters) and polymers (polylactones) obtained by ring-opening polymerization of cyclic esters (lactones) that are hydroxycarboxylic acid derivatives. Specific examples of polylactones include "Cellgreen" manufactured by Daicel Chemical Industries, Ltd., "Tonepolymer" manufactured by Union Carbide, and "Capa" manufactured by Solvay. The polymer is preferably polyhydroxypropionic acid, polyhydroxybutyric acid, polylactic acid, or polycaprolactone, with polylactic acid being particularly preferred for more efficient expression of moldability and plasticity.

[0068] [Aliphatic polyester resin] Aliphatic polyester resins obtained by reacting aliphatic dicarboxylic acids with aliphatic diols are not particularly limited as long as they are polyesters produced by various combinations of aliphatic dicarboxylic acids and aliphatic diols. Among these, those that are biodegradable are preferred from the viewpoint of reducing the burden on the environment.

[0069] [Aliphatic diols] Specific examples of aliphatic diols, which are one of the raw materials for aliphatic polyester resins, include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,4-benzenedimethanol. These can be used individually or in combination of two or more. Among these, ethylene glycol and 1,4-butanediol are preferred, and 1,4-butanediol is particularly preferred due to its reactivity and other factors.

[0070] [Aliphatic dicarboxylic acids] Specific examples of aliphatic dicarboxylic acids, which are the other raw materials for aliphatic polyester resins, include succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. These can be used individually or in combination of two or more. Among these, succinic acid and adipic acid are preferred due to their ease of handling.

[0071] As a method for producing aliphatic polyester resins, both direct polymerization, which involves directly polymerizing these materials to obtain high molecular weight products, and indirect polymerization, which involves polymerizing to the oligomer stage and then obtaining high molecular weight products using chain extenders, etc., can be employed. Specifically, in direct polymerization, high molecular weight products are obtained while removing water contained in the raw material compounds or water generated during polymerization. Indirect polymerization methods include selecting raw material compounds and polymerizing them to the oligomer stage, and then using a small amount of chain length extender (e.g., diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, etc.) to increase the molecular weight, and methods for obtaining high molecular weight aliphatic polyester carbonates using carbonate compounds. In the present invention, any of these methods can be used.

[0072] Examples of aliphatic polyester resins include polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, polyhexamethylene succinate, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene oxalate, polybutylene oxalate, polyhexamethylene oxalate, polyethylene sebacate, polybutylene sebacate, and polyhexamethylene oxalate. These can be used individually or in combination of two or more. Polyethylene succinate, polybutylene succinate, or polybutylene succinate adipate are particularly preferred due to their easy availability as they are already industrialized and the properties of the resulting polymers (melting point, biodegradability), with polybutylene succinate or polybutylene succinate adipate being particularly preferred.

[0073] Specific examples of polybutylene succinate include "Bionole" manufactured by Showa Polymer Co., Ltd. and "Skygreen" manufactured by SK Industries Co., Ltd. Specific examples of polybutylene succinate adipate include "Bionole" manufactured by Showa Polymer Co., Ltd. An example of polyethylene succinate is "Lunare" manufactured by Nippon Shokubai Co., Ltd.

[0074] The at least one resin selected from the group consisting of polymers obtained by dehydration polycondensation of these hydroxycarboxylic acids, or aliphatic polyester resins synthesized mainly from aliphatic dicarboxylic acids and aliphatic diols, is preferably at least one selected from the group consisting of polybutylene adipate terephthalate, polyethylene terephthalate succinate, 3-hydroxybutyrate-co-3-hydroxyhexanoate polymer, and 3-hydroxybutyrate-co-3-hydroxyvalate polymer, in addition to the specific examples mentioned above. Among these, polylactic acid is particularly preferred as the main component from the viewpoint of biodegradability and moldability.

[0075] [Polylactic acid] While polylactic acid is not particularly limited, for example, L-lactic acid, D-lactic acid, D,L-lactic acid, stereocomplex polylactic acid consisting of a mixture of L-lactic acid and D-lactic acid, and mixtures thereof can be preferably used. Among these, polylactic acid mainly composed of L-lactic acid is preferred from the viewpoint of biodegradability and moldability.

[0076] The D-isomer content in polylactic acid is preferably 0 to 7.0 mol%, more preferably 0.01 to 6.0 mol%, and particularly preferably 0.1 to 1.0 mol% per 100 mol% of polylactic acid. If the D-isomer content is higher than 7.0 mol%, biodegradability may decrease.

[0077] The ratio of L- and D-isomers (optical isomer ratio) constituting polylactic acid can be determined by hydrolyzing it, separating the resulting lactic acid into L-lactic acid and D-lactic acid using high-performance liquid chromatography equipped with an optical isomer separation column, and then quantifying them. Examples of hydrolysis methods include mixing D,L-lactic acid with a sodium hydroxide / methanol mixed solution using a water bath immersion chamber set to, for example, 65°C. When quantifying using high-performance liquid chromatography, it is preferable to use a solution that has been pre-neutralized with dilute hydrochloric acid or the like.

[0078] As for the polylactic acid, from the viewpoint of moldability, it is acceptable to use one in which the melt flow rate at 190°C and 2.16 kg is 0.3 to 30 g / 10 min as measured according to JIS K7210, preferably 1 to 25 g / 10 min, more preferably 2 to 20 g / 10 min, and particularly preferably 3 to 15 g / 10 min.

[0079] From the viewpoint of moldability, polylactic acid preferably has a melting point of 140 to 210°C, more preferably 150 to 200°C, and particularly preferably 160 to 190°C, as measured by differential scanning calorimetry (DSC).

[0080] Polylactic acid can be produced, for example, by condensation polymerization of lactic acid or by ring-opening polymerization of lactide, which is a cyclic dimer of lactic acid. Polycondensation of lactic acid is a method of esterifying the carboxyl and hydroxyl groups of lactic acid, and an example is azeotropic dehydration of L-lactic acid or D-lactic acid or a mixture thereof under reduced pressure in the presence of a high-boiling point solvent. Ring-opening polymerization using lactide is a method of esterifying ring-opened lactides, and an example is ring-opening of L-lactide or D-lactide in the presence of a polymerization regulator and a polymerization catalyst. Furthermore, D,L-lactide, which is a dimer of L-lactic acid and D-lactic acid, may be used in combination to the extent that the objectives of the present invention are achieved.

[0081] In the present invention, as polylactic acid, copolymers of polylactic acid with at least one hydroxycarboxylic acid derivative selected from the group consisting of polyglycolic acid having strength and toughness, polycaprolactone having flexibility, and polyhydroxybutyrate and polyhydroxyvallate with high plant-derived content are also preferably used.

[0082] Specific examples of polylactic acid include "LACTY9030" manufactured by Shimadzu Corporation, "Leicia" manufactured by Mitsui Chemicals, Inc., "Teramac" manufactured by Unitika Ltd., "Ecoloju" manufactured by Mitsubishi Plastics, Inc., "CPLA (tentative name)" manufactured by Dainippon Ink and Chemicals, Inc., "eco-PLA" manufactured by Cargill-Dow Corporation (USA), "Lactron" manufactured by Kanebo Synthetic Fiber Co., Ltd., and "FY801" manufactured by Anhui Fengyuan Group Co., Ltd.

[0083] [Plasticizer] The resin composition of the present invention contains a carbonate compound represented by the general formula (1) described above. Examples of the carbonate compound represented by the general formula (1) contained in the resin composition of the present invention include those similar to the carbonate compound of the present invention described above, and its preferred embodiments are also the same as those of the carbonate compound of the present invention described above.

[0084] The carbonate compound represented by general formula (1) acts as a plasticizer in the resin composition of the present invention. That is, the resin composition of the present invention contains a plasticizer (B) which includes the carbonate compound represented by general formula (1). In the resin composition of the present invention, it is preferable that the main component of the plasticizer (B) is the carbonate compound represented by general formula (1). It is preferable that the plasticizer (B) contained in the resin composition of the present invention contains 60 to 100% of the carbonate compound represented by general formula (1), more preferably 70 to 100%, and particularly preferably 80 to 100%. The plasticizer (B) may contain multiple types of the carbonate compound represented by general formula (1).

[0085] The plasticizer (B) may include compounds other than the carbonate compound represented by the general formula (1) above. Examples of such compounds include those mentioned above. These may be used individually or in combination of two or more.

[0086] [Other additives] The resin composition of the present invention may optionally contain additives, other synthetic resins, elastomers, etc., to the extent that they do not hinder the objectives of the present invention.

[0087] Examples of the aforementioned additives include curing agents such as amino resins, polyisocyanates, blocked polyisocyanates, melamine resins, carbodiimides, and polyols; antioxidants such as hindered phenols, phosphorus (phosphite esters, phosphate esters, etc.), and amines; ultraviolet absorbers such as benzotriazoles and benzophenones; light stabilizers such as hindered amines; internal lubricants such as aliphatic carboxylic acid esters, paraffins, silicone oils, and polyethylene waxes; release agents, flame retardants, flame retardant aids, antistatic agents, colorants, various organic fillers, inorganic fillers, antiblocking agents, various coupling agents, surfactants, colorants, foaming agents, and natural materials.

[0088] The curing agent is a component that accelerates the curing of the resin composition. By including the curing agent in the resin composition, the water resistance, chemical resistance, etc., of filaments, fibers, resin sheets, films, and molded articles obtained using the resin composition can be improved.

[0089] Examples of the curing agents include amino resins, polyisocyanates, blocked polyisocyanates, melamine resins, carbodiimides, and polyols.

[0090] Examples of amino resins include molar or fully methylolated amino resins obtained by the reaction of an amino component with an aldehyde component. Examples of the amino component include melamine, urea, benzoguanamine, acetoganaamine, steroguanamine, spiloganamine, and dicyandiamide. Examples of aldehyde components include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.

[0091] Examples of polyisocyanates include compounds having two or more isocyanate groups in one molecule, such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

[0092] Examples of blocked polyisocyanates include those obtained by adding a blocking agent to the isocyanate group of the aforementioned polyisocyanate. Examples of blocking agents include phenolic agents such as phenol and cresol, aliphatic alcohols such as methanol and ethanol, active methylene agents such as dimethyl malonate and acetylacetone, mercaptan agents such as butyl mercaptan and dodecyl mercaptan, acid amide agents such as acetanilide and acetic acid amide, lactam agents such as ε-caprolactam and δ-valerolactam, acid imide agents such as succinimide and maleimide, oxime agents such as acetaldehyde oxime, acetone oxime and methyl ethyl ketoxime, and amine agents such as diphenylaniline, aniline and ethyleneimine.

[0093] Examples of melamine resins include methylolmelamines such as dimethylolmelamine and trimethylolmelamine; alkyl ethers or condensates of these methylolmelamines; and condensates of alkyl ethers of methylolmelamine.

[0094] Incorporating an inorganic filler into the resin composition of the present invention is preferable because it improves mechanical strength, dimensional stability, and other properties. Furthermore, an inorganic filler may be incorporated into the resin composition of the present invention for the purpose of increasing its volume.

[0095] Examples of the inorganic fillers include metal sulfate compounds such as zinc sulfate, potassium bisulfate, aluminum sulfate, antimony sulfate, sulfate esters, potassium sulfate, cobalt sulfate, sodium bisulfate, iron sulfate, copper sulfate, sodium sulfate, nickel sulfate, barium sulfate, magnesium sulfate, and ammonium sulfate; titanium compounds such as titanium oxide; carbonate compounds such as potassium carbonate; metal hydroxide compounds such as aluminum hydroxide and magnesium hydroxide; silica compounds such as synthetic silica and natural silica; calcium aluminate, gypsum dihydrate, zinc borate, barium metaborate, and borax; nitrate compounds such as sodium nitrate, molybdenum compounds, zirconium compounds, antimony compounds and their modified products; and composite fine particles of silicon dioxide and aluminum oxide.

[0096] In addition, examples of inorganic fillers other than those mentioned above include potassium titanate whiskers, mineral fibers (rock wool, etc.), glass fibers, carbon fibers, metal fibers (stainless steel fibers, etc.), aluminum borate whiskers, silicon nitride whiskers, boron fibers, tetrapod-shaped zinc oxide whiskers, talc, clay, kaolin clay, natural mica, synthetic mica, pearl mica, aluminum foil, alumina, glass flakes, glass beads, glass balloons, carbon black, graphite, calcium carbonate, calcium sulfate, calcium silicate, titanium dioxide, zinc oxide, silica, asbestos, quartz powder, etc.

[0097] These inorganic fillers may be left untreated or may be pre-treated with chemical or physical surface treatments. Examples of surface treatment agents used for this treatment include silane coupling agents, higher fatty acid systems, fatty acid metal salt systems, unsaturated organic acid systems, organic titanate systems, resin acid systems, polyethylene glycol systems, and the like.

[0098] Examples of the aforementioned flame retardants include boric acid-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, halogen-based flame retardants, organic flame retardants, and colloidal flame retardants.

[0099] Other synthetic resins include polyethylene, polypropylene, polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and polymethyl methacrylate. Elastomers include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, and acrylic elastomers.

[0100] [Method for producing resin compositions] The resin composition is preferably manufactured by melt-mixing a resin (A) and a plasticizer (B) at 180 to 260°C. It is desirable to substantially prevent degradation and alteration of the polymer, and for this purpose, mixing at 185 to 220°C is preferable. There are no particular restrictions on the mixing time, but from the viewpoint of productivity, it may be 3 to 60 minutes, preferably 5 to 30 minutes. The mixing method can be carried out by conventional methods, for example, by using a ribbon blender, drum tumbler, Henschel mixer, Banbury mixer, single-screw extruder, twin-screw extruder, conneeder, multi-screw extruder, etc.

[0101] [Composition of the resin composition] The resin composition contains resin (A) and plasticizer (B). When the total mass of resin (A) and plasticizer (B) is 100 parts by mass, the content of resin (A) is preferably 50 to 95 parts by mass, more preferably 55 to 90 parts by mass, and even more preferably 70 to 90 parts by mass. The amount of plasticizer (B) is preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 10 to 30 parts by mass. By keeping the content of plasticizer (B) below the above upper limits, it becomes easier to mold into fibers, filaments, films, sheets, etc.

[0102] [Molded articles made from resin compositions] A molded article containing the resin composition of the present invention can be obtained by molding the resin composition of the present invention. Examples of molding methods for the resin composition include various extrusion molding methods (cold runner method, hot runner method, as well as injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection molding by supercritical fluid injection), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding). Furthermore, it is also possible to mold it as a heat-shrinkable tube by applying a specific stretching operation. In addition, it is possible to make a hollow molded article from the resin composition of the present invention by rotational molding or blow molding.

[0103] Examples of molded articles of the resin composition of the present invention include filaments, sheets, films, fibers, and the like.

[0104] Known manufacturing methods can be used for manufacturing the filament. For example, one method involves melting pellets of a resin composition using an extruder or the like, extruding them from a spinning nozzle, and cooling them in a refrigerant bath such as water or trichloroethylene.

[0105] Extrusion molding, inflation molding, calendering, and casting methods can also be used to form sheets and films.

[0106] For forming the fibers, methods such as melt spinning, dry spinning, and wet spinning can be used.

[0107] [Applications of molded articles made from resin compositions] The resin composition of the present invention can be used to form resin products for exterior materials of office automation equipment and home appliances, such as personal computers, laptop computers, game consoles, display devices (CRT, liquid crystal, plasma, projector, and organic EL, etc.), mice, and exterior materials for printers, copiers, scanners and fax machines (including multifunction devices thereof), keyboard keys and switch molded products, personal digital assistants (PDAs), mobile phones, portable books (dictionaries, etc.), portable televisions, drives for recording media (CDs, MDs, DVDs, next-generation high-density discs, hard disks, etc.), readers for recording media (IC cards, SmartMedia, Memory Sticks, etc.), optical cameras, digital cameras, parabolic antennas, power tools, VTRs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, lighting equipment, refrigerators, air conditioners, air purifiers, negative ion generators, and typewriters. It is also useful for trays, cups, plates, shampoo bottles, office equipment casings, cosmetic bottles, beverage bottles, oil containers, injection-molded products (golf tees, cotton swab cores, candy sticks, brushes, toothbrushes, helmets, syringes, plates, cups, combs, razor handles, tape cassettes and cases, disposable spoons and forks, ballpoint pens and other stationery, etc.).

[0108] Furthermore, it can be used in a wide range of applications, including fastening tape (cable ties), prepaid cards, balloons, pantyhose, hair caps, sponges, cellophane tape, umbrellas, raincoats, plastic gloves, hair caps, ropes, tubes, foam trays, foam cushioning materials, cushioning materials, packaging materials, and cigarette filters.

[0109] Furthermore, it can be used in various containers, general merchandise, lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts, car audio-visual parts, and auto mobile computer parts for vehicles. In other words, in one embodiment, a vehicle equipped with a molded product of the present invention is provided.

[0110] Resin molded products made from the resin composition of the present invention can be given other functions by surface modification. Surface modification, as referred to here, involves forming a new layer on the surface of the resin molded product by methods such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, and printing, and methods commonly used for resin molded products can be applied. Due to its good hue, the resin composition of the present invention makes it possible to provide a good product with a single coat, even with coatings that have low opacity.

[0111] When the molded article of the resin composition of the present invention is a filament, it is preferable to use it for three-dimensional molding. The filament can be molded into a molded article by a 3D printer, which is a three-dimensional object manufacturing device. There are no particular restrictions on the 3D printer, but an FDM (Fused Deposition Modeling) device is preferred. [Examples]

[0112] Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited to these.

[0113] The raw materials used in the examples and comparative examples are as follows:

[0114] <Resin> Polylactic acid: Manufactured by Anhui Fengyuan Group Co., Ltd. (Product name: FY801, polylactic acid mainly composed of L-lactic acid, D-isomer content 1 mol% or less, melting point 170-180°C, MFR (190°C / 2.16kg) 3-7g / 10min (all values ​​from catalog))

[0115] <Carbonate compounds> Carbonate (1): This is a novel compound synthesized by Manufacturing Example 1 described below, and is represented by the following structural formula. [ka] (In the formula, m is 2.2) 1 H-NMR(400 MHz,CDCl3)δppm 3.56-3.83(m,13H),4.20-4.37(m,6H),5.11-5.23(m,4H),7.29-7.44(m,9H)

[0116] Carbonate (2): This is a novel compound synthesized by Manufacturing Example 2, and is represented by the following structural formula. [ka] 1 H-NMR(400 MHz,CDCl3)δppm 0.80-0.95(m,12H),1.19-1.44(m,16H),1.51-1.64(m,2H),3.60-3.76(m,8H),3.97-4.09(m,4H),4.20-4.31(m,4H)

[0117] Carbonate (3): This is a novel compound synthesized by Manufacturing Example 3, and is represented by the following structural formula. [ka] 1 H-NMR(400 MHz,CDCl3)δppm 3.72-3.81(m,4H),3.81-3.90(m,4H),4.06-4.18(m,4H),4.25-4.39(m,4H),6.85-7.01(m,6H),7.20-7.35(m,4H)

[0118] Carbonate (4): This is a novel compound synthesized by Manufacturing Example 4, and is represented by the following structural formula. [ka] 1 H-NMR(400 MHz, CDCl3)δppm 3.58-3.64(m,4H),3.64-3.69(m,4H),3.69-3.74(m,4H),4.22-4.34(m,4H),4.48-4.63(m,4H),7.21-7.30(m,2H),7.30-7.38(m,8H)

[0119] Carbonate (5): This compound was synthesized by Manufacturing Comparative Example 1 and is represented by the following structural formula. [ka] (In the formula, m is 1.5) 1 H-NMR(400 MHz,CDCl3)δppm 0.83-0.97(m,12H),1.25-1.33(m,10H),1.34-1.47(m,10H),1.66(BS s,8H),3.95-4.18(m,10H)

[0120] Carbonate (6): This compound was synthesized by Comparative Example 2 of the manufacturing process and is represented by the following structural formula. [ka] 1 H-NMR(400 MHz, CDCl3)δppm 0.90(t,3H),1.21-1.46(m,21H),1.62-1.75(m,2H),4.10-4.22(m,2H),5.13-5.23(m,2H),7.29-7.48(m,1H),7.30-7.45(m,4H)

[0121] Carbonate (7): This compound was synthesized by Comparative Example 3 of the manufacturing process and is represented by the following structural formula. [ka] 1H-NMR (400 MHz, CDCl3) δ ppm 0.83 - 0.93 (m, 3H), 1.20 - 1.54 (m, 5H), 1.25 (s, 11H), 1.59 - 1.72 (m, 2H), 3.38 (s, 4H), 3.50 - 3.58 (m, 3H), 3.62 - 3.67 (m, 3H), 3.70 - 3.77 (m, 3H), 4.07 - 4.16 (m, 2H), 4.25 - 4.33 (m, 3H)

[0122] Carbonate (8): It was synthesized according to Production Comparative Example 4 and is a compound represented by the following structural formula.

Chemical formula

[0123] For Carbonate (1) and Carbonate (5), m in the formula was calculated using the weight average molecular weight measured by the following method.

[0124] (Weight average molecular weight) The weight average molecular weight of the carbonate compound was measured using gel permeation chromatography ("HLC - 8320GPC" manufactured by Tosoh Corporation) under the following conditions and calculated in terms of polystyrene conversion. Column: TSKgel G1000H manufactured by Tosoh Corporation XL Eluent: Tetrahydrofuran solution Temperature: 40 °C Flow rate: 1.0 mL / min. Sample concentration: 1.25% (mass / volume) Injection volume: 10 μL

[0125] (Production Example 1) A glass separable flask equipped with a rectification column, stirrer, thermometer, and nitrogen inlet tube contains 226.0 g (2.51 mol, purity 98% or higher) of dimethyl carbonate, 135.2 g (1.25 mol, purity 99% or higher) of benzyl alcohol, and 135.7 mg (5.67 × 10⁻¹⁴) of lithium hydroxide. -3 The mixture (in moles) was mixed and reacted at 100-110°C for 7-8 hours under atmospheric pressure, while removing the low-boiling components by distillation. After the reaction, the low-boiling components, including dimethyl carbonate, were removed by distillation at 100°C for 1 hour under reduced pressure (-0.050 to -0.10 MPaG). After removing the low-boiling components, 47.9 g (0.31 moles, purity 99% or higher) of triethylene glycol was added and reacted at 180°C for 1-2 hours under reduced pressure (-0.1 MPaG), while removing the low-boiling components by distillation. After the reaction was complete, 1.9 g (9.08 × 10⁻¹⁵) of dibutyl phosphate was added. -3 (mol) was added, and the catalyst was deactivated at 100°C for 2 hours under atmospheric pressure. After catalyst deactivation, simple distillation was carried out under reduced pressure (-0.050 to -0.10 MPaG) at 180 to 240°C for 5 to 6 hours to obtain 87.3 g of carbonate (1) as a pale yellow transparent liquid (yield based on triethylene glycol: 77.2%).

[0126] (Manufacturing Example 2) In a glass separable flask equipped with a dropping funnel, stirrer, thermometer, and nitrogen inlet tube, 37.5 g (0.25 mol, purity 99% or higher), 59.6 g (0.75 mol) of pyridine, and 200.0 g (2.17 mol) of toluene were mixed. Under atmospheric pressure, 107.3 g (0.56 mol, purity 99% or higher) of 2-ethylhexyl chlorocarbonate was added to the flask and the mixture was reacted for 4 hours while dropping it from a dropping funnel, ensuring that the internal temperature did not exceed 5°C. After the reaction was complete, simple distillation was carried out under reduced pressure (-0.050 to -0.10 MPaG) at 150°C for 2 to 3 hours to obtain 108.9 g of carbonate(2) as a pale yellow transparent liquid (yield: 94.1%).

[0127] (Manufacturing Example 3) A glass separable flask equipped with a rectification column, stirrer, thermometer, and nitrogen inlet tube contains 92.3 g (1.02 mol, purity 98% or higher) of dimethyl carbonate, 256.9 g (1.41 mol, purity 99% or higher) of diethylene glycol monophenyl ether, and 116.0 mg (4.84 × 10⁻¹⁴) of lithium hydroxide. -3 The mixture (in moles) was reacted at 100-190°C for 3 hours under normal pressure, while distilling off the low-boiling components. Furthermore, the reaction was carried out at 170°C for 3 hours under reduced pressure (-0.050 to -0.10 MPaG), while distilling off the low-boiling components. After the reaction was complete, 1.8 g of dibutyl phosphate (8.57 × 10⁻¹⁰) was added. -3 (mol) was added, and the catalyst was deactivated at atmospheric pressure at 100°C for 2 hours. After catalyst deactivation, simple distillation was carried out under reduced pressure (-0.050 to -0.10 MPaG) at 150 to 200°C for 1 to 2 hours to obtain 240.0 g of carbonate(3) as a yellow liquid (yield: 83.3%).

[0128] (Manufacturing Example 4) A glass separable flask equipped with a rectification column, stirrer, thermometer, and nitrogen inlet tube contains 89.5 g (0.99 mol, purity 98% or higher) of dimethyl carbonate, 254.8 g (1.30 mol, purity 99% or higher) of diethylene glycol monobenzyl ether, and 106.1 mg (4.43 × 10⁶) of lithium hydroxide. -3 The mixture (in moles) was reacted at 100-190°C for 4-5 hours under normal pressure, while distilling off the low-boiling components. Furthermore, the reaction was carried out at 170°C for 2 hours under reduced pressure (-0.050 to -0.10 MPaG), while distilling off the low-boiling components. After the reaction was complete, 1.8 g of dibutyl phosphate (8.85 × 10⁻¹⁴) was added. -3 The catalyst was inactivated at 100°C for 2 hours under atmospheric pressure after adding (molar) of the catalyst. After catalyst inactivation, the reaction mixture was extracted twice with approximately 200 g of pure water. Anhydrous magnesium sulfate was added to the organic layer after extraction, and the mixture was stirred for 10 minutes to dehydrate it. The reaction mixture was filtered under reduced pressure to obtain 240.8 g of carbonate(4) as a pale yellow transparent liquid (yield: 79.2%).

[0129] (Comparative example 1) In a 20 L glass reaction vessel equipped with a rectification column, stirrer, thermometer, and nitrogen inlet tube, 5714.8 g of dimethyl carbonate (63.5 mol, purity 98% or higher), 11039.1 g of 2-ethylhexanol (84.8 mol, purity 99% or higher), and 3.3 g of 28% NaOMe methanol solution (0.02 mol% NaOMe relative to 2-ethylhexanol) were mixed and reacted at 110-120°C for 7-8 hours under atmospheric pressure, while removing low-boiling components by distillation. After the reaction, low-boiling components, including dimethyl carbonate, were removed by distillation under reduced pressure (-0.050 to -0.10 MPaG) at 110-115°C for 5 hours. After removal of the low-boiling components, 121.2 g of activated clay was added, and the catalyst was deactivated at 60°C for 1 hour under atmospheric pressure. After catalyst deactivation, the mixture was filtered under reduced pressure to obtain a colorless, transparent liquid.

[0130] In a 5L glass reaction vessel equipped with a rectification column, stirrer, thermometer, and nitrogen inlet tube, 3599.8g (11.6 mol) of the above colorless liquid, 424.8g (3.59 mol, purity 99% or higher) of 1,6-hexanediol, and 4.1g of 28% NaOMe methanol solution (0.5 mol% NaOMe relative to 1,6-hexanediol) were mixed and reacted at 130-140°C for 4 hours under reduced pressure (-0.050 to -0.10 MPaG) while distilling off 2-ethylhexanol. After distillation, 22.0g of activated clay was added, and the catalyst was deactivated at 50-60°C for 1 hour under atmospheric pressure. After catalyst deactivation, the mixture was filtered under reduced pressure, and the filtrate was added to a 3L glass reaction vessel. The remaining raw materials were removed under reduced pressure (-0.050 to -0.10 MPaG) at 190-200°C. After distillation, 21.0 g of activated clay was added, and the mixture was heated and stirred at 50-60°C under atmospheric pressure for 1 hour. Then, it was filtered under reduced pressure to obtain 1070.1 g of carbonate(5) as a colorless, transparent liquid (yield based on 1,6-hexanediol: 81.0%).

[0131] (Manufacturing Comparison Example 2) A glass separable flask equipped with a rectification column, stirrer, thermometer, and nitrogen inlet tube contains 139.1 g (1.54 mol, purity 98% or higher) of dimethyl carbonate, 232.4 g (2.15 mol, purity 99% or higher) of benzyl alcohol, and 165.8 mg (6.92 × 10⁻¹⁶) of lithium hydroxide. -3The mixture (moles) was mixed and reacted at 100-190°C for 7-8 hours under normal pressure, while removing the low-boiling components by distillation. After the reaction, the low-boiling components, including dimethyl carbonate, were removed by distillation at 100°C for 1 hour under reduced pressure (-0.050 to -0.10 MPaG). After removing the low-boiling components, 117.2 g (0.63 mol, purity 99% or higher) of 1-dodecanol was added and the mixture was reacted at 180°C for 4 hours under reduced pressure (-0.1 MPaG), while removing the low-boiling components by distillation. After the reaction was complete, 3.0 g (14.4 × 10⁻⁶) of dibutyl phosphate was added. -3 (mol) was added, and the catalyst was deactivated at 100°C for 2 hours under atmospheric pressure. After catalyst deactivation, simple distillation was carried out under reduced pressure (-0.050 to -0.10 MPaG) at 150 to 200°C for 4 to 5 hours to obtain 160.5 g of carbonate(6) as a pale yellow transparent liquid (yield based on 1-dodecanol: 56.5%).

[0132] (Manufacturing Comparison Example 3) A glass separable flask equipped with a rectification column, stirrer, thermometer, and nitrogen inlet tube contains 232.2 g (2.58 mol, purity 98% or higher) of dimethyl carbonate, 149.7 g (1.24 mol, purity 99% or higher) of 2-(2-methoxyethoxy)ethanol, and 120.4 mg (5.03 × 10⁶) of lithium hydroxide. -3 The mixture (in moles) was mixed and reacted at 100-130°C for 7 hours under atmospheric pressure, while removing the low-boiling components by distillation. After the reaction, the low-boiling components, including dimethyl carbonate, were removed by distillation at 100°C for 1 hour under reduced pressure (-0.050 to -0.10 MPaG). After removing the low-boiling components, 87.3 g (0.47 moles, purity 99% or higher) of 1-dodecanol was added and reacted at 180°C for 1 hour under reduced pressure (-0.1 MPaG), while removing the low-boiling components by distillation. After the reaction was complete, 1.9 g (9.30 × 10⁻¹⁰) of dibutyl phosphate was added. -3 (mol) was added, and the catalyst was deactivated at atmospheric pressure at 100°C for 2 hours. After catalyst deactivation, simple distillation was carried out under reduced pressure (-0.050 to -0.10 MPaG) at 150 to 200°C for 2 to 3 hours to obtain 151.8 g of carbonate(7) as a colorless, transparent liquid (yield based on 1-dodecanol: 63.5%).

[0133] (Manufacturing Comparison Example 4) A glass separable flask equipped with a rectification column, stirrer, thermometer, and nitrogen inlet tube contains 271.8 g (3.02 mol, purity 98% or higher) of dimethyl carbonate, 138.6 g (1.00 mol, purity 99% or higher) of 2-phenoxyethanol, and 129.2 mg (5.39 × 10⁻¹⁴) of lithium hydroxide. -3 The mixture (in moles) was mixed and reacted at 100-110°C for 2-3 hours under normal pressure, while removing the low-boiling components by distillation. After the reaction, the low-boiling components, including dimethyl carbonate, were removed by distillation at 100°C for 1 hour under reduced pressure (-0.050 to -0.10 MPaG). After removing the low-boiling components, 107.6 g (0.58 moles, purity 99% or higher) of 1-dodecanol was added and the mixture was reacted at 150°C for 1 hour under reduced pressure (-0.1 MPaG), while removing the low-boiling components by distillation. After the reaction was complete, 1.9 g (9.18 × 10⁻¹⁵) of dibutyl phosphate was added. -3 (mol) was added, and the catalyst was deactivated at 100°C for 2 hours under atmospheric pressure. After catalyst deactivation, simple distillation was carried out under reduced pressure (-0.050 to -0.10 MPaG) at 150 to 200°C for 1 to 2 hours to obtain 205.5 g of carbonate(8) as a white solid (yield based on 1-dodecanol: 51.6%).

[0134] <Conditions for mixing> The mixing in the examples and comparative examples was carried out using a test mixer / extruder ("Laboplastmill® KF-70" manufactured by Toyo Seiki Co., Ltd.) under the conditions described for each example.

[0135] <Conditions for injection molding> Injection molding in the examples and comparative examples was performed using a small injection molding machine (Micro-3, manufactured by Meiho Co., Ltd.) under the conditions described for each example.

[0136] [Examples and Comparative Examples]

[0137] (Example 1) Polylactic acid (80 parts by mass) and carbonate (1) (20 parts by mass) obtained in Manufacturing Example 1 were melt-kneaded at 190°C for 5 minutes at 100 rpm to obtain a resin composition. The obtained resin composition was injection-molded at 180°C in an injection molding machine to obtain a dumbbell test specimen (JIS K7161-2: Test specimen type 1BA) with a total length of 78 mm, a chuck width of 5 mm, and a thickness of 2 mm.

[0138] (Example 2) Polylactic acid (80 parts by mass) and carbonate (2) (20 parts by mass) obtained in Manufacturing Example 2 were melt-kneaded at 190°C for 5 minutes at 100 rpm to obtain a resin composition. The obtained resin composition was injection-molded at 180°C in an injection molding machine to obtain a dumbbell test specimen (JIS K7161-2: Test specimen type 1BA) with a total length of 78 mm, a chuck width of 5 mm, and a thickness of 2 mm.

[0139] (Example 3) Polylactic acid (80 parts by mass) and carbonate (3) (20 parts by mass) obtained in Manufacturing Example 3 were melt-kneaded at 190°C for 5 minutes at 100 rpm to obtain a resin composition. The obtained resin composition was injection-molded at 175°C in an injection molding machine to obtain a dumbbell test specimen (JIS K7161-2: Test specimen type 1BA) with a total length of 78 mm, a chuck width of 5 mm, and a thickness of 2 mm.

[0140] (Example 4) Polylactic acid (80 parts by mass) and carbonate (4) (20 parts by mass) obtained in Manufacturing Example 4 were melt-kneaded at 190°C for 5 minutes at 100 rpm to obtain a resin composition. The obtained resin composition was injection-molded at 175°C in an injection molding machine to obtain a dumbbell test specimen (JIS K7161-2: Test specimen type 1BA) with a total length of 78 mm, a chuck width of 5 mm, and a thickness of 2 mm.

[0141] (Comparative Example 1) Polylactic acid (80 parts by mass) and carbonate (5) (20 parts by mass) obtained in Comparative Example 1 were melt-kneaded at 190°C for 5 minutes at 100 rpm to obtain a resin composition. The obtained resin composition was injection-molded at 175°C in an injection molding machine to obtain a dumbbell test specimen (JIS K7161-2: Test specimen type 1BA) with a total length of 78 mm, a chuck width of 5 mm, and a thickness of 3 mm.

[0142] (Comparative Example 2) Polylactic acid (80 parts by mass) and carbonate (6) (20 parts by mass) obtained in Comparative Example 2 were melt-kneaded at 190°C for 5 minutes at 100 rpm to obtain a resin composition. The obtained resin composition was injection-molded at 180°C in an injection molding machine to obtain a dumbbell test specimen (JIS K7161-2: Test specimen type 1BA) with a total length of 78 mm, a chuck width of 5 mm, and a thickness of 3 mm.

[0143] (Comparative Example 3) Polylactic acid (80 parts by mass) and carbonate (7) (20 parts by mass) obtained in Comparative Example 3 were melt-kneaded at 190°C for 5 minutes at 100 rpm to obtain a resin composition. The obtained resin composition was injection-molded at 175°C in an injection molding machine to obtain a dumbbell test specimen (JIS K7161-2: Test specimen type 1BA) with a total length of 78 mm, a chuck width of 5 mm, and a thickness of 2 mm.

[0144] (Comparative Example 4) Polylactic acid (80 parts by mass) and carbonate (8) (20 parts by mass) obtained in Comparative Example 4 were melt-kneaded at 190°C for 5 minutes at 100 rpm to obtain a resin composition. The obtained resin composition was injection-molded at 185°C in an injection molding machine to obtain a dumbbell test specimen (JIS K7161-2: Test specimen type 1BA) with a total length of 78 mm, a chuck width of 5 mm, and a thickness of 2 mm.

[0145] The compositions of the examples and comparative examples were measured and evaluated by the following methods.

[0146] (Evaluation of plasticity) 1BA dumbbell test specimens were prepared in accordance with JIS K7161-2, and the tensile modulus (MPa) and tensile elongation (%) were measured. Dumbbell thickness: 2mm (Examples 3, 4), 3mm (Comparative Examples 1, 2) Chuck spacing: 58mm Load cell: 1kN Test speed: 50 mm / min Test specimen type: N=5

[0147] (Evaluation of bleed resistance) A 1BA dumbbell test specimen was prepared in accordance with JIS K7161-2, its weight was measured, and it was aged in a constant temperature dryer at 50°C for 50 hours. After that, the test specimen was removed, its surface condition was visually observed, its weight was measured, and it was evaluated based on the weight loss rate (%). Visual observation Excellent: No plasticizer bleeding. Good: Slight plasticizer bleeding present. Defect: Plasticizer bleeding present. 《Weight reduction rate》 Excellent: Weight loss less than 0.50% Good: Weight loss less than 0.50-1.0% Defective: Weight loss of 1.0% or more

[0148] (Evaluation of water resistance) A 1BA dumbbell test specimen was prepared in accordance with JIS K7161-2, its weight was measured, and it was immersed in water at room temperature for 48 hours. After that, the test specimen was removed, the adhering water was thoroughly wiped off, and it was dried in a vacuum dryer for 8 hours. The weight was then measured, and the weight change rate (%) was used for evaluation. 《Weight reduction rate》 Excellent: Weight change less than 0.50% Good: Weight change of less than 0.50-1.0% Defective: Weight change of 1.0% or more

[0149] (Transparency assessment) 1BA dumbbell test specimens were prepared in accordance with JIS K7161-2, and the transparency was evaluated by visual inspection of the test specimens. Visual observation Excellent: Transparent Good: Translucent Defective: Opaque

[0150] (Evaluation of biodegradability) An inorganic salt medium was prepared according to OECD 301F, and one capsule of BOD Seed (manufactured by Kanto Chemical Co., Ltd.) was added to 500 mL of the inorganic salt medium as a seed source to prepare the seed solution. 10 mL of the seed solution was diluted to 1 L with the inorganic salt medium to prepare the seed dilution, and a carbonate compound was added to this seed dilution to a concentration of 100 mg / L to prepare the test solution. In a closed BOD test system, the test was performed in a low-temperature constant-temperature bath at 22 ± 1 °C for 28 days, and the biodegradability was evaluated by relatively comparing the biodegradability of the control sample and the biodegradability of the carbonate compound at the 28th day. Aniline and DAIFATTY-101 (manufactured by Daihachi Chemical Co., Ltd.) were used as control samples. The degree of biodegradability (%) and biodegradability of each sample were evaluated using the following formula. Biodegradability (%) = BOD of the sample during the test period (mg / mg) / ThOD of the sample (mg / mg) × 100 (BOD: Biochemical Oxygen Demand, ThOD: Theoretical Oxygen Demand) Relative comparison = Biodegradation rate of carbonate compound (%) / Biodegradation rate of control sample (%) Yes: Biodegradable (relative comparison of 0.6 or higher) None: Not biodegradable (relative comparison less than 0.6)

[0151] [Table 1]

[0152] Table 1 shows the following when comparing each example and each comparative example. It was found that by adding a carbonate represented by general formula (1) to a resin, plasticity can be imparted to the resin, resulting in a resin composition with excellent stability, such as resistance to bleeding and water resistance, of the molded product obtained from the resin composition. Therefore, it was found that a carbonate represented by general formula (1) can be suitably used as a plasticizer.

Claims

1. A carbonate compound represented by the following general formula (1). 【Chemistry 14】 (In the formula, R １ and R ２ R represents a branched alkyl group having 7 to 12 carbon atoms, which may be the same or different from each other and may be mediated by an oxygen atom, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom and include at least one of an aryl group and a cycloalkyl group. ３ represents a divalent hydrocarbon group with 4 to 8 carbon atoms mediated by an oxygen atom, and m represents 0 to 10. When m is 0, R １ and R ２ At least one of them is a hydrocarbon group mediated by an oxygen atom, and when m is 0, R １ and R ２ (Except when it simultaneously becomes a phenoxyethyl group.)

2. In general formula (1), R １ and R ２ may be the same or different from each other, and each represents a branched alkyl group having 7 to 12 carbon atoms which may be intervened by an oxygen atom, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms which may be intervened by an oxygen atom and contains at least one of an aryl group and a cycloalkyl group. The carbonate compound according to claim 1.

3. In general formula (1), R １ and R ２ The carbonate compound according to claim 1 or 2, wherein (the group) may be the same or different from each other, and represents a branched alkyl group having 7 to 12 carbon atoms mediated by an oxygen atom, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom and include at least one of an aryl group and a cycloalkyl group.

4. The carbonate compound according to claim 1, which exhibits biodegradability.

5. A plasticizer whose main component is a carbonate compound represented by the following general formula (1). 【Chemistry 15】 (In the formula, R １ and R ２ R represents a branched alkyl group having 7 to 12 carbon atoms, which may be the same or different from each other and may be mediated by an oxygen atom, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom and include at least one of an aryl group and a cycloalkyl group. ３ represents a divalent hydrocarbon group with 4 to 8 carbon atoms mediated by an oxygen atom, and m represents 0 to 10. When m is 0, R １ and R ２ At least one of them is a hydrocarbon group mediated by an oxygen atom, and when m is 0, R １ and R ２ (Except when it simultaneously becomes a phenoxyethyl group.)

6. In general formula (1), R １ and R ２ The plasticizer according to claim 5, wherein is a branched alkyl group having 7 to 12 carbon atoms, which may be the same or different from each other and may be mediated by an oxygen atom, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom and include at least one of an aryl group and a cycloalkyl group.

7. In general formula (1), R １ and R ２ The plasticizer according to claim 5 or 6, wherein (the group) may be the same or different from each other, and represents a branched alkyl group having 7 to 12 carbon atoms mediated by an oxygen atom, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom and include at least one of an aryl group and a cycloalkyl group.

8. The plasticizer according to claim 5, wherein the carbonate compound represented by general formula (1) exhibits biodegradability.

9. A resin composition comprising a resin and a carbonate compound represented by the following general formula (1). 【Chemistry 16】 (In the formula, R １ and R ２ R represents a branched alkyl group having 7 to 12 carbon atoms, which may be the same or different from each other and may be mediated by an oxygen atom, or a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom and include at least one of an aryl group and a cycloalkyl group. ３ represents a divalent hydrocarbon group with 4 to 8 carbon atoms mediated by an oxygen atom, and m represents 0 to 10. When m is 0, R １ and R ２ At least one of them is a hydrocarbon group mediated by an oxygen atom, and when m is 0, R １ and R ２ (Except when it simultaneously becomes a phenoxyethyl group.)

10. In general formula (1), R １ and R ２ The resin composition according to claim 9, wherein is a branched alkyl group having 7 to 12 carbon atoms, which may be the same or different from each other and may be mediated by an oxygen atom, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom and include at least one of an aryl group and a cycloalkyl group.

11. In general formula (1), R １ and R ２ The resin composition according to claim 9 or 10, wherein (the group) may be the same or different from each other, and represents a branched alkyl group having 7 to 12 carbon atoms mediated by an oxygen atom, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, which may be mediated by an oxygen atom and include at least one of an aryl group and a cycloalkyl group.

12. The resin composition according to claim 9, wherein the carbonate compound represented by general formula (1) exhibits biodegradability.

13. The resin composition according to claim 9, wherein the resin is a polyester resin.

14. The resin composition according to claim 13, wherein the resin is polylactic acid.

15. A molded article comprising the resin composition described in claim 9.

16. A vehicle equipped with the molded product described in claim 15.

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