Polyester carbonate and molded article

Abstract

There has been a demand for resin compositions that are highly biodegradable and have excellent properties such as thermal stability and hydrolysis resistance.　Known biodegradable resins have not necessarily been recognized as having these excellent properties. For example, no resin has been developed that is not only biodegradable but also has excellent properties such as thermal stability, hydrolysis resistance, and strength.　Therefore, there is a demand for resins that are highly biodegradable and have excellent properties such as thermal stability, hydrolysis resistance, and strength.　The abovementioned problem is solved by the following polyester carbonate.　A polyester carbonate comprising: a polyester having structural units derived from an aliphatic diol and an aliphatic dicarboxylic acid; and a structural unit derived from a carbonic acid diester, the acid value of the polyester carbonate being 0.01-0.24 mg KOH / g, and the amount of OH terminals of the polyester carbonate being 10-500 ppm.

Description

Polyester carbonate and molded articles

[0001] This invention relates to polyester carbonates and the like, and more particularly to polyester carbonates with excellent biodegradability, and molded articles containing them.

[0002] Conventionally, biodegradable resins such as polyester carbonate have been used in a wide range of fields (for example, in Patent Documents 1 to 3 below).

[0003] Patent Document 1: Japanese Unexamined Patent Publication No. 7-053695 Patent Document 2: Japanese Unexamined Patent Publication No. 8-301999 Patent Document 3: Japanese Unexamined Patent Publication No. 2004-359731

[0004] Conventional biodegradable resins have not always demonstrated superior properties. For example, resins that are particularly excellent in biodegradability as well as in properties such as thermal stability, hydrolysis resistance, and strength have not yet been realized. Therefore, there has been a demand for resins that possess high biodegradability and are also excellent in various properties including thermal stability, hydrolysis resistance, and strength.

[0005] The present invention provides the following polyester carbonates, molded articles, etc. [1] A polyester carbonate (PEC) having a polyester (PE) having structural units derived from an aliphatic diol and an aliphatic dicarboxylic acid, and structural units derived from a diester carbonate, wherein the acid value of the polyester carbonate is 0.01 to 0.24 mgKOH / g, and the amount of OH terminals of the polyester carbonate is 10 to 500 ppm. [2] The polyester carbonate according to [1], wherein the aliphatic diol and the aliphatic dicarboxylic acid have 20 or fewer carbon atoms. [3] The polyester carbonate according to [1] or [2], for example, the polyester carbonate according to [2], wherein the aliphatic diol contains 1,4-butanediol and the aliphatic dicarboxylic acid contains succinic acid. [4] The polyester carbonate according to any of [1] to [3], for example, the polyester carbonate according to [1], wherein the diester carbonate is diaryl carbonate. [5] The polyester carbonate according to [4], wherein the diaryl carbonate comprises diphenyl carbonate. [6] The polyester carbonate according to any one of [1] to [5], for example, the one described in [1], wherein the molecular weight retention rate in a heat retention test in which the polyester carbonate is heated by being left at 230°C for 30 minutes is 50% or more, and this molecular weight retention rate is the ratio of the weight-average molecular weight after heating to the weight-average molecular weight before heating. [7] The polyester carbonate according to any one of [1] to [6], for example, the one described in [1], wherein the molecular weight retention rate in a hydrolysis test in which the polyester carbonate is immersed in pure water at 58°C is 60% or more, and this molecular weight retention rate is the ratio of the weight-average molecular weight after immersion to the weight-average molecular weight before immersion. [8] The Charpy strength value is 15 (kJ / cm²). ２) or above, or the elastic modulus value in the tensile test is 300 MPa or more, any of the above [1] to [7], for example, the polyester carbonate described in [1] above. [9] The polyester carbonate described in any of the above [1] to [8], for example, the polyester carbonate described in [1] above, wherein the weight-average molecular weight of the polyester is 1,000 to 20,000.

[10] The polyester carbonate described in any of the above [1] to [9], for example, the polyester carbonate described in [1] above, wherein at least one of the raw material aliphatic diol and the aliphatic dicarboxylic acid is derived from biomass.

[11] The raw material diester carbonate is CO ２ The origin is any of the above [1] to

[10] , for example, the polyester carbonate described in [1] above.

[0006]

[12] A method for producing a polyester carbonate resin according to any of [1] to

[11] above, for example, the method described in [1] above, wherein the relationship between the amount of OH (mol) of the polyester (PE) and the amount of diphenyl carbonate (mol) is represented by the following formula (1): 1.00 < [Diphenyl carbonate (mol)] / [Amount of OH of PE (mol) × 1 / 2] < 1.20 ... Formula (1)

[13] A method for producing a polyester carbonate according to any of [1] to

[11] above, for example, the method described in [1] above, wherein the aliphatic diol or aliphatic dicarboxylic acid, which is the raw material, has an impurity content of 5000 μg / ml or less.

[0007]

[14] A molded article comprising any of [1] to

[11] above, for example, the polyester carbonate described in [1] above.

[15] A biodegradable agricultural material comprising any of [1] to

[11] above, for example, the polyester carbonate described in [1] above.

[16] A biodegradable fishing material comprising any of [1] to

[11] above, for example, the polyester carbonate described in [1] above.

[17] A biodegradable civil engineering material comprising any of [1] to

[11] above, for example, the polyester carbonate described in [1] above.

[0008] The polyester carbonate of the present invention has excellent biodegradability and also excellent properties such as thermal stability and hydrolysis resistance. Further, according to the present invention, there are provided a method for producing a polyester carbonate having excellent properties, a molded article containing such a polyester carbonate, and the like that can be used in a wide range of applications such as agriculture, fishery, and civil engineering.

[0009] It is an NMR chart of the polyester (PE) obtained in Production Example 1. It is an NMR chart of the polyester carbonate (PEC) obtained in Example 1. It is a partially enlarged view of the NMR chart in FIG. 2. It is a partially enlarged view of a region different from FIG. 3 in the NMR chart of FIG. 2.

[0010] The polyester carbonate of the present invention contains a polyester moiety having structural units derived from an aliphatic diol and an aliphatic dicarboxylic acid, and a structural unit derived from a dicarbonate ester that bonds the polyester moieties together. In the polyester carbonate of the present invention, the acid value is in the range of 0.01 to 0.24 mgKOH / g, and the OH end group amount is 10 to 500 ppm. Hereinafter, preferred embodiments of the present invention will be described in detail.

[0011] <1. Components of Polyester Carbonate> The polyester carbonate resin of the present invention contains at least a moiety derived from a polyester which is a prepolymer and a structural unit derived from a dicarbonate ester that links the polyester moieties at the ends.

[0012] 1-1. Components of Polyester The polyester moiety contained in the polyester carbonate contains at least structural units derived from an aliphatic diol and an aliphatic dicarboxylic acid. That is, the aliphatic diol and the aliphatic dicarboxylic acid are each used as a monomer for polymerizing the polyester.

[0013] Although the position of the hydroxyl group in the aliphatic diol is not particularly limited, those having hydroxyl groups at both ends are preferred. The aliphatic diol is represented by, for example, the following general formula (I). HO—Ra—OH... (I) As the aliphatic diol, those having 20 or less carbon atoms are preferred. In the general formula (I), Ra is preferably an alkylene group having 1 to 20 carbon atoms which may have a substituent. Although Ra in the formula (I) may be either a linear or branched alkylene group, it is preferably linear. The carbon number of the aliphatic diol is preferably 1 to 16, more preferably 2 to 12 or 2 to 16, even more preferably 3 to 8 or 3 to 10, and particularly preferably 3 to 6 or 4 to 8.

[0014] Ra in the formula (I) is represented by, for example, (CH ２ )n, and n is preferably an integer of 1 to 16. Further, Ra may be an alkylene group having 2 to 12 or 2 to 16 carbon atoms, preferably an alkylene group having 3 to 8 or 3 to 10 carbon atoms, and more preferably an alkylene group having 3 to 6 or 4 to 8 carbon atoms. In the diol compound represented by the formula (I), Ra is preferably formed only of carbon atoms that do not contain oxygen atoms, nitrogen atoms, etc., except for substituents. When Ra is an alkylene group having a substituent described later, the carbon number range described above does not include the carbon number of the substituent.

[0015] Preferred specific examples of the aliphatic diol as the monomer compound include ethylene glycol, propanediol, butanediol such as 1,4 - butanediol, pentanediol such as 1,5 - pentanediol, hexanediol, octanediol, cyclohexanedimethanol, etc. Among these, propanediol, butanediol such as 1,4 - butanediol, pentanediol such as 1,5 - pentanediol, etc. are more preferred, and butanediol such as 1,4 - butanediol is even more preferred. As the aliphatic diol for polymerizing the polyester, a single compound may be used, or two or more kinds may be used in combination.

[0016] In the aliphatic dicarboxylic acid for polymerizing polyester, although the position of the carboxyl group is not particularly limited, those having carboxyl groups at both ends are preferred. The aliphatic dicarboxylic acid is represented by, for example, the following general formula (II). R １ OOC−Rb−COOR ２ ... (II) As the aliphatic dicarboxylic acid, those having 20 or less carbon atoms are preferred. In the general formula (II), Rb is preferably an alkylene group having 1 to 20 carbon atoms which may have a substituent. Rb in the formula (II) may be either a linear or branched alkylene group, but is preferably linear. The number of carbon atoms of the aliphatic dicarboxylic acid is preferably 1 to 16, more preferably 2 to 12 or 2 to 16, still more preferably 3 to 8 or 3 to 10, and particularly preferably 3 to 6 or 4 to 8.

[0017] Rb in the formula (II) is represented by, for example, (CH ２ )m, and m is preferably an integer of 2 to 16. Further, Rb may be an alkylene group having 2 to 12, 2 to 16, etc. carbon atoms, preferably an alkylene group having 3 to 8 or 3 to 10 carbon atoms, and more preferably an alkylene group having 3 to 6 or 4 to 8 carbon atoms. In the aliphatic dicarboxylic acid represented by the formula (II), Rb is preferably formed only of carbon atoms excluding substituents and not containing oxygen atoms, nitrogen atoms, etc. When Rb is an alkylene group having a substituent described later, the number of carbon atoms of the substituent is not included in the above carbon number range.

[0018] Further, R １ and R ２ are each independently selected from a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and are preferably selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. R １ and R ２Preferably, each is independently a hydrogen atom or a C1-C3 alkyl group that may contain a substituent, more preferably each is independently a hydrogen atom or a C1 or C2 alkyl group that may contain a substituent, and even more preferably each is independently a hydrogen atom or a methyl group. Also, the above R １ and R ２ The substituents can be independently selected from halogens, hydroxyl groups, cyano groups, C1-C5 alkenyl groups, C6-C12 aryl groups, and the like. These substituents are preferably halogens, hydroxyl groups, cyano groups, etc. Note that R １ or R ２ If the alkyl group has substituents, the carbon number of the substituents is not included in the above-mentioned range of carbon numbers.

[0019] The monomer compound of formula (II) may be a dicarboxylic acid compound, a monoester compound, or a diester compound, or a mixture thereof. Preferred specific examples of monomer compounds represented by general formula (II) include compounds such as succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, and dodecanoic acid, or derivatives such as anhydrides and esters thereof. Of these, succinic acid, glutaric acid, adipic acid, and their derivatives are more preferred, and succinic acid and succinic acid derivatives are even more preferred. A single compound may be used as the aliphatic dicarboxylic acid for polymerizing the polyester, or two or more may be used in combination.

[0020] The substituents in Ra and Rb described above can each be independently selected from halogens, hydroxyl groups, cyano groups, C1-C5 alkenyl groups, etc. These substituents are preferably halogens, hydroxyl groups, cyano groups, etc. Also, the R described above... １ and R ２ The substituents can be independently selected from halogens, hydroxyl groups, cyano groups, C1-C5 alkenyl groups, C6-C12 aryl groups, and the like. These substituents are preferably halogens, hydroxyl groups, cyano groups, and the like.

[0021] In polyesters, it is preferable that constituent units derived from aliphatic diols and constituent units derived from aliphatic dicarboxylic acids are arranged alternately in substantially equal amounts (moles).

[0022] 1-2. Diester carbonates Diester carbonates are used to bond polyesters together and form carbonyl (CO) moieties. There are no particular limitations on the type of diester carbonate; dialkyl carbonates, monoalkyl monoaryl carbonates, diaryl carbonates, etc., are used, but diaryl carbonates are preferred.

[0023] Examples of diaryl carbonates include bisaryl carbonates such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Of these, diphenyl carbonate is more preferred. A single compound may be used as the diester carbonate, or two or more may be used in combination.

[0024] For the formation of polyester, it is preferable to use a slightly excess amount of diester carbonate relative to the total number of moles of terminal hydroxyl groups of polyester. Specifically, it is preferable to use more than 1.00 times and less than 1.20 times the total number of moles of terminal hydroxyl groups of polyester (the number of moles of one of the terminal hydroxyl groups at both ends of the polyester). The amount of diester carbonate used (in moles) is more preferably 1.002 to 1.150 times the total number of moles of terminal hydroxyl groups of polyester, even more preferably 1.005 to 1.100 times the total number of moles of terminal hydroxyl groups of polyester, and particularly preferably 1.008 to 1.050 times, for example 1.010 times, the total number of moles of terminal hydroxyl groups of polyester.

[0025] 1-3. Polyester Carbonate Polyester carbonate is produced by polymerization of polyester moieties by a manufacturing method described in detail later. In polyester carbonate, multiple polyester moieties are linked together by carbonyl structural units formed by diester carbonate. Therefore, polyester carbonate contains at least structural units derived from aliphatic diols and aliphatic dicarboxylic acids, and structural units derived from diester carbonate.

[0026] Polyester carbonate is preferably manufactured from biomass-derived raw materials. Biomass-derived raw materials are so-called biomass resources, which are biologically derived and renewable organic resources, excluding fossil resources. In other words, biomass-derived raw materials are organic matter produced by organisms through photosynthesis from water and carbon dioxide using solar energy, and are sustainably renewable resources. In the case of polyester carbonate, it is preferable that at least one of the raw material substances, aliphatic diols and aliphatic dicarboxylic acids, is of biomass origin. For example, aliphatic dicarboxylic acids obtained by fermenting biomass resources with microorganisms, and aliphatic diols obtained by reducing such aliphatic dicarboxylic acids, are preferred as raw materials for polyester carbonate.

[0027] Regarding diester carbonates, which are raw materials for polyester carbonates, it is preferable to use those obtained by a manufacturing method that minimizes environmental impact, even if they are not biomass-derived. For example, it is preferable to use diester carbonates obtained from dialkyl carbonates produced from carbon dioxide and alcohol as a precursor for polyester carbonates. In other words, from the viewpoint of reducing environmental impact, it is preferable to use diester carbonates derived from carbon dioxide as a raw material for polyester carbonates. In particular, in recent years, there has been growing concern about global warming and efforts are being made to reduce greenhouse gas emissions, and carbon dioxide is estimated to have the greatest impact among anthropogenically emitted greenhouse gases. For this reason, the development of countermeasures technologies to reduce carbon dioxide is being actively carried out in various places, and several attempts have been proposed to convert carbon dioxide emitted into the atmosphere into useful substances. Thus, in order to convert carbon dioxide into other substances and utilize it while reducing the environmental impact, it is desirable to synthesize diester carbonates from carbon dioxide and use them as a raw material for polyester carbonates.

[0028] 1-4. Secondary Components Secondary components may be added to polyester carbonate. For example, when polyester carbonate is used as a raw material for molded articles, etc., as described later, resins other than polyester carbonate, such as thermoplastic resins, and other appropriate additives may be added depending on the application. In a polyester carbonate resin composition to which secondary components have been added in this way, it is preferable that the composition contains, for example, 20 to less than 100% by mass or 25 to 100% by mass of polyester carbonate based on the total weight of the resin composition. The polyester carbonate content in the resin composition is preferably 20 to 85% by mass or 25 to 80% by mass, more preferably 25 to 70% by mass or 30 to 75% by mass, and particularly preferably 30 to 70% by mass or 33 to 75% by mass, based on the total weight of the resin composition.

[0029] Inorganic fillers are examples of additives that may be included in polyester carbonate resin compositions. Examples of inorganic fillers include talc, anhydrous silica, mica, vermiculite, titanium dioxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon, wollastonite, calcined perlite, silicates such as calcium silicate and sodium silicate, hydroxides such as aluminum oxide, magnesium carbonate, and calcium hydroxide, salts such as ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, and barium sulfate, smectite minerals such as montmorillonite, hectorite, fluoride hectorite, and saponite, and glass fibers. Preferred specific examples of inorganic fillers include talc, mica, and wollastonite. The addition of a small amount of inorganic filler may improve the gas barrier properties of the resin composition.

[0030] In the polyester carbonate resin composition, the inorganic filler is contained in an amount of, for example, 20 to 60% by mass or 30 to 50% by mass, based on the total weight of the resin composition. Preferably, the inorganic filler content in the resin composition is 30 to 45% by mass, more preferably 30 to 40% by mass, and even more preferably 32 to 40% by mass, based on the total weight of the resin composition.

[0031] Furthermore, the polyester carbonate resin composition may contain polylactic acid, for example, 0 to 50% by mass of polylactic acid based on the total weight of the resin composition. The polylactic acid content in the resin composition is preferably 3 to 40% by mass or 5 to 45% by mass, more preferably 5 to 40% by mass or 5 to 35% by mass, and even more preferably 10 to 35% by mass, based on the total weight of the resin composition.

[0032] The polylactic acid that may be included in the polyester carbonate resin composition is a polymer composed substantially only of monomer units derived from L-lactic acid and / or D-lactic acid. Furthermore, the polylactic acid may also contain monomer units other than L-lactic acid and D-lactic acid, to the extent that it does not impair the effects of the resin composition.

[0033] Any known polymerization method can be used to produce polylactic acid. The most representative method is the ring-opening polymerization of lactide, a cyclic dimer of lactic acid anhydride (lactide method), but direct condensation polymerization of lactic acid is also acceptable. Furthermore, the molecular weight of polylactic acid is preferably in the range of 50,000 to 1,000,000 by weight average molecular weight.

[0034] The polyester carbonate resin composition may contain additives other than those mentioned above. For example, the resin composition may contain mold release agents, antioxidants, etc., and may not contain phosphorus compounds that may be included as flame retardants, etc.

[0035] The polyester carbonate resin composition preferably contains an antioxidant as an additive. While commercially available antioxidants can be used, it is preferable that the composition contains at least one of, for example, an acid-phenol antioxidant and a phosphite-based antioxidant.

[0036] As phenolic antioxidants, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine e-2,4,6(1H,3H,5H)-trione, 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol, ocladecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, Examples include pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxospiro[5.5]undecane, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and preferably pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].Phosphate antioxidants include 2-ethylhexyldiphenyl phosphite, isodecyldiphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxy-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,2'-methylenbis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, and tri Examples include s(2,4-ditert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra-C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and preferably 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. As an antioxidant, one of the above types may be used alone, or a mixture of two or more types may be used.

[0037] The amount of antioxidant added is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, based on the total mass of the polyester carbonate resin composition. Furthermore, the amount of antioxidant added based on the total mass of the resin composition is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less. The polyester carbonate resin composition may contain only one type of antioxidant or two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0038] The polyester carbonate resin composition preferably contains a release agent as an additive. Examples of release agents include ester compounds, such as glycerin fatty acid esters such as mono- and diglycerides of glycerin fatty acids, glycol fatty acid esters such as propylene glycol fatty acid esters and sorbitan fatty acid esters, higher alcohol fatty acid esters, and full or mono fatty acid esters of aliphatic polyhydric alcohols and aliphatic carboxylic acids. When using an ester of aliphatic polyhydric alcohol and an aliphatic carboxylic acid as a release agent, monoesters, full esters, etc., can all be used, but other than full esters such as monoesters may also be used.

[0039] Specific examples of release agents include the following: sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, and sorbitan caprylate; propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate; higher alcohol fatty acid esters such as stearyl stearate; glycerin monohydroxystearate, glycerin monooleate, glycerin monobehenate, glycerin monocaprylate, glycerin monocaprate, and glycerin mono-hydroxystearate, glycerin monooleate, glycerin monobehenate, glycerin monocaprylate, and glycerin mono-caprate. Examples include monoglycerides such as monolaurate; mono-diglycerides such as glycerin mono-distearate, glycerin mono-distearate, glycerin mono-diolate; glycerin fatty acid ester monoglycerides such as glycerin diacetone monolaurate; glycerin fatty acid ester organic acid monoglycerides such as citrate fatty acid monoglyceride, succinate fatty acid monoglyceride, and diacetyltartrate fatty acid monoglyceride; and polyglycerin fatty acid esters such as diglycerin stearate, diglycerin laurate, diglycerin oleate, diglycerin monostearate, diglycerin monolaurate, diglycerin monomyristate, diglycerin monooleate, tetraglycerin stearate, decaglycerin laurate, decaglycerin oleate, and polyglycerin polyricinolate.

[0040] The proportion of the release agent added is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, based on the total mass of the polyester carbonate resin composition. Furthermore, the proportion of the release agent added based on the total mass of the resin composition is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less. The resin composition may contain only one type of release agent or two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0041] The polyester carbonate resin composition may contain additives other than the antioxidants and release agents mentioned above. For example, additives that the resin composition may contain include compounding agents, catalyst deactivators, heat stabilizers, plasticizers, fillers, UV absorbers, rust inhibitors, dispersants, defoamers, leveling agents, flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, clearing agents (specifically, sorbitol derivatives, hydroxy fatty acid amides, triaminobenzene compounds, nonitol compounds, various celluloses, etc.), starch (specifically, corn starch, waxy corn starch, High-amylose corn starch, wheat starch, rice starch, potato starch, sweet potato starch, tapioca starch, pea starch, etc.), light-resistant agents (specifically, bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl) ester decandioate, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl) -4-hydroxyphenyl]methyl]butylmalonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-ter Examples include hindered amine-based stabilizers such as t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine and poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], and end-cap encapsulants.

[0042] Examples of nucleating agents (crystal nucleating agents) and antiblocking agents that may be included in the polyester carbonate resin composition include talc, mica, calcium carbonate, and boron nitride. Calcium carbonate is a preferred specific example of a nucleating agent and antiblocking agent. Furthermore, the same additive, such as talc or mica, can be used in combination as both a nucleating agent and an inorganic filler. The addition of small amounts of nucleating agents and antiblocking agents can be expected to improve the properties of the resin composition.

[0043] The addition ratio of the nucleating agent and antiblocking agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more, based on the total mass of the resin composition. Furthermore, the addition ratio of the nucleating agent and antiblocking agent is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less, based on the total mass of the resin composition.

[0044] The total mass of all additives contained in the resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 3% by mass or less or 2% by mass or less, based on the total mass of the polyester carbonate resin composition.

[0045] <2. Polyester Carbonate> The properties of polyester carbonate will be described below. 2-1. Properties of Polyester The weight-average molecular weight (Mw) of the polyester contained in polyester carbonate is preferably 1,000 to 20,000, more preferably 1,500 to 18,000, even more preferably 2,000 to 15,000, and particularly preferably 2,500 to 12,000. The number-average molecular weight (Mn) of the polyester contained in polyester carbonate is preferably 500 to 10,000, more preferably 600 to 8,000, even more preferably 800 to 6,000, and particularly preferably 1,000 to 5,500.

[0046] In polyester used to form polyester carbonate, the amount of terminal hydroxyl groups (OH amount or OH terminal amount), measured by the method described in detail later, is preferably 0.10 to 10.0 (weight%), more preferably 0.30 to 8.00 (weight%), even more preferably 0.50 to 6.00 (weight%), and particularly preferably 1.00 to 4.00 (weight%), based on the weight of the polyester. The amount of terminal hydroxyl groups (OH amount) in polyester is preferably 0.01 to 1.00 (mol / g), more preferably 0.02 to 0.60 (mol / g), even more preferably 0.04 to 0.40 (mol / g), and particularly preferably 0.05 to 0.25 (mol / g), based on the weight of the polyester. Furthermore, when the amount of terminal hydroxyl groups in polyester is expressed as a neutralization value based on the weight of polyester, it is preferably 10 to 300 (mg KOH / g), more preferably 15 to 250 (mg KOH / g), even more preferably 20 to 200 (mg KOH / g), and particularly preferably 30 to 150 (mg KOH / g).

[0047] In polyesters for polyester carbonate formation, the acid value, as measured by the method described in detail later, is preferably 0.10 to 2.00 (mg KOH / g), more preferably 0.20 to 1.50 (mg KOH / g), even more preferably 0.30 to 1.20 (mg KOH / g), and particularly preferably 0.40 to 1.00 (mg KOH / g).

[0048] In the polyester used to form polyester carbonates, the intrinsic viscosity (η), measured by the method described in detail later, is preferably 0.02 to 0.60 (dl / g), more preferably 0.03 to 0.40 (dl / g), even more preferably 0.05 to 0.30 (dl / g), more preferably 0.07 to 0.20 (dl / g), and particularly preferably 0.08 to 0.19 (dl / g).

[0049] 2-2. Properties of Polyester Carbonate In polyester carbonate, the amount of terminal hydroxyl groups (OH amount or OH terminal amount), measured by the method described in detail later, is preferably 10 to 500 ppm (ppm by weight), more preferably 40 to 450 ppm (ppm by weight), even more preferably 60 to 400 ppm (ppm by weight), and particularly preferably 80 to 380 ppm (ppm by weight) or 100 to 400 ppm (ppm by weight), based on the weight of the polyester carbonate. Furthermore, in polyester carbonate, the amount of terminal hydroxyl groups (OH amount or OH terminal amount), measured by the method described in detail later, is preferably 0.01 to 0.24 (mg KOH / g), more preferably 0.03 to 0.22 (mg KOH / g), even more preferably 0.05 to 0.20 (mg KOH / g), and particularly preferably 0.06 to 0.18 (mg KOH / g) or 0.08 to 0.20 (mg KOH / g), based on the weight of the polyester carbonate.

[0050] In polyester carbonate, the amount of phenyl terminals, as measured by the method described in detail later, is preferably 500 ppm to 6000 ppm, more preferably 1000 ppm to 5000 ppm, and even more preferably 1200 ppm to 4200 ppm or 1500 ppm to 4500 ppm.

[0051] The weight-average molecular weight (Mw) of the polyester carbonate is, for example, 10,000 to 500,000, preferably 30,000 to 450,000 or 40,000 to 500,000, more preferably 50,000 to 400,000 or 60,000 to 350,000, even more preferably 70,000 to 35,000 or 80,000 to 350,000, and particularly preferably 100,000 to 300,000, 150,000 to 270,000, 160,000 to 250,000 or 180,000 to 230,000. Furthermore, the quantity-average molecular weight (Mn) of the polyester carbonate is, for example, 6,000 to 280,000, preferably 18,000 to 250,000 or 20,000 to 270,000, more preferably 30,000 to 220,000 or 32,000 to 200,000, even more preferably 36,000 to 180,000 or 42,000 to 200,000, and particularly preferably 60,000 to 180,000, 70,000 to 160,000, 80,000 to 140,000 or 90,000 to 120,000.

[0052] The carbonate bond content (mol%) of polyester carbonate is, for example, 1.0 to 40 mol%, preferably 2.0 to 30 mol%, more preferably 3.0 to 25 mol%, even more preferably 4.0 to 20 mol%, and particularly preferably 5.0 to 18 mol%. From the viewpoint of biodegradability, moldability, and heat resistance, it is preferable for polyester carbonate to have a carbonate bond content (mol%) within this range.

[0053] In polyester carbonates, the acid value, as measured by the method described in detail later, is preferably 0.01 to 1.00 (mg KOH / g), more preferably 0.03 to 0.50 (mg KOH / g), even more preferably 0.05 to 0.3 (mg KOH / g), and particularly preferably 0.06 to 0.24 (mg KOH / g), 0.07 to 0.21 (mg KOH / g), or 0.08 to 0.20 (mg KOH / g).

[0054] In the heat retention test, which involves heating by retaining the material at 230°C for 30 minutes, the molecular weight retention rate of the polyester carbonate, i.e., the ratio of the weight-average molecular weight after heating to the weight-average molecular weight before heating, is preferably 50% or more. Furthermore, the range of the molecular weight retention rate in the heat retention test is more preferably 55% or more, even more preferably 60% or more, and particularly preferably 64% or more or 65% or more.

[0055] In the hydrolysis test, which involves immersion in pure water at 58°C and will be described in detail later, the molecular weight retention rate of the polyester carbonate, that is, the molecular weight retention rate which is the ratio of the weight-average molecular weight after immersion to the weight-average molecular weight before immersion, is preferably 60% or more. Furthermore, the range of the molecular weight retention rate in the hydrolysis test is more preferably 65% ​​or more, even more preferably 70% or more, and particularly preferably 75% or more, 80% or more, 85% or more, or 90% or more.

[0056] In a biodegradability test of polyester carbonate in accordance with JIS K 6953-2, it is preferable that the biodegradability value 60 days after the start of the test is 40% or more. That is, in accordance with JIS K 6953-2, it is preferable that the biodegradation rate (%) of the polyester carbonate test piece under 58°C composting conditions is 40% or more of the value of the polyester carbonate immediately before the start of the test. The biodegradability value of the polyester carbonate calculated in this way is more preferably 50% or more, even more preferably 70% or more, and particularly preferably 80% or more or 85% or more.

[0057] In the case of polyester carbonate, as will be explained in detail later, the Charpy strength value measured according to the method conforming to JIS K 7111 standard-1 / 1eA is 15 kJ / cm². ２ The above is preferable. The Charpy strength value of the polyester carbonate is more preferably 18 kJ / cm². ２ The above is preferable, and more preferably 20 kJ / cm². ２ The above is a particularly preferred 22 kJ / cm².２ That concludes the explanation. While the upper limit of Charpy strength is not particularly important, the Charpy strength of polyester carbonate is, for example, 40 kJ / cm². ２ The following, or 50 kJ / cm² ２ The following applies:

[0058] In the case of polyester carbonate, as will be described in detail later, it is preferable that the elastic modulus value of the tensile test measured according to the method in accordance with JIS K 7161-1:2014 is 300 MPa or higher. More preferably, the elastic modulus value of polyester carbonate is 340 MPa or higher, even more preferably 370 MPa or higher, and particularly preferably 390 MPa or higher. Although the upper limit of the elastic modulus is not particularly important, the elastic modulus value of polyester carbonate is, for example, 450 MPa or less, or 500 MPa or less.

[0059] For polyester carbonate, as will be described in detail later, it is preferable that the maximum point stress value of the tensile test measured according to the method in accordance with JIS K 7161-1:2014 is 32 MPa or higher. More preferably, the maximum point stress value of polyester carbonate is 35 MPa or higher, even more preferably 38 MPa or higher, and particularly preferably 40 MPa or higher or 42 MPa or higher. Although the upper limit of the maximum point stress is not particularly important, the maximum point stress value of polyester carbonate is, for example, 55 MPa or lower, or 60 MPa or lower.

[0060] In the case of polyester carbonate, as will be described in detail later, it is preferable that the value of the breaking point (stroke strain) in the tensile test measured by the method in accordance with JIS K 7161-1:2014 is 300% or more. The value of the elastic modulus of polyester carbonate is more preferably 330% or more, even more preferably 350% or more, and particularly preferably 370% or more. Although the upper limit of the breaking point is not particularly important, the value of the breaking point of polyester carbonate is, for example, 600% or less, or 500% or less.

[0061] For polyester carbonate, as will be described in detail later, it is preferable that the yield stress value of the tensile test measured according to the method in accordance with JIS K 7161-1:2014 is 18 MPa or higher. More preferably, the yield stress value of polyester carbonate is 20 MPa or higher, even more preferably 22 MPa or higher, and particularly preferably 25 MPa or higher or 28 MPa or higher. Although the upper limit of the yield stress is not particularly important, the yield stress of polyester carbonate is, for example, 40 MPa or lower, or 50 MPa or lower.

[0062] <3. Method for producing polyester carbonate> The method for producing polyester carbonate includes a process for producing polyester as a prepolymer and a polymerization process in which polyester molecules are bonded together with diester carbonate.

[0063] 3-1. Polyester Manufacturing Process (First Polymerization Process) Polyester, used as a prepolymer for polyester carbonate, can be manufactured by conventional methods. For example, as follows: Polyester can be manufactured by polymerization through esterification reactions (dehydration or dealcoholization reactions) with the above-mentioned aliphatic diols and aliphatic dicarboxylic acids.

[0064] The amount of monomer in the first polymerization step is adjusted as appropriate. For example, in the first polymerization step, it is preferable to use an excess of aliphatic diol relative to aliphatic dicarboxylic acids. The amount of aliphatic diol (in moles) is, for example, 1.1 to 2.0 times, preferably 1.2 to 1.8 times, more preferably 1.3 to 1.6 times, and particularly preferably 1.3 to 1.5 times, 1.4 to 1.6 times, or 1.4 to 1.5 times the amount of aliphatic dicarboxylic acids (in moles). By using a slightly excess of aliphatic diol compared to aliphatic dicarboxylic acids in this way, it is possible to ensure that both ends of the resulting polyester are converted to hydroxyl groups. Furthermore, by adjusting the relative amounts of aliphatic diol and aliphatic dicarboxylic acids, it is possible to control the molecular weight of the polyester produced. Increasing the relative amount of aliphatic diol to aliphatic dicarboxylic acids results in an excess of hydroxyl groups in the polyester intermediate during the polymerization reaction, allowing the reaction rate to be adjusted and thus enabling the target molecular weight of the polyester to be lowered.

[0065] It is preferable to use a biomass-derived monomer as defined above in the first polymerization step. That is, in the polymerization of polyester, it is preferable to use an aliphatic diol or aliphatic dicarboxylic acid, which is a biomass-derived raw material, and it is more preferable to use aliphatic diols and aliphatic dicarboxylic acids derived from biomass.

[0066] It is preferable that the impurity content in the aliphatic diol, aliphatic dicarboxylic acid, or both thereof is 5000 μg / ml or less. When an aliphatic diol or aliphatic dicarboxylic acid with a total impurity content of 5000 μg / ml or less is used, the resulting polyester carbonate can be expected to have excellent properties, as will be described in detail later. The total impurity content in the aliphatic diol or aliphatic dicarboxylic acid is more preferably 4000 μg / ml or less, even more preferably 3600 μg / ml or less or 3000 μg / ml or less, and particularly preferably 2000 μg / ml or less, 1000 μg / ml or less or 600 μg / ml or less.

[0067] Examples of impurities contained in the aliphatic diol and aliphatic dicarboxylic acid used in the first polymerization step include analogues that differ only in the number of hydroxyl groups from the aliphatic diol and aliphatic dicarboxylic acid, and analogues that have the same number of hydroxyl groups but similar molecular structures, but differ in the total number of carbon atoms (the number of carbon atoms in Rb of formula (II) above). For example, when succinic acid is used as the aliphatic dicarboxylic acid, examples include malic acid, which has one more hydroxyl group, and acetic acid, which has fewer carbon atoms.

[0068] In the case of aliphatic dicarboxylic acids as monomers, the content of analogs that differ only in the number of hydroxyl groups as impurities is, for example, 4000 μg / ml or less, preferably 3600 μg / ml or less or 3000 μg / ml or less, and particularly preferably 2000 μg / ml or less, 1000 μg / ml or less or 600 μg / ml or less. In addition, in the case of aliphatic dicarboxylic acids as monomers, the content of analogs that have the same number of hydroxyl groups as impurities but have a similar molecular structure but differ in total carbon content is, for example, 1000 μg / ml or less, preferably 600 μg / ml or less or 400 μg / ml or less, and particularly preferably 300 μg / ml or less, 200 μg / ml or less or 100 μg / ml or less.

[0069] In each of the aliphatic diols and aliphatic dicarboxylic acids used in the first polymerization step, the total amount of anion ions, as measured by the method described in detail later, is, for example, 100 ppm (μg / ml) or less, preferably 80 ppm (μg / ml) or less or 60 ppm (μg / ml) or less, and particularly preferably 40 ppm (μg / ml) or less, 20 ppm (μg / ml) or less or 10 ppm (μg / ml) or less.

[0070] Anions that may be included in aliphatic diols and aliphatic dicarboxylic acids include PO ４ ３－ , Cl － SO ４ ２－ These are some examples. And for each of the aliphatic diols and aliphatic dicarboxylic acids as monomers, the PO is measured in detail by the method described later. ４３－ The content is, for example, 80 ppm (μg / ml) or less, preferably 60 ppm (μg / ml) or less or 50 ppm (μg / ml) or less, and particularly preferably 30 ppm (μg / ml) or less, 20 ppm (μg / ml) or less or 10 ppm (μg / ml) or less. In each of the aliphatic diol and aliphatic dicarboxylic acid, the Cl content is measured in detail by the method described later. － The content is, for example, 10 ppm (μg / ml) or less, preferably 8 ppm (μg / ml) or less or 6 ppm (μg / ml) or less, and particularly preferably 4 ppm (μg / ml) or less, 2 ppm (μg / ml) or less or 1 ppm (μg / ml) or less. Furthermore, for each of the aliphatic diol and aliphatic dicarboxylic acid, SO is measured in detail by the method described later. ４ ２－ The content is, for example, 80 ppm (μg / ml) or less, preferably 60 ppm (μg / ml) or less or 40 ppm (μg / ml) or less, and particularly preferably 20 ppm (μg / ml) or less, 10 ppm (μg / ml) or less or 6 ppm (μg / ml) or less.

[0071] Cationic ions that may be included in aliphatic diols and aliphatic dicarboxylic acids include NH ＋ Na ＋ _K ＋ Mg ２＋ Ca ２＋ These are some examples, and for each of the aliphatic diols and aliphatic dicarboxylic acids as monomers, the Na is measured by the method described in detail later. ＋ The content is, for example, 80 ppm (μg / ml) or less, preferably 60 ppm (μg / ml) or less or 40 ppm (μg / ml) or less, and particularly preferably 20 ppm (μg / ml) or less, 10 ppm (μg / ml) or less or 6 ppm (μg / ml) or less. In addition, in the aliphatic diol or aliphatic dicarboxylic acid, NH is measured in detail by the method described later. ＋ _K ＋ Mg ２＋ Ca ２＋The content of each is 10 ppm (μg / ml) or less, preferably 8 ppm (μg / ml) or less or 6 ppm (μg / ml) or less, and particularly preferably 4 ppm (μg / ml) or less, 2 ppm (μg / ml) or less, 1.2 ppm (μg / ml) or less, or 0.5 ppm (μg / ml) or less.

[0072] 3-2. Polymerization Process of Polyester (Second Polymerization Process) Polyester carbonate can be produced by further polymerizing polyester, which is a prepolymer. For example, methods such as a direct reaction of polyester with phosgene (phosgene method) or a transesterification reaction of polyester and carbonate esters such as bisaryl carbonate (two-step transesterification method) can be employed. Although any of these methods for producing polyester carbonate resin can be employed, the two-step transesterification method is preferred because it can reduce the environmental impact and achieve good reactivity.

[0073] The polymerization reaction of polyester is usually carried out at a temperature in the range of 150 to 350°C, preferably 200 to 300°C, and the degree of reduced pressure is preferably 1 mmHg or less in the final stage to remove phenols generated by the transesterification reaction from bisaryl carbonate. The reaction time depends on the reaction temperature and degree of reduced pressure, but is usually about 1 to 24 hours, preferably 2 to 12 hours, and more preferably 3 to 6 hours. The polymerization reaction of polyester is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and antioxidants and branching agents may be added as desired.

[0074] In the polymerization reaction of polyester by the transesterification method described above, the use of a transesterification catalyst is preferred. As a transesterification catalyst, for example, a compound containing a salt of at least one of the following metals is used: Y, La, Zn, Sn, Ga, Mn, Co, Mg, In, Ti, Zr, and Hf. Examples of such transesterification catalysts include fatty acid salts of the above-mentioned metals, hydroxides, alcoholates, phenolates, acetylacetonates, benzoylacetonates, halides, carbonates, sulfates, nitrates, oxides, etc. One type of compound may be used as the transesterification catalyst, or two or more types may be used in combination. Preferably, the transesterification catalyst is used in an amount of 5 × 10⁶ per 100 parts by weight of the raw material mixture. －５ It is used in the range of up to 1 part by weight.

[0075] In the polymerization reaction of polyester, the molar ratio of diester carbonate to the molar amount of diester carbonate (moles of diester carbonate / moles of single hydroxyl groups in PE) is preferably greater than 1.00 and less than 1.20, as shown in the following formula (1): 1.00 < [diphenyl carbonate (mol)] / [OH amount of PE (mol) × 1 / 2] < 1.20 ... formula (1) In formula (1), the value of [OH amount of PE (mol) × 1 / 2] represents the number of OH groups at one end of the polyester, where OH groups are present at both ends.

[0076] Thus, by carrying out the polymerization reaction of polyester using a slightly excessive amount of diester carbonate, a biodegradable polyester carbonate (PEC) with fewer terminal OH groups can be obtained. In such a PEC, the acid value can be kept low, and hydrolysis resistance and thermal stability can be improved. The molar ratio of the diester carbonate is more preferably 1.002 to 1.150, even more preferably 1.005 to 1.100, and particularly preferably 1.008 to 1.050, for example 1.010.

[0077] <4. Molded Articles and Various Materials> The molded articles of the present invention contain the polyester carbonate described above. Preferably, the molded articles contain biodegradable polyester carbonate as the main component. Molded articles containing biodegradable polyester carbonate as the main component are easily decomposed by microorganisms in soil, compost, seawater, rivers, lakes, etc. For this reason, polyester carbonate can be widely used even in cases where recycling is difficult. Furthermore, because polyester carbonate has excellent moldability, it can be processed and used in various molded articles such as films, sheets, laminates, fibers, nonwoven fabrics, yarns, and laminates.

[0078] Specific examples of such molded products include agricultural materials, fishing materials, and civil engineering materials. The following are examples of specific uses of resin compositions that can be specifically utilized. A specific example of agricultural materials is agricultural mulch film with excellent gas barrier properties. Agricultural mulch film is used for purposes such as covering the soil surface to retain soil heat and control weeds, preventing pest damage, and creating an environment suitable for growing vegetables and fruits by creating fine irregularities on the film surface to diffuse sunlight. Films stretched on the outside of greenhouses are used for purposes such as suppressing the generation of fog and mist, improving heat retention, and dust prevention.

[0079] Other agricultural materials include multipurpose films, pots and strings for plants, fertilizer coating materials, sustained-release coverings, horticultural films, pesticide wrap films, greenhouse films, fertilizer bags, seedling pots for transplanting, seedling pots, waterproof sheets, sandbags, construction films, weed control sheets, vegetation nets made of tape and yarn, water-retaining films for greening barren land and deserts, sandbags, vegetation nets, vegetable sunburn prevention tape, tree shelters, winter coverings, animal damage prevention nets, mulch films for paddy fields, hydroponic sheets, urethane alternative growing media, and floral foam for flower arranging.

[0080] Specific examples of fishing materials include fishing lines, fishing nets, seaweed nets, artificial bait, artificial seaweed, foam floats, oyster farming pipes, and buoys. Specific examples of civil engineering materials include underground pipes, sandbags, building films, sandbags, buried pipes for soil modification, drainage drains, wood waterproofing, waterproof sheets, weed control sheets, civil engineering sheets, and fumigation sheets. Polyester carbonate is also suitably used, for example, as suture thread, or as a fiber for nonwoven fabrics, woven fabrics, and bandages.

[0081] Other specific examples of molded products include helmets, various bags such as shopping bags, packaging materials for magnetic tape cassette products such as video and audio, flexible disc packaging materials, printing plate materials, packaging bands, adhesive tapes, tapes, yarn, cups, trays, cartons, lunch boxes, prepared food containers, food and confectionery packaging materials, food wrap materials, internal coating materials for food and beverage packs, shrink film for PET bottles, trays for fresh food, fast food containers and lunch boxes, garbage bags, cups, plates, chopsticks, spoons, forks, straws, and cosmetic wrap materials. Examples of applications include plastic shopping bags, diapers, sanitary napkins, medical wraps, pharmaceutical packaging materials, surgical adhesive patches for conditions such as stiff shoulders and sprains, various packaging materials for food, electronics, medical equipment, pharmaceuticals, cosmetics, etc., parts of artificial hair and wigs, artificial turf, body bags, pipette tips, biological research tags, signposts, bollards, scrubbing materials, shampoo and toothpaste tubes, 3D printer filaments, contact lenses, absorbent sheets for diapers, and polyester for fleece materials. If the molded product has a film-like shape, it can also be heat-sealed. In addition, it can be used for purposes such as garbage bags and compost bags.

[0082] The molded products can be used as medical and hygiene products, such as medical materials like sutures and bandages, and hygiene materials like disposable diapers and parts of sanitary products (superabsorbent polymers, waterproof films). They can also be used as disposable leisure goods for golf, fishing, and marine sports, as well as water treatment materials such as precipitants, dispersants, and detergents.

[0083] While there are no particular limitations on the shape of the molded body, for example, in the case of a molded body as a component other than a film, the thickness is, for example, 0.1 mm or more, preferably 0.3 mm or more. Furthermore, the thickness of a molded body as a film may be, for example, 500 μm or less, or 300 μm or less.

[0084] The following describes examples of polyester carbonate. 1) Amount of OH (Terminal Hydroxyl Groups) of PE (Polyester) The amount of terminal hydroxyl groups in polyester, which is the raw material for polyester carbonate, was calculated from NMR analysis as follows. NMR apparatus: Bruker AVNEO500 Solvent: Deuterated chloroform Analysis method: The amount of terminal hydroxyl groups was calculated from the integral value of σ3.7, which indicates terminal hydroxyl groups, and the integral value of σ4.2, which indicates ester bonds of succinic acid, using the following formula. Degree of polymerization n = ((Integral value of σ4.2 - Integral value of σ3.7) / Integral value of σ3.7) + 1 Theoretical molecular weight M = n × 172.17 + 90.12 Amount of OH (mass%) = (16 + 1.008) × 2 / M × 100 Amount of OH (mol / g) = 2 / M OH value (mgKOH / g) = 56.1 × 1000 × 2 / M

[0085] Furthermore, the OH value (mg KOH / g) can also be measured by the titration method described below, and there was no difference in the results obtained by the NMR method and the titration method. (Titration method) 1. Weigh 5.1045 g of acetic anhydride into a 100 ml volumetric flask and make up to 100 ml with pyridine. (Acetylation reagent below) 2. Weigh 0.5 g of polyester (PE sample below) into a 100 ml vial and record the weight (Y g). Each sample was weighed N=2. 3. Add a stirring bar and acetylation reagent (weighed 10.0 g: approximately 10 ml) to the vial containing the PE sample and close the lid. At this time, two blank vials without the PE sample were prepared. 4. Heat in an oil bath heated to 98°C for 90 minutes. 5. Remove from the oil bath, allow to cool to room temperature for 10 minutes, then rinse the walls with ultrapure water (UPW (approx. 10 ml)) and stir for about 5 minutes. At this time, the mixture will heat up due to the neutralization heat of acetic acid and pyridine, so add the UPW slowly while observing the mixture. For the blank, add UPW (approx. 10 ml) carefully to avoid splashing, and stir for about 5 minutes. 6. Add a few drops of phenolphthalein, and titrate the Blank twice with 0.2 N NaOH aqueous solution, and the solution containing the PE sample twice. 7. If there is no significant difference in the titration results of the blank, calculate the blank average (Z １ The amount of 0.2N NaOH aqueous solution required for the neutralization titration of the solution containing the PE sample (ml) and Z ２ The OH value was calculated from the difference (Z1 - Z2 ml) between the two values. 8. The amount of OH (mass %) was determined using the following formula (a). Furthermore, a smaller value for terminal hydroxyl groups indicates that the polymerization reaction during polyester production was more advanced.

[0086] 2) Acid value of PE (polyester) and PEC (polyester carbonate) was measured by titration using phenolphthalein in accordance with JIS K0070-1992. However, the base used for titration was changed from a 0.1 mol / L KOH aqueous solution to a 0.02 mol / L NaOH aqueous solution, and ethanol was added first. Apparatus: burette, magnetic stirrer, stirrer bar, Erlenmeyer flask Solvent: chloroform, ethanol, 0.02 mol / L NaOH aqueous solution, phenolphthalein (indicator) (Measurement method) 1. Weigh out approximately 1 g each of PE and PEC resin and record the weight. 2. Weigh out 30 ml of chloroform and completely dissolve the resin. 3. After confirming complete dissolution, weigh out 30 ml of ethanol and add it to the solution. 4. Add 4 drops of phenolphthalein as an indicator and titrate with 0.02 mol / L NaOH solution. 5. The difference in titration volume between the solution and the blank (chloroform: 30 ml, ethanol: 30 ml) was recorded. 6. The acid value was calculated using the following formula (b): Acid value (mg KOH / g) = 0.02 × difference in titration volume (ml) × 56.1 / resin weight (g) ... (b)

[0087] 3) Weight-average molecular weight (Mw) and number-average molecular weight (Mn) in polystyrene equivalent were analyzed by GPC. Instrument: Tosoh Corporation high-speed GPC HLC-8320 GPC column: Tosoh Corporation GPC column SuperMultiporeHZ-M (4.6mm I.D. × 150mm), 3 columns used in series. Flow rate: 0.35 mL / min Eluent: Chloroform Sample concentration: 0.2 w / v% Detection unit: Bryce type differential refractometer (RI detector)

[0088] 4) Diester carbonate (DPC) molar ratio The molar ratio of diester carbonate (DPC) was calculated using the following formula (c) based on the amount of OH in the polyester prepolymer (PE) and the amount ratio of diester carbonate (DPC). Diester carbonate theoretically reacts with two hydroxyl groups. Therefore, the amount of diester carbonate to be added was calculated using the following formula (d): Polymerization amount (g) = 214.216 × [Diester carbonate molar ratio] × [Amount of terminal hydroxyl groups (mass percent)] ÷ 17 ÷ 100 × PE weight (g) ... (d)

[0089] 5) Amount of OH end groups (ppm), phenyl (Ph) end groups (ppm), and carbonate bond content (mol%) of polyester carbonate (PEC) These were calculated by NMR analysis, similar to the amount of OH end groups of polyester described above. Instrument: Bruker AVNEO500 Solvent: Deuterated chloroform (CDCl3) Analytical method: End group analysis was performed 1 The molar ratios of each component were calculated from the integral ratios of the 1H NMR (solvent: CDCl3), and the molar ratios of each component were defined as follows from the integral values ​​of each peak. In the following equations, BD represents the integral value of the peak originating from 1,4-butanediol, SA represents succinic acid, and the Ph terminus represents the integral value of the peak originating from diphenyl carbonate (DPC). A: (δ4.16 + δ4.11) / 4 = BD B: δ3.67 / 2 = OH terminus C: δ2.63 / 4 = SA D: (δ4.16 + δ4.11 - δ2.63) / 4 = Amount of carbonate bond E: δ7.37 / 2 = Ph terminus (phenyl terminus originating from DPC) The amount of OH terminus (ppm) of PEC was calculated using the following equations. Calculation formula: OH terminal amount (ppm) = 17 × B / (88.12 × A + 84.09 × C + 28 × D + 17 × B + 93.11 × D) × 1,000,000 ... (e) Ph terminal amount (ppm) = 93.11 × E / (88.12 × A + 84.09 × C + 28 × D + 17 × B + 93.11 × D) × 1,000,000 ... (f) OH terminal concentration (mol / g) = B / (88.12 × A + 84.09 × C + 28 × D + 17 × B + 93.11 × D) ... (g) DPC terminal concentration (mol / g) = E / (88.12 × A + 84.09 × C + 28 × D + 17 × B + 93.11 × D) ... (h) Carbonate bond content (mol%) = C / A × 100 ... (i)

[0090] 6) Thermal Retention Test The molecular weight retention rate of polyester carbonate (PEC) at high temperatures was measured as follows using a thermal retention test with a differential thermogravimetric analyzer (TG-DTA). Apparatus: Hitachi High-Tech Science TG / DTA 7300 Atmosphere: air, flow rate: 250 ml / min Measurement temperature: Heating rate: 100°C / min, 230°C retention period: 30 minutes 230°C retention test: The molecular weight Mw of the PEC before heating with TG-DTA was set to 100%, and the change in weight-average molecular weight (Mw) after the PEC was retained in TG-DTA at 230°C for 30 minutes was calculated. That is, the molecular weight retention rate (%) was calculated when the molecular weight Mw before heating with TG / DTA was set to 100%.

[0091] 7) Hydrolysis Test The molecular weight retention rate of polyester carbonate (PEC) at moderately high temperatures was measured by hydrolysis test as follows: PEC was placed in a vial and immersed in pure water in an incubator set to 58°C. The change in weight-average molecular weight (Mw) before and after immersion was calculated using the same method as described above for GPC measurement. The molecular weight retention rate (%) after 28 days was calculated, with the weight-average molecular weight (Mw) before immersion set to 100%. Incubator: FMU-1801-HC low-temperature incubator manufactured by Fukushima Galilei Co., Ltd.

[0092] 8) Intrinsic viscosity (η) of PE (polyester) The intrinsic viscosity (η) of PE (polyester) was measured as follows using an absolute molecular weight measurement multi-detector GPC. Instrument: Malvern viscotech TDA 305 Column: Tosoh Corporation GPC column SuperMultiporeH ＸＬ -M (4.6 mm I.D. x 300 mm), 3 tubes used in series. Eluent: Chloroform Sample concentration: 2 w / v% Absolute molecular weight calibration standard: Polystyrene (PS99K) Detection unit: Intrinsic viscosity detector

[0093] Manufacturing Example: Polyester (PE-1) Manufacturing Example: In a 10L reaction vessel equipped with a stirrer, thermometer, glass tube, and fractionation receiver, the following raw materials were added: succinic acid 3453g (manufactured by Nippon Shokubai Co., Ltd.), 1,4-butanediol 3690g (manufactured by Mitsubishi Chemical Corporation), and Zr (acac) as a catalyst. ４ 122 mg (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) was charged and reacted under a nitrogen atmosphere at 225°C for 1 hour, allowing water to drain. Subsequently, the mixture was aged for 2 hours and 30 minutes under a reduced pressure of 200 to 20 hPa to allow the dehydration reaction to proceed. Furthermore, the reduced pressure was gradually increased until it was finally below 1 hPa, and water and 1,4-butanediol were distilled off for a total of 4 hours and 30 minutes during polymerization. The resulting polyester had a number-average molecular weight of 2113, an OH value of 2.06% by mass (wt%), and an acid value of 0.78 KOH mg / g. The physical properties of the obtained polyester are shown in Table 1.

[0094] Polyester (PE-2) was produced in the same manner as polyester prepolymer (PE-1), except that the amounts of the raw materials were changed to 2795.4 g of succinic acid and 3200 g of 1,4-butanediol, and the polymerization time was set to the time shown in Table 1. The physical properties of the obtained polyester are shown in Table 1.

[0095] Polyester (PE-3) was produced in the same manner as polyester prepolymer (PE-1), except that the amounts of the raw materials were changed to 2995.1 g of succinic acid and 3200 g of 1,4-butanediol, and the polymerization time was set to the time shown in Table 1. The physical properties of the obtained polyester are shown in Table 1.

[0096] In the example of producing polyester (PE-1-1), the amount of succinic acid was changed to 299.5 g and 1,4-butanediol to 320 g as raw materials, and the polymerization time was set to the time shown in Table 1, except that polyester prepolymer (PE-1-1) was obtained in the same manner as polyester prepolymer (PE-1). The physical properties of the obtained polyester are shown in Table 1.

[0097]

[0098] (Example 1) 25 g of polyester (PE-1) obtained in the above production example was placed in a 100 ml glass flask equipped with a stirrer, thermometer, glass tube, and distillation receiver. 3.2822 g of diphenyl carbonate (hereinafter referred to as DPC) in an amount equivalent to 1.01 molars relative to the terminal hydroxyl groups of the polyester, and 1 mg of zinc acetate dihydrate as a catalyst were added. The reaction was carried out at 225°C, with the pressure gradually reduced, while removing phenol by distillation, until the pressure was finally reduced to 1 hPa or less, for 4.5 hours. The pressure was released with nitrogen, and the obtained polyester carbonate was a colorless resin without gelation. The weight-average molecular weight (Mw) of the polyester carbonate was 220,000, with an OH terminal content of 285 ppm, a Ph terminal content of 1475 ppm, and an acid value of 0.23 mgKOH / g. The physical properties of the obtained resin are shown in Table 2.

[0099] (Examples 2-6, Reference Examples and Comparative Examples 1-3) Polyester carbonate resin was obtained in the same manner as in Example 1, except that the amount of polyester and DPC used (DPC molar ratio) was changed as shown in Table 2. The physical properties of the obtained resin are shown in Table 2.

[0100] Furthermore, a biodegradation test was conducted on the polyester carbonate obtained in Example 1, as described above, in accordance with JIS K 6953-2. The result showed a biodegradation rate of 94% after 60 days from the start of the test. Thus, it was confirmed that the polyester carbonate in the example exhibits good biodegradability.

[0101] (Examples 7-9) Using succinic acid as a raw material, the trace components measured by the method described in detail below are as shown in Table 3. Polyesters (PE-1-2) to (PE-1-4) were produced in the same manner as in the example of producing polyester (PE-1). Then, using these polyesters (PE-1-2) to (PE-1-4), polyester carbonate was produced in the same manner as in Example 1 (Examples 7-9). The properties of the polyester carbonate obtained in Examples 7-9 are shown in Table 3, along with the components of the succinic acid used as a raw material. In addition, Table 3 also shows the analysis results of the trace components contained in the succinic acid used in the production example of (PE-1) (Examples 1-3).

[0102] In Table 3, columns where an inequality sign (<) and a numerical value are listed together indicate that the result was less than the specified value. Columns marked with "-" in the table indicate that measurement was not performed, and the unit of concentration "ppm" means μg / ml.

[0103] The measurement method for succinic acid, as shown in Table 3 above, is described below. (1) Concentration measurement of malic acid and acetic acid The following conditions were used for analysis by HPLC. Apparatus: Waters 2695 Column: ODS-80Ts (4.6 mm ID × 250 mm) Column temperature: 40℃ Eluent composition: Water / phosphoric acid / acetonitrile = 97.9 / 2 / 0.1 g Eluent flow rate: 1 ml / min Detector: UV The analysis was performed using a sample whose concentration was adjusted so that the succinic acid to be measured was 5 wt%, under the above conditions. Detection limit: 100 μg / ml

[0104] (2) PO ４ ３－ , Cl － The concentration was measured by anion ion chromatography under the following conditions. Instrument: Dionex ICS-2100 Temperature: 35℃ Detector: Conductivity Sample volume: 100 μL Column: IonPacAG11-HC (inner diameter 4 mm, length 50 mm, semi-upright diameter 9 μm) + IonPacASH-HC (inner diameter 4 mm, length 250 mm, particle size 9 μm) Eluent: KOH Gradient conditions: 1 mM (0-8 min), 1-30 mM (8-28 min), 30-60 mM (28-38 min), 60-75 mM (38-40 min), 75 mM (38-40 min) Flow rate: 1.0 ml / min Suppressor: Dionex AERS 500 (4 mm) Regeneration mode: External mode SRS current value: 186 mA Prepare a 2 mg / ml aqueous solution of succinic acid, the target of measurement, and measure Cl, PO by anionic IC. ４ A quantitative analysis was performed. Detection limit: PO4 3- ; 10 ppm, Cl- ; 1.0 ppm

[0105] (3) NH ４＋ Na ＋ _K ＋ Mg ２＋ Ca ２＋ The concentration of NH4 was analyzed by cationic ion chromatography under the following conditions: Instrument: Dionex ICS-2100 Temperature: 35℃ Detector: Conductivity Sample volume: 100 μL (manual introduction) Column: IonPac CG17 (inner diameter 4 mm, length 50 mm, particle size 7 μm) + IonPac CS17 (inner diameter 4 mm, length 250 mm, particle size 7 μm) Eluent: 6 mM methanesulfonic acid Flow rate: 1.0 mL / min Suppressor: Dionex CERS 500e (4 mm) Regeneration mode: External mode SRS current value: 24 mA A 2 mg / mL aqueous solution of succinic acid, the target of measurement, was prepared, and quantitative analysis of NH4 was performed by cationic IC. Detection limit: NH4 4+ ; 1.0 ppm, Na + ; 5.0 ppm, K + ; 1.2 ppm, Mg 2+ ; 0.5 ppm, Ca 2+ ; 0.5 ppm

[0106] (4) SO ４ ２－The concentration was measured by anion ion chromatography under the following conditions. Instrument: Dionex ICS-2100 Temperature: 35℃ Detector: Conductivity Sample volume: 100μL (manual input) Column: IonPacAGH-HC (inner diameter 4 mm, length 50 mm, semi-vertical diameter 9μm) IonPacAS11-HC (inner diameter 4 mm, length 250 mm, semi-vertical diameter 9μm) Eluent: KOH Gradient conditions: 1-6 mM (0-1 min), 6-14.8 mM (25 min), 14.8-75 mM (25-26 min), 75 mM (26-30 min) with no data acquisition Flow rate: 1.0 ml / min Suppressor: Dionex AERS 500 (4 mm) Regeneration mode: External mode SRS current: 186 mA Sample preparation: A 1 mg / ml aqueous solution of succinic acid, the substance to be measured, was prepared and used as the sample. Detection limit: 3 ppb

[0107] (5) Sodium (Na) concentration was measured. The following conditions were used for analysis by ICP-AES: Apparatus: SPECTR0 ARCOS (EOP) Plasma output: 1400 W Plasma gas: 13 l / min Auxiliary gas: 0.8 l / min Nebulizer gas: 0.8 l / min Measurement time: 28 s Number of measurements: 5 Sample preparation: 1 g of succinic acid sample was heated and dissolved in 15 ml of hydrochloric acid aqueous solution, and then diluted to 50 ml with ultrapure water to prepare the sample.

[0108] The measurement method for the polyester carbonate (resin) component, as shown in Table 3 above, is described below. (6) Charpy impact strength The following conditions were met using a notched Charpy impact tester. Equipment: DG-CB manufactured by Toyo Seiki Seisakusho Test piece: Strip-shaped test piece 10mm x 80mm x 2mm Based on N=3 Impact direction: Edgewise Notch shape: A Notch tip radius: 0.25mm Standard Remaining width after notching: 8.0mm Test standard: In accordance with JIS K 7111 standard-1 / 1eA. However, the sample thickness was thinner than the recommended value (4mm) of the standard, and was set to 2mm. The above sample (test piece) was molded by injection molding as follows. Molding machine: Shinko Cellbic (now Epson Techform) C, Mobile-0813 Molding conditions: Injection speed 20 mm / s Injection time: 2 s Molding temperature - body: 150℃, manifold: 170℃ Mold temperature: 40℃ Holding pressure: 80% Cooling time: 10 s

[0109] The Charpy strength results are shown in Table 3 above, based on the following criteria: Excellent: No fractures were observed in the sample, indicating an excellent result. Good: Some fractures were observed in the sample, but the result was still good. Slightly Poor: Fractures were observed in the sample, but the result was still at a level suitable for practical use. Poor: Fractures were observed in the sample, resulting in a level unsuitable for practical use.

[0110] (7) Tensile strength (modulus of elasticity, maximum stress, fracture point (stroke (strain)), yield stress) was measured using a tensile testing machine under the following conditions. Equipment: Shimadzu Autograph AGS-X Test specimen: A12 dumbbell test specimen (N=3) Load cell maximum capacity: 500N Grips: Air chuck type grips Grip distance: 50mm Test speed: 0.5mm / min (modulus of elasticity) / 25mm / min (strength / elongation) Test specimen thickness measurement method: Measured directly with a micrometer Reference standard: Original (Base: JIS K 7161-2:2014) Note that the test specimen for the A12 dumbbell test described above is a 1 / 2 scale test specimen of the A1 type, so it was thought that the grip distance should be about 58mm, but when the length that fit inside the grip was short, slippage inside the grip and abnormal fracture were observed, so the grip distance was reduced to 50mm and the test was carried out. Furthermore, instead of using the recommended test speed in Table 1 of JIS K 7161-1:2014, we prioritized matching the general strain rate of 50% / min and set the injection speed to 25 mm / min. As stated in the JIS standard, evaluating the elastic modulus with small test specimens is technically difficult and therefore not adopted. The above test specimens were formed by injection molding as follows: Molding machine: Shinko Celvic (now Epson Techform) C,Mobile-0813 Molding conditions: Injection speed 20 mm / s Injection time: 2 s Molding temperature - body: 150℃, manifold: 170℃ Mold temperature: 40℃ Holding pressure: 80% Cooling time: 10 s

[0111] As is clear from the results of the above examples and comparative examples, in each example, a biodegradable polyester carbonate with fewer OH ends was obtained under conditions where the molar ratio of DPC, a diester carbonate, was slightly in excess. The polyester carbonate (PEC) of these examples was found to have a lower acid value and superior hydrolysis resistance and thermal stability compared to the comparative polyester carbonate produced under conditions with less DPC. Furthermore, by reducing the amount of terminal OH in PEC obtained by using an excess of diester carbonate in this way, the cyclization of terminal 1,4-butanediol, which is a side reaction, can be suppressed. This suppresses the formation of carboxylic acid ends that may occur during polymerization and reduces the hydroxyl groups that are reaction sites, resulting in high hydrolysis resistance and thermal stability.

[0112] Furthermore, in the polymerization of polyester, examples (Examples 7-9) using bio-derived raw materials with few impurities confirmed that the resulting polyester carbonates possessed high Charpy strength and tensile strength.

[0113] Although preferred embodiments of the present invention have been described in detail above, the present invention is not limited to these examples. It is clear to any person with ordinary skill in the art to which the present invention pertains that various modifications or alterations can be conceived within the scope of the technical idea described in the claims, and these are also understood to naturally fall within the technical scope of the present invention.

Claims

1. A polyester carbonate (PEC) having a polyester (PE) having structural units derived from aliphatic diols and aliphatic dicarboxylic acids, wherein the acid value of the polyester carbonate is 0.01 to 0.24 mgKOH / g, and the amount of OH terminals of the polyester carbonate is 10 to 500 ppm.

2. The polyester carbonate according to claim 1, wherein the aliphatic diol and aliphatic dicarboxylic acid have 20 or fewer carbon atoms.

3. The polyester carbonate according to claim 2, wherein the aliphatic diol comprises 1,4-butanediol and the aliphatic dicarboxylic acid comprises succinic acid.

4. The polyester carbonate according to claim 1, wherein the diester carbonate is a diaryl carbonate.

5. The polyester carbonate according to claim 4, wherein the diaryl carbonate comprises diphenyl carbonate.

6. The polyester carbonate according to claim 1, wherein the molecular weight retention rate in a heat retention test in which the polyester carbonate is heated by retaining it at 230°C for 30 minutes is 50% or more, and the molecular weight retention rate, which is the ratio of the weight-average molecular weight after heating to the weight-average molecular weight before heating.

7. The polyester carbonate according to claim 1, wherein the molecular weight retention rate in a hydrolysis test in which the polyester carbonate is immersed in pure water at 58°C is 60% or more, and the molecular weight retention rate is the ratio of the weight-average molecular weight after immersion to the weight-average molecular weight before immersion.

8. The Charpy strength value is 15 (kJ / cm²). ２ The polyester carbonate according to claim 1, wherein the elastic modulus in the tensile test is 300 MPa or higher.

9. The polyester carbonate according to claim 1, wherein the weight-average molecular weight of the polyester is 1,000 to 20,000.

10. The polyester carbonate according to claim 1, wherein at least one of the aliphatic diol and the aliphatic dicarboxylic acid, which are raw materials, is derived from biomass.

11. The raw material, diester carbonate, is CO ２ The polyester carbonate described in claim 1, which is the origin of the material.

12. A method for producing the polyester carbonate described in claim 1, wherein the relationship between the amount of OH in the polyester (PE) (mol) and the amount of diphenyl carbonate (mol) is expressed by the following formula (1): 1.00 < [Diphenyl carbonate (mol)] / [Amount of OH in PE (mol) × 1 / 2] < 1.20 ... Formula (1) 13. The polyester carbonate according to claim 1, wherein the raw material, the aliphatic diol or the aliphatic dicarboxylic acid, has an impurity content of 5,000 μg / ml or less.

14. A molded article comprising the polyester carbonate described in claim 1.

15. A biodegradable agricultural material comprising the polyester carbonate described in claim 1.

16. A biodegradable fishing material comprising the polyester carbonate described in claim 1.

17. A biodegradable civil engineering material comprising the polyester carbonate described in claim 1.

18. A biodegradable fiber comprising the polyester carbonate described in claim 1.

Images