Resin composition and molded body

Abstract

There has been a desire for a resin composition which has high biodegradability and has excellent properties including strength and hydrolytic resistance.　As a means for solving the problem, provided is a resin composition comprising a polyester carbonate resin that comprises a constituent unit (A) derived from a monomer represented by general formula (1) and a constituent unit (B) derived from a monomer represented by general formula (2), and an inorganic filler, wherein the amount of the inorganic filler in the resin composition is 30-50 mass%.　(1): HO-Ra-OH (In general formula (1), Ra represents an optionally substituted C1-C20 alkylene group.)　(2): R1OOC-Rb-COOR2 (In general formula (2), Rb represents an optionally substituted C1-C20 alkylene group, and R1 and R2 are each independently selected from among a hydrogen atom and optionally substituted C1-C5 alkyl groups.)

Description

Resin composition and molded article

[0001] The present invention relates to a resin composition, and more particularly to a resin composition containing a specific polyester carbonate resin.

[0002] Resin compositions containing resins such as polyester and polyester carbonate are used in a wide range of fields. Among such resin compositions, those containing biodegradable polyester carbonate are known (for example, Patent Documents 1 and 2 listed below).

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 8-134196 Patent Document 2: Japanese Patent Application Laid-Open No. 2003-034372

[0004] Conventional biodegradable resins and resin compositions containing such resins have not necessarily been recognized as having excellent properties. For example, resins and resin compositions that are particularly excellent in properties such as strength and hydrolysis resistance as well as biodegradability have not yet been realized. For this reason, there has been a demand for resin compositions that are highly biodegradable and also excellent in various properties including strength and hydrolysis resistance.

[0005] The present invention provides the following resin composition, molded article, etc. [1] A resin composition comprising a polyester carbonate resin containing a structural unit (A) derived from a monomer represented by the following general formula (1) and a structural unit (B) derived from a monomer represented by the following general formula (2), and an inorganic filler, in which the structural unit (A) is represented by the following general formula (1): HO-Ra-OH ... (1) (In general formula (1), Ra represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.) R １ OOC-Rb-COOR ２ ...(2) (In the general formula (2), Rb represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and R １ and R ２are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent.) A resin composition in which the amount of the inorganic filler in the resin composition is 30 to 50 mass %. [2] The resin composition according to the above item [1], further comprising polylactic acid and / or polyester. [3] A resin composition comprising 50 to 100 mass % of a polyester carbonate resin which comprises a structural unit (A) derived from a monomer represented by the following general formula (1) and a structural unit (B) derived from a monomer represented by the following general formula (2), and: HO-Ra-OH ... (1) (In general formula (1), Ra represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.) R １ OOC-Rb-COOR ２ ...(2) (In the general formula (2), Rb represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and R １ and R ２ are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent.) A resin composition comprising: 0 to 50 mass % of polylactic acid; and an inorganic filler. [4] The resin composition according to [3] above, wherein the amount of the inorganic filler in the resin composition is 30 to 50 mass %. [5] A resin composition comprising: a polyester carbonate resin containing a structural unit (A) derived from a monomer represented by the following general formula (1) and a structural unit (B) derived from a monomer represented by the following general formula (2); and a polyester, the resin composition comprising: HO-Ra-OH ... (1) (In general formula (1), Ra represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.) R １ OOC-Rb-COOR ２ ...(2) (In the general formula (2), Rb represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and R １ and R ２ are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent.) A resin composition, wherein the amount of the polyester in the resin composition is 10 to 30 mass %. [6] In the formula (1), the Ra's are each independently selected from (CH ２)n, each n is independently an integer of 4 to 16; in the formula (2), each Rb is independently (CH ２ ) m, wherein each m independently represents an integer of 2 to 16. The resin composition according to any one of [1] to [6] above, for example, [1], [3] or [5] above. [7] The resin composition according to any one of [2] and [3] above, for example, [2] above, wherein the mass ratio of polyester carbonate resin to polylactic acid (polyester carbonate resin:polylactic acid) in the resin composition is polyester carbonate resin:polylactic acid = 50 to 90:50 to 10. [8] The resin composition according to any one of [1] to [4] above, for example, [1] or [3] above, wherein the inorganic filler includes at least one of talc, mica and wollastonite. [9] The resin composition according to any one of [1] to [8] above, for example, [1], [3] or [5] above, further including a mold release agent and / or an antioxidant.

[10] The resin composition according to any one of [1] to [9] above, for example, [1], [3], or [5] above, which is substantially free of phosphorus-based compounds.

[11] The resin composition according to any one of [1] to

[10] above, for example, [1], [3], or [5] above, which has a flexural modulus of 2000 to 5000 MPa.

[12] The resin composition according to any one of [1] to

[11] above, for example, [1], [3], or [5] above, which has a biodegradability of 30% or more after 20 days in a biodegradability test based on JIS K 6953-2.

[13] The resin composition according to any one of [1] to

[11] above, for example, [1], [3], or [5] above, in which a test piece of the resin composition having a thickness of 1 mm, prepared in accordance with JIS K 6251, is allowed to stand at a temperature of 58°C and a humidity of 65%, and the tensile strength value thereof remains at 90% or more of the tensile strength before the test for 25 days or more.

[0006]

[14] A molded article comprising the resin composition according to any one of [1] to

[13] above, for example, the resin composition according to [1], [3], or [5] above.

[15] The molded article according to

[14] above, which is a pipe to be buried underground.

[16] The molded article according to

[14] above, which is a film having gas barrier properties or biodegradability.

[17] The molded article according to

[14] above, which has a thickness of 0.1 mm or more.

[0007]

[18] A resin composition comprising a polyester carbonate resin containing a structural unit (A) derived from a monomer represented by the following general formula (1) and a structural unit (B) derived from a monomer represented by the following general formula (2), and a polyester, the resin composition comprising: HO-Ra-OH (1) (in general formula (1), Ra represents an alkylene group having 1 to 20 carbon atoms which may have a substituent): １ OOC-Rb-COOR ２ ...(2) (In the general formula (2), Rb represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and R １ and R ２ are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent.) A resin composition, wherein the polyester comprises at least an aliphatic aromatic copolymer polyester.

[19] The resin composition according to

[18] above, wherein the polyester comprises a structural unit (A') derived from a monomer represented by the following general formula (I) and a structural unit (C) derived from a monomer represented by the following general formula (II): HO-Ra'-OH ... (I) (In general formula (I), Ra' represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.) R １ OOC-Rb'-COOR ２ ...(II) (In the general formula (II), Rb' represents an alkylene group having 1 to 20 carbon atoms which may have a substituent or an arylene group having 6 to 30 carbon atoms which may have a substituent, R １ and R ２are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent.)

[20] The resin composition according to

[18] or

[19] above, for example

[18] above, wherein the amount of the polyester in the resin composition is 1 to 60 mass%.

[0008] The resin composition of the present invention contains a specified polyester carbonate resin and has excellent biodegradability as well as excellent properties such as strength and hydrolysis resistance. Furthermore, according to the present invention, it is also possible to provide a molded article containing the resin composition having excellent properties and which can be widely used in applications such as underground pipes and agricultural mulch films.

[0009] The resin composition of the present invention contains a polyester carbonate resin having at least a predetermined structural unit. The resin composition may further contain at least one of an inorganic filler, polylactic acid, polyester, etc. Preferred embodiments of the present invention are described in detail below.

[0010] <1. Components of Resin Composition> 1-1. Polyester Carbonate Resin The polyester carbonate resin contained in the resin composition contains at least the following structural unit (A) and structural unit (B). Each structural unit will be described below.

[0011] The structural unit (A) in the polyester carbonate resin is derived from a monomer of a diol compound represented by the following general formula (1): HO-Ra-OH (1) In general formula (1), Ra represents an alkylene group having 1 to 20 carbon atoms which may have a substituent. Ra may be a linear, branched, or alicyclic alkylene group. Ra in formula (1) may be, for example, (CH ２)n, where n is preferably an integer of 4 to 16. Furthermore, 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. Furthermore, in the diol compound represented by formula (1), Ra is preferably formed solely from carbon atoms, excluding substituents, and does not contain oxygen atoms, nitrogen atoms, or the like. Preferred specific examples of the monomer compound represented by general formula (1) include ethylene glycol, propanediol, butanediols such as 1,4-butanediol, pentanediols such as 1,5-pentanediol, hexanediol, octanediol, and cyclohexanedimethanol. Two or more of these diols may be used in combination.

[0012] The structural unit (B) in the polyester carbonate resin is derived from a monomer represented by the following general formula (2): １ OOC-Rb-COOR ２ ...(2) In the general formula (2), Rb represents an alkylene group having 1 to 20 carbon atoms which may have a substituent. Rb may be a linear, branched or alicyclic alkylene group. Rb in the formula (2) is, for example, (CH ２) m, where m is preferably an integer of 2 to 16. Rb 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 compound represented by formula (2), Rb is preferably formed solely from carbon atoms, excluding substituents, and does not contain oxygen atoms, nitrogen atoms, or the like. Such a monomer compound represented by formula (2) may be any of a dicarboxylic acid compound, a monoester compound, a diester compound, or a mixture thereof. Preferred specific examples of the monomer compound represented by general formula (2) include compounds such as succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, and dodecanoic acid, as well as derivatives such as anhydrides and esters of these. Two or more of these dicarboxylic acid compounds may be used in combination.

[0013] In addition, R in general formula (2) １ and R ２ are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent. １ and R ２ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may contain a substituent, more preferably each independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms which may contain a substituent, and even more preferably each independently a hydrogen atom or a methyl group.

[0014] The substituents in the above-mentioned Ra and Rb can be independently selected from halogen, hydroxyl group, cyano group, alkenyl group having 1 to 5 carbon atoms, aryl group having 6 to 12 carbon atoms, etc. These substituents are preferably halogen, hydroxyl group, cyano group, etc. １ and R ２The substituents may be independently selected from halogen, hydroxyl group, cyano group, alkenyl group having 1 to 5 carbon atoms, aryl group having 6 to 12 carbon atoms, etc. These substituents are preferably halogen, hydroxyl group, cyano group, etc. When the substituents in the structural units (A) and (B) include an alkenyl group or an aryl group, the range of the number of carbon atoms in the above-mentioned monomer refers to the number of carbon atoms including the carbon of the substituent.

[0015] The polyester carbonate resin contained in the resin composition can be produced by a conventional method, for example, as follows: The polyester carbonate resin can be produced, for example, by reacting a diol compound that derives the structural unit (A), a compound such as a dicarboxylic acid that derives the structural unit (B), and a carbonate ester-forming compound. Known methods can be employed, such as I) a method in which a polyester is obtained by an esterification reaction (dehydration or dealcoholization reaction) between a diol compound and a dicarboxylic acid, and the polyester is then directly reacted with phosgene (the phosgene method); II) a method in which a polyester is obtained by an esterification reaction (dehydration or dealcoholization reaction) between a diol compound and a dicarboxylic acid, and the polyester is then subjected to a transesterification reaction between the polyester and a carbonate compound such as a bisarylcarbonate (a two-stage transesterification method); or III) a method in which a diol compound, a dicarboxylic acid, and a carbonate compound such as a bisarylcarbonate are simultaneously reacted in the same reactor (a method in which a transesterification reaction, i.e., a dehydration or dealcoholization reaction and a dealcoholization reaction proceed simultaneously (a one-stage transesterification method). Any of these methods for producing polyestercarbonate resins can be employed, but the above-mentioned II) two-stage transesterification method is preferred because it can reduce the environmental load and achieve good reactivity.

[0016] In the phosgene method, for example, compounds such as diols that derive the structural unit (A), dicarboxylic acids that derive the structural unit (B), and monohydric phenols that derive terminal structures are reacted with phosgene in the presence of a typical acid binder and a solvent. Examples of acid binders that can be used include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and solvents such as dichloromethane and chloroform. Furthermore, in order to promote the condensation polymerization reaction, it is preferable to use a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt such as benzyltriethylammonium chloride.

[0017] Compounds such as monohydric phenols that induce terminal structures function as polymerization modifiers, but it is also possible to use other monohydric phenols such as phenol, p-t-butylphenol, p-cumylphenol, and long-chain alkyl-substituted phenols in an amount of less than 50% by mass relative to the monohydric phenol that induces terminal structures. If desired, small amounts of antioxidants such as sodium sulfite and hydrosulfite, or branching agents such as phloroglucin and isatin bisphenol, may be added. The reaction is typically carried out at a temperature ranging from 0 to 150°C, preferably from 5 to 40°C. The reaction time varies depending on the reaction temperature, but is typically 0.5 minutes to 10 hours, preferably from 1 minute to 2 hours. It is also desirable to maintain the pH of the reaction system at 10 or higher during the reaction.

[0018] On the other hand, in the transesterification method, for example, diols that derive the structural unit (A), compounds such as dicarboxylic acids that derive the structural unit (B), and carbonate compounds such as bisarylcarbonate are reacted, preferably under reduced pressure and at high temperature. Specifically, production methods such as the two-step transesterification method described above in II) and the one-step transesterification method described above in III) are used. For example, in the two-step transesterification method, diols and dicarboxylic acids are reacted to obtain a polyester, and the polyester is then reacted with a carbonate compound such as bisarylcarbonate to react the OH group at the end of the polyester with the bisarylcarbonate to introduce a carbonate bond. Furthermore, when diols of the above formula (1) are reacted with dicarboxylic acids of the above formula (2) to polymerize a polyester, a molecular weight large enough to be suitable for a molded product is often not obtained. Therefore, it is preferable to further link the polyesters obtained by the polymerization reaction with a carbonate compound such as bisarylcarbonate to increase the molecular weight. Alternatively, a diol, a dicarboxylic acid and a carbonate compound such as a bisarylcarbonate may be polymerized in one pot by a one-step transesterification method.

[0019] Examples of bisaryl carbonates include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Two or more of these compounds can also be used in combination. The reaction is typically carried out at a temperature ranging from 150 to 350°C, preferably from 200 to 300°C, and the final pressure reduction is preferably 1 mmHg or less, allowing phenols derived from the bisaryl carbonate produced by the transesterification reaction to be distilled out of the system. The reaction time varies depending on the reaction temperature and the degree of vacuum, but is typically about 1 to 24 hours. The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. If desired, an antioxidant or branching agent may be added.

[0020] In the polymerization reaction by the above-mentioned transesterification method, it is preferable to use a transesterification catalyst. As the transesterification catalyst, for example, a compound containing a salt of at least one of Y, La, Zn, Sn, Ga, Mn, Co, Mg, In, Ti, Zr, and Hf is used. Examples of such a transesterification catalyst include fatty acid salts, hydroxides, alcoholates, phenolates, acetylacetonates, benzoylacetonates, halides, carbonates, sulfates, nitrates, and oxides of the above-mentioned metals. As the transesterification catalyst, only one type of compound may be used, or two or more types may be used in combination. The transesterification catalyst is preferably 5 × 10 per 100 parts by weight of the raw material mixture. －５ It is used in the range of 1 part by weight to 1 part by weight.

[0021] The weight average molecular weight (Mw) of the polyester carbonate resin 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, still 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, 200,000 to 250,000, or 230,000 to 250,000.

[0022] The resin composition contains, for example, 20 to less than 100 mass% or 25 to 100 mass% of polyester carbonate resin, based on the total weight of the resin composition. The content of the polyester carbonate resin in the resin composition is preferably 20 to 85 mass% or 25 to 80 mass%, more preferably 25 to 70 mass% or 30 to 75 mass%, and particularly preferably 30 to 70 mass% or 33 to 75 mass%, based on the total weight of the resin composition.

[0023] 1-2. Inorganic Filler Examples of inorganic fillers that can be contained in the resin composition include talc, anhydrous silica, mica, vermiculite, titanium oxide, 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, fluorine hectorite and saponite, and glass fibers. Specific examples of preferred inorganic fillers include talc, mica, and wollastonite. The addition of a small amount of inorganic filler can be effective in improving the gas barrier properties of the resin composition.

[0024] The resin composition contains, for example, 20 to 60 mass % or 30 to 50 mass % of the inorganic filler based on the total weight of the resin composition. The content of the inorganic filler in the resin composition is preferably 30 to 45 mass %, more preferably 30 to 40 mass %, and even more preferably 32 to 40 mass %, based on the total weight of the resin composition.

[0025] 1-3. The polylactic acid that can be contained in the polylactic acid resin composition is a polymer composed essentially of only monomer units derived from L-lactic acid and / or D-lactic acid. Furthermore, the polylactic acid may contain monomer units other than L-lactic acid and D-lactic acid, as long as the effects of the resin composition are not impaired.

[0026] Any known polymerization method can be used to produce polylactic acid. The most representative method is the ring-opening polymerization of lactide, an anhydrous cyclic dimer of lactic acid (the lactide method), but direct condensation polymerization of lactic acid is also possible. The molecular weight of polylactic acid is preferably in the range of 50,000 to 1,000,000 in weight average molecular weight.

[0027] The resin composition contains, for example, 0 to 50% by mass of polylactic acid based on the total weight of the resin composition. The content of polylactic acid 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.

[0028] 1-4. The polyester resin composition may contain a polyester. Examples of polyesters that can be contained in the resin composition include aliphatic-aromatic polyesters, aliphatic polyesters, and polyesters derived from hydroxy acids, and are preferably biodegradable.

[0029] Examples of aliphatic diols that form aliphatic aromatic polyesters include diol compounds represented by the above formula (1). Specific examples include ethylene glycol, propanediol, butanediols such as 1,4-butanediol, pentanediols such as 1,5-pentanediol, hexanediol, octanediol, and cyclohexanedimethanol, and two or more of these diols may be used in combination. Examples of aliphatic carboxylic acids that form aliphatic aromatic polyesters include diol compounds represented by the above formula (2). Specific examples include succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, and dodecanoic acid, and two or more of these aliphatic dicarboxylic acids may be used in combination. Furthermore, examples of aromatic carboxylic acids that form aliphatic aromatic polyesters include terephthalic acid, phthalic acid, and isophthalic acid, and two or more of these aromatic dicarboxylic acids may be used in combination.

[0030] The aliphatic aromatic polyester contains, for example, a structural unit (A') derived from a diol monomer represented by the following formula (I): HO-Ra'-OH (I) In general formula (I), Ra' represents an alkylene group having 1 to 20 carbon atoms which may have a substituent. The structural unit (A') derived from the monomer represented by formula (I) has the same structure as the structural unit (A) contained in the polyester carbonate resin. Ra' in general formula (I) is an alkylene group having 1 to 20 carbon atoms which may have a substituent, and may be a linear, branched, or alicyclic alkylene group.

[0031] Ra′ in formula (I) is, for example, (CH ２ )n, where n is preferably an integer of 4 to 16. 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. Ra' is preferably formed solely from carbon atoms, excluding substituents, and does not contain oxygen atoms, nitrogen atoms, or the like. Preferred specific examples of the monomer compound represented by general formula (I) include the following diols, for example, ethylene glycol, propanediol, butanediols such as 1,4-butanediol, pentanediols such as 1,5-pentanediol, hexanediol, octanediol, and cyclohexanedimethanol. Two or more of these diols may be used in combination.

[0032] Although the aliphatic aromatic polyester may contain structural units derived from diol monomers other than the diol represented by formula (I), it is preferable that all of the diol-derived structural units contained in the aliphatic aromatic polyester are structural units (A') (derived from monomers of formula (I)). The proportion of structural units (A') in the aliphatic aromatic polyester is preferably 20 to 50 mol%, more preferably 30 to 50 mol%, even more preferably 40 to 50 mol%, and particularly preferably 45 to 50 mol%, or 50 mol% (substantially all of the diol units contained in the aliphatic aromatic polyester are structural units (A')), based on the number of moles of all structural units in the aliphatic aromatic polyester.

[0033] The aliphatic aromatic polyester contains, for example, a structural unit (C) derived from a monomer represented by the following formula (II): １ OOC-Rb'-COOR ２ ...(II) In general formula (II), Rb' represents an alkylene group having 1 to 20 carbon atoms which may have a substituent or an arylene group having 6 to 30 carbon atoms which may have a substituent, such as a phenylene group, and R １ and R ２ are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent.

[0034] In formula (II), Rb' is preferably an alkylene group having 1 to 12 carbon atoms which may have a substituent or an arylene group having 6 to 20 carbon atoms which may have a substituent, more preferably an alkylene group having 2 to 8 carbon atoms which may have a substituent or an arylene group having 6 to 12 carbon atoms which may have a substituent, and even more preferably an alkylene group having 3 to 6 carbon atoms which may have a substituent or an arylene group having 6 to 10 carbon atoms which may have a substituent. Rb' may be a linear, branched, or alicyclic alkylene group.

[0035] The substituents contained in Rb' can be independently selected from halogen, hydroxyl group, cyano group, alkyl group having 1 to 5 carbon atoms, alkenyl group having 1 to 5 carbon atoms, aryl group having 6 to 12 carbon atoms, etc. These substituents are preferably halogen, hydroxyl group, cyano group, etc. When an alkyl group, alkenyl group, or aryl group is contained as a substituent in Rb', the range of the number of carbon atoms in the above-mentioned monomer refers to the number of carbon atoms including the carbon of the substituent.

[0036] In formula (II), R １ and R ２ are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent. １ and R ２ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may contain a substituent, more preferably each independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms which may contain a substituent, and even more preferably each independently a hydrogen atom or a methyl group. These substituents can be each independently selected from halogen, hydroxyl group, cyano group, alkyl group having 1 to 5 carbon atoms, alkenyl group having 1 to 5 carbon atoms, aryl group having 6 to 12 carbon atoms, etc. These substituents are preferably halogen, hydroxyl group, cyano group, etc. １ and R ２ When the substituent in the formula (I) contains an alkyl group, an alkenyl group, or an aryl group, the range of the carbon number in the above-mentioned monomer refers to the number of carbon atoms including the carbon of the substituent.

[0037] As is clear from formula (II), the structural unit (C) contained in the aliphatic aromatic polyester has a —OOC-Rb′-COO— structure (the “-” at both ends indicates a bond to an adjacent structural unit). Such an ester structural unit (C) includes an aliphatic structural unit in which Rb′ is an alkylene group having 1 to 20 carbon atoms, and an aromatic structural unit in which Rb′ is an arylene group having 6 to 30 carbon atoms.

[0038] Although the aliphatic aromatic polyester may contain ester structural units derived from monomers other than the monomer represented by formula (II), it is preferable that all of the ester structural units contained in the aliphatic aromatic polyester are structural units (C) (derived from the monomer of formula (II)). The proportion of structural units (C) in the aliphatic aromatic polyester is preferably 20 to 50 mol%, more preferably 30 to 50 mol%, even more preferably 40 to 50 mol%, and particularly preferably 45 to 50 mol%, or 50 mol% (substantially all of the ester units contained in the aliphatic aromatic polyester are structural units (C)), based on the number of moles of all structural units in the aliphatic aromatic polyester.

[0039] In the structural units (C) contained in the aliphatic aromatic polyester, the proportion of aliphatic structural units is, for example, 20 to 80 mol%, preferably 30 to 70 mol%, more preferably 40 to 60 mol%, based on the total number of moles of structural units (C).Furthermore, in the structural units (C) contained in the aliphatic aromatic polyester, the proportion of aromatic structural units is, for example, 20 to 80 mol%, preferably 30 to 70 mol%, more preferably 40 to 60 mol%, based on the total number of moles of structural units (C).

[0040] Examples of aliphatic polyesters that can be used include polyglycolic acid, polyhydroxybutyrates such as poly(3-hydroxybutyrate), etc. Preferred aliphatic polyesters include those containing, as a monomer, a hydroxyaliphatic carboxylic acid having 1 to 10 carbon atoms, preferably a hydroxyaliphatic carboxylic acid having 2 to 8 or 2 to 6 carbon atoms.

[0041] As the polyester derived from a hydroxy acid, a lactone, lactide, or the like of a hydroxy acid may be used, and examples of such polyesters include polycaprolactone (PCL), polyglycolide (PGA), polylactide (PLA), polydioxanone (PDO), polybutyrolactone (PBL), polyvalerolactone (PVL), poly(lactide-co-glycolide) (PLGA), etc. Furthermore, as the polyester derived from a hydroxy acid, for example, a polyester derived from polyhydroxyalkanoic acid (PHA) produced by a microorganism may be used. Examples of polyesters derived from PHA include polyesters derived from poly(3-hydroxybutanoic acid) or poly(3-hydroxybutyric acid) (PHB), polyesters derived from poly(hydroxyvaleric acid) or poly(3-hydroxypentanoic acid) (PHV), polyesters derived from poly(hydroxycaproic acid) or poly(3-hydroxyhexanoic acid) (PHH), polyesters derived from poly(hydroxycaprylic acid) (PHO), and polyesters derived from poly(3-hydroxybutanoic acid-co-)-3-hydroxyhexanoic acid (PHBH).

[0042] In place of or in combination with polyester, the resin composition may contain cellulose acetate and its derivatives, polyvinyl alcohol (PVA) and its derivatives, or two or more of these alternative components may be used in combination. The polyester that can be contained in the resin composition may be any one of the above-mentioned aliphatic-aromatic polyesters, aliphatic polyesters, polyesters derived from hydroxy acids, and the above-mentioned alternative components, or a mixture of two or more thereof.

[0043] The resin composition contains, for example, 0 to 50% by mass of polyester, based on the total weight of the resin composition. The content of polyester in the resin composition is preferably 3 to 40% by mass or 5 to 45% by mass, more preferably 5 to 30% by mass or 8 to 35% by mass, and even more preferably 10 to 30% by mass or 12 to 25% by mass, based on the total weight of the resin composition. Furthermore, the content of each alternative component, such as cellulose acetate and its derivatives (cellulose acetates), polyvinyl alcohol and its derivatives (polyvinyl alcohols), used in place of polyester, may be, for example, as described in this paragraph, and the total content of polyester, cellulose acetates, and polyvinyl alcohols may be as described in this paragraph.

[0044] The resin composition may contain the aliphatic aromatic polyester in the above-mentioned content range. Furthermore, the resin composition may contain 1 to 60 mass% of the aliphatic aromatic polyester based on the total weight of the resin composition. The content of the aliphatic aromatic polyester in the resin composition is preferably 2 to 50 mass% or 2.5 to 55 mass%, more preferably 3 to 30 mass% or 3.5 to 35 mass%, and even more preferably 4 to 20 mass% or 4.5 to 25 mass%, based on the total weight of the resin composition.

[0045] 1-5. Component Ratio in Resin Composition In the resin composition, the mass ratio of polyester carbonate resin to polylactic acid (polyester carbonate resin:polylactic acid) is preferably 50 to 90:50 to 10 (90:10 to 50:50). Furthermore, this mass ratio of polyester carbonate resin:polylactic acid is more preferably 50 to 85:50 to 15 (85:15 to 50:50), and even more preferably 50 to 80:50 to 20 (80:20 to 50:50).

[0046] 1-6. Additives The resin composition may contain additives other than the above-mentioned components. For example, the resin composition may contain a mold release agent, an antioxidant, etc., and may not contain a phosphorus-based compound that may be contained as a flame retardant, etc.

[0047] The resin composition preferably contains an antioxidant as an additive. As the antioxidant, generally commercially available ones can be used, but it is preferable to contain, for example, at least one of an acid phenol-based antioxidant and a phosphite-based antioxidant.

[0048] Phenolic antioxidants include 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'-butylidene-m-cresol, ocladecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentyl methyl acrylate ... Examples of the hydroxybenzoate 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, and pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and preferably pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].Examples of phosphite 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'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhex ...phenyl)-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, triphenyl phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxy- Examples of antioxidants include tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra-C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and preferably 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. As the antioxidant, any one of the above may be used alone, or a mixture of two or more may be used.

[0049] The proportion of the 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 resin composition. Furthermore, the proportion of the 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 resin composition may contain only one type of antioxidant, or two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0050] The resin composition preferably contains a release agent as an additive. Examples of the release agent include ester compounds, such as glycerin fatty acid esters such as mono- and diglycerides of glycerin fatty acid, glycol fatty acid esters such as propylene glycol fatty acid esters and sorbitan fatty acid esters, higher alcohol fatty acid esters, and full esters or mono-fatty acid esters of aliphatic polyhydric alcohols and aliphatic carboxylic acids. When an ester of aliphatic polyhydric alcohols and aliphatic carboxylic acids is used as the release agent, either a monoester or a full ester can be used, but a release agent other than a full ester, such as a monoester, may also be used.

[0051] Specific examples of the release agent 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 monohydroxystearates such as glycerin monostearate and glycerin mono-12-hydroxystearate, glycerin monooleate, glycerin monobehenate, glycerin monocaprylate, glycerin monocaprate, and glycerin Examples of the monoglycerides include monoglycerides such as monolaurate, and mono-diglycerides such as glycerin monodistearate, glycerin monodistearate, glycerin monodibehenate, and glycerin monodiolate; acetylated monoglycerides of glycerin fatty acid esters such as glycerin diacetomonolaurate; organic acid monoglycerides of glycerin fatty acid esters such as citric acid fatty acid monoglyceride, succinic acid fatty acid monoglyceride, and diacetyltartaric acid 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 polyricinoleate.

[0052] The addition ratio of the release agent 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 resin composition. Furthermore, the addition ratio of the release agent 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, based on the total mass of the resin composition. The resin composition may contain only one type of release agent, or two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0053] The resin composition may contain additives other than the antioxidant and the mold release agent.For example, additives that the resin composition may contain include compounding agents, catalyst deactivators, heat stabilizers, plasticizers, fillers, ultraviolet absorbers, rust inhibitors, dispersants, antifoaming agents, leveling agents, flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, clarifying agents (specifically, sorbitol derivatives, hydroxy fatty acid amides, triaminobenzene compounds, nonitol compounds, various celluloses, etc.), starches (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 stabilizers (specifically, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl)ester, reaction products 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]butyl malonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 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 hindered amine stabilizers such as [[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 the like; end-capping agents; and the like.

[0054] Examples of the nucleating agent (crystal nucleating agent) and antiblocking agent that can be contained in the resin composition include talc, mica, calcium carbonate, and boron nitride. A preferred example of the nucleating agent and antiblocking agent is calcium carbonate. Furthermore, the same additive, such as talc or mica, can be used in combination as both the nucleating agent and the inorganic filler. Adding a small amount of the nucleating agent and the antiblocking agent can be expected to improve the properties of the resin composition.

[0055] The proportion of the nucleating agent and antiblocking agent added 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. The proportion of the nucleating agent and antiblocking agent added 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.

[0056] The total mass of all additives contained in the resin composition is preferably 10 mass% or less, more preferably 5 mass% or less, even more preferably 3 mass% or less, and particularly preferably 3 mass% or less or 2 mass% or less, based on the total mass of the resin composition.

[0057] <2. Properties of Resin Composition> The resin composition preferably has a flexural modulus of 2000 to 5000 MPa, as measured by the method described in detail below. More preferably, the resin composition has a flexural modulus of 2200 MPa or more, even more preferably 2500 MPa or more. The upper limit is not particularly important, but may be, for example, 5000 MPa. The resin composition preferably has a tensile strength of 20 MPa or more, as measured by the method described in detail below. More preferably, the resin composition has a tensile strength of 25 MPa or more, even more preferably 27 MPa or more, and particularly preferably 30 MPa or more. The upper limit is not particularly important, but may be, for example, 60 MPa or less, 70 MPa or less, or 80 MPa or less. Furthermore, the resin composition preferably has a flexural strength of 35 MPa or more, as measured by the method described in detail below. More preferably, the flexural strength of the resin composition is 40 MPa or more, even more preferably 42 MPa or more, and particularly preferably 45 MPa or more. The upper limit is not particularly important, but is, for example, 80 MPa or less.

[0058] In the resin composition, the biodegradability (ratio to the biodegradability of cellulose (standard substance)) in a biodegradability test in accordance with JIS K 6953-2 is preferably 30% or more after 20 days. More preferably, the biodegradability value is 35% or more, even more preferably 40% or more, and particularly preferably 45% or more. Furthermore, in the resin composition, a test piece of the resin composition having a thickness of 1 mm, prepared in accordance with JIS K 6251, is preferably left at a temperature of 58°C and a humidity of 65%, and the tensile strength value thereof is 90% or more of the tensile strength before the start of the test for a period of 25 days or more. More preferably, the period is 30 days or more, even more preferably 40 days or more, and particularly preferably 45 days or more.

[0059] <3. Resin Properties> The resin contained in the resin composition preferably has a tensile strength of 25 MPa or more, measured by a method described in detail below. More preferably, the tensile strength of the resin is 30 MPa or more, even more preferably 32 MPa or more, and particularly preferably 34 MPa or more. The upper limit is not particularly important, but is, for example, 70 MPa or less, 60 MPa or less, or 50 MPa or less. Furthermore, the resin contained in the resin composition preferably has a tensile elongation of 200% or more, measured by a method described in detail below. More preferably, the tensile elongation of the resin is 300% or more, even more preferably 350% or more, and particularly preferably 400% or more or 450% or more. The upper limit is not particularly important, but is, for example, 600% or less or 550% or less.

[0060] The resin contained in the resin composition has a water vapor permeability coefficient of 25,000 g μm / m per day measured by a method described in detail below. ２ Below (25,000g・μm / (m ２ More preferably, the water vapor permeability coefficient of the resin per day is 20,000 g μm / m or less. ２ More preferably, it is 18,000 g μm / m or less. ２ More preferably, it is 16,000 g μm / m or less. ２ or less, and particularly preferably 16,000 g μm / m ２ The lower limit of the daily water vapor transmission coefficient of the resin is not particularly important, but for example, 8,000 g μm / m ２ or more, or 10,000 g μm / m ２ That's all.

[0061] The resin contained in the resin composition preferably has a weather resistance index value of 50 or more, measured by a method described in detail below. More preferably, the weather resistance index value of the resin is 60 or more, even more preferably 65 or more or 70 or more, and particularly preferably 75 or more. Furthermore, the resin contained in the resin composition preferably has a hydrolysis resistance index value of 35 or more, measured by a method described in detail below. More preferably, the hydrolysis resistance index value of the resin is 50 or more, even more preferably 60 or more or 70 or more, and particularly preferably 80 or more.

[0062] The resin contained in the resin composition preferably has an evaluation value of 10 or more in a biodegradation test measured by a method described in detail below. More preferably, the hydrolysis resistance index of the resin is 20 or more, even more preferably 30 or more or 40 or more, and particularly preferably 50 or more.

[0063] 4. Method for Producing Resin Composition The resin composition of the present invention can be produced by mixing the components, such as the polyester carbonate resin, by a known method.

[0064] <5. Molded Article> The molded article of the present invention contains the resin composition described above and is preferably produced using the resin composition described above as a main raw material. The molded article preferably contains a biodegradable resin composition as a main component. It can be widely used in fields where biodegradability is required. Specific examples of such molded articles include pipes and mulch films for agricultural use.

[0065] The resin composition of the present invention contains a biodegradable polyester carbonate resin as a main component, and therefore is easily decomposed by microorganisms in soil, compost, seawater, rivers, lakes, etc. Therefore, the resin composition can be widely used, for example, even in places where recycling is difficult. Furthermore, because of its excellent moldability, it can be processed into various molded articles such as films, sheets, laminates, fibers, nonwoven fabrics, threads, and laminates.

[0066] Examples of applications of the resin composition that can be specifically used include helmets, various bags such as shopping bags, packaging materials for magnetic tape cassettes for video and audio products, packaging materials for flexible disks, plate-making materials, packaging bands, adhesive tape, tape, yarn, cups, trays, cartons, lunch boxes, containers for prepared foods, food and confectionery packaging materials, food wrap materials, internal coating materials for food and drink packages, shrink film for PET bottles, trays for fresh food, fast food containers and lunch boxes, garbage bags, cups, plates, chopsticks, spoons, forks, straws, wrap materials for cosmetics and toiletries, shopping bags, diapers, sanitary napkins, wrap materials for pharmaceuticals, pharmaceutical packaging materials, packaging materials for surgical medicinal patches used for stiff shoulders, sprains, etc., various packaging materials for food, electronics, medical care, medicines, cosmetics, etc., parts of components for artificial hair and wigs, artificial turf, body bags, etc., and when in a film form, heat sealing is also possible.

[0067] Agricultural mulch films are used to cover the soil surface to insulate and weed, prevent pest damage, and create a finely textured surface to diffuse sunlight and create an environment suitable for growing vegetables and fruit or raising seedlings. Films deployed on the exterior of greenhouses are used to suppress fog and mist, improve heat retention, and protect against dust. Other agricultural materials include multipurpose films, plant pots and strings, fertilizer coating materials, sustained-release coatings, horticultural films, pesticide wrap, greenhouse films, fertilizer bags, seedling pots for transplanting, seedling raising pots, waterproof sheets, sandbags, construction films, weed control sheets, vegetation nets made from tape or yarn, water-retaining films for greening wastelands and deserts, sandbags, and vegetation nets. Further examples include underground pipes, fishing lines, fishing nets, seaweed nets, and artificial baits, as well as materials used in civil engineering and fisheries. They can also be used as garbage bags or compost bags.

[0068] It can be used in medical and sanitary products, such as medical materials such as sutures and bandages, sanitary materials such as disposable diapers and some sanitary products (polymer absorbents, waterproof films), disposable products for leisure activities such as golf, fishing, and marine sports, and water treatment materials such as precipitants, dispersants, and detergents.

[0069] Specific preferred examples of the molded article include pipes to be buried in the ground, and agricultural mulch films having gas barrier properties or biodegradability.

[0070] Although the shape of the molded body is not particularly limited, for example, the thickness of the molded body as a member other than a film is, for example, 0.1 mm or more, preferably 0.3 mm, and the thickness of the molded body as a film may be, for example, 500 μm or less, or 300 μm or less.

[0071] 1) Tensile test (tensile strength and tensile elongation) Tensile strength and tensile elongation were measured using an autograph as follows: Testing machine: Shimadzu Corporation autograph AGS-X (test condition: "original") Maximum load cell capacity: 500 N Grip distance: 21 mm Test speed: 0.21 mm / min (up to 1% strain) / 10.5 mm / min (1% strain or more) Test piece: In accordance with JIS K 6251, a No. 7 dumbbell (thickness: 1 mm) was used.

[0072] The test pieces for the tensile test were molded under the following conditions: Molding machine: Epson Techform C, Mobile-0813 (3t horizontal) Molding conditions: Manifold 200°C, body 220°C, tip 70%, mold temperature 60°C Screw rotation speed: 90 rpm Metering speed: 2 mm / s Injection speed: 20 mm / s

[0073] 2) Bending test (flexural modulus and flexural strength) Flexural modulus and flexural strength were measured using an autograph as follows: Testing machine: Shimadzu Corporation autograph AGS-X (test condition: "original") Load cell maximum capacity: 500 N Support distance: 20 mm (standard sample thickness: 1 mm) Test speed: 0.75 mm / min (flexural modulus) and 3.75 mm / min (flexural strength) Test piece: A dumbbell No. 7 (thickness: 1 mm) was used in accordance with JIS K 6251. The molding conditions for the test piece were the same as in 1) above.

[0074] 3) Biodegradability Biodegradability was evaluated in accordance with JIS K 6953-2 as follows. Testing machine: MODA-CS "Microbial Oxidative Decomposition Measuring Device" manufactured by Yawata Bussan Co., Ltd. Testing conditions: 58°C composting conditions Test specimen: Dumbbell No. 7 (thickness: 1 mm) was used in accordance with JIS K 6251. The molding conditions for the test specimen were the same as in 1) above. Reference material: Cellulose Testing period: 20 days Evaluation method: Calculated as a percentage of the biodegradability of cellulose (reference material). Judgment: For the above-mentioned "biodegradability," a score of 50 or more was rated as particularly good, 40 to 50 as good, 20 to 40 as slightly poor, and less than 20 as poor.

[0075] 4) Using a hydrolysis resistance environmental tester, the hydrolysis resistance was evaluated as follows based on the change in tensile strength of the sample. Testing machine: Espec Corporation's small environmental tester SH-222. Set temperature: 58°C. Set humidity: 65%. Test piece: A dumbbell No. 7 (thickness: 1 mm) was used in accordance with JIS K 6251. The molding conditions for the test pieces were the same as in 1) above. Test period: 8 weeks. Evaluation method: The tensile strength was measured as described above during the test period. Evaluation was based on the number of days in which 90% or more of the tensile strength at the start of the test was maintained. The number of days in which the strength was maintained was quantified as an original index, with 56 days being set as "100". 5) Weight average molecular weight (Mw) The polystyrene equivalent molecular weight (Mw) of the polycarbonate resin or polycarbonate resin composition was measured by gel permeation chromatography (GPC) under the following conditions. Measurement conditions Measuring equipment: HLC-8320 GPC manufactured by Tosoh Corporation Column: Shodex K-G + K-805L x 2 + K-800D Eluent: Chloroform Temperature: Column thermostat 40°C Flow rate: 1.0 ml / min Concentration: 0.1 wt / vol% Injection volume: 100 μl Pretreatment: Filtration through a 0.45 μm filter Detector: UV refractometer Standard polystyrene: EasiCal Type PS-1 polystyrene manufactured by GL Sciences Inc.

[0076] (Polymerization Example 1) 75.455 kg of succinic acid and 80.605 kg of 1,4-butanediol as raw materials, and 2.750 g of zirconium (IV) acetylacetonate as a catalyst were charged into a 400 L reactor, and the reaction was carried out for 110 minutes under a nitrogen atmosphere while the internal temperature was raised from 140 ° C to 215 ° C, and water was distilled off. Subsequently, the resulting reaction product was transferred to another 400 L reactor, and the reaction was carried out for 2 hours and 30 minutes at an internal temperature of 200 ° C and a reduced pressure of 100 to 0.3 kPa, and the dehydration reaction was further carried out. Subsequently, the reduced pressure was gradually increased to finally reach 0.1 kPa or less, and further water and unreacted 1,4-butanediol were distilled off, and polymerization was carried out at 200 ° C for 5 hours to obtain a prepolymer (polyester).

[0077] 77.025 kg of the prepolymer, 9.010 kg of diphenyl carbonate (DPC), and 5.860 g of zinc acetate dihydrate were charged into a 300 L reaction vessel, and the pressure was gradually reduced from 100 kPa at an internal temperature of 220°C, and while distilling off phenol, the pressure was finally reduced to 0.1 kPa or less, and the reaction was carried out for 4 hours to obtain a polyester carbonate (PEC) having a weight average molecular weight (Mw) of 200,000.

[0078] Example 5 The PEC obtained in Polymerization Example 1 and polylactic acid (PLA, Ingeo™ Biopolymer 2003D manufactured by NatureWorks) were each dried at 80°C for 3 hours. 74.3 g of the PEC, 24.8 g of the PLA, 49.5 g of talc (fine particle grade (High Filler Series), product name: #12 manufactured by Matsumura Sangyo Co., Ltd.) as an inorganic filler, 1 g of a mold release agent (Likestar™ EW-90 manufactured by Riken Vitamin Co., Ltd.), and 0.5 g of an antioxidant (Irganox 1010 manufactured by BASF) were weighed out, and all of these were mixed in a tumbler to form a homogeneous material, which was then extrusion-kneaded to obtain a resin composition. The physical properties of the resulting resin composition are shown in Table 1. The extrusion-kneading conditions were as follows: Mixing equipment: Labo Plastomill 4M150 manufactured by Toyo Seiki Seisakusho Extruder: Small twin-screw segment extruder 2D15W manufactured by Toyo Seiki Seisakusho (L / D=17) Mixing temperature (set temperature): C1 / C2 / die = 180°C / 200°C / 200°C Material input rate: 273g / h Labo Plastomill set rotation speed: 20rpm However, since the extruder 2D15W has a rotation ratio of 3, the actual screw rotation speed is 60rpm. In other words, the rotation speed is 3 times faster (basic device rotation speed x 3), or 20rpm x 3 = 60rpm.

[0079] (Examples 1 to 4, 6, Comparative Example 1) Resin compositions were obtained in the same manner as in Example 5, except that the amounts of PEC, PLA, inorganic filler, release agent, and antioxidant were changed as shown in the following Table 1. The physical properties of the obtained resin compositions are shown in Table 1.

[0080] Comparative Example 2 A resin composition was obtained in the same manner as in Example 5, except that PEC was replaced with polybutylene succinate (PBS, BioPBS (Product Name: FZ91PB) manufactured by PTT MCC Biochem Company Limited). The physical properties of the obtained resin composition are shown in Table 1.

[0081] Comparative Example 3 A resin composition was obtained in the same manner as in Example 5, except that PEC was replaced with polybutylene adipate terephthalate (PBAT, manufactured by BASF, ecoflex (registered trademark) F Blend C1200). The physical properties of the obtained resin composition are shown in Table 1.

[0082] Comparative Example 4 A resin composition was obtained in the same manner as in Example 5, except that PEC was replaced with polybutylene adipate terephthalate (PBAT, Ecoflex (registered trademark) F Blend C1200 manufactured by BASF) and the amounts of PLA, PBAT, and talc were changed as shown in the table. The physical properties of the obtained resin composition are shown in Table 1. The evaluation tests for Examples 1 to 6 and Comparative Examples 1 to 4, the results of which are shown in Table 1, were carried out under the conditions described in 1) to 5) above.

[0083] Example 7 The PEC obtained in Polymerization Example 1 and polybutylene adipate terephthalate (PBAT, Ecoflex® F Blend C1200 manufactured by BASF) were each dried at 80°C for 3 hours. 190.0 g of the PEC and 10.0 g of the PBAT were weighed out, and all of these were mixed in a tumbler to form a homogeneous material, which was then extrusion-kneaded to obtain a resin composition. The physical properties of the obtained resin composition are shown in Table 2. The extrusion-kneading conditions in Example 7 were as follows: Mixing equipment: Labo Plastomill 4M150 manufactured by Toyo Seiki Seisakusho Extruder: Small twin-screw segment extruder 2D15W manufactured by Toyo Seiki Seisakusho (L / D=17) Mixing temperature (set temperature): C1 / C2 / die = 180°C / 200°C / 200°C Material input rate: 400g / h Labo Plastomill set rotation speed: 30rpm However, since the extruder 2D15W has a rotation ratio of 3, the actual screw rotation speed is 90rpm. In other words, the rotation speed is 3 times faster (basic device rotation speed x 3), or 30rpm x 3 = 90rpm.

[0084] (Examples 8 to 12 and Comparative Example 5) Resins of Examples 8 to 12 and Comparative Example 5 were obtained in the same manner as in Example 7, except for the changes shown in Table 2. The physical properties of the obtained resins are shown in Table 2. Note that in these Examples and Comparative Examples, resins to which no inorganic filler was added were evaluated, but any resin with good properties shown in Table 2 can be used as a main component of a resin composition, similar to the above-mentioned Examples 1 to 6.

[0085] The evaluation tests for the resin examples and comparative examples, i.e., Examples 7 to 11 and Comparative Examples 5 and 6 whose results are shown in Table 2, were carried out by preparing test specimens as described in i) below, and then under the conditions described in ii) below. i) Molding of test specimens Dumbbell A12 test specimens conforming to JIS K7139 were prepared as follows. Dumbbell A12 test specimens: Tensile test, hydrolysis test, weather resistance test Equipment: Shinko Selvic (now Epson Techform) C,Mobile-0813 Molding temperature: Manifold 150°C, body 170°C, tip 70%, mold temperature 40°C Screw rotation speed: 90 rpm Metering speed: 2 mm / s Injection speed: 20 mm / s

[0086] ii) Tensile test: Tensile elongation / tensile strength equipment: Shimadzu Corporation Autograph AGS-X Test piece: Dumbbell-shaped test piece, A12-shaped test piece (N=3) Load cell maximum capacity: 500N Grip distance: 50mm Test speed: 25mm / min Test conditions: Original (based on JIS K 7161-2:2014)

[0087] iii-1) Water Vapor Permeability Test: Film Production The resins of the Examples and Comparative Examples were formed into films under the following conditions, and a water vapor permeability test was carried out. Equipment: inflation molding machine [LF-250] (manufactured by Labtech Engineering Co., Ltd.) Die diameter: φ30 mm, die lip gap: 0.8 mm Extruder (manufactured by Plastics Technology Research Institute Co., Ltd.): φ20, L / D=25, full flight screw (C / R=3.0) / single flight) Molding temperature: above die: 180 ° C, below die: 180 ° C, adapter 2: 180 ° C, adapter 1: 180 ° C, flange: 180 ° C, C3: 180 ° C, C2: 180 ° C, C1: 170 ° C Screw rotation speed: 20 rpm Take-up speed: 2.4 m / min Blow ratio: 3.0 iii-2) Water vapor transmission rate test: Measurement of water vapor transmission coefficient Using the resin films of each example and comparative example as described above, the water vapor transmission coefficient was measured under the following conditions (water vapor transmission rate test). Equipment: MOCON PERMATRAN-W 3 / 34 Test temperature: 40°C Test pressure: 1 atm Humidity: 90% (converted to data equivalent to 100%) Mass flow: 100 SCCM Test piece: Circular diameter approximately 2.5 cm N=2 Test piece area: 5 cm ２ Unit test time: 30 minutes Conditioning time: 1 hour Method: Isobaric method (Reference: JIS K7129:2008 B. The standard requires a minimum number of samples of 3, but it is stated that this may be changed, and evaluation was performed with N=2 as described above)

[0088] iv) Weather resistance index equipment: Eye Super UV Tester SUV-W161 (manufactured by Iwasaki Electric Co., Ltd.) Temperature: 50°C Humidity: 40% Illuminance: 100mW / cm ２Test piece: Dumbbell-shaped test piece A12 type test piece Evaluation method: Test pieces were periodically removed and the molecular weight was evaluated. Since high molecular weight components are generated due to gelation, especially in the early stages, the number average molecular weight Mn was evaluated. The period during which the number average molecular weight Mn reached 50% of the initial value was determined and indexed, with PEC set to 100. Since the PBAT was 2.5 at this time, the weather resistance index was calculated from the blending ratio. Note that when the molecular weight is reduced to less than half, the physical properties rapidly decrease (returning to less than 90% of the initial value), and this period can be considered to be the period during which desirable physical properties can be maintained. Thus, a weather resistance index of 50 or higher can be considered to be a desirable level suitable for practical use.

[0089] v) Molecular weight apparatus: High-speed GPC HLC-8320 manufactured by Tosoh Corporation GPC column: GPC column SuperMultiporeHZ-M (4.6 mm I.D. x 150 mm) manufactured by Tosoh Corporation, three columns used in series. Flow rate: 0.35 mL / min Eluent: Chloroform Concentration: 0.2 w / v% Detector: Bryce type differential refractometer (RI detector)

[0090] vi) Hydrolysis Resistance (Hydrolysis Resistance Index) Equipment: SH-222 manufactured by Espec Corporation Temperature: 58°C Humidity: 65% Test Specimens: Dumbbell-shaped test specimens, A12-shaped test specimens Test Period: 1, 2, 4, 6, and 8 weeks Evaluation Method: A tensile test was conducted to evaluate the period during which 90% or more of the tensile strength of the undegraded state was maintained. Since the period for PEC alone was 8 weeks and for PBAT alone was 1.5 weeks, the hydrolysis resistance index was calculated from the blending ratio, with PEC set to 100 and PBAT set to 22.1. Note that the hydrolysis resistance index for PBS is 2 weeks (25), so a hydrolysis resistance index of 37.5 or more, which is 1.5 times that, can be considered to be good properties.

[0091] vii) Biodegradability Equipment: MODA-CS manufactured by Yawata Bussan Co., Ltd. Conditions: JIS K 6953-2 (complies with the provisions of this standard that small parts of molded pieces may be used) Test piece: resin pellet Evaluation method: A biodegradation test was conducted under compost conditions at 58°C, and the biodegradability after the test was continued for 30 days was calculated as a ratio to the biodegradability of cellulose (standard substance) at that time. The result for PEC alone was 59.1, and the result for PBAT was 9.8, and biodegradability was evaluated from these blend ratios.

[0092] A calculated evaluation value of 50 or more was rated as "particularly good," a value of 40 or more but less than 50 was rated as "good," a value of 30 or more but less than 40 was rated as "fair," a value of 20 or more but less than 30 was rated as "fair," a value of 10 or more but less than 20 was rated as "fair," and a value less than 10 was rated as "poor." Since a product that can withstand actual use over several months and is biodegradable is preferred, it is desirable for this value to be 10 or more (a result that is "fair" or better), which is higher than that of PBAT alone (the value is 9.8).

[0093] As is clear from the above results, the resin compositions of each Example were confirmed to have excellent biodegradability as well as high tensile strength, flexural strength, and hydrolysis resistance. On the other hand, the resin compositions of the Comparative Examples did not achieve good results in any of these properties. For example, Comparative Example 1 showed good biodegradability and hydrolysis resistance, but poor strength. Furthermore, Comparative Examples 2 to 4 and 5 showed good strength, but poor biodegradability and hydrolysis resistance.

[0094] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited to these examples. It is clear that a person skilled in the art to which the present invention pertains can conceive of various modifications and alterations within the scope of the technical ideas set forth in the claims, and it is understood that these also naturally fall within the technical scope of the present invention.

Claims

1. A resin composition comprising a polyester carbonate resin containing a structural unit (A) derived from a monomer represented by the following general formula (1) and a structural unit (B) derived from a monomer represented by the following general formula (2), and an inorganic filler, wherein the structural unit (A) is a structural unit derived from a monomer represented by the following general formula (2): HO-Ra-OH (1) (In general formula (1), Ra represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.) R １ OOC-Rb-COOR ２ ...(2) (In the general formula (2), Rb represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and R １ and R ２ are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent. A resin composition, wherein the amount of the inorganic filler in the resin composition is 30 to 50 mass %.

2. The resin composition according to claim 1, further comprising polylactic acid and / or polyester.

3. 25 to 100% by mass of a polyester carbonate resin containing a structural unit (A) derived from a monomer represented by the following general formula (1) and a structural unit (B) derived from a monomer represented by the following general formula (2), and HO-Ra-OH (1) (in general formula (1), Ra represents an alkylene group having 1 to 20 carbon atoms which may have a substituent). １ OOC-Rb-COOR ２ ...(2) (In the general formula (2), Rb represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and R １ and R ２ are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent. A resin composition comprising: 0 to 50% by mass of polylactic acid; and an inorganic filler.

4. The resin composition according to claim 3, wherein the amount of the inorganic filler in the resin composition is 30 to 50% by mass.

5. A resin composition comprising a polyester carbonate resin containing a structural unit (A) derived from a monomer represented by the following general formula (1) and a structural unit (B) derived from a monomer represented by the following general formula (2), and a polyester, wherein the structural unit (A) is a structural unit derived from a monomer represented by the following general formula (2): HO-Ra-OH (1) (In general formula (1), Ra represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.) R １ OOC-Rb-COOR ２ ...(2) (In the general formula (2), Rb represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and R １ and R ２ are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent. A resin composition, wherein the amount of the polyester in the resin composition is 10 to 30 mass %.

6. In the formula (1), each Ra independently represents (CH ２ )n, each n is independently an integer of 4 to 16; in the formula (2), each Rb is independently (CH ２ ) m, wherein each m independently represents an integer of 2 to 16. The resin composition according to claim 1 , 3 or 5.

7. A resin composition according to claim 2, wherein the mass ratio of polyester carbonate resin to polylactic acid (polyester carbonate resin:polylactic acid) in the resin composition is polyester carbonate resin:polylactic acid = 50-90:50-10.

8. The resin composition according to claim 1 or 3, wherein the inorganic filler includes at least one of talc, mica, and wollastonite.

9. The resin composition according to claim 1, 3 or 5, further comprising a mold release agent and / or an antioxidant.

10. The resin composition according to claim 1, 3 or 5, which is substantially free of phosphorus-based compounds.

11. The resin composition according to claim 1, 3 or 5, having a flexural modulus of 2000 to 5000 MPa.

12. The resin composition according to claim 1, 3 or 5, which has a biodegradability of 30% or more after 20 days in a biodegradability test based on JIS K 6953-2.

13. A resin composition according to claim 1, 3 or 5, wherein a test piece of the resin composition having a thickness of 1 mm, prepared in accordance with JIS K 6251, is left to stand at a temperature of 58°C and a humidity of 65%, and the tensile strength remains at 90% or more of the tensile strength before the test for 25 days or more.

14. A molded article comprising the resin composition according to claim 1, 3 or 5.

15. The molded article according to claim 14, which is a pipe to be buried underground.

16. The molded article according to claim 14, which is a film having gas barrier properties or biodegradability.

17. The molded article according to claim 14, wherein the thickness of the molded article is 0.1 mm or more.

18. A resin composition comprising a polyester carbonate resin containing a structural unit (A) derived from a monomer represented by the following general formula (1) and a structural unit (B) derived from a monomer represented by the following general formula (2), and a polyester, the resin composition comprising: HO-Ra-OH (1) (in general formula (1), Ra represents an alkylene group having 1 to 20 carbon atoms which may have a substituent). １ OOC-Rb-COOR ２ ...(2) (In the general formula (2), Rb represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and R １ and R ２ are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent. ） 　 The resin composition, wherein the polyester contains at least an aliphatic-aromatic copolymer polyester.

19. The resin composition according to claim 18, wherein the polyester comprises a structural unit (A') derived from a monomer represented by the following general formula (I) and a structural unit (C) derived from a monomer represented by the following general formula (II): HO-Ra'-OH (I) (In general formula (I), Ra' represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.) R １ OOC-Rb'-COOR ２ ...(II) (In the general formula (II), Rb' represents an alkylene group having 1 to 20 carbon atoms which may have a substituent or an arylene group having 6 to 30 carbon atoms which may have a substituent, R １ and R ２ are each independently selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms which may have a substituent.

20. The resin composition according to claim 18, wherein the amount of the polyester in the resin composition is 1 to 60% by mass.

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