Resin composition and molded article

Abstract

The present invention provides a novel resin composition comprising a polyester resin using bifrangic acid and / or its ester as a biomass monomer, which is capable of practical molding processes such as injection molding, and a molded article thereof. [Solution] A polycondensate (A) of a component (a1) containing one or more selected from 2,2'-bifuran-5,5'-dicarboxylic acid ester and 2,2'-bifuran-5,5'-dicarboxylic acid and a component (a2) containing an alkylenediol with 2 or more carbon atoms, and a nucleating agent (B), wherein the semicrystallization time (Tc) at a temperature (T1) of (the glass transition temperature (Tg) of the polycondensate (A)) or higher and (the glass transition temperature (Tg) or lower (Tg + 80°C) is measured by differential scanning calorimeter (DSC). 1 / 2 A resin composition in which the time is 300 seconds or less.

Description

[Technical Field]

[0001] This disclosure relates to resin compositions and molded articles. [Background technology]

[0002] In recent years, climate change caused by global warming has become more serious, and there is a growing movement to transition to sustainable energy sources that do not rely on fossil fuels. Furthermore, plastics made from fossil fuels are a cause for concern due to various environmental burdens, such as marine pollution caused by microplastics. Accordingly, research into biomass plastics obtained using biomass monomers is progressing. Conventionally, biomass plastics such as polylactic acid and biomass polyethylene are known, which use lactic acid and ethanol obtained by fermenting corn and sugarcane as biomass monomers. However, since corn and sugarcane, which are the raw materials for these biomass monomers, are also used as food, various problems have been pointed out, such as soaring food prices, food problems in developing countries, and deforestation due to land conversion. For this reason, the use of components obtained from polysaccharides such as cellulose and hemicellulose contained in waste parts of food crops and wood (waste wood) as biomass monomers is being considered.

[0003] Examples of biomass monomers obtained from cellulose include ethanol obtained by saccharifying cellulose, 5-hydroxymethylfurfural obtained by dehydrating glucose, franfural carboxylic acid obtained by oxidizing furfural, and bifranfural carboxylic acid obtained by dehydrating and oxidizing hemicellulose. Patent Document 1 describes a polyester resin having 2,5-franfural carboxylic acid units, ethylene glycol units, and diethylene glycol units. Patent Document 2 proposes a furan oligomer polyester using furfural as a raw material. [Prior art documents] [Patent Documents]

[0004]

Patent Document 1

Patent Document 2

Non-Patent Document

[0005]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in these documents, only the synthesis of polyester resins using furfural oligomers or furocarboxylic acids as raw materials has been reported. When the inventors of the present application examined the moldability of a polyester resin containing bifuran dicarboxylic acid or its ester as a biomass monomer, it was found that it is difficult to perform practical molding processes such as injection molding on the resin composition containing the polyester resin.

[0007] The present disclosure is directed to providing a novel resin composition containing a polyester resin using bifuran dicarboxylic acid and / or its ester as a biomass monomer, which enables practical molding processes such as injection molding, and a molded article thereof.

Means for Solving the Problems

[0008] The present disclosure includes the following aspects. [1] A polycondensate (A) containing at least one component (a1) selected from 2,2'-bifuran-5,5'-dicarboxylic acid ester and 2,2'-bifuran-5,5'-dicarboxylic acid, and a component (a2) containing an alkylene diol having 2 or more carbon atoms, and a nucleating agent (B). The semi-crystallization time (Tc 1 / 2 ) at a temperature (T1) of (the glass transition temperature (Tg) of the polycondensate (A) + 60°C) or higher and (Tg + 80°C) or lower, measured by a differential scanning calorimeter (DSC), is 300 seconds or less, for the resin composition.

Advantages of the Invention

[0009] According to the present disclosure, there is provided a novel resin composition containing a polyester resin using bifran dicarboxylic acid and / or its ester as a biomass monomer, a resin composition capable of practical molding processes such as injection molding, and a molded product thereof.

Modes for Carrying Out the Invention

[0010] Hereinafter, an embodiment of the present disclosure will be described in detail. However, the scope of the present disclosure is not limited to the embodiment described here, and various modifications can be made without departing from the spirit of the present disclosure. Each aspect disclosed in this specification can be combined with any other features disclosed in this specification. When multiple upper and lower limit values are described for a specific parameter, any upper limit value and lower limit value can be combined to form a suitable numerical range. The lower limit value and / or upper limit value of the numerical range described in the present disclosure are numerical values within that numerical range and can be replaced with the numerical values shown in the examples. The expression "X~Y" indicating a numerical range means "X or more and Y or less". When the specific description given for one embodiment also applies to other embodiments, the description may be omitted in other embodiments.

[0011] [Resin Composition] The first embodiment of the present disclosure relates to a resin composition. The resin composition according to the first embodiment comprises a polycondensate (A) of a component (a1) containing one or more selected from 2,2'-bifuran-5,5'-dicarboxylic acid ester and 2,2'-bifuran-5,5'-dicarboxylic acid and a component (a2) containing an alkylenediol having 2 or more carbon atoms, and a nucleating agent (B), and the semicrystallization time (Tc) at a temperature (T1) of (the glass transition temperature (Tg) of the polycondensate (A)) or higher and (the glass transition temperature (Tg) or lower) (Tg + 80°C), as measured by differential scanning calorimeter (DSC). 1 / 2 The time required is 300 seconds or less. According to the resin composition of the first embodiment, practical molding processes such as injection molding are possible.

[0012] <Half crystallization time (Tc 1 / 2 )> The resin composition according to the first embodiment has a semicrystallization time (Tc) measured by differential scanning calorimeter (DSC) at a temperature (T1) between (Tg + 80°C) and (Tg + 60°C) of the polycondensate (A). 1 / 2 The semicrystallization time is 300 seconds or less. "Semicrystallization time" generally refers to the time it takes to reach half the area of ​​the exothermic peak due to crystallization in an isothermal crystallization process. The shorter the semicrystallization time, the faster the crystallization. In the resin composition according to the first embodiment, the semicrystallization time (Tc) at temperature (T1) is 300 seconds or less. 1 / 2 ) can be measured under the following conditions.

[0013] (Half crystallization time (Tc 1 / 2 (Measurement conditions) Using a differential scanning calorimeter (DSC) (e.g., PerkinElmer, product name "DSC8000"), the semi-crystallization time (Tc) was determined under the following conditions. 1 / 2Measure it. First, fill 10 mg of the resin composition sample into the device, heat it up to 240°C at a rate of 80°C / min under a nitrogen atmosphere, and hold it at 240°C for 3 minutes. Then, cool it down at a rate of 80°C / min to a temperature (T1) that is not less than (glass transition temperature (Tg) + 60°C) and not more than (Tg + 80°C) of the polycondensate (A), and then hold it at the temperature (T1) for 30 minutes. The time required to reach half of the heat generation amount in 30 minutes (the time when the area becomes half of the crystallization peak area) is defined as the half-crystallization time (Tc 1 / 2 ).

[0014] In one embodiment, from the perspective of being likely to have good moldability, the half-crystallization time (Tc 1 / 2 ) at the temperature (T1) of the resin composition is preferably 250 seconds or less, more preferably 200 seconds or less, even more preferably 120 seconds or less, and particularly preferably 60 seconds or less. Note that, as described above, in order to make the half-crystallization time (Tc 1 / 2 ) at the temperature (T1) 300 seconds or less, it is necessary to combine the polycondensate (A) and the nucleating agent (B). As the nucleating agent (B), it is preferable to combine an inorganic nucleating agent. Details of the nucleating agent (B) will be described later. From the perspective of the measurement limit value of the half-crystallization time (Tc 1 / 2 ) by DSC, the lower limit of the half-crystallization time (Tc 1 / 2 ) at the temperature (T1) is 0.01 seconds or more.

[0015] The temperature (T1) is in the range of not less than +60°C and not more than +80°C with respect to the glass transition temperature (Tg) of the polycondensate (A). For example, in the case of the polycondensate (A) obtained in Example 1, since Tg is 66°C, the temperature (T1) is not less than 126°C and not more than 146°C. The resin composition according to the first embodiment has a half-crystallization time (Tc 1 / 2 ) of 300 seconds or less within the above temperature (T1) range. The inventors of the present application have determined the half-crystallization time (Tc 1 / 2The reason we focused on the temperature range of +60°C to +80°C relative to the glass transition temperature (Tg) as the temperature that determines crystallization is that this temperature range shows the maximum crystallization rate. Specifically, at higher temperatures, the mobility of the molecular chains is too high, requiring more time for regular arrangement, and near the glass transition temperature, the mobility of the molecular chains is too low, making crystallization difficult. As a result, the crystallization rate is fastest in the intermediate temperature range between the two, from +60°C to +80°C relative to the glass transition temperature (Tg). The glass transition temperature (Tg) of the polycondensate (A) is determined using a differential scanning calorimeter (DSC) during the second heating process at a heating rate of 20°C / min under a nitrogen atmosphere.

[0016] <Polycondensate (A)> The resin composition according to the first embodiment comprises a polycondensate (A) of component (a1) containing one or more selected from 2,2'-bifuran-5,5'-dicarboxylic acid ester and 2,2'-bifuran-5,5'-dicarboxylic acid, and component (a2) containing an alkylenediol having two or more carbon atoms. The polycondensate (A) is a resin obtained by polycondensation of component (a1) and component (a2), and is a polyester resin containing two or more ester groups in its structure.

[0017] (Component (a1)) Component (a1) is a dicarboxylic acid component for obtaining polycondensate (A), and contains one or more selected from 2,2'-bifuran-5,5'-dicarboxylic acid ester and 2,2'-bifuran-5,5'-dicarboxylic acid. That is, component (a1) contains one or more compounds represented by the following formula (I). Hereinafter, 2,2'-bifuran-5,5'-dicarboxylic acid ester and 2,2'-bifuran-5,5'-dicarboxylic acid will be described as "compounds of formula (I)". [ka] (In formula (I), R1 and R2 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms.)

[0018] In formula (I), when R1 and R2 are alkyl groups, from the viewpoint of ease of purification and polymerizability, alkyl groups having 1 to 6 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group) are preferred, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, or hexyl group are more preferred, and methyl group, ethyl group, or isopropyl group are particularly preferred.

[0019] As described above, the compound of formula (I) is a dimer of bifrancicarboxylic acid or its ester. Furthermore, this compound is a biomass monomer. The compound of formula (I) can be synthesized by the method described in Non-Patent Document 1 or Non-Patent Document 2. For example, (1) a method of obtaining 5-bromofuran-2-carboxylic acid by reacting biomass-derived furfural in the order of oxidation, bromination and esterification, and dimerizing 5-bromo-2-furancarboxylic acid in the presence of a catalyst to obtain 2,2'-bifuran-5,5'-dicarboxylic acid (hereinafter sometimes referred to as "BFDCA"), and (2) a method of obtaining 2,2'-bifuran-5,5'-dicarboxylic acid ester by dehydration condensation of the BFDCA obtained in (1) with an alcohol having 1 to 6 carbon atoms. In addition, as a method for obtaining component (a1) in which R1 and R2 are ethyl groups, (3) a method of obtaining 5-bromofuran-2-carboxylic acid by reacting biomass-derived furfural in the order of oxidation, bromination and esterification. Another method involves further esterifying the carboxylic acid to obtain ethyl-5-bromofuran-2-carboxylate, and then dimerizing it in the presence of tetrabutylammonium bromide, a Ni catalyst, and zinc powder to obtain ethyl-2,2'-bifuran-5,5'-dicarboxylic acid ester. The compound of formula (I) can be prepared by any of the above methods (1) to (3), but from the viewpoint of industrial productivity and yield, it is preferable to use method (1) or (2).

[0020] Component (a1) contains one or more compounds of formula (I). In one embodiment, component (a1) is preferably a 2,2'-bifuran-5,5'-dicarboxylic acid ester from among the compounds of formula (I), from the viewpoint of polymerizability and ease of purification as a monomer, and more preferably a dicarboxylic acid ester in which R1 and R2 are isopropyl.

[0021] Component (a1) may contain components other than the compound of formula (I) (other dicarboxylic acid components). Examples of other dicarboxylic acid components include halides of 2,2'-bifuran-5,5'-dicarboxylic acid; 2,5-frandicarboxylic acid (FDCA) or its ester-forming derivatives (FDCA esters, FDCA halides, etc.); terephthalic acid or its ester-forming derivatives; isophthalic acid or its ester-forming derivatives; naphthalenedicarboxylic acid or its ester-forming derivatives; cyclohexanedicarboxylic acid or its ester-forming derivatives, etc. These other dicarboxylic acid components may be included individually or in groups of two or more.

[0022] The proportion of the compound of formula (I) in component (a1) is preferably 50 to 100% by mass, more preferably over 50% by mass and 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 100% by mass.

[0023] In one embodiment, the proportion of monomer units derived from component (a1) in the polycondensate (A) is preferably 45 to 55 mol%, more preferably 48 to 52 mol%, and even more preferably 49 to 51 mol%, from the viewpoint of the mechanical properties and heat resistance of the resin.

[0024] (ingredient (a2)) Component (a2) is a glycol component for obtaining the polycondensate (A), and contains an alkylenediol with 2 or more carbon atoms. Examples of alkylenediols with 2 or more carbon atoms include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, 1,3-octanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol, which have 2 to 10 carbon atoms. These alkylenediols may be used individually or in combination of two or more. Of these, from the viewpoint of the mechanical properties and heat resistance of the resin, component (a2) preferably contains an alkylenediol with 2 to 4 carbon atoms, and more preferably contains 1,4-butanediol.

[0025] Component (a2) may contain components other than alkylenediols having 2 or more carbon atoms (other glycol components). Examples of other glycol components include polyoxyalkylene glycols such as alkylene oxide adducts of diethylene glycol, alkylene oxide adducts of triethylene glycol, and alkylene oxide adducts of dipropylene glycol; alicyclic diols such as cyclohexanedimethanol and hydrogenated bisphenol A; aromatic diols such as bisphenol A and 4,4'-dihydroxybiphenyl; alkylene oxide adducts of bisphenol A such as a 2-mol ethylene oxide adduct of bisphenol A and a 3-mol propylene oxide adduct of bisphenol A; or ester-forming derivatives of these glycols (acetylated compounds, etc.). These other glycol components may be used individually or in combination of two or more.

[0026] The proportion of alkylenediols having 2 or more carbon atoms in component (a2) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 100% by mass.

[0027] In one embodiment, the proportion of monomer units derived from component (a2) in the polycondensate (A) is preferably 45 to 55 mol%, more preferably 48 to 52 mol%, and even more preferably 49 to 51 mol%, from the viewpoint of polymerization reactivity and resin properties.

[0028] In one embodiment, the polycondensate (A) has monomer unit 1 derived from the compound of formula (I) and monomer unit 2 derived from 1,4-butanediol, and the proportion of monomer unit 1 is 45 to 55 mol% and the proportion of monomer unit 2 is 45 to 55 mol% with respect to the total number of monomer units constituting the polycondensate (A) (100 mol%).

[0029] In one embodiment, the polycondensate (A) is preferably one having a tensile strength of 50 MPa or more. In one embodiment, the weight-average molecular weight (Mw) of the polycondensate (A) is preferably 10,000 to 200,000, more preferably 20,000 to 150,000, and even more preferably 50,000 to 12,000. The Mw can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC). Hexafluoroisopropanol is used as the measurement solvent, and the measurement is performed at a column temperature of 40°C.

[0030] <Method for producing polycondensate (A)> The polycondensate (A) can be produced, for example, by polymerizing component (a1) and component (a2) using the method described in Patent Document 2, or Non-Patent Document 1 or Non-Patent Document 2. Specifically, it can be produced by heating component (a1) and component (a2) in the presence of a polymerization catalyst.

[0031] As a polymerization catalyst, conventionally known catalysts for the production of polyesters can be used. For example, titanium tetramethoxide, titanium tetra(n-propoxide), titanium tetra(n-butoxide), titanium tetraisopropoxide, titanium tetraisobutoxide, titanium tetra(t-butoxide), cyclohexyl titanate, phenyl titanate, benzyl titanate, and tolyl titanate can be used. Of these, titanium tetra(n-propoxide), titanium tetra(n-butoxide), and titanium tetraisopropoxide are preferred, with titanium tetra(n-butoxide) being more preferred. Other metal oxides such as lead oxide and copper(II) oxide; Sn(OC8H 17 ) You may also use stannic acid esters of the 4th class, etc.

[0032] The heating temperature is preferably 100 to 300°C, more preferably 150 to 250°C, and even more preferably 150 to 230°C. The reaction temperature may also be increased in stages. The reaction time is preferably 0.5 to 20 hours, more preferably 0.5 to 15 hours, and even more preferably 0.5 to 5 hours. In the polymerization method of the present invention, solid-phase polymerization may be performed after melt polycondensation.

[0033] The molar ratio of component (a1) to component (a2) can be arbitrarily adjusted within the range of 1:1.05 to 1:10. In one embodiment, the molar ratio is preferably 1:2.

[0034] After polymerization is complete, the strand-like material may be cut by pelletizing to obtain a pellet-shaped polycondensate (A).

[0035] <Nuclear agent (B)> The resin composition according to the first embodiment comprises the above-mentioned polycondensate (A) and nucleating agent (B). The nucleating agent (B) is used in combination with the polycondensate (A) to achieve a semi-crystallization time (Tc) at a temperature (T1). 1 / 2Any nucleating agent can be selected from inorganic and organic nucleating agents, as long as the half-crystallization time can be adjusted to 300 seconds or less. Examples of inorganic nucleating agents include talc, boron nitride, silicon nitride, silica, mica, kaolin, barium sulfate, sodium phosphate, and calcium carbonate. As for organic nucleating agents, alkylbenzene sulfonates are preferred from the viewpoint of easily reducing the half-crystallization time. Among alkylbenzene sulfonates, those with 8 to 20 carbon atoms in the alkyl group are more preferred.

[0036] In one embodiment, the semi-crystallization time (Tc) at temperature (T1) is defined as the semi-crystallization time (Tc 1 / 2 From the viewpoint of shortening the semicrystallization time (Tc) at temperature (T1), it is preferable that the nucleating agent (B) contains one or more selected from talc, boron nitride, halloysite, calcium carbonate, silica, and alkylbenzene sulfonate. 1 / 2 From the viewpoint of easily adjusting the semicrystallization time (Tc) at temperature (T1) to 250 seconds or less, the nucleating agent (B) preferably includes an inorganic nucleating agent, and more preferably includes one or more selected from talc, boron nitride, halloysite, calcium carbonate, and silica. 1 / 2 From the viewpoint of easily adjusting the time to 120 seconds or less, it is even more preferable to include one or more selected from talc, boron nitride, and halloysite, and it is particularly preferable to include one or more selected from talc and boron nitride.

[0037] If the nucleating agent (B) contains talc and / or boron nitride, the talc is preferably of an average particle size (D50) of 0.1 to 50 μm, more preferably of 0.1 to 25 μm, and even more preferably of 0.1 to 15 μm. In one embodiment, the average particle size (D50) of the talc may be 0.1 to 3 μm. Furthermore, the average particle size (D50) of boron nitride is preferably 0.1 to 30 μm, more preferably 0.1 to 20 μm, and even more preferably 0.1 to 10 μm. When the nucleating agent (B) contains halloysite, the average length of the halloysite is preferably 1 to 15 μm, its average diameter is preferably 20 to 100 nm, more preferably 30 to 70 nm, even more preferably 35 to 65 nm, and particularly preferably 40 to 60 nm. In one embodiment, the halloysite may have a tubular structure, in which case the average length is preferably 0.5 to 5 μm, more preferably 1 to 3 μm, even more preferably 1.2 to 2.8 μm, and particularly preferably 1.5 to 2.5 μm. Also, the specific surface area of ​​the halloysite is 40 to 120 m². 2 / g is preferred, 50-100m 2 / g is more preferable, 55-80m 2 / g is more preferable, 60-70m 2 / g is particularly preferred. The average particle size (D50) of talc and boron nitride refers to the value measured by laser diffraction. The average diameter and length of halloysite refer to the values ​​calculated as the arithmetic mean of 100 halloysite particles randomly selected from images taken with a scanning electron microscope (SEM) using ImageJ, open software developed by the National Institutes of Health in the United States. The SEM measurement conditions were an acceleration voltage of 15kV and a magnification of 10,000x.

[0038] If the nucleating agent (B) contains talc and / or boron nitride, the proportion of talc and / or boron nitride in the nucleating agent (B) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 95 to 100% by mass, based on the total mass of the nucleating agent (B). In one embodiment, the nucleating agent (B) may contain only talc and / or boron nitride.

[0039] In one embodiment, the ratio of nucleating agent (B) to 100 parts by mass of polycondensate (A) is preferably 0.01 to 10.0 parts by mass, more preferably 0.01 to 10.0 parts by mass, even more preferably 0.1 to 5.0 parts by mass, and particularly preferably 0.1 to 3.0 parts by mass, from the viewpoint of the strength of the molded article. In one embodiment, 1.0 to 3.1 parts by mass of nucleating agent (B) may be blended with 100 parts by mass of polycondensate (A).

[0040] <Other ingredients> The resin composition according to the first embodiment may optionally contain other components besides the polycondensate (A) and the nucleating agent (B). These other components include thermoplastic resins other than the polycondensate (A) (other thermoplastic resins), as well as known additives that can be blended into polyester resins. Examples include, but are not limited to, inorganic fillers such as glass fibers, antioxidants, weather stabilizers, molecular weight modifiers, ultraviolet absorbers, antistatic agents, dyes, pigments, lubricants, crystallization accelerators, crystal nucleating agents other than the nucleating agent (B), near-infrared absorbers, flame retardants, flame retardant aids, organic fillers, and colorants. These other components may be used individually or in combination of two or more. Other thermoplastic resins may include, for example, polypropylene (PP), polyethylene (PE), polycarbonate (PC), polyphenylene ether (PPE), polystyrene (PS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), as well as thermoplastic elastomers (TPE), styrene elastomers (SBC), and polyester elastomers (TPEE). Of these, from the viewpoint of compatibility during melt mixing, the resin composition may contain only polycondensate (A) as the thermoplastic resin.

[0041] In one embodiment, the crystallization enthalpy (ΔH(J / g)), which is the total area of ​​the crystallization peak observed when the resin composition is held at a temperature of Tg + 60 to 80°C for 30 minutes, is preferably -60 to -10 J / g, more preferably -60 to -20 J / g, and even more preferably -60 to -25 J / g. The semi-crystallization time (Tc) at temperature (T1) is also specified. 1 / 2If the reaction time is 300 seconds or less and ΔH is within the above range, the resin composition is more likely to be capable of practical molding processes such as injection molding. The ΔH of the resin composition can be easily controlled to the above preferred range by adjusting the content of the nucleating agent (B).

[0042] As described above, the resin composition according to the first embodiment contains a specific polycondensate (A) and a nucleating agent (B) as essential components. When the inventors of the present invention investigated the moldability of polyester resins using bifranciocarboxylic acid and / or its esters as biomass monomers, they found that even when the polyester resin was simply molded, the molded articles did not have sufficient release properties or strength. The inventors of the present invention found that the polyester resin obtained from bifranciocarboxylic acid and / or its esters had a slow crystallization rate, which resulted in insufficient moldability. Furthermore, as a result of diligent investigation by the inventors of the present invention, they found that by combining a nucleating agent (B), preferably an inorganic nucleating agent, more preferably talc and / or boron nitride, with the polyester resin, the semi-crystallization time (Tc 1 / 2 We found that this can shorten the time required for injection molding and enable practical molding processes such as injection molding.

[0043] [Method for producing resin compositions] The resin composition according to the first embodiment can be prepared by mixing a polycondensate (A), a nucleating agent (B), and other components as needed, in any manner. For example, after dry blending each component, the mixture can be melt-kneaded using a single-screw or twin-screw extruder and then extruded from a die to obtain pellets. The melt-kneading temperature is preferably 200 to 350°C.

[0044] [Molded products] A second embodiment of this disclosure relates to a molded article comprising a resin composition according to the first embodiment. The molded article according to the second embodiment can preferably be obtained by molding pellets comprising the resin composition according to the first embodiment (more preferably pellets comprising only the resin composition according to the first embodiment). More specifically, this molding includes molding the pellets comprising the resin composition according to the first embodiment using generally known molding methods for thermoplastic resins, such as injection molding, extrusion molding, vacuum molding, and compression molding. As described above, the resin composition according to the first embodiment has a semicrystallization time (Tc) at a temperature (T1). 1 / 2 Since the time is 300 seconds or less, practical molding is possible. Preferably, the molded product according to the second embodiment is an injection molded product.

[0045] A preferred embodiment for manufacturing a molded article according to the second embodiment involves injection molding a resin composition comprising the polycondensate (A) and a nucleating agent (B) containing one or more selected from talc, boron nitride, and halloysite, under injection molding conditions of a cylinder temperature of 200 to 300°C and a mold temperature of 80 to 180°C. Preferably, the resin composition contains 0.01 to 10.0 parts by mass of the nucleating agent (B) per 100 parts by mass of the polycondensate (A). More preferably, the nucleating agent (B) contains one or more selected from talc and boron nitride.

[0046] [Application] The molded article according to the second embodiment contains a component (a1) which is a biomass monomer, and a polycondensate (A) of component (a1). As mentioned above, since the compound of formula (I) can be obtained from cellulose contained in waste parts of food crops and waste materials, the molded article according to the second embodiment is a biomass plastic with a lower environmental impact. Because such a molded article according to this embodiment has excellent heat resistance, it can be applied to electrical and electronic equipment and automobiles.

[0047] Other embodiments of the present disclosure provide a polycondensate (A) of a component (a1) comprising one or more components selected from 2,2'-bifuran-5,5'-dicarboxylic acid ester and 2,2'-bifuran-5,5'-dicarboxylic acid and a component (a2) comprising an alkylenediol having two or more carbon atoms, with a semicrystallization time (Tc) at the temperature (T1). 1 / 2 A method to shorten ) to 300 seconds or less, A method comprising adding 0.01 to 10.0 parts by mass of a nucleating agent (B) containing one or more selected from talc, boron nitride, halloysite, calcium carbonate, silica, and alkylbenzene sulfonate to 100 parts by mass of the polycondensate (A). The nucleating agent (B) more preferably comprises one or more selected from talc, boron nitride, and halloysite, and particularly preferably comprises one or more selected from talc and boron nitride.

[0048] Other embodiments of the present disclosure are resin compositions comprising 0.01 to 10.0 parts by mass of a nucleating agent (B) containing one or more selected from talc, boron nitride, and halloysite, per 100 parts by mass of a polycondensate (A) of a component (a1) containing one or more selected from 2,2'-bifuran-5,5'-dicarboxylic acid ester and 2,2'-bifuran-5,5'-dicarboxylic acid and a component (a2) containing an alkylenediol having two or more carbon atoms. The proportion of the nucleating agent (B) is more preferably 0.1 to 10.0 parts by mass, even more preferably 0.5 to 8.0 parts by mass, and particularly preferably 0.5 to 6.0 parts by mass. The nucleating agent (B) preferably contains talc and / or boron nitride. The talc is preferably of average particle size (D50) of 0.1 to 3.0 μm.

[0049] A non-limiting list of exemplary embodiments and combinations of exemplary embodiments of this disclosure are disclosed below. [1] A polycondensate (A) of a component (a1) containing one or more selected from 2,2'-bifuran-5,5'-dicarboxylic acid ester and 2,2'-bifuran-5,5'-dicarboxylic acid and a component (a2) containing an alkylenediol having 2 or more carbon atoms, and a nucleating agent (B), The semicrystallization time (Tc) at a temperature (T1) between (the glass transition temperature (Tg) of the polycondensate (A) + 60°C) and (the glass transition temperature (Tg) + 80°C), as measured by differential scanning calorimeter (DSC). 1 / 2 A resin composition in which the time is 300 seconds or less. [2] The resin composition according to [1], wherein the nucleating agent (B) comprises one or more selected from talc, boron nitride, halloysite, calcium carbonate, silica, and alkylbenzene sulfonates. [3] The resin composition according to [1] or [2], wherein the nucleating agent (B) comprises one or more selected from talc, boron nitride, and halloysite. [4] The semi-crystallization time (Tc 1 / 2 A resin composition according to any one of [1] to [3], wherein the time is 120 seconds or less. [5] The semi-crystallization time (Tc 1 / 2 A resin composition according to any one of [1] to [4], wherein the time is 60 seconds or less. [6] The resin composition according to any one of [1] to [5], wherein the component (a2) comprises an alkylenediol having 2 to 4 carbon atoms. [7] A resin composition according to any one of [1] to [6], wherein the component (a2) comprises 1,4-butanediol. [8] The resin composition according to any one of [1] to [7], wherein the ratio of the nucleating agent (B) to 100 parts by mass of the polycondensate (A) is 0.01 to 10.0 parts by mass. A molded article comprising the resin composition described in any of [9], [1], to [8].

[10] The molded product described in [9], which is an injection molded product. Each configuration and its combination in each embodiment is an example, and additions, omissions, substitutions, and other modifications can be made as appropriate without departing from the spirit of this disclosure. This disclosure is not limited by the embodiments. [Examples]

[0050] The present disclosure will be further illustrated by the following examples, but these examples will not limit the interpretation of the present disclosure.

[0051] <Synthesis Example 1>: Compound of formula (I): Preparation of 2,2'-bifuran-5,5'-dicarboxylic acid 89 g of 5-bromo-2-furancarboxylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 47 g of NaOH, and 5 g of palladium-carbon catalyst (Pd / C) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a mixed solvent of 800 mL of distilled water and 180 mL of methanol, and the mixture was stirred at 90°C for 24 hours. After cooling to room temperature, the mixture was filtered to separate the Pd / C. Next, hydrochloric acid was added to the filtrate to precipitate the compound, and the solid was recovered by suction filtration and washed with distilled water. The compound was then vacuum dried at 80°C for 3 hours to obtain the target compound (yield 88%). 1 Analysis by 1H-NMR confirmed that it was 2,2'-bifuran-5,5'-dicarboxylic acid (BFDCA). 1 H-NMR(DMSO-d6,400MHz);7.065-7.075(d,2H),7.344-7.353(d,2H)

[0052] <Synthesis Example 2>: Compound of formula (I): Preparation of 2,2'-bifuran-5,5'-dicarboxylic acid isopropyl To a suspension of 38.5 g of BFCDA obtained in Synthesis Example 1 in isopropanol (400 g), sulfuric acid (25 g) was added and the mixture was stirred under reflux at 90°C for 24 hours. After cooling to room temperature, the solid was collected by suction filtration and washed with methanol and distilled water. The obtained solid was recrystallized in chloroform and dried at 100°C to obtain the target compound (yield: 33%). 1 Analysis by 1H-NMR confirmed that it is isopropyl 2,2'-bifuran-5,5'-dicarboxylate. 1 H-NMR(CDCl3,500MHz);3.922(s,6H),6.889-6.898(d,2H),7.243-7.252(d,2H)

[0053] <Synthesis Example 3>: Preparation of polycondensate (A) 39 g of isopropyl 2,2'-bifuran-5,5'-dicarboxylic acid obtained in Synthesis Example 2, 17 g of 1,4-butanediol (manufactured by Kanto Chemical Co., Ltd.), and 17 mg of titanium(IV) tetrabutoxide (manufactured by Kanto Chemical Co., Ltd.) (500 ppm relative to the theoretical yield of the resin) were charged into a reaction vessel equipped with a stirrer, nitrogen inlet, heater, thermometer, and rectification column, and the inside of the reaction vessel was filled with a nitrogen atmosphere. Next, the temperature was raised to 230°C over 2 hours and 30 minutes while stirring, and then held for 1 hour to carry out melt polymerization. After that, the obtained polycondensate (A) was discharged in strand form from the bottom of the reaction vessel, cooled in a cooling water bath, cut with a strand cutter to obtain pellet-shaped polycondensate (A) approximately 2 mm long.

[0054] (Tg measurement of polycondensate (A)) The Tg of polycondensate (A) obtained in Synthesis Example 3 was measured under the following conditions. The result showed that the Tg was 66°C. For each example of resin composition, the glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) (PerkinElmer, product name: DSC8000) under the following conditions. First, 10 mg of the resin composition sample was placed in the apparatus and heated to 240°C at a rate of 20°C / min under a nitrogen atmosphere, and held at 240°C for 3 minutes. After that, it was cooled to room temperature at a rate of 20°C / min, and then heated again to 240°C at a rate of 20°C / min. From the DSC curve of this second heating process, the midpoint temperature of the baseline shift was determined as the glass transition temperature (Tg).

[0055] <Examples 1-18, Comparative Examples 1-7> The polycondensate (A) obtained in Synthesis Example 3 and the nucleating agent (B) shown in Table 1 were mixed according to the compositions described in Tables 2-3 so that the total amount of resin composition was 1 g. The mixture was then placed in a 5 mL screw-top tube and melt-kneaded at 240°C to obtain the resin compositions for each example.

[0056] [Table 1]

[0057] (Half crystallization time (Tc 1 / 2 (Measurement) For each example of resin composition, the semi-crystallization time (Tc) was measured using a differential scanning calorimeter (DSC) (PerkinElmer, product name: DSC8000) under the following conditions: 1 / 2 The semi-crystallization time (Tc) was measured. First, 10 mg of a resin composition sample was placed in the apparatus and heated to 240°C at a rate of 80°C / min under a nitrogen atmosphere, and held at 240°C for 3 minutes. Then, it was cooled to 140°C (Tg of polycondensate (A) (=66°C) + 74°C) at a rate of 80°C / min, and held at 140°C for 30 minutes. The time required to reach half of the heat generated in 30 minutes (the time when the area of ​​the crystallization peak becomes half) was defined as the semi-crystallization time (Tc). 1 / 2 )

[0058] (Measurement of enthalpy (ΔH (J / g))) Half crystallization time (Tc 1 / 2 In the measurement of ), the total area of ​​the crystallization peak observed when held at 140°C for 30 minutes was determined as the crystallization enthalpy (ΔH(J / g)).

[0059] [Table 2]

[0060] [Table 3]

[0061] Among the resin compositions in Tables 2-3, the semi-crystallization time (Tc) at temperature (T1) 1 / 2 For resin compositions with a curing time of 300 seconds or less, the moldability evaluation was deemed "passable" as they could withstand practical molding such as injection molding. From Tables 2-3, the resin composition of Comparative Example 1 (containing only polycondensate (A)) has a semicrystallization time (Tc) at temperature (T1). 1 / 2 The semi-crystallization time (Tc) is over 300 seconds. 1 / 2If the time to crystallize within the mold is this long, it will take time for crystallization to occur in the injection molding cycle, which will not only prevent sufficient productivity from being ensured, but may also cause molding defects such as deformation when demolding from the mold. As shown in Comparative Examples 2 to 7, by adding a nucleating agent to the polycondensate (A), the semi-crystallization time (Tc) at temperature (T1) can be reduced compared to Comparative Example 1. 1 / 2 Although the semi-crystallization time (Tc) is shortened, in all cases the semi-crystallization time (Tc) is shortened. 1 / 2 The semicrystallization time (Tc) at temperature (T1) exceeds 300 seconds, indicating insufficient moldability. On the other hand, the resin compositions of Examples 1 to 18 have a semicrystallization time (Tc) at temperature (T1). 1 / 2 Since the incubation period was 300 seconds or less, it was determined that these resin compositions are suitable for practical molding processes such as injection molding. [Industrial applicability]

[0062] The resin composition according to the first embodiment is a novel resin composition comprising a polyester resin using bifrangic acid and / or its ester as a biomass monomer. Since the resin composition according to the first embodiment can be subjected to practical molding processes such as injection molding, it can be applied to various fields as a molded product made of biomass plastic.

Claims

1. The compound comprises a polycondensate (A) of a component (a1) containing one or more selected from 2,2'-bifuran-5,5'-dicarboxylic acid ester and 2,2'-bifuran-5,5'-dicarboxylic acid, and a component (a2) containing an alkylenediol having two or more carbon atoms, and a nucleating agent (B), The semicrystallization time (Tc) at a temperature (T1) between (the glass transition temperature (Tg) of the polycondensate (A) + 60°C) and (the glass transition temperature (Tg) + 80°C), as measured by differential scanning calorimeter (DSC). １／２ A resin composition in which the time is 300 seconds or less.

2. The resin composition according to claim 1, wherein the nucleating agent (B) comprises one or more selected from talc, boron nitride, halloysite, calcium carbonate, silica, and alkylbenzene sulfonate.

3. The resin composition according to claim 1 or 2, wherein the nucleating agent (B) comprises one or more selected from talc, boron nitride, and halloysite.

4. The aforementioned semi-crystallization time (Tc １／２ The resin composition according to claim 1 or 2, wherein the time is 120 seconds or less.

5. The aforementioned semi-crystallization time (Tc １／２ The resin composition according to claim 1 or 2, wherein the time is 60 seconds or less.

6. The resin composition according to claim 1 or 2, wherein the component (a2) comprises an alkylenediol having 2 to 4 carbon atoms.

7. The resin composition according to claim 1 or 2, wherein the component (a2) comprises 1,4-butanediol.

8. The resin composition according to claim 1 or 2, wherein the ratio of the nucleating agent (B) to 100 parts by mass of the polycondensate (A) is 0.01 to 10.0 parts by mass.

9. A molded article comprising the resin composition according to claim 1 or 2.

10. The molded article according to claim 9, which is an injection-molded article.

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