Polyester and resin moldings

Abstract

To provide polyester which is excellent in heat resistance.SOLUTION: Polyester has a constitutional unit represented by formula (1). In the formula, R1 to R13 each independently represent hydrogen, an alkyl group or an alkoxy group; a is an integer of 0 to 10; b is an integer of 0 to 10; c is 0 or 1.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyester and also to a resin molded article containing the polyester. [Background technology]

[0002] BACKGROUND ART Plastic materials such as polyesters and polycarbonates have traditionally been used to produce molded articles in a variety of fields, including automotive parts, electronic parts, optical parts, and daily necessities, due to their excellent properties such as heat resistance, transparency, and moldability.

[0003] For example, Patent Document 1 proposes a polyester fiber with high shrinkage, which is obtained by copolymerizing a dicarboxylic acid component and a diol component with a compound having a norbornane skeleton, as a polyester fiber that has not only unprecedented high shrinkage but also light resistance when spun at high speed. In particular, it proposes the use of tricyclodecane dimethanol as part of the compound having a norbornane skeleton. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 9-95820 Summary of the Invention [Problem to be solved by the invention]

[0005] However, there is room for improvement in the heat resistance of the polyester proposed in Patent Document 1.

[0006] Therefore, an object of the present invention is to provide a polyester having excellent heat resistance, and a resin molded article containing such a polyester. [Means for solving the problem]

[0007] As a result of extensive investigations, the present inventors have found that polyesters having excellent heat resistance can be obtained by using polyesters having structural units derived from specific alicyclic olefins. The present invention is based on this finding.

[0008] The present invention includes the following inventions. [1] The following formula (1): [ka] [In the formula, R 1 ~R 13 each independently represents hydrogen, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer from 0 to 10, c is 0 or 1] A polyester having a structural unit represented by the formula: [2] In the above formula (1), R 1 ~R 13 are all hydrogen atoms. [3] The polyester according to [1] or [2], wherein in the formula (1), a is an integer of 0 to 3, and b is an integer of 0 to 3. [4] The polyester according to any one of [1] to [3], which is a reaction product of a diol with a dicarboxylic acid and / or an ester-forming derivative thereof. [5] The diol is represented by the following formula (2): [ka] [In the formula, R 1 ~R 13 each independently represents hydrogen, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer from 0 to 10, c is 0 or 1] The polyester according to [4], which contains a compound represented by the formula: [6] The diol is represented by the following formula (3): [ka] [In the formula, R 1 ~R 13 each independently represents hydrogen, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer between 0 and 10. The polyester according to [5], which contains a compound represented by the formula: [7] The diol is represented by the following formula (4): [ka] [In the formula, R 2 ~R 4 and R 6 ~R 13 each independently represents hydrogen, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer between 0 and 10. The polyester according to [8], which contains a compound represented by the formula: [8] The polyester according to any one of [4] to [7], wherein the dicarboxylic acid and / or its ester-forming derivative is at least one selected from the group consisting of an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and an ester-forming derivative thereof. [9] A resin molded product comprising the polyester according to any one of [1] to [8]. [Effects of the Invention]

[0009] According to the present invention, a polyester having excellent heat resistance can be provided. Furthermore, the polyester according to the present invention has excellent mechanical properties such as toughness, flexural strength, and flexural modulus. In particular, according to the present invention, a polyester having an excellent balance between heat resistance and mechanical properties can be provided. Furthermore, according to the present invention, a resin molded product containing such a polyester can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0010] [polyester] The polyester of the present invention is a polyester represented by the following formula (1): [ka] [In the formula, R 1 ~R 13 each independently represents hydrogen, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer from 0 to 10, c is 0 or 1] It has a structural unit represented by the following formula:

[0011] In the above formula (1), R 1 ~R 13 are each independently selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group. Among these, hydrogen is particularly preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5. The alkyl group may be either linear or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 5. Particularly preferred is R 1 ~R 13 are all hydrogen.

[0012] In the above formula (1), a is an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and even more preferably 1. Furthermore, b is an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and even more preferably 1.

[0013] The polyester of the present invention can have a structural unit derived from a dicarboxylic acid and / or an ester-forming derivative thereof in addition to a structural unit derived from a diol represented by the above formula (1). The structure of the structural unit derived from a dicarboxylic acid is not particularly limited, but is preferably a structural unit derived from a dicarboxylic acid and / or an ester-forming derivative thereof as described in [Dicarboxylic Acid] below in detail.

[0014] The content of the diol-derived structural units in the polyester of the present invention is preferably 40 mol% or more, more preferably 45 mol% or more, and even more preferably 48 mol% or more, and preferably 50 mol% or less, based on all structural units. The content of the structural units derived from the above dicarboxylic acids and / or their ester-forming derivatives in the polyester of the present invention is preferably 40 mol% or more, more preferably 45 mol% or more, more preferably 48 mol% or more, and preferably 50 mol% or less, based on all structural units. The total content of the structural units derived from the diol and the structural units derived from the dicarboxylic acid and / or its ester-forming derivative in the polyester of the present invention is preferably 80 mol % or more, more preferably 90 mol % or more, and even more preferably 96 mol % or more, and preferably 100 mol % or less, based on all structural units.

[0015] The polyester of the present invention may contain other structural units in addition to the structural units derived from the diols and the structural units derived from the dicarboxylic acids and / or ester-forming derivatives thereof.

[0016] [Polyester manufacturing method] The polyester of the present invention can be obtained by a polymerization reaction between a diol and a dicarboxylic acid and / or its ester-forming derivative. Preferred embodiments of the raw materials for the polyester and the polymerization reaction will be described in detail below.

[0017] [Diol] The diol that is the raw material of the polyester of the present invention is a diol represented by the following formula (2): [ka] The compound includes a compound represented by the formula:

[0018] R in the above formula (2) 1 ~R 13 , a, b, and c are all as defined in the above formula (1). 1 ~R13 The preferred embodiments of a, b, and c are also as explained in the above formula (1).

[0019] When c is 0 in the above formula (2), the diol is a compound represented by the following formula (3). [ka] In a particularly preferred embodiment, R 1 ~R 13 are both hydrogen, a is 1, and b is 1.

[0020] When c is 1 in the above formula (2), the diol is a compound represented by the following formula (4). [ka] In a particularly preferred embodiment, R 2 ~R 4 and R 6 ~R 13 are both hydrogen, a is 1, and b is 1.

[0021] Polyesters made from the diol represented by formula (3) or the diol represented by formula (4) as raw materials have improved heat resistance compared to polyesters made from conventionally known tricyclodecane dimethanol as raw materials. Furthermore, polyesters made from the diol represented by formula (3) or the diol represented by formula (4) as raw materials have superior mechanical properties such as toughness, flexural strength, and flexural modulus compared to conventionally known polyesters made from dicyclopentadiene as raw materials. This is because the polyesters contain more structural units having a cyclic skeleton structure derived from the diol represented by formula (3) or (4) than dicyclopentadiene.

[0022] Furthermore, polyesters using the diol represented by the above formula (3) as a raw material are superior in mechanical properties such as toughness, flexural strength, and flexural modulus compared to polyesters using the diol represented by the above formula (4) as a raw material, and have a good balance between heat resistance and mechanical properties.

[0023] The method for producing the diol represented by the above formula (2) is not particularly limited, but includes, for example, a step of obtaining an aldehyde by a hydroformylation reaction of an alicyclic olefin represented by the following formula (5), and a step of obtaining a diol by a reduction reaction of the aldehyde. 1 ~R 13 , c are as defined in the above formula (1). 1 ~R 13 The preferred embodiments of c are also as explained in the above formula (1). [ka]

[0024] (Hydroformylation reaction) An aldehyde can be obtained by introducing a formyl group (-CH=O) into each of two carbon-carbon double bonds through the hydroformylation reaction of an alicyclic olefin represented by the above formula (5). The hydroformylation reaction is not particularly limited, and an example thereof includes a method in which an internal olefin is reacted with hydrogen and carbon monoxide in the presence of a catalyst comprising a Group 8, 9, or 10 metal complex obtained by modifying a Group 8, 9, or 10 metal compound with a ligand such as an organophosphorus compound to convert it into an aldehyde.

[0025] The Group 8, 9, and 10 metal compounds used in the hydroformylation reaction are compounds that originally have catalytic activity to promote the hydroformylation reaction of internal olefins or that acquire such catalytic activity under the conditions of the hydroformylation reaction, and examples thereof include rhodium compounds, cobalt compounds, ruthenium compounds, iron compounds, etc., which have conventionally been used as catalysts in hydroformylation reactions. Of these compounds, it is preferable to use cobalt compounds and rhodium compounds, from the viewpoint that the reaction conditions for the hydroformylation reaction are mild.

[0026] Examples of cobalt compounds include Co2(CO)8, and examples of rhodium compounds include rhodium oxides such as RhO, Rh2O, Rh2O3, and RhO2; rhodium salts such as rhodium nitrate, rhodium sulfate, rhodium chloride, rhodium iodide, and rhodium acetate; and Rh4(CO) 12 , Rh6(CO) 16 , RhH(CO)(PPh3)3, RhCl(CO)(PPh3)2, RhCl(PPh3)3, RhBr(CO)(PPh3)2, RhCl(CO)(AsPPh3)2, Rh(acac)(CO)2 (where acac represents an acetylacetonato ligand; the same applies below).

[0027] The organophosphorus compound used in the hydroformylation reaction is not particularly limited, and examples thereof include tricyclohexylphosphine, triisopropylphosphine, tributylphosphine, tri-t-butylphosphine, tribenzylphosphine, triphenylphosphine, tris(para-methoxyphenyl)phosphine, tris(para-N,N-dimethylaminophenyl)phosphine, tris(para-fluorophenyl)phosphine, tris(para-chlorophenyl)phosphine, tri-o-toluylphosphine, tri-meta-toluylphosphine, tri-para-toluylphosphine, tris(pentafluorophenyl)phosphine, and bis(pentafluorophenyl)phosphine. Examples of the organic phosphorus compounds include phenylphosphine, diphenyl(pentafluorophenyl)phosphine, methyldiphenylphosphine, ethyldiphenylphosphine, cyclohexyldiphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, 2-furyldiphenylphosphine, 2-pyridyldiphenylphosphine, 4-pyridyldiphenylphosphine, meta-diphenylphosphinobenzenesulfonic acid or a metal salt thereof, para-diphenylphosphinobenzoic acid or a metal salt thereof, and para-diphenylphosphinophenylphosphonic acid or a metal salt thereof, with triphenylphosphine, tricyclohexylphosphine, triisopropylphosphine, etc. being preferred. These organic phosphorus compounds may be used alone or in combination of two or more.

[0028] From the viewpoint of obtaining good catalyst stability and reaction rate, the amount of the organic phosphorus compound used is preferably in the range of 1 to 10,000 moles, more preferably 1 to 1,000 moles, and even more preferably 1.5 to 100 moles, calculated as phosphorus atoms per mole of the Group 8, 9, or 10 metal compound calculated as Group 8, 9, or 10 metal atoms.

[0029] The method for preparing the Group 8, 9, or 10 metal complex is not particularly limited, but for example, the complex can be prepared by separately introducing a solution of a Group 8, 9, or 10 metal compound and a solution of an organophosphorus compound, each of which has been prepared using a solvent that does not affect the hydroformylation reaction, into a hydroformylation reaction system, and reacting the two in the system to form a complex. Alternatively, the complex can be prepared by adding the organophosphorus compound to the above Group 8, 9, or 10 metal compound solution, and then adding a solvent that does not affect the hydroformylation reaction to prepare a homogeneous solution.

[0030] The H2 / CO molar ratio of the mixed gas of hydrogen and carbon monoxide used in the hydroformylation reaction is preferably in the range of 0.1 to 10 as the gas composition at the time of charging, and more preferably in the range of 0.5 to 2 from the viewpoint of easily maintaining the mixed gas composition. The reaction pressure is preferably in the range of 0.1 to 10 MPa, and more preferably in the range of 0.5 to 8 MPa from the viewpoint of the reaction rate. The reaction temperature is preferably in the range of 40 to 150°C, and more preferably in the range of 60 to 140°C from the viewpoint of suppressing catalyst deactivation.

[0031] The hydroformylation reaction can be carried out using a stirred reactor, a liquid circulation reactor, a gas circulation reactor, a bubble column reactor, etc. The reaction can be carried out continuously or batchwise.

[0032] From the viewpoints of reaction rate and catalyst cost, the amount of Group 8, 9, or 10 metal complex used is preferably selected so that the amount is in the range of 0.1 to 1000 mmol, and more preferably 0.5 to 100 mmol, calculated as Group 8, 9, or 10 metal atom per 1000 g of raw material.

[0033] When hydroformylating an internal olefin using a Group 8, 9, or 10 metal complex, a solvent may be present in the reaction system. Examples of the solvent include aprotic polar solvents such as toluene, dimethyl sulfoxide, 1-methyl-2-pyrrolidinone, sulfolane, dimethylformamide, acetonitrile, acetone, 1,4-dioxane, and tetrahydrofuran; alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, s-butyl alcohol, and t-butyl alcohol; glycols such as ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol, triethylene glycol dimethyl ether, tetraethylene glycol, and tetraethylene glycol dimethyl ether; and polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, and polyethylene glycol dimethyl ether. These solvents may be used alone or in combination. Among these, aprotic polar solvents such as toluene, dimethyl sulfoxide, acetone, and tetrahydrofuran are preferred. The amount of these solvents used is preferably selected so that it accounts for 50% by volume or less of the hydroformylation reaction mixture, and more preferably 20% by volume or less.

[0034] There is no particular limitation on the method for charging the raw materials in the hydroformylation reaction. However, it is preferable to charge an internal olefin, a separately prepared solution of a metal complex of Groups 8, 9, and 10, and a solvent as needed, and then introduce a mixed gas of hydrogen and carbon monoxide at a predetermined pressure and stir the mixture at a predetermined temperature to carry out the reaction in a homogeneous system.

[0035] (Reduction reaction) A diol can be obtained by converting the two formyl groups (-CH=O) of the aldehyde obtained by the above hydroformylation reaction into alkoxy groups through a reduction reaction.

[0036] The reduction reaction is not particularly limited, but is preferably a hydrogen reduction reaction. The hydrogen reduction reaction is not particularly limited, and may be carried out by a known method, such as a method of reducing by adding NaBH4 (sodium borohydride) or a method of reducing with hydrogen gas in the presence of a metal catalyst.

[0037] In the method of hydrogen reduction by adding NaBH4, the amount of NaBH4 added is preferably equimolar or more relative to the aldehyde, more preferably 1 to 3 times by mole, and even more preferably 1.2 to 1.5 times by mole. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 50°C, and even more preferably 10 to 30°C.

[0038] In the method of reducing with hydrogen gas using a metal catalyst, the metal catalyst used for hydrogen reduction is not particularly limited, but preferred are catalysts in which Ru, Pd, Rh, or Pt is supported on alumina, activated carbon, silica, zirconia, or silica-alumina; Cu-based catalysts such as Cu-Cr, Cu-Fe, or Cu-Zn; and Ni-based catalysts such as Raney Ni, nickel / diatomaceous earth, or nickel / silica-alumina. The amount of metal catalyst added is preferably 20 wt% or less, more preferably 0.1 to 5 wt%, relative to the aldehyde. The reaction temperature varies depending on the catalyst used, but is preferably 300°C or less, more preferably 20 to 250°C, and even more preferably 20 to 150°C. The hydrogen gas pressure is preferably atmospheric pressure to 30 MPa, more preferably atmospheric pressure to 25 MPa.

[0039] [Dicarboxylic acid] The dicarboxylic acid and / or its ester-forming derivative, which are raw materials for the polyester of the present invention, are not particularly limited, and conventionally known raw materials for polyesters can be used.

[0040] Examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2-methylterephthalic acid, biphenyldicarboxylic acid, and tetralindicarboxylic acid; succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decalindicarboxylic acid, norbornanedicarboxylic acid, tricyclodecanedicarboxylic acid, pentacyclododecanedicarboxylic acid, 3,9-bis(1,1-dimethyl-2-carboxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 5-carboxy-5-ethyl-2-(1,1-dimethyl-2-carboxyethyl) ... aliphatic dicarboxylic acids such as 1,4:5,8-dimethanodecahydronaphthalenedicarboxylic acid, adamantanedicarboxylic acid, and dimer acid; and dicarboxylic acids having a cardo structure such as 9,9-bis(carboxymethyl)fluorene, 9,9-bis(1-carboxyethyl)fluorene, 9,9-bis(2-carboxyethyl)fluorene, 9,9-bis(1-carboxypropyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene, 9,9-bis(2-carboxy-1-methylethyl)fluorene, 9,9-bis(2-carboxy-1-methylpropyl)fluorene, 9,9-bis(2-carboxybutyl)fluorene, 9,9-bis(2-carboxy-1-methylbutyl)fluorene, 9,9-bis(5-carboxypentyl)fluorene, and 9,9-bis(4-carboxyphenyl)fluorene. Furthermore, ester-forming derivatives of these dicarboxylic acids can also be used. These dicarboxylic acids and their ester-forming derivatives may be used singly or in combination of two or more. Among these, at least one selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and their ester-forming derivatives is preferred.

[0041] (Polymerization reaction) In the production of the polyester of the present invention, the polymerization reaction between the diol and the dicarboxylic acid and / or its ester-forming derivative is not particularly limited and can be carried out by a conventionally known method. For example, the polyester can be produced by melt polymerization alone. Alternatively, the polyester can be produced by preparing a prepolymer by melt polymerization and then further solid-phase polymerizing the prepolymer.

[0042] A catalyst may or may not be used in the polymerization reaction. The catalyst used may be a conventional catalyst known for polyester polymerization. Examples of the catalyst include metal salt catalysts such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide; nitrogen-containing heterocyclic compounds such as N-methylimidazole; and organic compound catalysts. The amount of catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 parts by weight per 100 parts by weight of the total amount of raw material monomers.

[0043] The polymerization reactor for melt polymerization is not particularly limited, but a reactor generally used for reactions of high-viscosity fluids is preferably used. Examples of such reactors include stirred tank-type polymerization reactors having stirrers with stirrer blades of various shapes, such as anchor type, multi-stage type, spiral belt type, or spiral shaft type, or modified versions of these, as well as mixing devices generally used for kneading resins, such as kneaders, roll mills, and Banbury mixers.

[0044] [Resin molding] The resin molded article of the present invention contains the polyester described above. The resin molded article of the present invention may further contain various additives within a range that does not impair its properties. Examples of additives include fillers, silane coupling agents, antifoaming agents, antioxidants, light stabilizers, colorants such as pigments and dyes, plasticizers, pH adjusters, UV stabilizers, color inhibitors, matting agents, deodorizers, flame retardants, weather resistance agents, antistatic agents, thread friction reducers, slip agents, mold release agents, antioxidants, and ion exchange agents. The resin molded article of the present invention may contain one or more of the additives described above.

[0045] The uses of the resin molded article of the present invention are not particularly limited, and it can be used in a variety of products such as automobile parts, electronic parts, optical parts, and daily necessities. Specific examples include paints to be applied to substrates such as metals, resin films, glass, paper, and wood; surface protective films for semiconductor elements and organic thin-film elements (e.g., organic electroluminescence elements and organic thin-film solar cell elements); coating agents such as hard coating agents, antifouling films and antireflection films; adhesives, pressure-sensitive adhesives; lenses, prisms, filters, image display materials, lens arrays, encapsulants and reflector materials for optical semiconductor elements, encapsulants for semiconductor elements, various optical components such as optical waveguides, light guide plates, light diffusers, diffraction elements, and optical adhesives; casting materials, interlayer insulators, protective insulating films for printed alignment substrates, and fiber-reinforced composite materials. [Example]

[0046] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0047] [Synthesis example of aldehyde (A1)] Under an argon stream, a 3L autoclave was charged with 1997g (10.72mol) of 3a,4,4a,5,8,8a,9,9a-octahydro-4,9-methanocyclopenta[b]naphthalene (DCPB), 1.48mg (1.608mmol) of RhH(CO)(PPh3), and 28.12g (0.1072mol) of PPh3. H2 / CO gas (3.5MPa) was introduced into the vessel, and the internal temperature was raised to 120°C. After 30 minutes of reaction, the internal temperature was raised to 130°C and the reaction proceeded for 9 hours according to the formula below. Additional H2 / CO gas was introduced until the pressure reached 4.5MPa, and the reaction was continued for 2 days. The reaction mixture was then diluted with 48 L of tetrahydrofuran (THF), and 7.44 kg of saturated aqueous NaHCO3 was added. The mixture was then reacted overnight at 50 °C under an argon atmosphere. After cooling to room temperature, the THF layer was removed by separation, and the resulting aqueous layer was washed twice with 8 L of chloroform. The resulting aqueous layer was adjusted to pH 12 by adding 15 wt% aqueous NaOH (13.34 kg), and the resulting suspension was extracted three times with 4 L of chloroform. The combined organic layers were dried over MgSO4, filtered, and concentrated to yield 2536 g of aldehyde (A1) with a purity of 98%. [ka]

[0048] [Synthesis example of diol (B1)] Under an argon atmosphere, 634 g (2.57 mol) of the aldehyde (A1) obtained above and 5 L of MeOH were charged into a 10 L flask. NaBH4 was added in small amounts so that the temperature did not exceed 20 °C, and finally 71.1 g (1.879 mol) was added, and the reaction described below was carried out. After the addition was completed, the temperature was raised to room temperature. 0.5 L of water was added to the reaction solution to terminate the reaction, and MeOH was distilled off. 5 L of AcOEt and 5 L of water were added to the obtained crude product, and the organic layer was separated. The aqueous layer was further extracted twice with 5 L of AcOEt, mixed with the previous organic layer, washed with 2 L of saturated brine, dried over NasSO4, filtered, and concentrated to obtain 647 g of crude product. The obtained crude product was purified by distillation at 0.05 mmHg at a column overhead temperature of 185-193 °C, and 480 g of diol (B1) with a purity of 99.9% was obtained. [ka]

[0049] [Synthesis example of diol (B2)] Aldehyde (A2) was obtained in the same manner as in the synthesis example of aldehyde (A1), except that dicyclopentadiene (DCPD) was used instead of DCPB. Subsequently, diol (B2) was obtained in the same manner as in the synthesis example of diol (B1), except that aldehyde (A2) was used instead of aldehyde (A1).

[0050] (Polyester Synthesis Example 1) [Example 1] 50 mol% of the DCPB-derived diol (B1) obtained above and 50 mol% of cyclohexanedicarboxylic acid (C1) were added to a polymerization vessel equipped with a stirring blade, and tetrabutyl titanate was charged as a catalyst. After reducing the pressure and injecting nitrogen into the polymerization vessel three times, the temperature was raised to 160°C and stirring was continued for 30 minutes. The temperature was further raised to 180°C and stirring was continued for 20 minutes. The temperature was then raised to 230°C at a rate of 0.6°C / min, and stirring was continued at 230°C for 1 hour. The temperature was then further raised to 260°C at a rate of 0.6°C / min, and the degree of vacuum was adjusted to 1 Torr, and stirring was continued until a predetermined torque value was reached. After the reaction was completed, nitrogen was blown into the reaction vessel to return to normal pressure, and A polyester (D1) was obtained.

[0051] [Comparative Example 1] Polyester (D2) was obtained in the same manner as in Example 1, except that 50 mol % of the DCPD-derived diol (B2) obtained above was added instead of diol (B1).

[0052] Comparative Example 2 Polyester (D3) was obtained in the same manner as in Example 1, except that 50 mol % of cyclohexanedimethanol (B3) was added instead of diol (B1).

[0053] (Evaluation of the thermal properties of polyester 1) The glass transition temperature (Tg) and thermal decomposition temperature (Td) of the polyesters (D1) to (D3) obtained above were measured by the following method. The measurement results are shown in Table 1.

[0054] (glass transition temperature (Tg)) The glass transition temperature (Tg) was measured using a differential scanning calorimetry (DSC, Hitachi High-Tech Science Corporation, Model: X-DSC-7000). First, the sample was heated from room temperature to 280°C at a rate of 10°C / min, then cooled to 30°C at a rate of 10°C / min, and then further heated to 280°C at a rate of 10°C / min. The inflection point obtained when the sample was heated again was taken as the glass transition temperature (Tg).

[0055] (Thermal decomposition temperature (Td)) Using a differential scanning calorimetry simultaneous analyzer (SII Nanotechnology, model number: TG / DTA7200), the temperature was raised from room temperature to 500°C at a constant rate of 10°C / min in dry air, and the temperature at which the weight of the polyester decreased by 1% compared to the start of the measurement (1% Td) was measured.

[0056] [Table 1]

[0057] The results of Example 1 and Comparative Examples 1 and 2 showed that the polyester obtained using a diol derived from DCPB as a raw material had superior heat resistance compared to polyesters obtained using a diol derived from DCPD or cyclohexanedimethanol as a raw material.

[0058] (Polyester Synthesis Example 2) [Example 2] Polyester (D4) was obtained in the same manner as in Example 1, except that 50 mol % of the DCPB-derived diol (B1) obtained above and 50 mol % of dimethyl terephthalate (C2) were added to a polymerization vessel equipped with a stirring blade.

[0059] Comparative Example 3 Polyester (D5) was obtained in the same manner as in Example 2, except that 50 mol % of the DCPD-derived diol (B2) obtained above was added instead of diol (B1).

[0060] (Evaluation of the thermal properties of polyester 2) The thermal properties of each of the polyesters (D4) to (D5) were evaluated in the same manner as in Evaluation of Thermal Properties of Polyesters 1. The evaluation results are shown in Table 2.

[0061] [Table 2]

[0062] The results of Example 2 and Comparative Example 3 showed that the polyester obtained using a diol derived from DCPB as a raw material had superior heat resistance compared to the polyester obtained using a diol derived from DCPD as a raw material.

Claims

1. 1. A polyester which is the reaction product of a diol with a dicarboxylic acid and / or an ester-forming derivative thereof, The diol is represented by the following formula (3): 【Chemical 1】 [In the formula, R １ ~R ３ , R ５ ~R ７ and R ９ ~R １３ each independently represents hydrogen, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer from 0 to 10. The compound includes a compound represented by the dicarboxylic acid and / or its ester-forming derivative comprises cyclohexanedicarboxylic acid and / or its ester-forming derivative, The polyester is represented by the following formula (1): 【Chemistry 2】 [In the formula, R １ ~R ３ , R ５ ~R ７ and R ９ ~R １３ each independently represents hydrogen, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer from 0 to 10. A polyester having a structural unit represented by the formula:

2. In the above formulas (1) and (3), R １ ~R ３ , R ５ ~R ７ and R ９ ~R １３ The polyester of claim 1 wherein all are hydrogen.

3. 3. The polyester according to claim 1, wherein in the formulas (1) and (3), a is an integer of 0 to 3, and b is an integer of 0 to 3.

4. the content of the structural unit derived from the diol of the formula (3) in the polyester is 40 mol% or more based on all structural units; 4. The polyester according to claim 1, wherein the content of structural units derived from cyclohexanedicarboxylic acid and / or its ester-forming derivative in the polyester is 40 mol % or more based on all structural units.

5. the content of the diol-derived structural unit of the formula (3) in the polyester is 45 mol% or more based on all structural units; 4. The polyester according to claim 1, wherein the content of structural units derived from cyclohexanedicarboxylic acid and / or its ester-forming derivative in the polyester is 45 mol % or more based on all structural units.

6. the content of the structural unit derived from the diol of the formula (3) in the polyester is 48 mol% or more based on all structural units; 4. The polyester according to claim 1, wherein the content of structural units derived from cyclohexanedicarboxylic acid and / or its ester-forming derivative in the polyester is 48 mol% or more based on all structural units.

7. A resin molded article comprising the polyester according to any one of claims 1 to 6.

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