Polycarbonate resin

Abstract

The present invention makes it possible to provide a polycarbonate resin including structural units (A) represented by general formula (1) and structural units (B) represented by general formula (4). Formula (1) (In general formula (1), R1, R2, R3, R4, R5, R6, R7, and R8 each independently represents a hydrogen atom, etc., X represents –O-, etc.), formula (4) (in general formula (4), Rz and Rx each independently represents a hydrogen atom or a C1-3 alkyl group, i represents an integer 3-10 and p represents an integer 5-600.)

Description

Technical Field

[0001] The present invention relates to a novel polycarbonate resin.

Background Art

[0002] It is known to blend polyethylene glycol or poly(2-methyl)ethylene glycol, etc. with a thermoplastic resin such as polycarbonate resin. Patent Document 1 describes a polycarbonate resin containing this and having γ-ray irradiation resistance, and Patent Document 2 describes a thermoplastic resin composition excellent in antistatic properties and surface appearance when blended with PMMA or the like. Further, Patent Document 3 proposes improving the transmittance and hue by blending a polyalkylene glycol composed of a linear alkyl group. By blending polytetramethylene ether glycol, improvement can be seen in the transmittance and yellowing degree (Yellow Index: YI). Furthermore, Patent Document 4 describes a method for producing a polycarbonate copolymer using a diol obtained by diesterifying a polyalkylene glycol as a raw material (comonomer), but this polycarbonate copolymer has unstable diester diol of polyalkylene glycol, insufficient impact resistance, and poor hue and heat discoloration resistance.

[0003] For the molding of optical parts, a high-temperature barrel temperature and high-speed injection are required. Along with this, there is a problem that the gas generated during molding increases and mold contamination tends to progress. Therefore, the resin used for the molding of optical parts is required to have not only excellent optical properties but also little mold contamination due to gas generation during injection molding at high temperature and excellent impact resistance.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to provide a polycarbonate resin with less gas generation.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventor has found that gas generation during molding can be suppressed by a specific polycarbonate resin, and has completed the present invention. That is, the present invention relates to the following polycarbonate resin. <1> A polycarbonate resin containing a structural unit (A) represented by the following general formula (1) and a structural unit (B) represented by the following general formula (4).

Chemical Formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0007] The polycarbonate resin of the present invention generates little gas and also has the effect of expanding the range of resin design according to various applications.

Mode for Carrying Out the Invention

[0008] Hereinafter, the present invention will be described in detail with reference to embodiments, exemplifications, and the like. In this specification, “~” is used to mean including the numerical values described before and after it as the lower limit value and the upper limit value, unless otherwise specified.

[0009] The first embodiment of the present invention is a polycarbonate resin containing a structural unit (A) represented by the following general formula (1) and a structural unit (B) represented by the following general formula (4).

Chemical formula

[0010] In general formula (1), X represents -O-, -S-, -SO-, -SO 2 -, -CO-, a cycloalkylene group having 6 to 12 carbon atoms, or a divalent group represented by the following general formula (2) or the following general formula (3), and the cycloalkylene group may be substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms. Preferably, X represents a divalent group represented by the following general formula (2) or a divalent group represented by the following general formula (3). [Chemical formula] In general formula (2), R 9 and R 10 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably 6 to 8 carbon atoms), an aralkyl group having 7 to 17 carbon atoms (preferably 7 to 10 carbon atoms), and an alkenyl group having 2 to 15 carbon atoms (preferably 2 to 10 carbon atoms), and preferably are selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and a phenyl group. More preferably, both R 9 and R 10 represent a methyl group. R 9 and R 10 The alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group in may each have a substituent. R 9 and R 10They may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms (preferably 5 to 15 carbon atoms) or a heterocyclic ring having 1 to 20 carbon atoms (preferably 5 to 10 carbon atoms), and the carbocyclic ring and the heterocyclic ring may each have a substituent. Preferred examples of the substituent include a cyclohexyl group, an adamantyl group, a cyclododecane group, and a norbornane group. In the general formula (2), n represents an integer of 0 to 20, preferably represents an integer of 0 to 5, and more preferably represents an integer of 0 to 2.

[0011]

Chemical formula

[0012] The structural unit represented by the general formula ( 4 ) ( BExamples of the monomer that constitutes the ( ) include poly-n-propylene glycol, polytetramethylene ether glycol, etc., and poly-n-propylene glycol is more preferable.

Chemical formula

[0013] In the general formula ( 1 ), examples of the monomer that constitutes the structural unit ( A ) include bisphenol A, bisphenol S, 4,4'-oxydiphenol, 4,4'-biphenol, 4,4'-thiodiphenol, etc., and bisphenol A and bisphenol S are more preferable. In particular, bisphenol A is preferred from the viewpoint of obtaining a polycarbonate resin with a small YI value and excellent heat resistance and market availability. Bisphenol S is also preferred from the viewpoint of heat resistance.

[0014] For the polycarbonate resin of the present invention, the mass ratio (A / B) of the structural unit (A) to the structural unit (B) is preferably 1 / 99 to 50 / 50, more preferably 5 / 95 to 50 / 50, further preferably 5 / 95 to 40 / 60, even more preferably 5 / 95 to 35 / 65, and particularly preferably 10 / 90 to 30 / 70.

[0015] The polycarbonate resin of the present invention is preferably a polycarbonate resin containing a carbonate bond derived from bisphenol A and a carbonate bond derived from poly-n-propylene glycol which may have a substituent.

[0016] The mass ratio of bisphenol A to poly-n-propylene glycol constituting the polycarbonate resin is preferably 5 to 50% by mass of bisphenol A and 50 to 95% by mass of poly-n-propylene glycol based on a total of 100% by mass of both, more preferably 5 to 40% by mass of bisphenol A and 60 to 95% by mass of poly-n-propylene glycol, and even more preferably 5 to 35% by mass of bisphenol A and 65 to 95% by mass of poly-n-propylene glycol. When the poly-n-propylene glycol is less than 50% by mass, the hue of the polycarbonate resin deteriorates, and when it exceeds 95% by mass, it is likely to become cloudy.

[0017] The polycarbonate resin of the present invention is preferably represented by the following general formula (5), that is, it is preferably a polycarbonate resin composed of a polycarbonate unit derived from bisphenol A and a polycarbonate unit derived from poly-n-propylene glycol.

Chemical formula

[0018] The polycarbonate resin of the present invention can be produced by conventional production methods such as the interfacial polymerization method and the melt polymerization method. For example, it can be produced by reacting at least bisphenol A, poly n-propylene glycol, and a carbonate precursor such as phosgene or diphenyl carbonate.

[0019] As the poly n-propylene glycol which may have a substituent, various poly-n-propylene glycols can be used. For example, poly n-propylene glycol in which the methylene group represented by the following general formula (6) may have a substituent is preferably mentioned.

[0020]

Chemical formula

[0021] The poly n-propylene glycol represented by the above general formula (6) may be a homopolymer composed of one kind of R a , R b , R c , or different R a , R b , R cIt may be a copolymer consisting of

[0022] Examples of commercially available poly(n-propylene glycol) represented by the general formula (6) include, in the general formula (6), R a , R b and R c All of which are hydrogen atoms, that is, poly(n-propylene glycol), namely, commercially available polytrimethylene glycol, and the product name "VELVETOL" manufactured by Allessa can be mentioned.

[0023] The poly(n-propylene glycol) represented by the general formula (6) may be, for example, a copolymer with a linear polyalkylene glycol such as polyethylene glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol, etc. However, since the transparency of the resulting molded product is improved, a homopolymer consisting of polytrimethylene glycol is preferably used.

[0024] The poly(n-propylene glycol) may include a polyalkylene glycol copolymer having a branched alkylene ether unit (P2) selected from the units represented by the following general formulas (8-1) to (8-4) in addition to the n-propylene ether unit (P1) represented by the following general formula (7).

[0025]

Chemical formula

[0026]

Chemical formula

[0027] As the n-propylene ether unit represented by the above general formula (7), when described as a glycol, it is n-propylene glycol. In addition to n-propylene glycol, any one or more of ethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, etc. may be mixed, but it is preferably only n-propylene glycol, and the above-mentioned R a , R b and R C It is more preferably only n-propylene glycol (i.e., trimethylene glycol) in which all are hydrogen atoms.

[0028] Trimethylene glycol is industrially produced by a method of obtaining 3-hydroxypropionaldehyde by hydroformylation of ethylene oxide and then hydrogenating it, or a method of hydrating acrolein to obtain 3-hydroxypropionaldehyde and then hydrogenating it with a Ni catalyst. Recently, a biological method has also been used to produce trimethylene glycol by reducing glycerin, glucose, starch, etc. with microorganisms.

[0029] As the branched alkylene ether unit represented by the above general formula (8-1), when described as a glycol, examples include (2-methyl)ethylene glycol, (2-ethyl)ethylene glycol, (2,2-dimethyl)ethylene glycol, etc., and these may be mixed, preferably (2-methyl)ethylene glycol and (2-ethyl)ethylene glycol.

[0030] As the branched alkylene ether unit represented by the general formula (8-2) above, when described as a glycol, examples include (2-methyl)trimethylene glycol, (3-methyl)trimethylene glycol, (2-ethyl)trimethylene glycol, (3-ethyl)triethylene glycol, (2,2-dimethyl)trimethylene glycol, (2,2-methylethyl)trimethylene glycol, (2,2-diethyl)trimethylene glycol (i.e., neopentyl glycol), (3,3-dimethyl)trimethylene glycol, (3,3-methylethyl)trimethylene glycol, (3,3-diethyl)trimethylene glycol, etc., and these may be mixed.

[0031] As the branched alkylene ether unit represented by the general formula (8-3) above, when described as a glycol, examples include (3-methyl)tetramethylene glycol, (4-methyl)tetramethylene glycol, (3-ethyl)tetramethylene glycol, (4-ethyl)tetramethylene glycol, (3,3-dimethyl)tetramethylene glycol, (3,3-methylethyl)tetramethylene glycol, (3,3-diethyl)tetramethylene glycol, (4,4-dimethyl)tetramethylene glycol, (4,4-methylethyl)tetramethylene glycol, (4,4-diethyl)tetramethylene glycol, etc., and these may be mixed, and (3-methyl)tetramethylene glycol is preferred.

[0032] As the branched alkylene ether unit represented by the general formula (8-4) above, when described as a glycol, (3-methyl)pentamethylene glycol, (4-methyl)pentamethylene glycol, (5-methyl)pentamethylene glycol, (3-ethyl)pentamethylene glycol, (4-ethyl)pentamethylene glycol, (5-ethyl)pentamethylene glycol, (3,3-dimethyl)pentamethylene glycol, (3,3-methylethyl)pentamethylene glycol, (3,3-diethyl)pentamethylene glycol, (4,4-dimethyl)pentamethylene glycol, (4,4-methylethyl)pentamethylene glycol, (4,4-diethyl)pentamethylene glycol, (5,5-dimethyl)pentamethylene glycol, (5,5-methylethyl)pentamethylene glycol, (5,5-diethyl)pentamethylene glycol, etc. may be mentioned, and these may be mixed.

[0033] As described above, the units represented by the general formulas (8-1) to (8-4) constituting the branched alkylene ether unit have been described by taking glycol as an example for convenience, but it is not limited to these glycols, and these alkylene oxides or these polyether-forming derivatives may also be used.

[0034] Examples of preferred poly-n-propylene glycol copolymers include copolymers composed of n-propylene ether units and the units represented by the general formula (8-2), and particularly preferred is a copolymer composed of trimethylene ether units and 3-methyltrimethylene ether units.

[0035] The poly-n-propylene glycol copolymer may be a random copolymer or a block copolymer.

[0036] The copolymerization ratio of the n-propylene ether unit (P1) represented by the general formula (7) of the poly-n-propylene glycol copolymer and the branched alkylene ether unit (P2) represented by the general formulas (8-1) to (8-4) is the molar ratio of (P1) / (P2), preferably 95 / 5 to 5 / 95, more preferably 93 / 7 to 40 / 60, still more preferably 90 / 10 to 65 / 35, and it is more preferable that the n-propylene ether unit (P1) is rich. The mole fraction is 1 measured using an H-NMR measuring device with deuterated chloroform as a solvent.

[0037] Among those described above, a particularly preferred poly-n-propylene glycol is a homopolymer of n-propylene glycol without a substituent, that is, trimethylene glycol.

[0038] As the above poly-n-propylene glycol, a structure derived from a polyol such as 1,4-butanediol, glycerol, sorbitol, benzenediol, bisphenol A, cyclohexanediol, spiroglycol, etc. may be included in the structure. By adding these polyols during the polymerization of the polyalkylene glycol, these organic groups can be imparted to the main chain. Particularly preferred examples include glycerol, sorbitol, bisphenol A, etc.

[0039] Examples of the poly-n-propylene glycol containing an organic group in the structure include poly-n-propylene glycol glyceryl ether, poly(2-methyl)-n-propylene glycol glyceryl ether, poly-n-propylene glycol glyceryl ether, poly-n-propylene glycol-poly(2-methyl)-n-propylene glycol glyceryl ether, poly-n-propylene glycol-poly(2-ethyl)poly-n-propylene glycol glyceryl ether, poly-n-propylene glycol sorbitol ether, Poly(2-methyl)-n-propylene glycol sorbitol ether, Poly-n-propylene glycol sorbitol ether, Poly-n-propylene glycol-poly(2-methyl)ethylene glycol sorbitol ether, Bisphenol A-bis(poly-n-propylene glycol) ether, Bisphenol A-bis(poly(2-methyl)-n-propylene glycol) ether, Bisphenol A-bis(poly-n-propylene glycol-poly(2-methyl)ethylene glycol) ether, Bisphenol A-bis(poly-n-propylene glycol-poly(2-ethyl)poly-n-propylene glycol) ether and the like are preferably cited.

[0040] The weight average molecular weight (Mw) of poly-n-propylene glycol is preferably 600 to 8,000, more preferably 800 or more, still more preferably 1,000 or more, more preferably 6,000 or less, still more preferably 5,000 or less, and particularly preferably 4,000 or less. When the weight average molecular weight exceeds the above upper limit, the compatibility tends to decrease. When the weight average molecular weight is below the above lower limit, the impact resistance of the polycarbonate resin may decrease. The weight average molecular weight (Mw) is the polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC) using THF as the eluent solvent. Specifically, as GPC, a high-speed GPC device "HLC-8320" manufactured by Tosoh Corporation is used, column: manufactured by Tosoh Corporation, HZ-M (4.6 mm × 150 mm) × 3 in series, eluent: chloroform, and it is the value obtained as the polystyrene equivalent molecular weight (weight average molecular weight).

[0041] Among the monomers used as raw materials for the polycarbonate resin, examples of carbonate precursors include carbonyl halides, carbonate esters, etc. The carbonate precursor may be used alone, or two or more may be used in combination at any combination and ratio.

[0042] Examples of the carbonyl halide include, specifically, phosgene; haloformates such as bischloroformate of dihydroxy compound and monochloroformate of dihydroxy compound.

[0043] Examples of the carbonate ester include, specifically, diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; carbonate bodies of dihydroxy compounds such as biscarbonate of dihydroxy compound, monocarbonate of dihydroxy compound, and cyclic carbonate.

[0044] As the polycarbonate resin of the present invention, bisphenol A-poly-n-propylene glycol copolymer polycarbonate represented by the following general formula (9) is particularly preferable.

Chemical formula

[0045] The second embodiment of the present invention is a polycarbonate resin containing only the structural unit (B) represented by the following general formula (4).

Chemical formula

[0046] The method for producing the polycarbonate resin of the present invention is not particularly limited, and any known method can be adopted. Examples thereof include the interfacial polymerization method, the melt transesterification method, the pyridine method, the ring-opening polymerization method of cyclic carbonate compounds, and the solid-phase transesterification method of prepolymers. Among these, the melt transesterification method and the interfacial polymerization method are preferable, and the melt transesterification method is more preferable.

[0047] The polystyrene-reduced weight-average molecular weight (Mw) of the polycarbonate resin of the present invention is preferably from 1,000 to 60,000, more preferably from 5,000 to 40,000. The lower limit is more preferably 6,000 or more, particularly preferably 7,000 or more, and the upper limit is more preferably 37,000 or less, particularly preferably 35,000 or less. When the weight-average molecular weight (Mw) exceeds the above upper limit, the compatibility tends to decrease. When the weight-average molecular weight is below the above lower limit, gas tends to be generated during molding.

[0048] The adjustment of the weight-average molecular weight (Mw) of the polycarbonate resin of the present invention can be achieved by selecting the Mw of the polyalkylene glycol which is one of the comonomer diol raw materials, adjusting the ratio of the carbonate precursor, adding a terminator, adjusting the temperature and pressure during polymerization, etc. For example, in the melt transesterification method, to increase Mw, the monomer raw material ratio is adjusted so that the reaction ratio of diphenyl carbonate, which is the carbonate precursor monomer, and the diol monomer is close to 1, the polymerization temperature is kept high so that the by-product phenol is easily removed from the polymerization system, the pressure is made as low as possible, and the interface renewal by stirring is actively carried out, etc.

[0049] The weight-average molecular weight (Mw) of the polycarbonate resin of the present invention is the polystyrene-reduced molecular weight measured with chloroform as the eluent solvent by GPC. Specifically, using a high-speed GPC device "HLC-8320" manufactured by Tosoh Corporation as GPC, column: manufactured by Tosoh Corporation, HZ-M (4.6 mm × 150 mm) × 3 in series, eluent: chloroform, measurement temperature: 25 °C, it is the value obtained as the polystyrene-reduced molecular weight (weight-average molecular weight).

[0050] The polycarbonate resin of the present invention preferably has a terminal hydroxyl group concentration of 1 ppm to 3000 ppm for maintaining hydrolysis resistance, more preferably 1 to 1000 ppm, and particularly preferably 1 to 500 ppm. In the present invention, as the method for measuring the terminal hydroxyl group concentration, the method described in the following examples can be used.

[0051] The polycarbonate resin of the present invention preferably has a glass transition temperature (Tg) of -100 to 140 °C for easy handling, more preferably -70 to 120 °C, and particularly preferably -70 to 110 °C. In the present invention, as the method for measuring the glass transition temperature, the method described in the following examples can be used.

[0052] [Additives, etc.] The polycarbonate resin of the present invention can contain additives other than those described above, for example, antioxidants, mold release agents, ultraviolet absorbers, fluorescent brighteners, pigments, dyes, polymers other than polycarbonate resins, flame retardants, impact resistance improvers, antistatic agents, plasticizers, compatibilizers, and the like. These additives may be blended singly or in combination of two or more.

Examples

[0053] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.

[0054] <Method for Measuring Terminal Hydroxyl Group Concentration (ppm)> 0.05 g of the resin sample was dissolved in 1 ml of deuterated chloroform (containing 0.05 w / v% TMS), and 1 1H-NMR was measured to determine it. Specifically, the terminal hydroxyl group concentration (OH concentration) was calculated from the integration ratio of the peak related to the hydroxyl group and the peaks contained in other resin skeletons. Apparatus: BRUKER 500 MHz Nuclear Magnetic Resonance Apparatus AVANCE III HD

[0055] <Method for Measuring Weight-Average Molecular Weight (Mw)> Using GPC, with chloroform as the eluent, a calibration curve was created using standard polystyrene (manufactured by Tosoh Corporation, "PStQuick MP-M") with a known molecular weight (molecular weight distribution = 1). The elution time and molecular weight values of each peak were plotted from the measured standard polystyrene, and approximation was performed using a cubic equation to obtain the calibration curve. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined as polystyrene conversion values using the following calculation formulas. [Calculation Formulas] Mw = Σ(Wi × Mi) ÷ Σ(Wi) Here, i represents the i-th division point when the molecular weight M is divided, Wi represents the weight of the i-th division, and Mi represents the molecular weight of the i-th division. Also, the molecular weight M represents the polystyrene molecular weight value at the same elution time of the calibration curve. [Measurement Conditions] Apparatus; HLC-8320GPC manufactured by Tosoh Corporation Column; Guard column: TSKguardcolumn SuperMPHZ-M × 1 piece Analysis column: TSKgel SuperMultiporeHZ-M × 3 pieces Solvent; HPLC grade chloroform Injection volume; 10 μL Sample concentration; 0.2 w / v% HPLC grade chloroform solution Solvent flow rate; 0.35 ml / min Measurement temperature; 40 °C Detector; RI

[0056] <Measurement of Gas Generation Amount> Measurement was performed using a thermogravimetric-differential thermal simultaneous measurement device (TG / TDA) (product name "TGDTA7300", manufactured by Hitachi High-Tech Science Corporation). The measurement sample was prepared by accurately weighing 5 mg of the sample into a platinum pan (Pt open-type sample container, a cylindrical container with a diameter of 5.2 mm and a height of 5.0 mm). The measurement was carried out under a nitrogen atmosphere (nitrogen flow rate: 250 ml / min), and 5.52 mg of α-alumina was used as a reference substance in the reference cell. Then, the measurement sample was heated as described below and its weight was measured. Assuming that all the decreased weight was gasified, the gas generation amount (%) from "120°C to 350°C" was calculated as follows. Gas generation amount (%) from "120°C to 350°C" = (weight at 350°C - weight at 120°C) / weight at 120°C × 100 The gas generation amount (%) from "120°C to 320°C" was calculated as follows. Gas generation amount (%) from "120°C to 320°C" = (weight at 320°C - weight at 120°C) / weight at 120°C × 100 Here, the weight at 350°C is the weight of the measurement sample when it is heated from 120°C at a rate of 10°C / min until it reaches 350°C. The weight at 120°C is the weight of the measurement sample after it is heated from room temperature to 120°C at a rate of 10°C / min and held at 120°C for 2 hours. The weight at 320°C is the weight of the measurement sample when it is heated from 120°C at a rate of 10°C / min until it reaches 320°C.

[0057] <Measurement of glass transition temperature (Tg)> The measurement was carried out using a differential scanning calorimeter (DSC) (product name "DSC-7000", manufactured by Hitachi High-Tech Science Corporation). For the measurement sample, a test piece of 7 - 12 mg was precisely weighed into a sample container for AI auto sampler (RDC aluminum pan, a cylindrical container with a diameter of 6.8 mm and a height of 2.5 mm), and the upper part of the sample container was sealed with a cover for AI auto sampler. The measurement was carried out under a nitrogen atmosphere (nitrogen flow rate: 50 ml / min), and 10.0 mg of alumina was used as a standard substance in the reference cell. Then, the measurement sample adjusted to -70°C was heated to 200°C at a rate of 10°C / min, and then cooled to -70°C at a rate of 10°C / min. After that, it was heated to 200°C again at a rate of 10°C / min for measurement.

[0058] <Measurement of YI value> Measurement was carried out using a spectrocolorimeter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. Specifically, 12 g of a resin sample was dissolved in 60 mL of dichloromethane, and measurement was carried out using a quartz cell with an optical path length of 6 cm. Dichloromethane was used as a blank.

[0059] <Example 1> Into a polymerization apparatus equipped with a three-necked flask, as raw materials, poly-n-propylene glycol manufactured by ALLESA, 85% by mass equivalent of Velvetol H500 (Mw: 1700), 15% by mass equivalent of bisphenol A (hereinafter, BPA), and diphenyl carbonate (hereinafter, DPC) were added at a molar ratio of 1.16 to the diol. Further, as a catalyst, an aqueous solution of Cs 2 CO 3 was added at 11 μmol (as Cs) per mole of the diol. After drying the inside of the system for 1 hour, the pressure in the polymerization apparatus was restored with nitrogen. Polymerization was started when the pressure-restored polymerization apparatus was immersed in an oil bath, and polymerization was carried out according to the temperature-raising and pressure-reducing program shown in Table 1. The physical properties of the obtained polycarbonate resin are shown in Table 5. The OH concentration of the polycarbonate resin obtained in Example 1 was 70 ppm.

Table 1

[0060] <Examples 2 and 3> The reaction was carried out in the same manner as in Example 1 except that the raw materials were changed to the raw materials shown in Table 5. The physical properties of the obtained polycarbonate resin are shown in Table 5. The OH concentration of the polycarbonate resin obtained in Example 2 was 240 ppm, and the OH concentration of the polycarbonate resin obtained in Example 3 was 1100 ppm.

[0061] <Example 4> The reaction was carried out in the same manner as in Example 1 except that the raw materials were changed to the raw materials shown in Table 5 and the temperature-raising and pressure-reducing program was changed to that shown in Table 2. The physical properties of the obtained polycarbonate resin are shown in Table 5.

Table 2

[0062] <Example 5> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to the raw materials shown in Table 5 and the temperature increase and pressure reduction program was changed to that shown in Table 3. The physical properties of the obtained polycarbonate resin are shown in Table 5. The OH concentration of the polycarbonate resin obtained in Example 5 was 2200 ppm.

Table 3

[0063] <Examples 6 and 7> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to the raw materials shown in Table 5 and the temperature increase and pressure reduction program was changed to that shown in Table 4. The physical properties of the obtained polycarbonate resin are shown in Table 5.

Table 4

[0064] <Comparative Example> The reaction was carried out in the same manner as in Example 4, except that the raw materials were changed to those shown in Table 5. The physical properties of the obtained polycarbonate resin are shown in Table 5. The OH concentration of the polycarbonate resin obtained in the comparative example was 850 ppm.

Table 5

[0065] <Example 8> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to the raw materials shown in Table 16 and the temperature increase and pressure reduction program was changed to that shown in Table 6. The physical properties of the obtained polycarbonate resin are shown in Table 17.

Table 6

[0066] <Example 9> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to the raw materials shown in Table 16 and the temperature increase and pressure reduction program was changed to that shown in Table 7. The physical properties of the obtained polycarbonate resin are shown in Table 17.

Table 7

[0067] <Example 10> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to the raw materials shown in Table 16 and the temperature-raising and pressure-reducing program was changed to that shown in Table 8. The physical properties of the obtained polycarbonate resin are shown in Table 17.

Table 8

[0068] <Example 11> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to the raw materials shown in Table 16 and the temperature-raising and pressure-reducing program was changed to that shown in Table 9. The physical properties of the obtained polycarbonate resin are shown in Table 17.

Table 9

[0069] <Example 12> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to the raw materials shown in Table 16 and the temperature-raising and pressure-reducing program was changed to that shown in Table 10. The physical properties of the obtained polycarbonate resin are shown in Table 17.

Table 10

[0070] <Example 13> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to the raw materials shown in Table 16 and the temperature-raising and pressure-reducing program was changed to that shown in Table 11. The physical properties of the obtained polycarbonate resin are shown in Table 17.

Table 11

[0071] <Examples 14 and 15> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to those shown in Table 16 and the temperature-raising and pressure-reducing program was changed to that shown in Table 12. The physical properties of the obtained polycarbonate resin are shown in Table 17.

Table 12

[0072] <Example 16> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to those shown in Table 16 and the temperature-raising and pressure-reducing program was changed to that shown in Table 13. The physical properties of the obtained polycarbonate resin are shown in Table 17.

Table 13

[0073] <Example 17> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to those shown in Table 16 and the temperature-raising and pressure-reducing program was changed to that shown in Table 14. The physical properties of the obtained polycarbonate resin are shown in Table 17.

Table 14

[0074] <Example 18> The reaction was carried out in the same manner as in Example 1, except that the raw materials were changed to those shown in Table 16 and the temperature-raising and pressure-reducing program was changed to that shown in Table 15. The physical properties of the obtained polycarbonate resin are shown in Table 17.

Table 15

[0075]

Table 16

[0076]

Table 17

Industrial Applicability

[0077] The polycarbonate resin of the present invention generates extremely little gas, so it can be suitably used for various molded products. Generally, since polycarbonate resins have a high Tg, when melt-molding, it is necessary to heat and melt them at a high temperature of 180°C or higher. In order to reduce the molding cost, molding at a lower temperature has been desired. Also, polycarbonates with a low Tg have been demanded as materials for various industrial products. For example, the Tg of the generally well-known bisphenol A type polycarbonate resin is approximately 150°C, but materials with a lower Tg have been demanded. Among them, the copolymer polycarbonate of polytetramethylene glycol and bisphenol A in the present invention, and particularly the copolymer polycarbonate of poly-n-propylene glycol and bisphenol A, have a low Tg and can be widely and usefully used as materials for industrial products.

Claims

1. A polycarbonate resin comprising a structural unit (A) represented by the following general formula (1) (wherein the monomer constituting the structural unit (A) is not bisphenol A) and a structural unit (B) represented by the following general formula (4), wherein the monomer constituting the structural unit (B) is poly-n-propylene glycol or polytetramethylene ether glycol, and the polystyrene-reduced weight average molecular weight (Mw) of the polycarbonate resin is 5,000 to 40,000. 【Chemical 1】 [In general formula (1), R １ 、 R ２ 、 R ３ 、 R ４ 、 R ５ 、 R ６ 、 R ７ 、 and R ８ are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and an aralkyl group having 7 to 17 carbon atoms, and the alkyl group, the aryl group, the alkenyl group, the alkoxy group, and the aralkyl group may each have a substituent. X is -O-, -S-, -SO-, -SO ２ -, -CO-, a cycloalkylene group having 6 to 12 carbon atoms, or a divalent group represented by the following general formula (2) or the following general formula (3), and the cycloalkylene group may be substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms, [Chemical Formula 2] (In general formula (2), R ９ and R １０ each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, R ９ and R １０ the alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group in may each have a substituent, R ９ and R １０ may be combined with each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and the carbocyclic ring and the heterocyclic ring may each have a substituent, n represents an integer of 0 to 20.) 【Chemical Formula 3】 (In general formula (3), R １１ and R １２ are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, and the alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. R １１ and R １２ may be combined with each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and the carbocyclic ring and the heterocyclic ring may each have a substituent.)] 【Chemical Formula 4】 (In general formula (4), R z and R ｘ represent a hydrogen atom, i represents an integer of 3 or 4, and p represents an integer of 5 to 600.)

2. The polycarbonate resin according to claim 1, wherein the mass ratio (A / B) of the structural unit (A) to the structural unit (B) is 1 / 99 to 50 / 50.

3. A polycarbonate resin comprising only the structural unit (B) represented by the following general formula (4), wherein the monomer constituting the structural unit (B) is poly-n-propylene glycol or polytetramethylene ether glycol, and the polystyrene-reduced weight average molecular weight (Mw) of the polycarbonate resin is 5,000 to 40,000. 【Chemical Formula 5】 (In general formula (4), R z and R ｘ represent a hydrogen atom, i represents an integer of 3 or 4, and p represents an integer of 5 to 600.)

4. The polycarbonate resin according to any one of claims 1 to 3, wherein the terminal hydroxyl group concentration of the polycarbonate resin is 1 ppm to 3000 ppm.

5. The polycarbonate resin according to any one of claims 1 to 4, wherein the glass transition temperature (Tg) of the polycarbonate resin is -100 to 140 °C.

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