JP2006111794A - Alicyclic polyester resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alicyclic polyester resin having excellent transparency, heat resistance, weather resistance and the like, and excellent chemical stability and safety.
An alicyclic polyester resin obtained from a dicarboxylic acid component mainly composed of 4,4′-bicyclohexyldicarboxylic acid and a diol component mainly composed of an alicyclic diol. The gist is a polyester resin.
[Selection figure] None.

Description

The present invention relates to an alicyclic polyester resin. More specifically, the present invention relates to an alicyclic polyester resin having a high melting point and excellent heat resistance.

Cycloaliphatic polyester resin consisting of cycloaliphatic dicarboxylic acid and cycloaliphatic diol has excellent transparency, heat resistance, weather resistance, etc., chemical stability, safety (including when used and discarded), etc. Therefore, it is expected as a material for producing films, fibers, parts of various devices and the like, and its uses are gradually expanding. Among alicyclic polyester resins, alicyclic polyester resins comprising 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid component and 1,4-cyclohexanedimethanol as a diol component have been known (patents). Literature example 1). It is known that the ratio of trans isomers (hereinafter simply referred to as trans isomers) contained in these raw material components is closely related to the melting point of the resulting alicyclic polyester resin. These raw material components are about 95% of trans isomers of 1,4-cyclohexanedicarboxylic acid that are commercially available, and about 70% of trans isomers of 1,4-cyclohexanedimethanol. Even if a component having such a ratio of the trans isomer is used as a raw material, the resulting alicyclic polyester resin has a maximum melting point of about 220 ° C., and has a limited use temperature (Patent Document Example 2).
U.S. Pat. No. 2,901,466 JP 2000-290356 A

In the above situation, the present inventors have intensively studied to provide an alicyclic polyester resin technology having a high melting point and excellent heat resistance. As a result, alicyclic dicarboxylic acid having a plurality of cyclohexane rings, and alicyclic The inventors have found that the problem can be solved by an alicyclic polyester resin obtained by polycondensation of a raw material containing diol as a main component, and have completed the present invention. An object of the present invention is to provide an alicyclic polyester resin having excellent transparency, heat resistance, weather resistance, and the like, and excellent chemical stability and safety.

  In order to solve the above problems, the present invention is obtained from a dicarboxylic acid component mainly composed of 4,4′-bicyclohexyldicarboxylic acid and a diol component mainly composed of an alicyclic diol. An alicyclic polyester resin is provided.

The present invention is as described in detail below, has the following particularly advantageous effects, and its industrial utility value is extremely large.
1. Since the alicyclic polyester resin according to the present invention has an alicyclic structure in the molecular chain, it has a high melting point of 235 ° C. and excellent heat resistance. It is suitable as a manufacturing material.
2. The alicyclic polyester resin according to the present invention is excellent in transparency, weather resistance, chemical stability, safety, etc. in addition to heat resistance. Suitable as a material.

Hereinafter, the present invention will be described in detail. However, the description of the constituent elements (embodiments) described below is representative of examples of the present invention, and the present invention is not limited to these descriptions. The alicyclic polyester resin according to the present invention is obtained from a dicarboxylic acid component (a) having 4,4′-bicyclohexyldicarboxylic acid as a main component and a diol component (b) having an alicyclic diol as a main component. It is what was done.

The dicarboxylic acid component (a) is mainly composed of 4,4′-bicyclohexyldicarboxylic acid (a1), and the remaining components are dicarboxylic acid components (a2) other than 4,4′-bicyclohexyldicarboxylic acid, It means that the polymer component (c) may be included. Here, the main component means that the ratio of the 4,4′-bicyclohexyldicarboxylic acid (a1) to the total dicarboxylic acid component (a) exceeds 50 mol%. When the ratio of 4,4′-bicyclohexyldicarboxylic acid (a1) to the total dicarboxylic acid component is 50 mol% or less, the resulting alicyclic polyester resin tends to be inferior in heat resistance. The ratio of 4,4'-bicyclohexyldicarboxylic acid (a1) to the total dicarboxylic acid component is preferably 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

The 4,4'-bicyclohexyldicarboxylic acid (a1), which is the main component of the raw material for producing the alicyclic polyester resin, includes a dicarboxylic acid form and an ester-forming derivative form thereof. Examples of the ester-forming derivative include alkyl esters and acid halides. Among them, alkyl esters having an alkyl group having 1 to 6 carbon atoms are preferable, and a methyl group is particularly preferable.

The 4,4′-bicyclohexyldicarboxylic acid (a1) has three stereoisomers of cis isomer structure, cis isomer structure, cis isomer structure, trans isomer structure, and trans isomer structure depending on the arrangement state of two cyclohexyl groups. There is a body. According to the experiments by the present inventors, in order to increase the heat resistance of the resulting alicyclic polyester resin, the trans isomer-trans isomer structure occupies in the 4,4′-bicyclohexyldicarboxylic acid component (a1). It turned out that it is so preferable that there are many. In particular, when the proportion of the trans isomer-trans isomer structure in the raw material 4,4′-bicyclohexyldicarboxylic acid component (a1) is 80%, the 4,4′-bi acrylate in the resulting alicyclic polyester resin is used. Since the unit derived from the cyclohexyldicarboxylic acid component (a1) also has a trans isomer-trans isomer structure of 80% or more, an alicyclic polyester resin having a melting point of 220 ° C. or more is easily obtained. The structure of the stereoisomer can be confirmed by gas chromatography in the case of 4,4′-bicyclohexyldicarboxylic acid or an ester-forming derivative thereof, and in the case of an alicyclic polyester resin obtained by polycondensation of these. Can be confirmed by a method in which ¹ H and ¹³ C spectra are measured by nuclear magnetic resonance (NMR) spectroscopy for a solution obtained by dissolving the resin in deuterated chloroform or the like.

  The dicarboxylic acid component (a) of the raw material for producing the alicyclic polyester resin according to the present invention is mainly composed of 4,4′-bicyclohexyldicarboxylic acid (a1) as described above, but other dicarboxylic acid components. (A2) may be included. Examples of the dicarboxylic acid component (a2) include terephthalic acid, phthalic acid, isophthalic acid, 1,4-phenylenedioxydicarboxylic acid, 1,3-phenylenedioxydiacetic acid, 4,4′-diphenyldicarboxylic acid, 4 , 4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid, 4,4′-diphenoxyethane dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid and other aromatics Examples include dicarboxylic acids and aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid, and cyclohexanedicarboxylic acid. These dicarboxylic acid components (a2) may be one type or two or more types.

The dicarboxylic acid component (a2) includes not only the dicarboxylic acid form but also its ester-forming derivative form. Examples of the ester-forming derivative include alkyl esters, acid anhydrides, acid halides, etc. Among them, alkyl esters are more preferable. The alkyl group of the alkyl ester preferably has 1 to 6 carbon atoms, and particularly preferably a methyl group. Specific examples of the alkyl ester include dimethyl terephthalate, dimethyl phthalate, dimethyl isophthalate, dimethyl 1,4-phenylenedioxydicarboxylate, dimethyl 1,3-phenylenedioxydiacetate, and 4,4′-diphenyldicarboxylic acid. Dimethyl, dimethyl 4,4'-diphenyl ether dicarboxylate, dimethyl 4,4'-diphenyl ketone dicarboxylate, dimethyl 4,4'-diphenoxyethanedicarboxylate, dimethyl 4,4'-diphenylsulfone dicarboxylate, 2,6- Aromatic dicarboxylic acid dimethyl esters such as dimethyl naphthalenedicarboxylate, and dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, undecad Carboxylic acid dimethyl, dodecamethylene dicarboxylic acid, dimethyl esters and the like of aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid dimethyl. These ester-forming derivatives may also be one kind or two or more kinds.

  As described above, the diol component (b) of the raw material for producing an alicyclic polyester resin according to the present invention contains an alicyclic diol as a main component. The diol component (b) may be mainly composed of the alicyclic diol component (b1), and the rest may be another diol component (b2) and a small amount of the copolymer component (c). Here, the main component means that the proportion of the alicyclic diol component (b1) in the total diol component (b) exceeds 50 mol%. When the proportion of the alicyclic diol component (b1) in the total diol component is 50 mol% or less, the resulting alicyclic polyester resin tends to have poor heat resistance. The ratio of the alicyclic diol component (b1) to the total diol component (b) is preferably 70 mol%, more preferably 80 mol%, and particularly preferably 90 mol% or more.

  Examples of the alicyclic diol component (b1) include 1,2-, 1,3-cyclopentanediol, 1,2-, 1,3-cyclopentanedimethanol, bis (hydroxymethyl) tricyclo [5.2. .1.0] 5-membered ring diol such as decane, 1,2-, 1,3-, 1,4-cyclohexanediol, 1,2-, 1,3-, 1,4-cyclohexanedimethanol, 2, And 6-membered ring diols such as 2-bis- (4-hydroxycyclohexyl) -propane. Preferred examples include 1,2-, 1,3-, 1,4-cyclohexanedimethanol. Among these, 1,4-cyclohexanedimethanol is particularly preferable because an alicyclic polyester resin having a high polymerization degree and a high glass transition point can be obtained. 1,4-Cyclohexanedimethanol has a trans isomer and a cis isomer, and is usually a mixture thereof. The molar ratio of the trans isomer to the cis isomer is 80:20 to 60:40. The trans isomer and cis isomer of 1,4-cyclohexanedimethanol can be quantified by gas chromatography.

  Examples of the diol component (b2) other than the alicyclic diol component (b1) include ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl. Aliphatic diols such as glycol, diethylene glycol, polyethylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, tricyclodecane dimethanol, and xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone Aromatic diols such as bis (4-beta-hydroxyethoxyphenyl) sulfonic acid. These diol components (b2) may be one type or two or more types.

  As described above, the raw material for producing the alicyclic polyester resin according to the present invention can contain a small amount of the copolymer component (c) in addition to the dicarboxylic acid component (a) and the diol component (b). It is as follows. Examples of the copolymer component (c) include hydroxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, and p-β-hydroxyethoxybenzoic acid, alkoxycarboxylic acids, tricarballylic acid, trimellitic acid, trimesic acid, Trifunctional or more polyfunctional components such as pyromellitic acid, naphthalenetetracarboxylic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, sugar ester and the like can be mentioned. The trifunctional or higher polyfunctional component is useful for adjusting the melt viscosity of the alicyclic polyester resin and enhancing the moldability.

  The alicyclic polyester resin according to the present invention includes a dicarboxylic acid component mainly composed of 4,4′-bicyclohexyldicarboxylic acid, a diol component mainly composed of alicyclic diol, and if necessary, a small amount of copolymer component ( c). The reaction at this time is preferably melt polycondensed via an esterification reaction, but can also be melt polycondensed via an ester exchange reaction. The obtained alicyclic polyester resin preferably has an intrinsic viscosity (IV) of 0.5 dl / g or more measured by using an equal mixture of phenol and tetrachloroethane as a solvent. If the IV is less than 0.5 dl / g, the molding material is weak and unfavorable. IV is more preferably 0.6 dl / g or more, and particularly preferably 0.7 dl / g or more.

When dicarboxylic acid is used as a raw material and the diol component is esterified, the molar ratio of the diol component to the dicarboxylic acid component is usually greater than 100/100, less than 110/100, preferably greater than 102/100. Performed at less than 110/100. When the molar ratio is 100/100 or less, the terminal acid value of the resulting alicyclic polyester resin becomes high and the hydrolysis resistance may be inferior. When it exceeds 110/100, the reactivity tends to decrease. In some cases, a polyester resin having a high intrinsic viscosity may not be obtained. When an alkyl ester of a dicarboxylic acid is used as the raw material, the molar ratio of the diol component to the dicarboxylic acid component subjected to the transesterification reaction is usually greater than 100/100, less than 110/100, preferably greater than 102/100. Performed at less than 110/100.

  The esterification reaction or transesterification reaction can be carried out in the presence or absence of a catalyst, preferably in the presence of a catalyst. When a catalyst is present in the reaction system, the type of the catalyst is not particularly limited. For example, when producing a polyester resin, a titanium compound, germanium compound, or antimony compound known as an esterification reaction or transesterification reaction catalyst is used. And tin compounds. Of these, titanium compounds are preferred because of their high activity in any of esterification, transesterification, and polycondensation reactions described below. Examples of the titanium compound include tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, and hydrolysates of these organic titanates. These catalysts may be one kind or two or more kinds. The amount of the catalyst used is usually in the range of 5 ppm to 2000 ppm, preferably in the range of 10 ppm to 1000 ppm, in terms of metal atoms, with respect to the polyester resin to be produced.

  In the esterification reaction or transesterification reaction, for example, the raw dicarboxylic acid component and the diol component are charged into a reaction vessel (or reactor) equipped with a stirrer and a distillation pipe, a reaction catalyst is added, and an inert gas atmosphere is added. The water or alcohol produced by the reaction can be distilled off while stirring. In the esterification reaction or transesterification reaction, the reaction temperature is usually 150 ° C. to 230 ° C., preferably 180 ° C. to 220 ° C., and the absolute pressure is 1000 to 1100 kPa, and the reaction time depends on the reaction temperature. Is carried out in the range of 10 minutes to 10 hours, preferably in the range of 30 minutes to 5 hours.

  After completion of the esterification reaction or transesterification reaction, a polycondensation reaction is performed. In the polycondensation reaction, for example, the reaction liquid of the esterification reaction or transesterification reaction is transferred to a polycondensation tank equipped with a stirrer, a distillation pipe and a vacuum addition device, and a polycondensation catalyst or the like is added as necessary. The melt polycondensation reaction is performed while gradually reducing the pressure in the reaction vessel. Examples of the polycondensation catalyst include titanium compounds, germanium compounds, antimony compounds, and tin compounds.

  The polycondensation catalyst is usually used in the range of 5 ppm to 2000 ppm, preferably 10 ppm to 1000 ppm in terms of metal atom, based on the polyester resin to be produced. When the esterification reaction or transesterification reaction catalyst is used also as a polycondensation catalyst, a metal compound added as an esterification reaction or transesterification reaction catalyst and a metal compound added later as a polycondensation catalyst Is adjusted so as to be within the above range with respect to the polyester resin to be produced. When the amount of the catalyst is less than 5 ppm, the effect of promoting the reaction is poor, and when it is more than 2000 ppm, problems such as coloring of the produced polyester resin occur, which are not preferable. In addition, in the process of esterification reaction or transesterification reaction, and / or the process of polycondensation reaction, a magnesium compound, a phosphorus compound, etc. which are mix | blended with a polyester resin can be added as needed.

In addition, the reaction tank can be equipped with a decompression device, and the esterification reaction or the transesterification reaction and the polycondensation reaction can be performed in one tank. The reaction conditions are, for example, an esterification or transesterification end temperature or higher, 270 ° C. or lower, preferably 265 ° C. or lower, and a pressure at which the internal pressure of the tank finally becomes 1 kPa or lower from normal pressure to absolute pressure, preferably absolute pressure. At 0.5 kPa or less for 10 minutes to 10 hours, preferably 30 minutes to 5 hours, and an alicyclic polyester resin having an intrinsic viscosity (IV) of 0.5 dl / g or more can be obtained.

  After completion of the reaction, the polycondensation reaction product (polyester) is usually obtained as a pellet by extracting it from the bottom of the reaction vessel into a strand shape and cutting it while cooling with water. In order to further increase the degree of polymerization of the alicyclic polyester resin, solid phase polycondensation can also be performed. The method of solid phase polycondensation is not particularly limited, and can be carried out in a standing inert oven or a vacuum dryer after crystallizing the pellet, or a double cone type solid phase polycondensation apparatus or moving bed, It can also be carried out using a fluidized bed. The solid phase polycondensation is usually performed at a temperature 10 to 50 ° C. lower than the melting point of the alicyclic polyester resin, preferably 10 to 40 ° C. under an inert gas such as nitrogen, or under a vacuum of 1 kPa or less. The reaction is performed for 48 hours, preferably 2 to 48 hours.

  When the alicyclic polyester resin according to the present invention is used as a molding material, various resin additives can be blended as necessary. Examples of the resin additive include glass beads, glass powder, glass balloons, mica, talc, calcium carbonate and other inorganic fillers, antioxidants, heat stabilizers, ultraviolet absorbers, neutralizers, lubricants, and compatibilizers. , Antifogging agents, antiblocking agents, plasticizers such as paraffin oil, fluororesin powders, slip agents, dispersants, colorants, antibacterial agents, rust inhibitors, fluorescent whitening agents, and the like.

  Since the alicyclic polyester resin thus obtained has a high melting point, it can be suitably used for the production of films, fibers and various molded products (products) that require heat resistance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by the following description examples, unless the meaning is exceeded. Hereinafter, methods for evaluating physical properties of the raw material dicarboxylic acid (a) and the alicyclic polyester resin, and preparation examples of the raw material dicarboxylic acid (a) are shown.

[Evaluation methods]
1. Gas chromatography method: Measured using a gas chromatography machine (manufactured by Shimadzu Corporation, model: GC-14C, column: manufactured by GL Sainz Co., Ltd., Neutrabond-1).
2. Intrinsic viscosity (IV): Polyester pellets were measured at a temperature of 30 ° C. using a mixed solution of phenol / tetrachloroethane (weight ratio 1/1) as a solvent and using an Ubbelohde viscometer.
3. Melting point: A differential scanning calorimeter (manufactured by Seiko Instruments Inc., model: DSC220) was used, and the temperature was raised from room temperature to 300 ° C. at a rate of 20 ° C./min.
4). Infrared absorption curve: Polyester resin pellets were formed into a film by a compression molding method at a temperature of 250 ° C., and the film was drawn using an infrared spectrometer (manufactured by Nicole, Magna 550).
5. NMR: Polyester resin pellets were dissolved in deuterated chloroform, and ¹ H and ¹³ C spectra were measured with a nuclear magnetic resonance (NMR) spectrometer (manufactured by Varian, Model: Unity Plus 400).

[Example of production of dicarboxylic acid]
In a reactor having a capacity of 2 L equipped with a stirrer and a thermometer, 100 g of dimethyl 4,4′-biphenyldicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 5% ruthenium / carbon (ruthenium converted to 5% carbon) (N・ Eg Chemcat Co., Ltd.) 10 g, water 395 g, and sodium hydroxide 31 g were charged. After purging the reactor with hydrogen, under stirring, the hydrogen pressure was adjusted to 1 MPa with a gauge pressure, the internal temperature was raised to 150 ° C., and the reaction was continued for 4 hours while maintaining the hydrogen pressure at 10 MPa with the gauge pressure. It was. After the completion of the reaction, the reactor internal temperature was cooled to around room temperature, and then the reaction solution was filtered to remove the catalyst, and 35% hydrochloric acid aqueous solution was added to the filtrate to precipitate 4.4′-bicyclohexyldicarboxylic acid. The obtained solid product was filtered, washed twice with 3 L of water, and sufficiently dried at 100 ° C. and 5 mmHg. It was 225-240 degreeC when melting | fusing point of the obtained product was measured. This solid product was methyl esterified according to a conventional method and confirmed by gas chromatography, and three isomers were observed. The area ratio of the peaks derived from each isomer was 53.0 / 39.9 / 7.1 in the cis isomer-cis isomer structure / cis isomer-trans isomer structure / trans isomer-trans isomer structure.

  For subsequent isomerization, 5 g of the above product was charged into a cylindrical reaction tube with a length of 30 cm and an inner diameter of 20 mm, equipped with a gas inlet and outlet cock at the top. An argon-introducing thin tube was inserted into the reaction tube from the gas inlet, and the reaction tube was sufficiently replaced with argon. Thereafter, the outlet cock was closed and the reaction tube was sealed with argon, and then the reaction tube was placed in an electric furnace heated to 350 ° C., the temperature in the reaction tube was set to 350 ° C., and this temperature was maintained for 10 minutes. The carboxylic acid dissolved during the temperature increase and remained dissolved during the isomerization reaction. After holding for 10 minutes, the reactor was removed from the electric furnace and cooled to 170 ° C. or lower within 5 minutes. When the obtained solid product was dissolved in deuterated chloroform and confirmed by gas chromatography, three types of isomers were observed. As for the area ratio of the peak derived from each isomer, cis isomer-cis isomer structure / cis isomer-trans isomer structure / trans isomer-trans isomer structure was 0.2 / 7.4 / 92.4.

[Example 1]
In a reactor equipped with a stirrer, a distilling tube, a stirring blade, a thermometer and a pressure reducing device, 105 g of 4,4′-bicyclohexyldicarboxylic acid produced by the method shown in Production Example 1 and 1,4-cyclohexanedi 61.3 g of methanol (molar ratio of trans to cis isomer of 70:30) (molar ratio of diol to dicarboxylic acid of 103/100) and 6% butanol solution of tetra-n-butyl titanate as a catalyst Prepared. After substituting the inside of the reactor with nitrogen, the reactor was heated under a nitrogen stream until the internal temperature reached 150 ° C., and then heated to 200 ° C. over 1 hour. Thereafter, the mixture was held at 200 ° C. for 1 hour, and further heated from 200 ° C. to 250 ° C. over 45 minutes to carry out an esterification reaction. Thereafter, the reaction temperature was raised to 275 in 30 minutes, and a polycondensation reaction was performed while gradually reducing the pressure in the reactor. After polymerization for 3 hours at a reactor internal pressure of 0.1 kPa and a reaction temperature of 275 ° C., the obtained polyester resin was drawn out into water in the form of strands and cut into pellets. The obtained pellets were dried for 5 hours in a vacuum dryer set at a temperature of 80 ° C. The intrinsic viscosity (IV) of the polyester resin after drying was 0.60 dl / g, and the melting point was 235 ° C. Further, when the distribution of isomers derived from 4,4′-bicyclohexyldicarboxylic acid was analyzed by NMR, the ratio of cis isomer-cis isomer structure + cis isomer-trans isomer structure / trans isomer-trans isomer structure was 20/80. Met. Moreover, the infrared absorption curve figure of this polyester resin was drawn, and the result was shown in FIG. As a result, the absorption of ester carbonyl wavelength near 1730 cm ^-1, absorption of methylene cyclohexane ring around 2930,2840,1450Cm ^-1, absorption of the skeleton of a cyclohexane ring around 1040,990Cm ^-1 is observed, alicyclic It was confirmed that a polyester resin was obtained.

[Comparative Example 1]
In the example described in Example 1, 184.2 g of 1,4-cyclohexanedicarboxylic acid (molar ratio of trans isomer to cis isomer 95: 5) as a raw material and 1,4-cyclohexanedimethanol (trans isomer to cis isomer) The molar ratio of 70:30 is 158.1 g (the molar ratio of diol to dicarboxylic acid is 102.5 / 100), and 0.9 g of a 6% butanol solution of tetra-n-butyl titanate as a catalyst is used. Except for the change, the reaction and post-treatment were performed in the same procedure as in the same example. The obtained alicyclic polyester resin had an intrinsic viscosity (IV) of 1.19 dl / g and a melting point of 196 ° C. In this example, since the raw material dicarboxylic acid does not have a plurality of cyclohexane rings, the melting point of the alicyclic polyester resin does not reach 200 ° C., and the object of the present invention cannot be achieved.

  Since the alicyclic polyester resin according to the present invention has a high melting point, it can be suitably used as a raw material for producing films, fibers, and molded articles (products). The film is suitable for retort food packaging, medicine storage, etc. exposed to high-temperature sterilization, and uses such as fibers and molded products are products in the electrical / electronic equipment field, automotive field, mechanical field, medical field, etc. Examples include parts.

2 is an infrared absorption curve of the alicyclic polyester resin obtained in Example 1. FIG.

Explanation of symbols

1: Infrared absorption curve

Claims (4)

An alicyclic polyester resin obtained from a dicarboxylic acid component containing 4,4'-bicyclohexyldicarboxylic acid as a main component and a diol component containing alicyclic diol as a main component. The alicyclic polyester resin according to claim 1, having an intrinsic viscosity of 0.5 dl / g or more and a melting point of 220 ° C or more.   The alicyclic polyester resin according to claim 1 or 2, wherein a unit derived from 4,4'-bicyclohexyldicarboxylic acid in the alicyclic polyester resin is 80% or more of a trans isomer-trans isomer structure. The alicyclic polyester resin according to any one of claims 1 to 3, wherein the alicyclic diol is 1,4-cyclohexanedimethanol.

Images