JP2008291151A - Heat-resistant polyester resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin of excellent heat resistance and impact resistance. <P>SOLUTION: This heat resistant polyester resin is a heat resistant polyester resin (III) constituted of a diol component (I) and a dicarboxylic acid component (II), and having a content of 5-99 mol.% of a bisphenol-A ethylene oxide adduct (A) in the diol component (I). The bisphenol-A ethylene oxide adduct (A) is a reaction mixture comprising 0-1 mol.% of bisphenol-A ethylene oxide one-molar adduct (A1), 92-100 mol.% of bisphenol-A ethylene oxide two-molar adduct (A2), and 0-7 mol.% of bisphenol-A ethylene oxide three-or-more-molar adduct (A3). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyester resin using an alkylene oxide adduct of bisphenol A as a raw material for a diol component, and more particularly to a polyester resin excellent in heat resistance and impact resistance.

  Thermoplastic polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyarylate are excellent in mechanical strength and heat resistance, and are used in various industrial fields such as films, fibers, and molded articles.

  Although these thermoplastic polyester resins have excellent features, in order to meet various industrial performance requirements, the performance of the resin alone is limited, and other components can be used together for the purpose of modification. Attempts have been made to polymerize.

For example, since polyethylene terephthalate is hard and brittle due to its high crystallinity, it has a drawback of poor impact resistance and poor adhesion to other members.
As a solution to this problem, it is known to copolymerize an alkylene oxide adduct of bisphenols as a diol component.
As a result, non-crystalline improvement, flexibility to the resin are imparted, advantageous changes in impact resistance and extensibility appear, and various useful effects such as being effective in water dispersibility. It has been reported (for example, Patent Documents 1 to 5).

However, when the copolymerization ratio of the bisphenol A alkylene oxide adduct used for the above copolymerization is increased until the impact resistance is exhibited, the glass transition point is lowered and the heat resistance is adversely affected. Further, when the copolymerization ratio is lowered, there is a problem that a sufficient effect on impact resistance is not exhibited.
JP 2004-155187 A Japanese Patent Laid-Open No. 11-2000154 JP-A-9-110773 JP-A-6-116487 Japanese Patent Laid-Open No. 5-147180

  Then, this invention makes it a subject to provide the polyester resin excellent in heat resistance and impact resistance even if it copolymerizes the alkylene oxide adduct of bisphenol A, and the film, fiber, and molded article using the same.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention relates to a polyester resin (III) composed of a diol component (I) and a dicarboxylic acid component (II), wherein 5 to 99 mol% of the diol component (I) comprises the following bisphenol A ethylene oxide: It is a heat-resistant polyester resin (III) characterized by being an adduct (A).
However, the bisphenol A ethylene oxide adduct (A) has a content of (i) bisphenol A ethylene oxide 1 mol adduct (A1) of 0 to 1 mol%, (ii) bisphenol A ethylene oxide 2 mol adduct (A2 ) Is a reaction mixture having a content of 92 to 100 mol% and (iii) a content of adduct (A3) of 3 mol or more of bisphenol A ethylene oxide is 0 to 7 mol%.

  The heat-resistant polyester resin of the present invention has an effect of being excellent in heat resistance and impact resistance as compared with conventional polyester resins.

The bisphenol A ethylene oxide adduct (A) essential as the diol component (I) constituting the heat-resistant polyester resin (III) of the present invention is a reaction mixture characterized by the following addition molar distribution.
(i) 0 to 1 mol% of bisphenol A ethylene oxide 1 mol adduct (A1),
(ii) 92-100 mol% of bisphenol A ethylene oxide 2 mol adduct (A2),
(iii) Bisphenol A ethylene oxide 3 mol or more of adduct (A3) is 0 to 7 mol%

Each ratio of (A1), (A2), and (A3) constituting (A) that is the reaction mixture needs to be within a specific range.
In particular, the content of (A2) is usually 92 to 100 mol% in order that the 2 mol adduct (A2) of the main component improves heat resistance and impact resistance. Preferably it is 95-100 mol%, More preferably, it is 98-100 mol%, Most preferably, it is 99-100 mol%.

  The phenolic hydroxyl group of 1 mol adduct (A1) has low esterification reactivity with carboxylic acid, and the content of (A1) is usually 0 to 1 mol%. Preferably, it is 0-0.5 mol%, More preferably, it is 0-0.2 mol%, Most preferably, it is 0.1 mol% or less.

  3 mol or more of adduct (A3) has a high ether bond concentration, and when the ratio is high, when introduced into a polyester resin, the glass transition point of the resin is lowered and the heat resistance deteriorates as a performance. The amount is usually from 0 to 7 mol%. Preferably, it is 0-5 mol%, More preferably, it is 0-2 mol%, Most preferably, it is 1 mol% or less.

  The content of the bisphenol A ethylene oxide adduct (A) in the diol component (I) is usually 5 to 99 mol%. If it is less than the lower limit, the heat resistance and impact resistance effects of the polyester resin do not appear. Preferably, it is 10-99 mol%, More preferably, it is 15-75 mol%, Most preferably, it is 20-99 mol%.

  The content of the bisphenol A ethylene oxide adduct (A) in the diol component (I) is determined by hydrolyzing the obtained polyester resin in alkaline water and analyzing the decomposition product by liquid chromatography and gas chromatography. Can be quantified.

As a method of introducing the bisphenol A ethylene oxide adduct (A) into the polyester resin,
(i) a method in which (A) as the diol component (I) and another diol (for example, ethylene glycol) are polycondensed to the dicarboxylic acid component (II) (for example, terephthalic acid),
(ii) Dicarboxylic acid low-molecular alkyl ester (terephthalic acid both-end dimethyl ester or both-end ethylene glycol ester) as dicarboxylic acid component (II), and (A) as diol component (I) and other diols (for example, A method of transesterifying ethylene glycol),
(iii) A method in which (A) itself is melt-mixed with an existing polyester resin such as polyethylene glycol terephthalate (PET) or polybutylene glycol terephthalate (PBT) for transesterification,
(iv) There is a method in which a commercially available polyester resin and a polyester resin separately polymerized (A) are melt-mixed and transesterified.
Among these, the methods (i) and (ii) are preferable, and the method (ii) is preferable when it is necessary to obtain a high molecular weight product.

In the diol component (I) constituting the heat-resistant polyester (III) of the present invention, diol components other than the bisphenol A ethylene oxide adduct (A) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene. Glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,3-pentanediol, 1,6-hexanediol, 2,3-hexanediol, 3,4-hexanediol , Alkane diols such as neopentyl glycol; polyalkylene ether glycols such as diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; alkylene oxides having 2 to 4 carbon atoms of the above aliphatic diols having 2 to 36 carbon atoms (hereinafter referred to as AO and Abbreviate Adduct (addition mole number 2-30); C6-C36 alicyclic diol such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A; C2-C4 AO of the above alicyclic diol Adducts (addition mole number 2 to 30); bisphenols such as bisphenol F and bisphenol S; AO adducts having 2 to 4 carbon atoms (2 to 30 addition moles) of the bisphenols, etc. May be used in combination.
Among these diol components other than (A), ethylene glycol, 1,3-propylene diol, and 1,4-butanediol are preferable, and ethylene glycol and 1,4-butanediol are more preferable. is there.

In the heat-resistant polyester (III) of the present invention, a trihydric or higher polyhydric alcohol may be partially used together as necessary.
Among the polyhydric alcohols, alcohols having 3 to 8 or more valences are aliphatic having 3 to 8 or more carbon atoms having 3 to 36 carbon atoms such as glycerin, triethylolethane, trimethylolpropane, pentaerythritol and sorbitol. Polyhydric alcohol; AO adduct having 2 to 4 carbon atoms of the above aliphatic polyhydric alcohol (addition mole number 2 to 30); AO adduct having 2 to 4 carbon atoms of trisphenol such as trisphenol PA (addition) Mole number 2-30); C2-C4 AO adduct (addition mole number 2-30) etc. of novolak resins (average polymerization degree 3-60), such as a phenol novolak and a cresol novolak, etc. are mentioned.

  The dicarboxylic acid component (II) constituting the heat-resistant polyester (III) of the present invention is not necessarily limited to the dicarboxylic acid at both ends, and derivatives thereof (esterified products, acid halides, acid anhydrides, etc.) are also included. Specific examples include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid; alkane dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, repargic acid, and sebacic acid; dodecenyl succinic acid Alkenyl succinic acids such as acids, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, alkenedicarboxylic acids such as glutaconic acid; and monovalent or divalent alcohols having 2 to 4 carbon atoms of the above carboxylic acids Esterified products, halides of the above carboxylic acids; acid anhydrides and the like.

  Among the dicarboxylic acid components described above, a dihydric alcohol that is an esterified product of a carboxylic acid with a divalent alcohol and forms an ester bond by an esterification reaction and is incorporated into the polyester skeleton is defined in claim 1. It shall be included in the diol component (I).

In the heat-resistant polyester (III) of the present invention, a trivalent or higher polyvalent carboxylic acid may be used in combination as necessary.
Examples of polycarboxylic acids include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), vinyl polymers of unsaturated carboxylic acids (styrene / maleic acid copolymer, styrene / acrylic acid). Copolymer, α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.).

  Of these dicarboxylic acids (II), aromatic dicarboxylic acids are preferred in that heat resistance and impact resistance can be improved.

Furthermore, among aromatic dicarboxylic acids, the case where terephthalic acid is used is most preferable as the heat resistant polyester (III).
When the terephthalic acid is used, the polyester resin of the present invention usually has a glass transition point of 73 to 150 ° C. measured by a method (DSC method) defined in ASTM D3418-82. Preferably it is 75-150 degreeC.

  The polyester resin (III) obtained by the present invention is processed as a film excellent in heat resistance and impact resistance by being processed by an ordinary method, for example, a biaxial stretching method.

  The polyester resin (III) obtained by the present invention is useful as a fiber that is spun by a usual method, for example, a melt spinning method, and has excellent heat resistance and impact resistance.

  The polyester resin (III) obtained according to the present invention is useful as a molded product that is molded by an ordinary method, for example, an injection molding method and is excellent in heat resistance and impact resistance.

  The content ratio of (A1), (A2), (A3) in the bisphenol A ethylene oxide adduct (A) constituting the polyester resin (III) of the present invention was pre-treated with a silylating agent and then gas chromatograph ( GC). As an example, the measurement conditions were as follows.

<Preparation method of sample>
A 1 g sample is taken and then 19 g acetone is added and dissolved. To this sample, 0.1 ml of TMS-H1 (Trimethylchlorosilane silylating agent, manufactured by Tokyo Chemical Industry Co., Ltd.) is added and heated to 50-70 ° C. for 2-3 minutes to complete the silylation reaction. 1 μl of this supernatant is sampled and measured with a gas chromatograph.

<Measurement conditions for GC>
GC model: GC-14B (manufactured by Shimadzu Corporation)
Packing agent: Silicon GE-SE-52 (4%), carrier Cromosorb G (AW-DM CS); 150 to 180 μm (packed column made by Wako Pure Chemical Industries)
Column temperature: 250-350 ° C. (temperature increase rate: 10 ° C./min)
Detector: FID
Carrier gas: Nitrogen flow rate 50ml / min

  Hereinafter, the present invention will be further described with reference to production examples, examples and comparative examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

Production Example 228.0 g (1.0 mol) of bisphenol A and 228.0 g of water were charged into a glass autoclave having an internal volume of 1100 ml, and after nitrogen substitution, the temperature was raised to 90 ° C. to disperse bisphenol A in water. . To this was added 3.0 g (0.054 mol) of potassium hydroxide (KOH). Nitrogen substitution was performed again, and EO 88.0 g (2.0 mol) was dropped and reacted in a range of 90 ° C. and a reaction pressure of 0.2 MPa or less. Four hours after the start of dropping, 1.4 g (0.014 mol) of phosphoric acid was added, and 22.0 g (0.5 mol) of EO was added dropwise at 90 ° C. and a reaction pressure of 0.2 MPa or less. Two hours after the dropping, the reaction was terminated, and the reaction product was transferred to a four-necked flask.
Water was removed by liquid separation after heating to 90 ° C. Furthermore, since ethylene glycol and diethylene glycol by-produced were contained in the system, in order to remove this, 300 g of water was added and the mixture was stirred and washed at 90 ° C. for 1 hour. Thereafter, water was removed by liquid separation, and the mixture was treated with activated clay and filtered. This was dehydrated under reduced pressure at 130 ° C. to obtain 265 g (yield 84%) of bisphenol A dioxyethylene ether (A-1) of the present invention.
When this (A-1) was analyzed by GC, bisphenol A was not detected (hereinafter abbreviated as “ND”, EO 1 mol adduct ND, EO 2 mol adduct 97.3%, EO 3 mol adduct). 2.7%, EO 4 mol or more was adduct ND.

Comparative Production Example A glass autoclave with an internal volume of 1100 ml was charged with 228.0 g (1.0 mol) of bisphenol A and 72.0 g of (A-1) obtained in the production example, and after nitrogen substitution, the mixture was cooled to 90 ° C. Bisphenol A was dispersed in (A-1). To this, 3.0 g (0.054 mol) of KOH was added. Nitrogen substitution was performed again, and EO 101.2 g (2.3 mol) was dropped and reacted in a range of 90 ° C. and a reaction pressure of 0.2 MPa or less. The reaction was terminated 6 hours after the start of dropping, and the reaction product was transferred to a four-necked flask. The mixture was heated to 90 ° C., treated with activated clay, and filtered to obtain 312 g (yield 95%) of bisphenol A dioxyethylene ether (A′-1) for comparison.
When this (A′-1) was analyzed by GC, bisphenol A was ND, EO 1 mol adduct ND, EO 2 mol adduct 80.5%, EO 3 mol adduct 17.3%, EO 4 mol or more adduct 2 2%.

Example 1
Into a reaction vessel having an internal capacity of 1300 ml, 332 g (2.0 mol) of terephthalic acid, 211 g (3.4 mol) of ethylene glycol, 190 g (0.6 mol) of (A-1) obtained in the production example, and tetraisoester as an esterification catalyst were obtained. 0.03 g of propoxy titanium was charged and the temperature was raised to 220 ° C. The reaction was carried out while removing the condensed water, and when the condensed water was no longer distilled at normal pressure, the temperature was raised to 230 ° C. and the pressure in the system was gradually reduced. The reaction proceeded while removing ethylene glycol, and the molecular weight was followed by GPC. When the number average molecular weight reached 18000, the contents were taken out to obtain a polyester resin (C-1) of the present invention. The removed ethylene glycol was 124 g (2.0 mol).

Example 2
The reaction was advanced in the same manner as in Example 1 except that the amount of (A-1) in Example 1 was changed to 316 g (1.0 mol) to obtain a polyester resin (C-2) of the present invention. The removed ethylene glycol was 148 g (2.4 mol).

Example 3
The reaction was advanced in the same manner as in Example 1 except that the amount of (A-1) in Example 1 was changed to 442 g (1.4 mol) to obtain a polyester resin (C-3) of the present invention. The removed ethylene glycol was 173 g (2.8 mol).

Comparative Example 1
Into 1300 ml separable colben, 508 g (2.0 mol) of bis-2-hydroxyethyl terephthalate and 0.03 g of tetraisopropoxytitanium as an esterification catalyst were charged, the temperature was raised to 230 ° C., and the pressure in the system was gradually reduced. I made it. The reaction proceeded while removing ethylene glycol, and the molecular weight was followed by GPC. When the number average molecular weight reached 18,000, the contents were taken out to obtain a comparative polyester resin (C′-1).

Comparative Example 2
Comparative polyester was used in the same manner as in Example 1 except that 324 g (1.0 mol) of (A′-1) obtained in Comparative Production Example was used instead of (A-1) in Example 1. Resin (C′-2) was obtained. The removed ethylene glycol was 148 g (2.4 mol).

Comparative Example 3
166 g (1 mol) of terephthalic acid, 324 g (1.0 mol) of (A′-1) obtained in the comparative production example and 0.03 g of tetraisopropoxytitanium as an esterification catalyst were charged, and the temperature was raised to 220 ° C. The reaction was carried out while removing the condensed water, and when the condensed water was no longer distilled at normal pressure, the temperature was raised to 230 ° C. and the pressure in the system was gradually reduced. Since the number average molecular weight did not increase from 13000 even when the reaction was advanced, it was taken out to obtain a comparative polyester resin (C′-3).

  The molecular weight of the polyester resin was measured by GPC under the following conditions.

Molecular weight measurement by GPC Device: HLC-8120 manufactured by Tosoh Corporation
Column: 2 TSK GEL GMH6 (manufactured by Tosoh Corporation)
Measurement temperature: 25 ° C
Sample solution: 0.25 wt% tetrahydrofuran (THF) solution Injection amount: 200 μl
Detection apparatus: Refractive index detector The molecular weight calibration curve was prepared using standard polystyrene.

  The heat resistance and impact resistance of the polyester resins obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured and determined by the following methods. The measurement results are shown in Table 1.

<Evaluation of heat resistance>
The heat resistance of the polyester resin was measured by measuring the glass transition point by the method (DSC method) defined in ASTM D3418-82, and the measurement result was evaluated according to the following criteria.
DSC20 and SSC / 580 manufactured by Seiko Denshi Kogyo were used as measuring devices.
◎ ・ ・ ・ 80 ℃ or more, less than 150 ℃ ○ ・ ・ ・ 75 ℃ or more, less than 80 ℃ △ ・ ・ ・ 70 ℃ or more, less than 75 ℃ × ・ ・ ・ 70 ℃ or less

<Evaluation of impact resistance>
For the impact resistance of the polyester resin, an Izod impact test was performed according to the method prescribed in ASTM D256, and the measurement results were evaluated according to the following criteria.
The measuring device includes a D-type impact tester NO. 258-D was used.
◎ ・ ・ ・ 50J / m or more ○ ・ ・ ・ 40J / m or more, less than 50J / m △ ・ ・ ・ 35J / m or more, less than 40J / m × ・ ・ ・ less than 35J / m

  It can be seen that the polyester resin of the present invention has an extremely large glass transition point and excellent impact resistance as compared with a polyester resin using bisphenol A dioxyethylene ether obtained by a conventional method.

  The heat-resistant polyester resin of the present invention is excellent in heat resistance and impact resistance by copolymerizing an addition molar distribution of bisphenol A ethylene oxide as a diol component in a specific range, so that a film, fiber, molded product Useful as.

Claims (7)

It is polyester resin (III) comprised from diol component (I) and dicarboxylic acid component (II), Comprising: 5-99 mol% of this diol component (I) is the following bisphenol A ethylene oxide adduct (A). A heat-resistant polyester resin (III) characterized by being.
Bisphenol A ethylene oxide adduct (A):
(i) Content of bisphenol A ethylene oxide 1 mol adduct (A1) is 0 to 1 mol%, (ii) Content of bisphenol A ethylene oxide 2 mol adduct (A2) is 92 to 100 mol%,
(iii) A reaction mixture in which the content of adduct (A3) of 3 mol or more of bisphenol A ethylene oxide is 0 to 7 mol%.   The heat-resistant polyester resin according to claim 1, wherein the content of the bisphenol A ethylene oxide adduct (A) in the diol component (I) is 10 to 80 mol%.   The heat-resistant polyester resin according to claim 1 or 2, wherein the dicarboxylic acid component (II) is an aromatic dicarboxylic acid.   The heat resistance according to any one of claims 1 to 3, wherein the dicarboxylic acid component (II) is terephthalic acid, and has a glass transition point of 73 to 150 ° C measured by a method (DSC method) defined in ASTM D3418-82. Polyester resin.   The heat resistant film formed by processing the polyester resin (III) in any one of Claims 1-4.   A heat resistant fiber obtained by spinning the polyester resin (III) according to any one of claims 1 to 4.   A heat-resistant molded product obtained by molding the polyester resin (III) according to any one of claims 1 to 4.