JP2000063645A - Polyester resin composition and molded product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition and a molded product thereof excellent in flexibility, heat resistance, mechanical strengths, and chemical resistance. SOLUTION: There is provided a polyester resin composition comprising 90-99.9 wt.% polyester resin component made from (A) a dicarboxylic acid component, (B) a diol component, (C) at least one polyoxyalkylene glycol component having a weight-average molecular weight of 400-3,000, and (D) a hydroxysuccinic acid component and having a limiting viscosity [η] of 0.5 d1/g or above as measured in a phenol/tetrachloroethane (1/1) mixed solvent at 25 deg.C and 0.1-10 wt.% (E) epoxy compound containing at least two epoxy groups in the molecule, wherein component C is contained in an amount of 5-65 wt.% based on the polyester resin component, and the hydroxysuccinic acid component is contained in an amount of 0.1-10 mol.% based on the total acid component.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin composition and a molded article which are excellent in flexibility and heat resistance, have impact resistance, and have excellent characteristics such as heat resistance, surface gloss and chemical resistance. It is about.

[0002]

2. Description of the Related Art Thermoplastic polyester elastomers are
It is composed of polyester and a polyether repeating unit, or polyester and a multi-block copolymer having the same in the main chain, and has excellent mechanical properties, heat resistance and oil resistance. Therefore, the applications of the thermoplastic polyester elastomer have expanded to industrial materials such as sheets, films and fibers, automobiles, and electric / electronic parts. However, since a thermoplastic polyester elastomer having excellent heat resistance has a drawback that it has high hardness and poor flexibility as an elastomer, various proposals have been made to improve it. For example, Japanese Patent Application Laid-Open No. 56-14525 proposes a method of crosslinking molecular chains during molding, but satisfactory results have not been obtained.

Japanese Patent Laid-Open No. 2-173059 proposes a method of adding a polyamide and a sulfur-based antioxidant or a phosphorus-based antioxidant, but the polyamide resin to be added has an elastic modulus higher than that of a polyester elastomer. Since it is high, there is a problem that the elastic modulus of the composition after addition becomes large and other mechanical properties also change. Further, JP-A-5-239198 proposes a method of increasing Tg by using 2,6-naphthalenedicarboxylic acid or the like, but it was not satisfactory in a temperature range of 100 ° C. or higher. Also, as is done with normal rubber,
A method has also been proposed in which flexibility and heat resistance are made compatible by adding a crosslinking agent on a rubber roll containing a vulcanizable rubber and then vulcanizing it (Japanese Patent Publication No. 55-3505).
No. 7). However, in this method, the temperature at which the cross-linking agent is added is significantly lower than the melting point of the polyester, so it is difficult to disperse and knead the cross-linking agent, and it is difficult to obtain a stable composition in the actual production. Further, an elastomer having good heat resistance has been desired.

[0004]

The present invention has been made in view of the above circumstances, and provides a polyester resin composition and a molded article having excellent flexibility, heat resistance, mechanical strength, and chemical resistance. is there.

[0005]

Means for Solving the Problems The inventors of the present invention have made earnest studies in view of such a situation, and as a result, by blending a polyester resin with specific components, heat resistance, surface appearance, and mechanical properties were improved. The inventors of the present invention have found that a composition according to the present invention can be obtained and arrived at the present invention. The polyester resin composition of the present invention comprises (A) a dicarboxylic acid component, (B) a diol component, and (C) at least one weight average molecular weight of 400 to
3000 polyoxyalkylene glycol components,
(D) 90 to 99.9% by weight of a polyester resin component consisting of a hydroxysuccinic acid component and having an intrinsic viscosity [η] of 0.5 dl / g or more measured in a phenol / tetrachloroethane equivalent mixed solvent at 25 ° C. And (E) 0.1 to 10% by weight of an epoxy compound containing at least two epoxy groups in one molecule, wherein the component (C) is a polyester resin component. 5 to 65% by weight of (D) hydroxysuccinic acid component is 0.1 to 10 mol% based on the total acid component.
It is characterized by being contained. The molded body of the present invention,
It is a molded product obtained by molding the above polyester resin composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The component (A) used in the present invention is not particularly limited,
From the viewpoint of heat resistance, it is preferable to use aromatic dicarboxylic acids and their ester-forming derivatives as the main acid components. As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, naphthalene-1,4 or 2,6-dicarboxylic acid, anthracene dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5- Examples thereof include sulfoisophthalic acid and sodium 3-sulfoisophthalate, and examples of the ester-forming derivative thereof include lower alkyl ester, aryl ester, carbonic acid ester, acid halide and the like. These dicarboxylic acids are used alone or in combination of two or more. The aromatic dicarboxylic acid component is preferably contained in the total acid component in an amount of 80 mol% or more, more preferably 85 mol% or more. This is because if the aromatic dicarboxylic acid component is less than 80 mol%, the mechanical strength and productivity of the molded product may be reduced.

As the dicarboxylic acid component (A) in the polyester resin of the present invention, in addition to the aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an ester-forming derivative thereof is contained in the total acid component in an amount of less than 20 mol%. , Preferably less than 15 mol%. This is because if the content is 20 mol% or more, the mechanical strength of the molded product may be reduced. Examples of the aliphatic dicarboxylic acid used in the present invention include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3 or 1,4-cyclohexane. Examples thereof include dicarboxylic acid, cyclopentanedicarboxylic acid, 4,4′-dicyclohexyldicarboxylic acid and the like.

The diol (B) component used in the present invention is
From the viewpoint of imparting color tone, transparency, heat resistance, impact resistance, etc., ethylene glycol, diethylene glycol,
Triethylene glycol, propylene glycol, 1,
4-butanediol, 1,6-hexanediol, neopentyl glycol, dimer diol, cyclohexane diol, cyclohexane dimethanol, alcohol components represented by the following general formulas (1) and (2), and ethylene oxide of their derivatives Preference is given to using adducts.

[0009]

[Chemical 1]

[0010]

[Chemical 2]

Of these, an ethylene oxide adduct of bisphenol A having a structure represented by the following general formula (3) is preferable.

[0012]

[Chemical 3]

If necessary, a polyvalent carboxylic acid having a valence of 3 or more and a polyhydric alcohol may be used for crosslinking the polyester resin. Specific examples include polycarboxylic acids such as trimellitic acid, pyromellitic acid and their anhydrides, and polyhydric alcohols such as trimethylolpropane, pentaerythritol and glycerin. When blending polyvalent carboxylic acid and polyhydric alcohol,
0 to 1 mol% each in the acid or alcohol component
Is preferred. If it is higher than this range, it is difficult to control the reaction due to gelation, and the mechanical properties tend to be deteriorated. More preferably 0.05-
It is in the range of 0.5 mol%.

The component (C) used in the present invention is at least one kind of polyoxyalkylene glycol having a weight average molecular weight of 400 to 3000 and is a component which imparts flexibility to the polyester resin. Weight average molecular weight is 400
Specific examples of the polyoxyalkylene glycol in the range of to 3000 include polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymer, polytetramethylene glycol, polyhexamethylene glycol and the like, either alone or as a mixture. Can be used. When the weight average molecular weight of the component (C) is less than 400, the flexibility is insufficient, and when it exceeds 3,000, the compatibility with the polymer is poor and the polymerization reaction is stagnant, and the mechanical properties of the molded article tend to be deteriorated. is there. The content of the component (C) is 5% of the polyester resin composed of the components (A) to (D).
To 65% by weight, more preferably 20 to 20% by weight.
It is 50% by weight. If the content is less than 5% by weight, it is ineffective and the flexibility is insufficient. If it exceeds 65% by weight, the heat resistance tends to decrease.

The hydroxysuccinic acid (D) component used in the polyester resin of the present invention is a heat resistance imparting component, and its content is the total acid component, that is, the total of the (A) component and the (D) component. On the other hand, it is 0.1 to 10 mol%.
When the content is less than 0.1 mol%, the heat resistance imparting effect is insufficient, and when it exceeds 10 mol%, the heat resistance improving effect is no more and conversely the elastic modulus becomes large and the flexibility is lost. Tend to be A more preferable content range is 0.5 to 5 mol%.

In the present invention, as the method for obtaining the polyester resin comprising the components (A) to (D), a known direct polymerization method, transesterification method or the like can be used.
In the polymerization, known polymerization catalysts such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like can be used. Further, the polymerization temperature and the amount of catalyst are not particularly limited and may be arbitrarily set as needed. Regarding the degree of polymerization of the polyester resin, it is preferable that the intrinsic viscosity [η] measured in a mixed solvent of phenol / tetrachloroethane at 25 ° C. is 0.5 dl / g or more, and further 0.6 dl. / G or more is more preferable. If it is less than 0.5 dl / g, the viscosity is low,
It is difficult to cool the strands, and the loss during pelletizing tends to be large.

The component (E) used in the present invention is added from the viewpoint of heat resistance and mechanical strength of the resin molded product obtained by curing, and has at least two epoxy groups in the molecule. Is. Examples of such an epoxy compound include a bisphenol A-based epoxy resin, a bisphenol F-based epoxy resin, and a bisphenol S-based epoxy resin obtained by a reaction of bisphenol A and epichlorohydrin, and these have a molecular weight of 30.
Those of about 0 to 5000 are suitable. Examples of the epoxy compound having three or more epoxy groups include novolac-based epoxy resins obtained by reaction of phenol novolac resin or cresol novolac resin with epichlorohydrin, triglycidyl isocyanurate, tris (α-methylglycidyl) isocyanurate, tris. (Β-methylglycidyl) isocyanurate, tris (hydroxyphenyl) methane triglycidyl ether, 1,3,5-tri (glycidyloxy) benzene,
1,3,5-trimesic acid triglycidyl ester and the like can be mentioned. As the aliphatic epoxy compound, polyol polyglycidyl ethers such as glycerin polyglycidyl ether, pentaerythritol polyglycidyl ether and trimethylolpropane polyglycidyl ether may be used in combination. The content of the component (E) is from (A) to
90 to 99.9% by weight of polyester resin composed of (D)
On the other hand, the range of 0.1 to 10% by weight is preferable. 10
Care must be taken because the mechanical properties tend to deteriorate when the content exceeds the weight percentage. If it is less than 0.1% by weight, the above effect is small. It is more preferably in the range of 0.3 to 5% by weight.

A molded article using the polyester resin composition of the present invention may be subjected to various conventionally known processing treatments or may be blended with suitable additives in order to impart further specific performance. Examples of processing include ultraviolet rays, α rays,
Irradiation with β rays, γ rays or electron rays, corona treatment, plasma irradiation treatment, flame treatment, etc., coating of vinylidene chloride, polyvinyl alcohol, polyamide, polyolefin or other resin, lamination, or metal deposition . Examples of additives include resins such as polyether, polyamide, polyolefin, polymethylmethacrylate, inorganic particles such as silica, talc, kaolin and calcium carbonate, pigments such as titanium oxide and carbon black, ultraviolet absorbers and release agents. , Antistatic agents, flame retardants and the like.

Further, the method for producing the composition of the present invention is not particularly limited, and known methods can be used. For example, melt kneading can be performed using a uniaxial or biaxial extruder and various kneaders. Biaxial high speed kneading is particularly preferable. In the melt-kneading, the cylinder set temperature of the kneader is preferably 200 to 360 ° C, more preferably 230 to 350 ° C.

[0020]

EXAMPLES The present invention will be specifically described below with reference to examples. As the glycidyl compound blended with the polyester resin, triglycidyl isocyanurate manufactured by Nissan Kagaku KK; trade name TEPIC-L was used. -Intrinsic viscosity: measured in a mixed solvent of phenol / tetrachloroethane equivalent at 25 ° C. -Tensile strength: Carried out according to ASTM-D638. -Izod impact test: Carried out according to ASTM-D256. -Shore A hardness: It carried out based on ASTM-K7215. High temperature shape retention property: Dynamic viscoelastic modulus measurement by DMS, elastic modulus change between room temperature and 170 ° C. was calculated based on the following equation, and 80
% Or more was judged to be good. (Dynamic elastic modulus at 170 ° C.) / (Dynamic elastic modulus at 23 ° C.) ×
100 (%) ・ Molding appearance: A compound having a thickness of 200 μm was molded by a T-die method using a 40φ single-screw extruder, and the appearance of the sheet was rubbed with acetone at 23 ° C. and then the appearance. Was visually evaluated.

Example 1: 463.6 g of terephthalic acid, 19.7 g of hydroxysuccinic acid, ethylene glycol 2
73.7 g, weight average molecular weight 1000 of polytetramethylene glycol 400 g (40% by weight based on the polymer)
Was placed in a reaction vessel, and heated and stirred at 190 to 225 ° C. for 3 hours to carry out an esterification reaction. Then, the temperature was raised to 280 ° C., 0.3 g of antimony trioxide was added as a polymerization catalyst to proceed the polymerization reaction, and a polyester resin having a composition (molar ratio) shown in Table 1 was obtained. The obtained polyester resin had an intrinsic viscosity [η] = 0.83 dl / g. 1 part by weight of TEPIC-L manufactured by Nissan Kagaku Co., Ltd. was added to 99 parts by weight of pellets obtained by drying this resin at 130 ° C. for 8 hours, and 280 ° C., 200 using a 40φ twin-screw extruder.
After kneading at rpm, an ASTM-D638 test piece was injection molded at 280 ° C. to obtain a molded body. The evaluation results of this molded product are shown in Table 1.

Example 2: Dimethyl terephthalate 475.
Polytetramethylene glycol 400 having 4g, 1,4-butanediol 252.9g and a weight average molecular weight of 1000
g (40% by weight based on the polymer), tetra-
After 0.4 g of n-butoxytitanium was placed in a reaction vessel and transesterification reaction was performed, 17.3 g of hydroxysuccinic acid was added.
The polyester resin having the composition (molar ratio) shown in Table 1 was obtained by holding at 30 ° C. for 20 minutes and then proceeding the polymerization reaction. The obtained polyester resin has an intrinsic viscosity [η] = 1.06d
It was 1 / g. A molded body obtained from a composition obtained by kneading 1 part by weight of TEPIC-L with 99 parts by weight of pellets obtained by drying this resin at 130 ° C. for 8 hours was evaluated in the same manner as in Example 1. Shown in 1.

Example 3: Dimethyl terephthalate 754.
1 g, 1,4-butanediol 382.4 g, polytetramethylene glycol 100 having a weight average molecular weight of 2000
g (10% by weight based on the polymer), trimethylolpropane (1.57 g) and tetra-n-butoxytitanium (0.6 g) as a catalyst were placed in a reaction vessel and transesterified. Then, 2.6 g of hydroxysuccinic acid was added and the mixture was heated at 230 ° C. After holding for minutes, the polymerization reaction was allowed to proceed to obtain a polyester resin having the composition (molar ratio) shown in Table 1. The obtained polyester resin had an intrinsic viscosity [η] = 1.12 dl / g. A molded body obtained from a composition obtained by kneading 8 parts by weight of TEPIC-L with 92 parts by weight of pellets obtained by drying this resin at 130 ° C. for 8 hours was evaluated in the same manner as in Example 1 and the results are shown in Table 1. Show.

Example 4: Dimethyl terephthalate 38.4
g, 1,4-butanediol 204.4 g, polytetramethylene glycol having a weight average molecular weight of 1000, 250 g
(25% by weight relative to polymer), weight average molecular weight 200
250 g of polytetramethylene glycol of 0 (25% by weight with respect to the polymer) and 0.4 g of tetra-n-butoxytitanium as a catalyst were placed in a reaction vessel, and after transesterification,
Add 22.9 g of hydroxysuccinic acid at 230 ° C for 20
After holding for minutes, the polymerization reaction was allowed to proceed to obtain a polyester resin having the composition (molar ratio) shown in Table 1. The obtained polyester resin had an intrinsic viscosity [η] = 1.00 dl / g. Pellets 9 obtained by drying this resin at 130 ° C for 8 hours
Table 1 shows the evaluation results of the molded product obtained from the composition obtained by kneading 0.5 parts by weight of TEPIC-L with respect to 9.5 parts by weight in the same manner as in Example 1.

Comparative Example 1: 475.9 g of terephthalic acid, 7.8 g of hydroxysuccinic acid, 27 of ethylene glycol
400 g of polytetramethylene glycol having a weight average molecular weight of 1000 (400 g, 40% by weight based on the polymer) was placed in a reaction vessel to carry out an esterification reaction, and then 0.3 g of antimony trioxide was added as a polymerization catalyst to carry out a polymerization reaction. Was carried out to obtain a polyester resin having the composition (molar ratio) shown in Table 1. The obtained polyester resin has an intrinsic viscosity [η] =
It was 0.77 dl / g. Table 1 shows the results of evaluation of a molded product obtained by molding the resin in the same manner as in Example 1 except that the resin was dried at 130 ° C. for 8 hours and the component (E) was not added.

Comparative Example 2: Dimethyl terephthalate 493.
6 g, 1,4-butanediol 249.0 g, weight average molecular weight 1000 polytetramethylene glycol 400
g (40% by weight based on the polymer), tetra-
0.4 g of n-butoxytitanium was placed in a reaction vessel, and a transesterification reaction and then a polymerization reaction were allowed to proceed to obtain a polyester resin having a composition (molar ratio) shown in Table 1. The obtained polyester resin had an intrinsic viscosity [η] = 0.98 dl / g. Pellets 99 obtained by drying this resin at 130 ° C. for 8 hours
Table 1 shows the evaluation results of the molded product obtained from the composition obtained by kneading 1 part by weight of TEPIC-L with respect to parts by weight in the same manner as in Example 1.

Comparative Example 3: 645.8 g of terephthalic acid, 27.4 g of hydroxysuccinic acid, ethylene glycol 3
81.2 g, 200 g of polytetramethylene glycol having a weight average molecular weight of 1000 (20% by weight based on the polymer)
Was placed in a reaction vessel to carry out an esterification reaction, 0.4 g of antimony trioxide was added as a polymerization catalyst to allow the polymerization reaction to proceed, and a polyester resin having a composition (molar ratio) shown in Table 1 was obtained. The obtained polyester resin has an intrinsic viscosity [η]
= 0.45 dl / g. This resin at 130 ℃, 8
TEPIC-based on 95 parts by weight of dried pellets
Table 1 shows the results of evaluation of the molded product obtained from the composition obtained by kneading 5 parts by weight of L in the same manner as in Example 1.

Comparative Example 4 terephthalic acid 141.0 g, hydroxysuccinic acid 9.9 g, ethylene glycol 7
4.5 g, 750 g of polytetramethylene glycol having a weight average molecular weight of 1000 (75% by weight based on the polymer) was placed in a reaction vessel to carry out an esterification reaction, and then 0.2 g of antimony trioxide was added as a polymerization catalyst to carry out a polymerization reaction. Was carried out to obtain a polyester resin having the composition (molar ratio) shown in Table 1. The obtained polyester resin has an intrinsic viscosity [η] =
Although it was 0.65 dl / g, pelletizing was not possible. A composition obtained by kneading 8 parts by weight of TEPIC-L with 92 parts by weight of this resin also became amorphous at room temperature.

Comparative Example 5: Dimethyl terephthalate 593.
7 g, 1,4-butanediol 354.1 g, weight average molecular weight 2000 polytetramethylene glycol 200
g (20% by weight based on the polymer), tetra-
0.5 g of n-butoxytitanium was placed in a reaction vessel, and after transesterification reaction, 72.4 g of hydroxysuccinic acid was added.
When the mixture was kept at 30 ° C. for 20 minutes and then the polymerization reaction was allowed to proceed, gelation occurred.

Comparative Example 6: Dimethyl terephthalate 665.
0 g, 1,4-butanediol 339.0 g, polytetramethylene glycol 200 having a weight average molecular weight of 2000
g (20% by weight based on the polymer), tetra-
0.5 g of n-butoxytitanium was placed in a reaction vessel, and after transesterification, 4.6 g of hydroxysuccinic acid was added.
Hold at 0 ° C. for 20 minutes, then allow the polymerization reaction to proceed.
A polyester resin having the composition (molar ratio) shown in was obtained. The obtained polyester resin has an intrinsic viscosity [η] = 1.02 dl
/ G. A molded body obtained from a composition obtained by kneading 15 parts by weight of TEPIC-L with 85 parts by weight of pellets obtained by drying this resin at 130 ° C. for 8 hours was evaluated in the same manner as in Example 1 and the results are shown in Table 1. Shown in.

[0031]

[Table 1]

From the results shown in Table 1, it is understood that the molded products obtained in Examples 1 to 4 have good shape retention at high temperature, excellent heat resistance and flexibility, and high mechanical strength and chemical resistance. . On the other hand, Comparative Example 1 (a composition not containing the component (E)) and Comparative Example 2 (a composition not containing the component (D)) have low shape retention at high temperature, and Comparative Example 3 (of the polyester component). Intrinsic viscosity is 0.
45) and Comparative Example 6 (15% by mole of the component (E)) have low chemical resistance, and Comparative Example 4 (75% by weight of the component (C) in the polyester resin) and Comparative Example 5 (the component (E)) not included,
Molding could not be performed when the component (D) was 15 mol% of the total acid component).

[0033]

As described above, the molded product obtained from the polyester resin composition of the present invention has high flexibility, mechanical strength and heat resistance, and excellent processability and chemical resistance. So, direct blow molding of parts such as hollow containers, pipes, tubes, etc., as well as bottles, boots, plates,
It is useful for applications such as blown film, laminate coating, and other molded articles, films, and sheets produced by extrusion molding.

Continued front page    F-term (reference) 4J002 CD012 CD052 CD062 CD112                       CD142 CD202 CF101 CF131                       CF201                 4J029 AA05 AB01 AC02 AD01 AE01                       AE03 BA02 BA03 BA05 BA08                       BA10 BD03A BD05A BD06A                       BF09 BF18 BF25 BF26 CA01                       CA02 CA04 CA05 CA06 CB05A                       CB06A CB10A CC03A CC05A                       CC06A CD03 CD07 CF08                       CH02 CH06 DB02 FC03 FC05                       FC08 FC14 FC16 FC36 HA01                       HB01 HB03A HB04A HB05                       HB07 JE152 JE153 JE163                       JE182                 4J036 AB02 AB03 AC02 AD08 AD21                       AF06 AF08 AG13 AJ18 FB11

Claims (2)

[Claims] 1. A weight average molecular weight of 40 of (A) dicarboxylic acid component, (B) diol component, and (C) at least one kind.
0-3000 polyoxyalkylene glycol component,
(D) 90 to 99.9% by weight of a polyester resin component consisting of a hydroxysuccinic acid component and having an intrinsic viscosity [η] of 0.5 dl / g or more measured in a phenol / tetrachloroethane equivalent mixed solvent at 25 ° C. And (E) 0.1 to 10% by weight of an epoxy compound containing at least two epoxy groups in one molecule, wherein the component (C) is a polyester resin component. 5 to 65 in
(D) hydroxysuccinic acid component is contained in
A polyester resin composition comprising 0.1 to 10 mol% of all acid components. 2. A molded product obtained by molding the polyester resin composition according to claim 1.