JP2000327889A - Polyester resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition excellent in moldability, flexible and exhibiting excellent heat resistance, chemical resistance and the like and to provide a molded article thereof. SOLUTION: The title polyester resin composition comprises (I) a polyester- based elastomer comprising a polyester containing as a constituting unit a silicone compound, (II) a polymethylol type alkyl phenol compound and (III) a crosslinking agent. The polyester is caused to contain 5-30 wt.% of the silicone compound as a constituting unit, and as the crosslinking agent (III) can be employed an epoxy compound having 3 or more functionalities. Blow moldings are composed of a polyester resin composition comprising 100 pts.wt. of the polyester resin composition having incorporated therewith 0.05-5.0 pts.wt. of a pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition having excellent moldability, flexibility, heat resistance, chemical resistance and the like, and a molded product thereof.

[0002]

2. Description of the Related Art A thermoplastic polyester elastomer is a resin comprising a polyester and a polyether repeating unit or a polyester and a multi-block copolymer having the polyester in a main chain, and has mechanical properties, heat resistance and oil resistance. Are better. Therefore, it is widely used for industrial materials such as sheets, films, and fibers, automobiles, electric and electronic parts, and the like. However, elastomers having excellent heat resistance have problems that hardness is high, flexibility is inferior, and molding is difficult. As a method for solving such a problem, for example, JP-A-56-14525 proposes a method of improving the moldability by cross-linking a molecular chain at the time of molding a polyester-based elastomer, which is sufficiently satisfactory. No results were obtained. Therefore, various proposals have been made to solve this drawback.

For example, JP-A-5-239198 proposes a method of increasing the glass transition temperature by using 2,6-naphthalenedicarboxylic acid or the like. In addition, a method has been reported in which flexibility and heat resistance are both achieved by adding a cross-linking agent on a rubber roll containing a vulcanizable rubber and then vulcanizing, as is done with normal rubber. (Japanese Patent Publication No. 55-35057). Further, Japanese Patent Application Laid-Open
No. 152604 proposes a composition having excellent initial flexibility and mechanical properties by using a silicone compound.

[0004]

SUMMARY OF THE INVENTION However, 2,6
-A polyester elastomer using naphthalenedicarboxylic acid or the like could not be used satisfactorily in a temperature range of 100 ° C or higher. In addition, in the method of vulcanizing after adding the crosslinking agent, since the temperature at which the crosslinking agent is added is significantly lower than the melting point of the polyester, it is difficult to disperse and knead the crosslinking agent, and to produce a stable composition. And the heat resistance was not sufficient. Further, the method using a silicone compound has a problem that the silicone compound bleeds out with time.

The present invention has been made in view of the above circumstances, and an object of the present invention is to improve flexibility and moldability while maintaining excellent mechanical properties and heat resistance of a polyester elastomer.

[0006]

According to the first aspect of the present invention, there is provided a polyester-based elastomer (I) containing a polyester containing a silicone compound as a constituent unit, a multi-methylol-type alkylphenol compound (II), and a crosslinking agent. The problem can be solved by a polyester resin composition characterized by comprising (III). The polyester contains 5 to 30% by weight of a silicone compound as a constituent unit, and the crosslinking agent (III) is preferably an epoxy compound having three or more functions. The polyester resin composition is prepared by adding 0.1 to 10 parts by weight of a polymethylol-type alkylphenol compound (II) to 100 parts by weight of the polyester-based elastomer (I), and the polyester-based elastomer (I) and the multi-methylol. 0.7 equivalent to 1 equivalent of hydroxyl group of the alkylphenol compound (II)
It is preferable that the crosslinking agent (III) is blended with the crosslinking agent (III) in an amount to give a ratio of up to 1.4 equivalents. In the polyester resin composition, the relationship between the Shore A hardness and the temperature at which the dynamic elastic modulus starts to decrease preferably satisfies the following expression. 3.5 × A-155 ≦ T ≦ 4.5 × A-200 (where A represents Shore A hardness and 45 ≦ A ≦ 100
To be satisfied. Further, T indicates the temperature at which the dynamic elastic modulus starts to decrease.) Further, the polyester-based elastomer (I) includes a silicone compound, terephthalic acid and / or an ester-forming derivative thereof, 1,4-butanediol, It is preferably obtained by reacting with oxytetramethylene glycol. The multimethylol-type alkylphenol compound (II) is a compound obtained by reacting phenol and / or alkylphenol with formaldehyde in the presence of a basic catalyst,
Alternatively, a compound obtained by reacting phenol and / or an alkylphenol with formaldehyde in the presence of a basic catalyst is preferably a compound in which at least a part of a hydroxyl group in a methylol group is substituted with a halogen atom.

According to the invention of claim 7, the problem can be solved by a molded product obtained by molding the polyester resin composition. In the invention according to claim 8, the pigment is added in an amount of from 0.05 to 5% based on 100 parts by weight of the polyester resin composition.
The problem can be solved by a hollow molded product obtained by blow molding a polyester resin composition containing 0 [parts by weight].

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester elastomer (I) used in the present invention contains a polyester containing a silicone compound as a constituent unit. For example, such a polyester-based elastomer (I) comprises an aromatic dicarboxylic acid as a main acid component, a polyester portion comprising the acid component and a glycol component as a hard component, and an aromatic dicarboxylic acid and a polyoxyalkylene glycol. It is preferable that the polyester component and the polyester component comprising an aromatic dicarboxylic acid and a silicone compound are used as soft components. As the glycol of the hard component, 1,4-butanediol is inexpensive and preferably used.

Specific examples of the aromatic dicarboxylic acid used for obtaining the polyester elastomer (I) used in the present invention include terephthalic acid, isophthalic acid, naphthalene-1,4 or 2,6-dicarboxylic acid, anthracene Dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5-
Sulfoisophthalic acid, sodium 3-sulfoisophthalate, etc., and the ester-forming derivatives thereof include lower alkyl esters, aryl esters, carbonates, acid halides and the like. Of these, terephthalic acid and its esters Formable derivatives are inexpensive and are preferably used. It is preferable that the aromatic dicarboxylic acid component is contained in an amount of 80 mol% or more of all the acid components. 80 [mol%] of aromatic dicarboxylic acid component
If it is less than the above, there is a possibility that the mechanical strength of the molded article is reduced, and the productivity may be reduced. The polyester-based elastomer (I) used in the present invention contains an aliphatic dicarboxylic acid or an ester-forming derivative thereof as an acid component other than the aromatic dicarboxylic acid in the total acid component.
It can be contained in a range of less than [mol%]. 20
If it exceeds [mol%], the mechanical strength of the molded article may be reduced. As the aliphatic dicarboxylic acid used,
Oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecanedioic acid,
Dimer acid, 1,3 or 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, 4,4′-
Dicyclohexyl dicarboxylic acid and the like, and as their ester-forming derivatives, lower alkyl esters,
Aryl esters, carbonates, acid halides and the like can be mentioned.

As the glycol component, 1,4-butanediol is inexpensive and preferred, but glycols such as 1,3-propanediol and 1,6-hexanediol may be used. Examples of the polyoxyalkylene glycol include polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymer, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and the like, and the balance between flexibility and heat resistance of the resin composition. Is preferred, and polyoxytetramethylene glycol is preferably used. Polyoxyalkylene glycol is
It can be used alone or as a mixture, and preferably has a number average molecular weight in the range of 400 to 3000.
When the number average molecular weight is less than 400, flexibility is insufficient, and 3
If it exceeds 000, the compatibility with the polymer to be produced is poor, so that the polymerization reaction tends to stagnate or the mechanical properties of the molded article tend to decrease.

The silicone compound used in the polyester elastomer (I) is incorporated into the polyester molecule as a soft component, and forms a polyester skeleton together with an acid component, preferably an aromatic dicarboxylic acid component. The silicone compound is a silicone oil or the like having a siloxane bond as a skeleton and having various degrees of polymerization. In some cases, a compound having various organic groups in a side chain may be used. Examples of the silicone compound include those represented by the general formula (1). Specific examples include polydimethylsiloxane, polyphenylmethylsiloxane, polydiphenylsiloxane, and polymethylbenzylsiloxane, among which polydimethylsiloxane is preferable.

[0012]

Embedded image In the chemical formula, R ₁ and R ₂ each independently represent an alkyl group, an aryl group, or an aralkyl group.

As the silicone compound, a compound having an arbitrary degree of polymerization and having an arbitrary viscosity can be used. Among them, a viscosity of 6.5 × 10 ^-4 or more at a measurement temperature of 23 ° C.
Those having a range of 2.0 × 10 ^-2 [Pa · s] are preferable in terms of reactivity with polyester. Silicone compound is 1
Only the types may be used, or two or more types may be mixed and used. As long as the effects of the present invention are not substantially adversely affected, a silicone compound containing an additive may be used. Such a silicone compound is preferably contained as a structural unit in the polyester in a ratio of 5 to 30% by weight. The amount of the silicone compound used is 5 to
Flexibility and mechanical properties become better as the content is larger within the range of 30% by weight, and the compounding effect is less when the content is less than 5% by weight.
In some cases, sufficient flexibility cannot be imparted to the polyester elastomer (I). On the other hand, if it exceeds 30 [% by weight], the reaction rate with the polyester is lower than the theoretical amount, so that the unreacted silicone compound may bleed out over time. As a method for introducing a silicone compound, a polycondensation reaction is completed in a polymerization system for producing a polyester elastomer using a dicarboxylic acid and / or an ester-forming derivative thereof, a glycol and a polyoxyalkylene glycol. The reaction is preferably carried out at the above ratio until the above ratio, or a polymerization system for producing a polyester elastomer using dicarboxylic acid and / or its ester-forming derivative and glycol. A polyester reaction product obtained by adding and reacting a silicone compound until the polycondensation reaction is completed and a polyester reaction product having a polyoxyalkylene glycol are melted such that the silicone compound has the above ratio. A method of mixing under conditions is preferred.

The polyester-based elastomer (I) used in the present invention may be copolymerized with the following glycol components for imparting color tone, transparency, heat resistance, impact resistance and the like. Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
1,4-butanediol, 1,6-hexanediol,
Neopentyl glycol, 2,2-diethyl-propanediol, dimer diol, cyclohexanediol, cyclohexanedimethanol, the following general formula (2),
The alcohol components represented by (3) and (4), and ethylene oxide adducts of these derivatives.

[0015]

Embedded image In the chemical formula, X is CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ )
Represents any of ₂ , O, S, and SO ₂ , and p and q satisfy 1 ≦ p + q ≦ 4.

Embedded image In the chemical formula, X is CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ )
₂ , O, S, or SO ₂ , wherein R is C1
Represents an alkyl group of -C5, wherein p and q are 1 ≦ p + q
Satisfies ≦ 4. Among them, an ethylene oxide adduct of bisphenol A having a structure represented by the following general formula (4) is preferable.

Embedded image In the chemical formula, P and q satisfy 1 ≦ p + q ≦ 4.

Further, the polyester elastomer (I)
In addition, trihydric or higher polyhydric carboxylic acids and polyhydric alcohols can also be used. Specific examples include polycarboxylic acids such as trimellitic acid, pyromellitic acid and anhydrides thereof, and polyhydric alcohols such as trimethylolpropane, pentaerythritol and glycerin. When polyhydric carboxylic acid and polyhydric alcohol are used, the content is preferably in the range of 0.01 to 5 [mol%] in the acid component and the glycol component, respectively. Care must be taken when using beyond this range, as the reaction tends to be difficult to control due to gelation.

The polyester-based elastomer (I) of the present invention can be produced by a known direct polymerization method, transesterification method or the like. As the degree of polymerization of the polyester-based elastomer (I), the intrinsic viscosity [η] measured in a mixed solvent of phenol / tetrachloroethane at 25 [° C.] is 0.1.
The degree of polymerization is preferably 5 [dl / g] or more, and more preferably 0.6 [dl / g] or more. If it is less than 0.5 [dl / g], the viscosity is low, the strand is difficult to cool, and the loss at the time of pelletizing tends to be large.

The multi-methylol type alkylphenol compound (II) used in the present invention is a compound obtained by reacting phenol and / or alkylphenol with formaldehyde in the presence of a basic catalyst, or a compound obtained by reacting phenol and / or alkylphenol. And formaldehyde in the presence of a basic catalyst in which at least a part of the hydroxyl groups in the methylol group of the compound is substituted with a halogen atom such as chlorine or bromine. Specific examples include compounds having at least one unit represented by the following general formula (5) or (6), such as poly (2-hydroxy-1,4-phenylenemethylene) and poly (2hydroxy-1,3- Phenylenemethylene), poly-4-hydroxy-1,3-phenylenemethylene), poly (3-hydroxy-1,2-phenylenemethylene), poly (2-hydroxy-3-methyl-)
1,4-phenylenemethylene), poly (4-hydroxy-
5-methyl-1,3-phenylenemethylene), poly (3
-Hydroxy-4-methyl-phenylenemethylene), poly (oxymethylene-2-hydroxy-1,4-phenylenemethylene), poly (oxymethylene-2-hydroxy-1,3-phenylenemethylene), poly (oxymethylene-4) -Hydroxy-1,3-phenylenemethylene) and the like.

[0019]

Embedded image In the chemical formula, R represents —H, —CH ₃ , and m represents 15 ≦
Satisfies m ≦ 25.

Embedded image In the chemical formula, n satisfies 10 ≦ n ≦ 25.

The multi-methylol type alkylphenol (I)
I) is a heat-resistance-imparting component and serves as a crosslinking point at the same time. The amount used in the polyester resin composition of the present invention is not particularly limited, but is preferably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the polyester elastomer (I). If the amount is less than 0.1 [parts by weight], the effect of thickening by post-crosslinking is insufficient, and if it exceeds 10 [parts by weight], the viscosity of the molten resin does not increase, and the viscosity decreases as a plasticizer. Tend. A more preferred addition range is 0.5 to 5 parts by weight.

The crosslinking agent (III) used in the polyester resin composition of the present invention includes an amino group-containing compound, a carboxylic anhydride-containing compound, an oxazolyl group-containing compound,
In addition to the isocyanate group-containing compound, a trifunctional or higher functional epoxy compound is particularly preferable because of a good balance between reactivity and physical properties. Specific examples include a novolak-based epoxy resin obtained by reacting a phenol novolak resin or a cresol novolak 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. 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 crosslinking agent (I) in the polyester resin composition of the present invention
The preferred usage ratio of II) is preferably from 0.7 to 1.4 equivalents to 1 equivalent of hydroxyl groups in the polyester resin composition. When the amount exceeds 1.4 equivalents, a side reaction compound such as polymerization of an excessive amount of epoxy groups occurs to cause a decrease in mechanical properties. When the amount is less than 0.7 equivalents, the effect of increasing viscosity and imparting heat resistance by a crosslinking reaction is not sufficient, Chemical resistance may be reduced due to unreacted hydroxyl groups.

The polyester resin composition of the present invention preferably has a Shore A hardness (A) and a temperature (T) at which the dynamic modulus of elasticity starts to fall which satisfies the following formulas. 3.5 × A-155 ≦ T ≦ 4.5 × A-200 (45 ≦ A ≦ 100) When T exceeds 4.5 × A-200, the flexibility of the resin composition is insufficient, and T is 3 If it is less than 0.5 × A-155, heat resistance may be insufficient. When the Shore A hardness is less than 45, the formula does not hold, and the Shore A does not exceed 100 by definition. The Shore A hardness is ASTM-K7215.
The dynamic elastic modulus onset temperature is 2 [° C./m at 100 [Hz] by DMS.
in. ] Is the shoulder value of the dynamic viscoelastic modulus change when the temperature is raised. The shoulder value is determined from the intersection of the baseline before the dynamic elastic modulus decreases and the tangent to the point where the slope becomes constant after the decrease in the plot of the temperature versus the dynamic elastic modulus.

The above-described polyester resin composition of the present invention is usually prepared using a high-speed mixer such as a Henschel mixer or a mixing and kneading apparatus such as a tumbler or a pelletizer, which is used for resin blending. It is molded by injection molding, extrusion molding, etc., and becomes a molded product. A molded article using the polyester resin composition of the present invention may be subjected to various conventionally known processing treatments to impart specific performance, or may be blended with an appropriate additive. Examples of processing include ultraviolet, α-ray, β-ray, γ-ray or electron beam irradiation, corona treatment, plasma irradiation treatment, flame treatment, etc., vinylidene chloride, polyvinyl alcohol,
Examples include application and lamination of a resin such as polyamide and polyolefin, and vapor deposition of a metal. Examples of additives include polyether, polyamide, polyolefin,
Resins such as polymethyl methacrylate, silica, talc,
Inorganic particles such as kaolin and calcium carbonate, titanium oxide,
Examples include pigments such as carbon black, ultraviolet absorbents, release agents, antistatic agents, flame retardants, and the like.

The molded article using the polyester resin composition of the present invention is not particularly limited.
Suitable for use in boots, pipes, tubes, etc., as well as molded products by extrusion molding methods such as direct blow molded products of parts, extruded sheets, plates, blown films, laminate coatings, etc., but with flexibility, heat resistance and mechanical properties Is good, especially the pigment 0.05 to 100 parts by weight of the polyester resin composition is further added.
It is suitable for a blow molded product obtained by blow molding a composition obtained by blending 5.0 parts by weight.

[0025]

The present invention will be specifically described below with reference to examples. [Preparation of Polyester Elastomer 1] 2.16 [kg] of dimethyl terephthalate, 1.40 [kg] of 1,4-butanediol, and 2.50 [kg] of polytetramethylene glycol having a number average molecular weight of 1500 And 2.2 g of tetrabutyl titanate in a reaction vessel.
The mixture was heated and stirred at 50 to 225 [° C] for 3 hours to carry out a transesterification reaction. Then, the temperature was raised to 250 [° C.] to allow the polymerization reaction to proceed. The obtained polyester resin had an intrinsic viscosity [η] of 1.00. Further, in another reaction vessel, 2.64 [kg] of dimethyl terephthalate, 1.72 [kg] of 1,4-butanediol, and a viscosity measured at 23 ° C. of 2 × 10 ⁻³ [Pa · s] 2000 g of polydimethylsiloxane, and 2. g of tetrabutyl titanate.
The polymerization reaction was advanced in the same manner as in 6 [g]. The obtained polyester resin had an intrinsic viscosity [η] of 0.87. The intrinsic viscosity was measured in a mixed solvent of phenol / tetrachloroethane equivalent at 25 [° C.]. These two types of polyester resins were dried at 130 ° C. and 8 hours, and the pellets obtained were 280 using a 40φ twin screw extruder at a ratio of 50 parts by weight / 50 parts by weight, respectively.
Kneading was performed at [° C.] and 200 [rpm]. The resulting polymer is called elastomer 1.

[Preparation of Polyester Elastomer 2] Dimethyl terephthalate (2.73 kg), 1,4-butanediol (1.78 kg), and a number average molecular weight of 10
Polytetramethylene glycol of 1.50 [k
g] and the viscosity measured at 23 ° C. is 1 × 10 ⁻² [Pa ·
s] of 400 [g] and tetrabutyl titanate of 2.7 [g] in elastomer 1
The polymerization reaction was allowed to proceed in the same manner as in the preparation of The resulting polyester resin had an intrinsic viscosity [η] = 0.92.
The resulting polymer is called elastomer 2.

Examples 1 and 2 As shown in Table 1, poly (4-hydroxy-5-methyl) having an average molecular weight of 2200 and a hydroxyl equivalent of 120 was used with respect to 100 parts by weight of each of the above-prepared elastomers. -1,3-phenylenemethylene) and 5 parts by weight of epoxy resin shown in Table 1 so that the epoxy equivalent / hydroxyl equivalent ratio becomes 1.0.
Using a 0φ twin screw extruder, 210 ° C., 200 rpm
m], and each test sample was injection molded at 210 ° C. For each sample, each test and evaluation of Shore A hardness, heat resistance, Izod impact, chemical resistance, change with time, and tensile strength retention were performed. Table 2 shows the evaluation results.

The Shore A hardness is ASTM-K72
The measurement was performed according to No. 15 (no unit). Regarding heat resistance, 2 [° C.] at 100 [Hz] by DMS
/ Min. ], The shoulder value of the dynamic viscoelastic change when the temperature was raised was defined as the temperature [° C.] at which the dynamic elastic modulus decreased, and this was displayed. The shoulder value was determined from the intersection of the baseline before the dynamic elastic modulus decreased and the tangent to the point where the slope became constant after the decrease in the plot of the temperature versus the dynamic elastic modulus. Izod impact was performed in accordance with ASTM-D256, and NB in the table indicates that the NB was not broken. The chemical resistance was evaluated by visually observing the change in appearance of a 2 mm press-formed plate rubbed with acetone at 23 ° C. With respect to the evaluation of the change with time, 50
Leave for 120 hours in an environment of [° C], then 23
For samples left standing at [° C.] for 24 hours, visual observation of appearance changes such as bleed-out and ASTM-6
A tensile strength measurement according to No. 38 was performed. The initial value of the tensile strength was X ₁ , the value after the test at 50 [° C.] was X _2, and the retention rate Y [%] was calculated by the following equation.
≧ 90 was evaluated as ○, 90> Y ≧ 80 as Δ, and 80> Y as ×. Y = X ₂ / X ₁ × 100

Example 3 Polyester Elastomer 1
With respect to 100 [parts by weight] of poly (4-hydroxy-5-methyl-) having an average molecular weight of 2200 and a hydroxyl equivalent of 120.
1,3-phenylenemethylene) and 1 [part by weight] and triglycidyl isocyanurate ("TEPIC-G" manufactured by Nissan Chemical Co., Ltd., epoxy equivalent: 91) so that the epoxy equivalent / hydroxyl equivalent ratio becomes 1.3. Table 2 shows the results of evaluating the composition obtained by kneading 1 part by weight in the same manner as in Example 1.

Comparative Example 1 Polyester Elastomer 3
"Perprene GP-300" (a silicone compound is not included in the structural unit) manufactured by Toyobo Co., Ltd., and 100 parts by weight of polyester elastomer 3
Has an average molecular weight of 2200 and a hydroxyl equivalent of 120
Of poly (4-hydroxy-5-methyl-1,3-phenylenemethylene) of 5 [parts by weight] and tris (hydroxyphenyl) methane triglycidyl ether ("Tactics 742" manufactured by Dow Chemical Co., Ltd .: epoxy equivalent: 14)
Table 2 shows the results of evaluating a composition obtained by kneading 6) by 6 parts by weight so that the epoxy equivalent / hydroxyl equivalent ratio becomes 1.0 in the same manner as in Example 1.

[0031]

[Table 1]

[0032]

[Table 2]

As can be seen from Table 2, Comparative Example 1 has high heat resistance but high Shore A hardness, and is 3.5 × A-155.
≦ T ≦ 4.5 × A-200} The formula is not applicable and the flexibility is insufficient. On the other hand, for example, Example 2 has high heat resistance and flexibility. As described above, the molded article obtained from the polyester resin composition of this example is:
It has both heat resistance and flexibility, excellent Izod impact and chemical resistance, and was stable over time.

[0034]

As described above, the polyester resin composition of the present invention maintains the excellent mechanical properties and heat resistance of the conventional polyester elastomer while maintaining the properties.
Moreover, it is a material having unprecedented flexibility, moldability and chemical resistance. Therefore, molded products using the polyester resin composition of the present invention, without impairing the processability of polyester, heat resistance, flexibility, high mechanical properties,
It satisfies the durability and can be used very effectively for a wide range of soft material applications such as electric / electronic parts, automobile parts, machine parts, bottles, boots, films, sheets, plates, etc., and is particularly suitable for hollow molded products.

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Claims (8)

[Claims] 1. A polyester resin composition comprising a polyester-based elastomer (I) containing a polyester containing a silicone compound as a constituent unit, a multimethylol-type alkylphenol compound (II), and a crosslinking agent (III). object. 2. A polyester comprising a silicone compound 5 to 3
0 [% by weight] as a structural unit, and a crosslinking agent (III)
Is a trifunctional or higher functional epoxy compound, The polyester resin composition according to claim 1, wherein 3. A polyester elastomer (I) 10
0.1 to 10 parts by weight of the polymethylol-type alkylphenol compound (II) is added to 0 [parts by weight], and the total hydroxyl group 1 of the polyester-based elastomer (I) and the polymethylol-type alkylphenol compound (II) is 1 The polyester resin composition according to claim 1 or 2, wherein a crosslinking agent (III) is added in an amount of 0.7 to 1.4 equivalents relative to the equivalents. 4. The relationship between the Shore A hardness and the temperature at which the dynamic elastic modulus starts to decrease satisfies the following expression.
4. The polyester resin composition according to any one of items 1 to 3. 3.5 × A-155 ≦ T ≦ 4.5 × A-200 (where A represents Shore A hardness and 45 ≦ A ≦ 100
To be satisfied. T indicates the temperature at which the dynamic elastic modulus starts to decrease. ) 5. The polyester-based elastomer (I)
A silicone compound, terephthalic acid and / or an ester-forming derivative thereof, and 1,4-butanediol;
The polyester resin composition according to any one of claims 1 to 4, which is obtained by reacting with polyoxytetramethylene glycol. 6. The polymethylol-type alkylphenol compound (II) is a compound obtained by reacting phenol and / or alkylphenol with formaldehyde in the presence of a basic catalyst, or a compound obtained by reacting phenol and / or alkylphenol with And a compound obtained by reacting formaldehyde with a formaldehyde in the presence of a basic catalyst, wherein at least a part of the hydroxyl group in the methylol group of the compound is substituted with a halogen atom. The polyester resin composition as described in the above. 7. A molded article obtained by molding the polyester resin composition according to claim 1. 8. A polyester resin composition obtained by mixing 0.05 to 5.0 parts by weight of a pigment with 100 parts by weight of the polyester resin composition according to claim 1. Blow molded products.