JPH11236493A - Polyester resin composition and manufacturing method - Google Patents

Abstract

(57) [Summary] (with correction) [PROBLEMS] To provide a polyester resin composition comprising two or more polyester components and having excellent moldability, mechanical properties, hydrolysis resistance and the like. (A) At least 70 mol% of dicarboxylic acid units of each polyester component are aromatic dicarboxylic acid units, and (b) at least 70 mol% of diol units of each polyester component are fats having 2 to 6 carbon atoms. (D) one or more polyester components, wherein (c) a combination of components having different structural units, or (c) a combination of components having different intrinsic viscosities. The aromatic dicarboxylic acid unit is a terephthalic acid unit or a naphthalenedicarboxylic acid unit, and the weight fraction thereof is 50% by weight or more based on the whole composition, and (e) the intrinsic viscosity of the whole composition is 0.4 to (F) the hydroxyl group concentration of the entire composition is 10 μeq / g;
The following is a polyester resin composition.

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 comprising two or more polyesters, which has improved moldability, mechanical properties, heat resistance, hydrolysis resistance and the like, and production of the polyester resin composition. About the method. The present invention also relates to a molded article comprising the polyester resin composition.

[0002]

2. Description of the Related Art A polyester resin composition composed of two or more polyesters having similar constitutional units is
Interfacial adhesion is very high due to high affinity between polyesters, and it has the advantage of very good interfacial adhesion and small dispersion particle size.However, in a short time melt blend, the structure changes to a random polymer by transesterification. Therefore, the original objectives such as moldability and mechanical properties have not been achieved.

For the purpose of suppressing the transesterification reaction, a method has been proposed in which the catalyst is deactivated with phosphoric acid, phosphorous acid, their esters, ammonium salts, metal salts and the like (Japanese Patent Publication No. 46-35500). However, these additives have the disadvantage that the durability such as hydrolysis resistance of the polyester is reduced. Further, the above compound may have little effect depending on the polymerization catalyst used for producing the polyester.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer composition comprising two or more polyester components each having a different constitutional unit or the same constitutional unit. An object of the present invention is to provide a polyester resin composition having excellent mechanical properties, hydrolysis resistance and the like, and a method for producing the same. Still another object is to provide a molded article comprising the polyester resin composition.

[0005]

Means for Solving the Problems The present inventors have intensively studied to achieve the above object. And, as a result of such a study, an aromatic dicarboxylic acid unit and a C 2-6
Of two or more polyester components having different constitutional units or identical constitutional units differing only in intrinsic viscosity, and having an intrinsic viscosity of 0.4 to 1. 5 dl / g, the hydroxyl group concentration is 10 μequivalent / g or less, and the aromatic dicarboxylic acid unit is a terephthalic acid unit or a naphthalenedicarboxylic acid unit. I found that my goal was achieved.

That is, the present invention comprises two or more polyester components mainly comprising a dicarboxylic acid unit and a diol unit, and (a) at least 70 mol% of the dicarboxylic acid units of each polyester component is an aromatic dicarboxylic acid unit; (B) 70 of diol units of each polyester component
Mol% or more is an aliphatic α, ω-diol unit having 2 to 6 carbon atoms, and (c) at least two of the polyester components are different from each other in an aromatic dicarboxylic acid unit and / or an aliphatic α having 2 to 6 carbon atoms. , Ω-diol units, and (d) the aromatic dicarboxylic acid unit of at least one polyester component is a terephthalic acid unit or a naphthalenedicarboxylic acid unit, and its weight fraction is 50% by weight based on the whole composition. % Or more, and (e) the intrinsic viscosity of the entire composition is in the range of 0.4 to 1.5 dl / g,
(F) The present invention relates to a polyester resin composition, wherein the hydroxyl group concentration of the whole composition is 10 μeq / g or less.

Further, the present invention comprises two or more polyester components mainly comprising a dicarboxylic acid unit and a diol unit, and (a) at least 70 mol% of the dicarboxylic acid units of each polyester component is an aromatic dicarboxylic acid unit; (B) 70 mol% or more of the diol unit of each polyester component is an aliphatic α, ω-diol unit having 2 to 6 carbon atoms, and (c) each polyester component has the same aromatic dicarboxylic acid unit and 2 to 2 carbon atoms. 6 aliphatic α, ω-diol units, but with different intrinsic viscosities,
(D) The aromatic dicarboxylic acid unit of each polyester component is a terephthalic acid unit or a naphthalenedicarboxylic acid unit, and (e) the intrinsic viscosity of the entire composition is 0.4 to 1.5.
dl / g, (f) the hydroxyl group concentration of the entire composition is 10 μeq / g or less, and (g) the molecular weight distribution of the entire composition; Mw / Mn (weight average molecular weight / number average molecular weight) A polyester resin composition having a molecular weight of 3.0 or more.

Next, the present invention relates to a process for producing a polyester resin composition by melt-mixing two or more polyester components mainly comprising a dicarboxylic acid unit and a diol unit, wherein (a ') 70 mol% of the dicarboxylic acid unit The above are aromatic dicarboxylic acid units, (b ′) at least 70 mol% of diol units are aliphatic α, ω-diol units having 2 to 6 carbon atoms, and (c ′) at least two of the polyester components, It has different aromatic dicarboxylic acid units and / or aliphatic α, ω-diol units having 2 to 6 carbon atoms, and (d ′) the aromatic dicarboxylic acid unit of at least one polyester component is a terephthalic acid unit or (E ') a naphthalenedicarboxylic acid unit and a weight fraction of 50% by weight or more based on the whole composition;
The intrinsic viscosity of each of the polyester components is 0.4 to 1.5.
dl / g, and (f ′) a method for producing a polyester resin composition, comprising melt-mixing a polyester component having a hydroxyl group concentration of 10 μeq / g or less.

The present invention also relates to a process for producing a polyester resin composition by melt-mixing two or more polyester components mainly comprising a dicarboxylic acid unit and a diol unit, wherein (a ') 70 mol% or more of the dicarboxylic acid unit. Is an aromatic dicarboxylic acid unit, (b ′) 70 mol% or more of the diol unit is an aliphatic α, ω-diol unit having 2 to 6 carbon atoms, and (c ′) each polyester component has the same aromatic dicarboxylic acid. An acid unit and an aliphatic α having 2 to 6 carbon atoms,
(d ') an aromatic dicarboxylic acid unit of each polyester component is a terephthalic acid unit or a naphthalenedicarboxylic acid unit, and (e') a polyester The intrinsic viscosity of each component is 0.4 to 1.5 dl / g, and (f ′)
The hydroxyl concentration of the polyester component is 10 μequivalent /
The present invention relates to a method for producing a polyester resin composition, which comprises melt-mixing a polyester component having a weight of not more than g.

[0010] The present invention further relates to a molded article comprising the above polyester resin composition.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The polyester component used in the present invention is mainly composed of a dicarboxylic acid unit and a diol unit, and at least 70 mol% of the dicarboxylic acid units are aromatic dicarboxylic acid units (constituent requirement (a)). 70 mol% or more is an aliphatic α, ω- having 2 to 6 carbon atoms.
It must be at least one diol unit selected from diol units (constituent requirement (b)).

If the proportion of aromatic dicarboxylic acid units in the polyester component is less than 70 mol% based on the total dicarboxylic acid units constituting the aromatic polyester segment, the crystallinity and the like of the polyester deteriorate, and the moldability decreases. In addition, a polyester resin composition having excellent mechanical properties and the like cannot be obtained. From the viewpoint of improving the moldability and mechanical properties of the polyester resin composition, it is preferable that 80 mol% or more of the dicarboxylic acid units are aromatic dicarboxylic acid units, and 90 mol% or more of the aromatic dicarboxylic acid units. More preferably, it is an acid unit.

The aromatic dicarboxylic acid unit is not particularly limited as long as it is an aromatic dicarboxylic acid unit derived from an aromatic dicarboxylic acid having a molecular weight of 400 or less. For example, phthalic acid, terephthalic acid, isophthalic acid, 2,6 Units derived from aromatic dicarboxylic acids such as -naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenylketonedicarboxylic acid, and sodium sulfoisophthalate can be given. . The polyester component may have one or more of these aromatic dicarboxylic acid units, and preferred aromatic dicarboxylic acids include terephthalic acid,
2,6-Naphthalenedicarboxylic acid can be mentioned.

In the dicarboxylic acid unit, if necessary, 3
Less than 0 mol%, preferably 20 mol% or less, more preferably 10 mol% or less of non-aromatic dicarboxylic acid units,
For example, one kind of an alicyclic dicarboxylic acid unit such as a 1,4-cyclohexanedicarboxylic acid unit, an aliphatic dicarboxylic acid unit including an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid, or 2
It may have more than one species.

The diol unit has 2 carbon atoms.
When the proportion of at least one diol unit selected from the aliphatic α, ω-diol units of from 6 to 6 is less than 70 mol% based on all diol units constituting the polyester, the crystallinity of the polyester also decreases. However, a polyester resin composition having excellent moldability, mechanical properties, and the like cannot be obtained. In order to improve the moldability, mechanical properties, and the like of the polyester resin composition, the proportion of at least one diol unit selected from aliphatic α, ω-diol units having 2 to 6 carbon atoms is a polyester. Is preferably at least 80 mol%, more preferably at least 90 mol%, of all diol units constituting the above.

The aliphatic α, ω-diol unit having 2 to 6 carbon atoms includes 1,2-ethylene glycol and 1,3-ethylene glycol.
Examples thereof include units composed of propanediol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol. The polyester may have only one of these diol units, or 2
It may have more than one species. Preferred aliphatic α, ω-diol units having 2 to 6 carbon atoms include 1,2-ethylene glycol and 1,4-butanediol.

The diol unit may have 3
Less than 0 mol%, preferably no more than 20 mol%, more preferably no more than 10 mol% of other diol units, e.g.
5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol,
Aliphatic diols such as 1,9-nonanediol and 1,10-decanediol; alicyclic diols such as cyclohexanediol; aromatic diols such as 1,4-bis (2-hydroxyethoxy) benzene and p-xylene glycol And may have one or more diol units. If the polyester is used in a small amount (preferably 1 mol% or less of the total polyol), a polyhydric alcohol such as trimethylolethane, trimethylolpropane, glycerin, 1,2-hexanetriol, or pentaerythritol may be used, if necessary. May be included.

In the present invention, at least two of the polyester components are a combination of components having different aromatic dicarboxylic acid units and / or aliphatic α, ω-diol units having 2 to 6 carbon atoms ( Constituent requirement (c)) requires that at least one aromatic dicarboxylic acid unit in each polyester component be a terephthalic acid unit or a naphthalenedicarboxylic acid unit (constituent requirement (d)). In this case, the proportion of each polyester component needs to be such that the weight fraction of the polyester component whose aromatic dicarboxylic acid unit is a terephthalic acid unit or a naphthalenedicarboxylic acid unit is 50% by weight or more. Thereby, the polyester component forms a matrix. The weight fraction of the polyester component is preferably at least 60% by weight, more preferably at least 70% by weight. On the other hand, when the weight fraction is less than 50% by weight, the obtained polyester resin composition is inferior in mechanical properties, moldability and the like, which is not preferable. Further, when each polyester component has the same aromatic dicarboxylic acid unit and aliphatic α, ω-diol unit having 2 to 6 carbon atoms but is a combination of components having different intrinsic viscosities (structural requirement (c)) Is
It is necessary that the aromatic dicarboxylic acid unit of each polyester component is a terephthalic acid unit or a naphthalenedicarboxylic acid unit (structural requirement (d)). The polyester component having these aromatic dicarboxylic acid units is a crystalline polyester, and improves the mechanical properties and moldability of the polyester resin composition. Preferred crystalline polyester components that provide such a polyester resin composition include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, and polybutylene-2,6-naphthalenedicarboxylate.

The combination of two or more polyester components is not particularly limited as long as the above requirements are satisfied. Preferred combinations include polyethylene terephthalate and polybutylene terephthalate, polyethylene terephthalate and polybutylene-2,6-naphthalenedicarboxylate, and polyethylene-2,6-naphthalenedicarboxylate having excellent heat resistance, moldability, mechanical properties, and surface appearance. And polybutylene-2,6-naphthalenedicarboxylate, polyethylene-2,6-naphthalenedicarboxylate and polybutylene terephthalate, and combinations of low and high molecular weight polybutylene terephthalates.

The intrinsic viscosity of the polyester resin composition of the present invention as a whole is 0.4 to 1.5 dl when measured at 30 ° C. in a phenol / tetrachloroethane mixed solvent (1/1 weight ratio). / G (configuration requirement (e)). When the intrinsic viscosity of the polyester resin composition is not in the range of 0.4 to 1.5 dl / g, mechanical properties or moldability are poor, which is not preferable. A preferred range of the intrinsic viscosity is 0.6 to 1.3 dl / g, more preferably a range of 0.8 to 1.2 dl / g.

It is important that the polyester resin composition of the present invention does not undergo transesterification between the respective polyester components. In the present invention, the term "not reacted" means that the melting point of the polyester component in which the aromatic dicarboxylic acid is terephthalic acid or naphthalenedicarboxylic acid, that is, the crystalline polyester component, is independent of the number of kinds even after the composition is formed. Melting point (crystal melting temperature)
Indicates no change or a change of less than 5 ° C. before and after the composition.

In the polyester resin composition of the present invention, it is necessary that the hydroxyl group concentration in the whole composition is 10 μeq / g or less (component (f)). When the hydroxyl group concentration of the polyester resin composition exceeds 10 μequivalent / g, when molding using the polyester resin composition, a transesterification reaction proceeds between the two, and a transition to a random copolymer or a molecular weight distribution occurs. Because of narrowing, mechanical properties inherent in the polyester resin composition,
Moldability, heat resistance, surface appearance, etc. are deteriorated, which is not preferable. In order to further suppress the transesterification reaction between the polyester components, the hydroxyl group concentration of the polyester resin composition is 5
It is preferably at most μ equivalent / g, more preferably at most 3 equivalent / g. The value of “hydroxyl group concentration” in the present invention refers to the hydroxyl group concentration measured by the method described in the following examples.

Further, the polyester resin composition of the present invention
It is preferable that the value of the molecular weight distribution: Mw / Mn (weight average molecular weight / number average molecular weight) of the entire composition is 3.0 or more, because both mechanical properties and moldability are excellent. further,
When the polyester component is a combination of components having the same aromatic dicarboxylic acid unit and aliphatic α, ω-diol unit having 2 to 6 carbon atoms but different intrinsic viscosities, the molecular weight distribution value is 3. Must be 0 or more (configuration requirement (g)). A more preferred value of Mw / Mn is 3.5.
Or more, more preferably 4.0 or more. When the transesterification reaction proceeds between the polyester components, the final value of Mw / Mn is narrowed to 2.0, which is the same value as the polyester obtained by one-time polymerization or random copolymerization. Thus, characteristics such as mechanical properties and moldability are lost.

Furthermore, the polyester resin composition of the present invention preferably has a carboxyl group concentration of 20 μeq / g or less in the whole composition. If the carboxyl group concentration exceeds 20 μeq / g, when the polyester resin composition is melted and retained at a high temperature of 270 ° C. or more when melt-molded, the reaction between the polyester components may be promoted, which is not preferable. . In addition, the resulting polyester resin composition has poor hydrolysis resistance and heat aging resistance, which is not preferable. The carboxyl group concentration is preferably 10 μeq / g or less, more preferably 5 μeq / g or less. Such a polyester resin composition having a low carboxyl group concentration has a carbodiimide group such as N, N'-di-2,6-diisopropylphenylcarbodiimide at the time of producing a polyester component or melt-mixing the composition. It can be obtained by reacting a carboxyl group-capping agent such as a compound. In addition, the value of the "carboxyl group concentration" in the present invention refers to the carboxyl group concentration measured by the method described in the following examples.

The polyester resin composition of the present invention is excellent in various properties such as mechanical properties, moldability, heat resistance and surface appearance by satisfying the requirements (a) to (g) described above. Further, even if the polyester resin composition is kept in a molten state at a high temperature for a long time, the excellent properties inherent in the polyester resin composition itself are exposed to the molten state at a high temperature without causing a randomization reaction by a transesterification reaction. It can be kept good afterwards.

In order to produce the polyester resin composition of the present invention, there is provided a method for producing a polyester resin composition by melt-mixing two or more polyester components mainly comprising a dicarboxylic acid unit and a diol unit, wherein (a ') 70 mol% or more of the dicarboxylic acid units are aromatic dicarboxylic acid units, and 70 mol% or more of the (b ′) diol unit are aliphatic α, ω-diol units having 2 to 6 carbon atoms,
(C ′) at least two of the polyester components have different aromatic dicarboxylic acid units and / or aliphatic α, ω-diol units having 2 to 6 carbon atoms,
Or each polyester component has the same aromatic dicarboxylic acid unit and aliphatic α, ω-diol unit having 2 to 6 carbon atoms but different intrinsic viscosities, and (d ′) at least one polyester component The aromatic dicarboxylic acid unit is a terephthalic acid unit or a naphthalenedicarboxylic acid unit, and the weight fraction thereof is 50% based on the whole composition.
% By weight or more, and the intrinsic viscosity of each of the (e ′) polyester components is 0.4 to 1.5 dl / g,
(F ') The hydroxyl concentration of the polyester component is 10
It can be produced by melt-mixing using a polyester component having a μ equivalent / g or less.

Here, in the manufacturing method of the present invention,
The contents of the dicarboxylic acid unit and the diol unit of the polyester component used are the same as those described in detail above for the polyester resin composition of the present invention.

When at least two of the polyester components used are a combination of components having different aromatic dicarboxylic acid units and / or aliphatic α, ω-diol units having 2 to 6 carbon atoms, at least one The aromatic dicarboxylic acid unit of the polyester component is a terephthalic acid unit or a naphthalenedicarboxylic acid unit, and the weight fraction thereof must be 50% by weight or more based on the whole composition. The polyester is preferably used so that the weight fraction of the polyester component is 70% by weight or more, and more preferably 90% by weight or more. Further, each polyester component used has the same aromatic dicarboxylic acid unit and 2 to 6 carbon atoms.
In the case of a combination of components having different aliphatic viscosities but having different intrinsic viscosities, the aromatic dicarboxylic acid unit of each polyester component must be a terephthalic acid unit or a naphthalenedicarboxylic acid unit. Polyester component having these aromatic dicarboxylic acid units,
It is a crystalline polyester and is necessary for improving the mechanical properties and moldability of the obtained polyester resin composition.

The intrinsic viscosity of each of the polyester components used in the production method of the present invention is 0.4 to 1.5 dl /.
It must be in the range of g. When it is not within this range, the mechanical properties and moldability of the obtained polyester resin composition are inferior, which is not preferable. When each polyester component is a combination of components having the same aromatic dicarboxylic acid unit and aliphatic α, ω-diol unit having 2 to 6 carbon atoms, it is necessary to use components having different intrinsic viscosities. From the viewpoint of excellent mechanical properties and moldability of the obtained polyester resin composition, at least one intrinsic viscosity of the polyester component is in the range of 0.4 to 0.8 dl / g, and the intrinsic viscosity of other polyester components is 0. It is preferably in the range of 0.9 to 1.5 dl / g, more preferably at least one intrinsic viscosity is in the range of 0.6 to 0.7 dl / g and the other intrinsic viscosity is in the range of 1.1 to 1 0.5 dl / g.

In producing the polyester resin composition by melt mixing, each of the polyester components must have a hydroxyl group concentration of 10 μeq / g or less. When a polyester component having a hydroxyl group concentration of more than 10 μeq / g is used, it is extremely difficult to produce the above-mentioned requirements for the polyester resin composition with good reproducibility.

The polyester component having a reduced hydroxyl group concentration of 10 μeq / g or less can be produced by reacting a hydroxyl group-blocking agent with the hydroxyl groups of the polyester. The hydroxyl group blocking agent may be any compound as long as it reacts with a hydroxyl group present in the reaction system and does not release the hydroxyl group again after the reaction.

Specific examples of the hydroxyl group blocking agent include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, benzoic acid, toluic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid. Compounds having a carboxyl group such as succinic anhydride, phthalic anhydride, etc .; Acyllactams, among which benzoylcaprolactam, benzoyllaurolactam,
N-acyl lactams such as terephthaloylbiscaprolactam and terephthaloylbislaurolactam are preferred. One or more of these hydroxyl group blocking agents can be added to the reaction system as needed.

In the production method of the present invention, when at least one of the polyester components is produced using a potassium titanium oxalate catalyst, the polyester resin is more excellent in durability and color tone such as hydrolysis resistance and heat aging resistance. It is preferable because a polyester resin composition can be obtained. The term “potassium titanium oxalate” used herein refers to a salt in which the carboxyl group of oxalic acid is in the form of a salt with titanium and potassium.
Generally, about 0.5 mole of titanium atoms and about 1 mole of potassium atoms are bonded per mole of oxalic acid, and are typically represented by the chemical formula: K ₂ TiO (C ₂ O ₄ ) ₂ .nH ₂ O You. Such titanium potassium oxalate can be produced, for example, by reacting oxalic acid with potassium titanate that has been sufficiently hydrolyzed, but of course the production method is not limited and is represented by the chemical formula described above. Any titanium potassium oxalate can be used.

The temperature, pressure, etc., at which the above polyester components are melt-mixed can be adjusted according to the contents of the polyester components to be used. In general, the polyester having a higher melting point (crystal melting temperature) is used. Both polyester components are preferably melt-kneaded under nitrogen or under reduced pressure at a temperature of about 10 to 30 ° C. higher than the melting point of the components.

The above-mentioned polyester component can be melted and mixed by using a polycondensation tank or a single-screw or twin-screw extruder used for ordinary polymerization of polyester. When melt-mixing in a polycondensation tank, for example, the first polyester component is polymerized, and after the polymerization, a hydroxyl group-blocking agent is added and reacted, and then another hydroxyl-blocked polyester component is added, and the mixture is melt-mixed. Can be manufactured. When an extruder is used, for example, a polyester resin composition that satisfies the above constitutional requirements can be obtained by dry-blending and kneading the hydroxyl-blocked polyester components in advance. At the time of mixing, additives such as a stabilizer, a lubricant, a filler, an antistatic agent, and a pigment for further improving light resistance and heat resistance may be added in an amount that does not impair the effects of the present invention.

If necessary, the polyester resin composition of the present invention may be modified with a compound having a sulfonate group so as to be capable of cationic dyeing, or may be modified with a phosphorus-containing compound to make it flame-retardant. And additives that can be added to the polyester resin composition, if necessary, such as colorants, flame retardants, ultraviolet absorbers, antioxidants, hydrolysis stabilizers, Various additives such as fungicides and internal release agents, various fibers such as glass fibers and organic fibers, talc, silica, other inorganic fillers, various coupling agents, etc. before, during and during melt mixing It may be added appropriately later.

The polyester resin composition of the present invention is thermoplastic and has excellent melt moldability, and the transesterification does not occur even if the polyester resin composition is kept in a molten state at a high temperature, for example, at a high temperature of 270 ° C. or more, for a long time. No deterioration in physical properties due to random structuring. Therefore, various molded articles can be produced smoothly by performing melt molding using the polyester resin composition of the present invention alone. Further, the polyester resin composition of the present invention, in combination with polyethylene terephthalate and other high melting point polymers that need to be melted at a high temperature, melt-molded at a high temperature, and a polyester resin composition and a high melting point polymer. Can be manufactured.

Although not limited, the polyester resin composition of the present invention may be used alone or in combination with another polymer to form a sheet, a film, a belt, a roll, a curled cord, a hose, a tube, a packing material. Effective for a wide range of applications such as anti-vibration materials, vibration damping materials, cushioning materials, shoe soles, sports shoes, machine parts, automobile parts, electric / electronic parts, various molded products such as sports equipment, raw materials for fibers and adhesives Can be used for In producing the above-mentioned molded article from the polyester resin composition of the present invention, various melt molding methods conventionally used for thermoplastic resins and the like, for example, extrusion molding, injection molding,
Various molding methods such as extrusion blow molding, injection blow molding, calendar molding, and press molding can be employed.

EXAMPLES Next, the polyester resin composition of the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In addition, each measured value in an Example is a value measured and calculated by the following method.

[Hydroxy Group Concentration] The hydroxyl group concentration of the polyester component and the polyester resin composition is determined by the proton NM
R (“GX-500” manufactured by JEOL Ltd.) was determined from the intensity of methylene protons adjacent to hydroxyl groups.

[Carboxyl group concentration] The carboxyl group concentration of the polyester resin composition was determined by drying pellets of the polyester resin composition, and adding 215 ° C to benzyl alcohol.
The solution was dissolved at a temperature of 3 to 5 minutes, chloroform was added after the solution was dissolved, and then a neutralization point was obtained by titration with a methanol solution of potassium hydroxide using phenol red as an indicator to calculate a carboxyl group concentration. .

[Melting Point] The melting points of the polyester component and the polyester resin composition before melt-kneading were measured using a differential scanning calorimeter (“TA-3000” manufactured by METTLER CORPORATION) under nitrogen flow in the following steps 1 to 3. Step 3 was performed sequentially, and the temperature was determined as the crystal melting peak temperature in step 3. Step 1
The end point temperatures of (3) and (3) and the start point temperature of step (2) were appropriately changed depending on the melting point of the polyester sample used. Step 1: The temperature was raised from 20 ° C. to 250 to 280 ° C. at 20 ° C./min and held for 5 minutes. Step 2: The temperature was lowered from 250 to 280 ° C. to 50 ° C. at 20 ° C./min and held for 1 minute. Temperature rise from 50 ° C to 250-280 ° C at 20 ° C / min

[Intrinsic Viscosity] The polyester component and the polyester resin composition were dissolved in a mixed solvent of phenol / tetrachloroethane (1/1 weight ratio) and measured at 30 ° C. with an Ubbelohde viscometer.

[Molecular weight distribution (GPC measurement)] A polyester resin composition was dissolved in HFIP (hexafluoroisopropanol) / chloroform (20/80% by volume), and HFIP / chloroform (20/80% by volume) was used as an eluent.
A solution obtained by adding 5% by volume of acetic acid to the mixture was used, and a GPC apparatus (“GPC-510” manufactured by WATERS, column: ZO)
It was measured with an ultraviolet detector using RBAK “TRIMODAL-S”). The analysis of the molecular weight distribution was performed except for the peak of the oligomer portion.

[Melting point change after melt kneading] Using a Labo Plastomill (“20R200” manufactured by Toyo Seiki Seisaku-sho, Ltd.)
At a temperature of 70 ° C., the mixture is melt-kneaded for 30 minutes while flowing nitrogen, and the melting point of the polyester resin composition after the melt-kneading treatment is measured by the same method as the above-mentioned measurement of the melting point before the melt-kneading. The melting point change was calculated.

[Moldability] The polyester resin composition was treated with 8
Using a 0-ton injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.), injection molding was continuously performed, and a minimum necessary cooling time for which continuous molding was possible was measured. The molding conditions were varied depending on the polyester resin composition used, but the mold temperature was 80 ° C.

[Tensile Strength and Tensile Elongation] A test piece was sampled from an injection-molded product, and a tensile test was performed using the test piece at a temperature of 23 ° C. and a humidity of 65% RH. The tensile elongation at break was measured.

[Heat deformation temperature] Using an injection molded product,
The heat distortion temperature was measured according to TM-D648.

[Hydrolysis resistance] A molded article obtained by injection molding was subjected to a hydrolysis resistance test at 120 ° C, 2 atm and 40 hours using an autoclave. The evaluation of the hydrolysis resistance was performed by determining the tensile strength before and after the hydrolysis test and determining the retention rate.

Example 1 Ethylene glycol, terephthalic acid and a catalyst (antimony oxide [Sb ₂ O ₃ ]) were charged into a reactor, and water produced at 260 ° C. under normal pressure was distilled off outside the system while ester was removed. The reaction was carried out. Thereafter, the temperature was raised to 280 ° C., and the degree of reduced pressure was gradually increased to continue the reaction. When the intrinsic viscosity reaches 0.59 dl / g, the pressure is released and benzoylcaprolactam is added to the polycondensate by 2.0% by weight.
, And then reduced in pressure again and stirred for 30 minutes.
Polyethylene terephthalate (PET-1) having a hydroxyl group concentration of 3 μeq / g and a melting point of 256 ° C. was obtained. The pressure was released and the polybutylene terephthalate (PBT-1; diol component; 1,4-butanediol, dicarboxylic acid component; terephthalic acid, catalyst) titanium potassium oxalate [K ₂ TiO (C ₂ O (C ₂ O) ₄ ) ₂ · nH ₂ O], intrinsic viscosity: 1.20 dl / g, hydroxyl concentration 4 μeq / g,
Melting point: 227 ° C., hydroxyl-blocking agent: benzoylcaprolactam 2.0% by weight), weight ratio of PET-1 / PBT-1
= 70/30. Then reduce the pressure,
10 minutes after the PBT-1 was completely melted, the pressure was released,
N, N'- to the composition (PET-1 / PBT-1)
0.5% by weight of di-2,6-diisopropylphenylcarbodiimide was added, and the mixture was stirred under reduced pressure for 15 minutes to obtain a polyester resin composition-1. The hydroxyl group concentration of the obtained polyester resin composition-1 was as low as 3 μeq / g,
It has two crystal melting peaks at 5 ° C and 224 ° C,
Since the difference between the crystal melting temperature on the high temperature side and the melting point of PET-1 is 1 ° C., it can be seen that there is no transition to the random polymer. Further, at 270 ° C, 3
Even when the mixture was melted and kneaded for 0 minutes, the crystal melting temperature did not decrease at all. Polyester resin composition-1 is superior in heat resistance and moldability to polyester resin composition-8 having a high hydroxyl group concentration and a narrow molecular weight distribution in Comparative Example 3 below, and also has a high tensile strength and hydrolysis resistance. It can be seen from Table 2 that it is excellent.

Example 2 A reactor was charged with 2,6-naphthalenedicarboxylic acid, ethylene glycol, and a catalyst (antimony oxide [Sb ₂ O ₃ ]) and heated to 270 ° C. under normal pressure.
The esterification reaction was carried out while distilling off the water generated in the above step. Thereafter, the temperature was raised to 290 ° C., and the degree of reduced pressure was gradually increased to continue the reaction. When the intrinsic viscosity reaches 0.57 dl / g, the pressure is released, benzoylcaprolactam is added to the polycondensate at a ratio of 2.0% by weight, and then the pressure is reduced again, and the mixture is stirred for 20 minutes. Polyethylene-2,6-naphthalate having a melting point of 3 μequivalent / g and a melting point of 272 ° C. (P
EN-1) was obtained. Release the reduced pressure and prepare polybutylene-2,6-naphthalate (PBN-1; diol component; 1,4-butanediol, dicarboxylic acid component; 2,6-naphthalenedicarboxylic acid, catalyst; potassium titanium oxalate prepared in advance [K ₂ TiO (C ₂ O ₄ ) ₂ .nH ₂ O], intrinsic viscosity: 1.12 dl / g, hydroxyl group concentration 5 μeq / g,
Melting point: 245 ° C., hydroxyl-blocking agent: benzoylcaprolactam 2.0% by weight) in a weight ratio of PEN-1 / PBN-1
= 70/30. Then reduce the pressure and P
Ten minutes after the BN-1 was completely melted, the reduced pressure was released, and N, N'- with respect to the composition (PEN-1 / PBN-1).
0.5% by weight of di-2,6-diisopropylphenylcarbodiimide was added, and the mixture was stirred under reduced pressure for 10 minutes to obtain a polyester resin composition-2. The hydroxyl group concentration of the obtained polyester resin composition-2 was as low as 5 μequivalent / g.
It has two crystal melting peaks at 0 ° C and 243 ° C,
Since the difference between the crystal melting temperature on the high temperature side and the melting point of PEN-1 is 2 ° C., it can be seen that there is no transition to the random polymer. Further, at 270 ° C, 3
Even after 0 minutes of melt-kneading, there was no decrease in both crystal melting temperatures. Table 2 shows that the polyester resin composition-2 is excellent in heat resistance and moldability, and also excellent in tensile strength and elongation and hydrolysis resistance.

Example 3 A polyester having two crystal melting peaks at 255 ° C. and 244 ° C. in exactly the same manner as in Example 1 except that PBN-1 was used instead of PBT-1. Resin composition-3 was produced. Tables 1 and 2 show the physical properties and the like of the polyester resin composition-3. All are good results.

Example 4 Hydroxyl concentration 4 μm prepared in advance
Polybutylene terephthalate (PBT-2; diol component; 1,4-butanediol, dicarboxylic acid component; terephthalic acid, catalyst) having an equivalent weight / g, an intrinsic viscosity of 0.70 dl / g, and a melting point of 227 ° C. potassium titanium oxalate [K ₂ TiO
(C ₂ O ₄ ) ₂ .nH ₂ O], a hydroxyl group blocking agent: benzoylcaprolactam 2.0% by weight), a previously prepared hydroxyl group concentration of 3 μeq / g, an intrinsic viscosity of 1.20 dl / g, and a melting point of 22.
7 ° C. polybutylene terephthalate (PBT-3; diol component; 1,4-butanediol, dicarboxylic acid component; terephthalic acid, catalyst; titanium potassium oxalate [K
₂ TiO (C ₂ O ₄ ) ₂ .nH ₂ O], a hydroxyl group blocking agent; benzoylcaprolactam 2.0 wt%) was melt-kneaded using a twin-screw extruder, and the single crystal melting peak was 227 ° C. A polyester resin composition-4 was obtained. Comparative Example 2 below
It can be seen that the tensile strength and elongation are superior to those of the polyester resin-7 having a high hydroxyl group concentration and a narrow molecular weight distribution and the polyester resin-9 having a narrow molecular weight distribution of Comparative Example 4.

[Example 5] The same procedure as in Example 1 was repeated except that PBT-2 was used instead of PBT-1.
Polyester resin composition-5 having a narrow molecular weight distribution having two crystal melting peaks at 55 ° C and 225 ° C was produced.
It can be seen that the moldability is superior to that of the polyester resin-5 of Comparative Example 1 described below, which has a similar molecular weight distribution value but does not include a PBT component.

[Comparative Examples 1 and 2] As Comparative Example 1, polyethylene terephthalate: PET-2 (diol component; ethylene glycol, dicarboxylic acid component; terephthalic acid, catalyst; antimony oxide [Sb ₂ O ₃ ], no hydroxyl group blocking agent) As Comparative Example 2, polybutylene terephthalate: P
A polyester resin was obtained using BT-4 (diol component; 1,4-butanediol, dicarboxylic acid component; terephthalic acid, catalyst; tetraisopropyl titanate, no hydroxyl group blocking agent). Tables 1 and 2 show the physical properties and the like.

Comparative Example 3 Ethylene glycol, terephthalic acid and a catalyst (antimony oxide [Sb ₂ O ₃ ]) were charged into a reactor, and water produced at 180 to 220 ° C. under normal pressure was not distilled out of the system. Performed an esterification reaction. Then 2
The temperature was raised to 80 ° C., and the pressure was gradually increased to continue the reaction.
Polyethylene terephthalate (PET-3) having an intrinsic viscosity of 0.62 dl / g and a hydroxyl group concentration of 92 μeq / g and not reacted with a hydroxyl group-blocking agent was obtained. Release the decompression,
Polybutylene terephthalate (PBT-5; diol component;
1,4-butanediol, dicarboxylic acid component; terephthalic acid, catalyst; tetraisopropyl titanate, intrinsic viscosity: 0.72 dl / g, no hydroxyl group-blocking agent) in a weight ratio of PET-3 / PBT-5 = 70/30. It was charged to become. Then, the pressure was reduced and PBT-5 was completely melted.
After 0 minute, the pressure was released to obtain a polyester resin composition-8. The physical properties of the polyester resin composition-8 are shown in Tables 1 and 2.
It writes in. By blending PET-3 and PBT-5 having a high hydroxyl group concentration, the transesterification reaction proceeds excessively, so that all physical properties are deteriorated as compared with the polyester resin composition-1 of Example 1. I have. Further, the polyester resin composition-8 was 270
When melt-kneaded at ℃, the crystal melting peak becomes a single peak.
The temperature dropped to 5 ° C.

[Comparative Example 4] The PBT- obtained in Comparative Example 2
4, a benzoylcaprolactam was added at a ratio of 2.0% by weight to the polycondensate, and the mixture was melt-stirred under reduced pressure for 30 minutes to obtain a polyester resin having a hydroxyl group concentration of 4 μeq / g
9 (PBT-6) was obtained. It can be seen that the hydrolysis resistance is inferior to the polyester resin composition-4 of Example-4 due to the high carboxyl group concentration.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

The polyester resin composition of the present invention does not undergo transesterification between the polyester components, and is excellent in heat stability, moldability, mechanical properties, heat resistance, hydrolysis resistance and the like. . According to the production method of the present invention,
The above polyester resin composition can be manufactured stably.

Claims (10)

[Claims] 1. A composition comprising two or more polyester components mainly comprising a dicarboxylic acid unit and a diol unit,
(A) 70 mol% or more of the dicarboxylic acid unit of each polyester component is an aromatic dicarboxylic acid unit, and (b) 70 mol% or more of the diol unit of each polyester component is an aliphatic α, ω having 2 to 6 carbon atoms. A diol unit, and (c)
At least two of the polyester components have different aromatic dicarboxylic acid units and / or aliphatic α, ω-diol units having 2 to 6 carbon atoms, and (d) at least one aromatic dicarboxylic acid of the polyester component The unit is a terephthalic acid unit or a naphthalenedicarboxylic acid unit, and the weight fraction is 50% by weight or more based on the whole composition, and (e) the intrinsic viscosity of the whole composition is 0.4%.
(F) a polyester resin composition, wherein the hydroxyl group concentration of the entire composition is 10 μeq / g or less. 2. Molecular weight distribution of the whole composition; Mw / Mn
The polyester resin composition according to claim 1, wherein (weight average molecular weight / number average molecular weight) is 3.0 or more. 3. The polyester resin composition according to claim 1, comprising a polyester component comprising a terephthalic acid unit and an ethylene glycol unit and a polyester component comprising a terephthalic acid unit and a 1,4-butanediol unit. 4. A composition comprising two or more polyester components mainly comprising a dicarboxylic acid unit and a diol unit,
(A) 70 mol% or more of the dicarboxylic acid unit of each polyester component is an aromatic dicarboxylic acid unit, and (b) 70 mol% or more of the diol unit of each polyester component is an aliphatic α, ω having 2 to 6 carbon atoms. A diol unit, and (c)
Each polyester component has the same aromatic dicarboxylic acid unit and aliphatic α, ω-diol unit having 2 to 6 carbon atoms, but has different intrinsic viscosities. The dicarboxylic acid unit is a terephthalic acid unit or a naphthalenedicarboxylic acid unit, (e) the intrinsic viscosity of the whole composition is in the range of 0.4 to 1.5 dl / g, and (f) the hydroxyl group concentration of the whole composition is (G) molecular weight distribution of the whole composition; Mw
/ Mn (weight average molecular weight / number average molecular weight) is 3.0 or more, wherein the polyester resin composition is characterized in that: 5. A carboxyl group concentration of the whole composition is 20.
The polyester resin composition according to any one of claims 1 to 4, wherein the amount is not more than μ equivalent / g. 6. A method for producing a polyester resin composition, comprising melting and mixing two or more polyester components mainly comprising a dicarboxylic acid unit and a diol unit,
(A ′) 70 mol% or more of dicarboxylic acid units are aromatic dicarboxylic acid units, and (b ′) 70 mol% or more of diol units are aliphatic α, ω-diol units having 2 to 6 carbon atoms, (C ′) at least two of the polyester components have different aromatic dicarboxylic acid units and / or aliphatic α, ω-diol units having 2 to 6 carbon atoms, and (d ′) at least one polyester component The aromatic dicarboxylic acid unit is a terephthalic acid unit or a naphthalenedicarboxylic acid unit, and the weight fraction of the aromatic dicarboxylic acid unit is 50% by weight or more based on the whole composition, and the intrinsic viscosity of the polyester component (e ′) is 0 or less. 0.4 to 1.5 dl /
2. The method of producing a polyester resin composition according to claim 1, wherein the polyester component is melt-mixed using a polyester component having a hydroxyl group concentration of 10 μe / g or less. 7. A method for producing a polyester resin composition, comprising melting and mixing two or more polyester components mainly comprising a dicarboxylic acid unit and a diol unit,
(A ′) 70 mol% or more of dicarboxylic acid units are aromatic dicarboxylic acid units, and (b ′) 70 mol% or more of diol units are aliphatic α, ω-diol units having 2 to 6 carbon atoms, (C ′) each polyester component has the same aromatic dicarboxylic acid unit and aliphatic α, ω-diol unit having 2 to 6 carbon atoms, but has different intrinsic viscosities; The aromatic dicarboxylic acid unit of the polyester component is a terephthalic acid unit or a naphthalenedicarboxylic acid unit, (e ′) the intrinsic viscosity of the polyester component is 0.4 to 1.5 dl / g, and (f ′) the polyester component The method for producing a polyester resin composition according to claim 4, wherein the polyester component is melt-mixed using a polyester component having a hydroxyl group concentration of 10 μeq / g or less. 8. The method for producing a polyester resin composition according to claim 6, wherein each polyester component is produced by reacting a hydroxyl group blocking agent. 9. The method for producing a polyester resin composition according to claim 6, wherein at least one of the polyester components is produced using a potassium titanium oxalate catalyst. 10. A molded article comprising the polyester resin composition according to any one of claims 1 to 5.