JP2018053230A - Thermoplastic polyester resin composition and molding thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent chemical resistance and allowing stretch blow molding.SOLUTION: A resin composition contains a resin component composed of (A) a thermoplastic polyester resin showing no liquid crystallinity (component A) 95-50 wt.% and (B) a thermoplastic polyester resin showing liquid crystallinity (component B) 5-50 wt.%, and contains (C) a carbodiimide compound (component C) 0.1-5 pts.wt. relative to 100 pts.wt of the resin component.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition having excellent chemical resistance and capable of stretch blow molding, and a molded article comprising the same.

  Containers for storing chemicals and fragrances are required to have high chemical resistance, and glass containers and resin containers such as sealer bottles are used. While a glass container is excellent in chemical resistance, it is inconvenient to handle because the container itself is heavy, and may be broken by dropping. In particular, when handling highly toxic chemicals such as in the semiconductor field and the medical field, there is a risk of serious health damage due to chemical exposure. On the other hand, a resin container is lighter than a glass container and thus is easy to handle, and has a feature that the risk of container cracking due to dropping is small. However, since the chemical resistance is inferior to glass, its field of use has been limited.

  Since thermoplastic polyester resins (hereinafter abbreviated as thermoplastic polyester) including polybutylene terephthalate (hereinafter abbreviated as PBT) and polybutylene naphthalate (hereinafter abbreviated as PBN) are easily crystallized, mechanical properties, thermal properties, It has excellent chemical resistance, electrical properties, and moldability, and is used in various applications. Examples of thermoplastic polyesters that have crystallinity but are slow to crystallize include polyethylene terephthalate (hereinafter abbreviated as PET) and polyethylene naphthalate (hereinafter abbreviated as PEN). There is a feature that can. However, chemical resistance is still insufficient for wide use as a chemical container in the semiconductor field and medical field, and the range of use has been limited to a part. On the other hand, the thermotropic liquid crystal polyester resin (hereinafter abbreviated as liquid crystal polyester) has excellent chemical resistance as compared with PEN. However, since it is a hard and brittle resin, it is not suitable for stretch blow molding, and since it is easy to draw down, it is not suitable for direct blow molding, so it is difficult to mold into a container shape.

Patent Document 1 exemplifies a direct blow-molded product and chemical resistance of an amorphous polyester resin that is a mixture of thermoplastic polyester, polycarbonate resin, and liquid crystal polyester. However, the amorphous polyester resin described in Patent Document 1 has a problem that sufficient chemical resistance against strong chemicals used in the semiconductor field and the medical field cannot be obtained.
Patent Document 2 exemplifies a composition containing an epoxy compound having two or more glycidyl ester groups with respect to thermoplastic polyester and liquid crystal polyester. However, when an epoxy compound having two or more glycidyl ester groups is used, there is a problem of deteriorating blowability.

JP 2007-302845 A JP-A-5-86267

  An object of the present invention is to provide a thermoplastic resin composition having excellent chemical resistance and capable of stretch blow molding.

  As a result of intensive studies to achieve the above object, the present inventors have excellent chemical resistance by adding a carbodiimide compound to a thermoplastic polyester resin that does not exhibit liquid crystallinity and a thermoplastic polyester resin that exhibits liquid crystallinity. The inventors have found that a thermoplastic resin composition that can be stretch blow molded is obtained, and have solved the above-mentioned problems.

  That is, the above-mentioned problems are (A) 95 to 50% by weight of a thermoplastic polyester resin (component A) that does not exhibit liquid crystallinity, and (B) a resin comprising 5 to 50% by weight of a thermoplastic polyester resin (component B) that exhibits liquid crystallinity. This can be achieved by a resin composition containing 0.1 to 5 parts by weight of (C) a carbodiimide compound (C component) with respect to 100 parts by weight of the component.

  According to the present invention, a thermoplastic polyester resin composition having excellent chemical resistance and capable of stretch blow molding can be provided. The blow-drawn container obtained from the resin composition of the present invention can provide a container for storing chemicals, fragrances and the like, and a resin container capable of storing high-purity chemicals in the semiconductor field with high purity.

Hereinafter, the preparation method and molding processing method of the resin used in the present invention will be sequentially described.
<About component A>
The thermoplastic polyester resin that does not exhibit liquid crystallinity of the A component of the present invention includes a condensation reaction mainly composed of a dicarboxylic acid component comprising a dicarboxylic acid or a reactive derivative thereof and a diol component comprising a diol or an ester derivative thereof. Preferably, at least 50 mol% of the dicarboxylic acid component is naphthalenedicarboxylic acid and at least 50 mol% of the diol component is ethylene glycol and does not exhibit liquid crystallinity. It is a thermoplastic polyester resin.

  Examples of dicarboxylic acid components other than the above naphthalenedicarboxylic acid include, for example, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Na sulfo Aromatic dicarboxylic acids such as isophthalic acid, ethylene-bis-p-benzoic acid, fats such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid Group dicarboxylic acid can be exemplified , Among them, terephthalic acid is preferred. These dicarboxylic acids can be used alone or in admixture of two or more.

  Examples of the diol component other than the ethylene glycol include diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or -2,2, 4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3 -Cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A and the like can be mentioned. These can be used alone or in admixture of two or more.

  The above-mentioned thermoplastic polyester resin that does not exhibit liquid crystallinity can be produced by a conventionally known production method. That is, the dicarboxylic acid component and the diol component are directly reacted to distill off water and esterify, and then the direct esterification method in which polycondensation is performed under reduced pressure, or the dicarboxylic acid dimethyl ester and the diol component are reacted to produce methyl alcohol. Is distilled off and subjected to transesterification, followed by a transesterification method in which polycondensation is performed under reduced pressure. Further, solid state polymerization can be performed to increase the intrinsic viscosity number.

  In the transesterification reaction, esterification reaction and polycondensation reaction, it is preferable to use a catalyst and a stabilizer. As the transesterification catalyst, Mg compound, Mn compound, Ca compound, Zn compound and the like are used. Examples thereof include acetates, monocarboxylates, alcoholates and oxides thereof. Further, the esterification reaction can be carried out only with dicarboxylic acid and diol without adding a catalyst, but can also be carried out in the presence of a polycondensation catalyst described later. As the polycondensation catalyst, Ge compounds, Ti compounds, Sb compounds, and the like can be used. Examples thereof include germanium dioxide, germanium hydroxide, germanium alcoholate, titanium tetrabutoxide, titanium tetraisopropoxide, and titanium oxalate. . As the stabilizer, a phosphorus compound is preferably used. Preferable phosphorus compounds include phosphoric acid and its ester, phosphorous acid and its ester, hypophosphorous acid and its ester, and the like. In addition, in the esterification reaction, a tertiary amine such as triethylamine, a quaternary ammonium hydroxide such as tetraethylammonium hydroxide, and a basic compound such as sodium carbonate can be added to suppress diethylene glycol by-product. Moreover, various stabilizers and modifiers can be blended in the obtained polyester resin.

  The intrinsic viscosity of the component A is preferably 0.6 to 1.0 dl / g, more preferably 0.65 to 0.95 dl / g, and still more preferably 0.7 to 0.9 dl / g. . If the intrinsic viscosity of component A is less than 0.6 dl / g, chemical resistance is insufficient, and if it exceeds 1.0 dl / g, molding may not be possible.

<About B component>
The resin composition of the present invention contains a thermoplastic polyester resin exhibiting liquid crystallinity (hereinafter abbreviated as liquid crystal polyester). The main repeating units constituting the liquid crystal polyester are aromatic oxycarbonyl repeating units, aromatic dicarbonyl repeating units, aromatic dioxy repeating units, aromatic aminooxy repeating units, aromatic diamino repeating units, aromatic aminocarbonyl repeating units, It is at least one selected from aromatic oxydicarbonyl repeating units and aliphatic dioxy repeating units.

  In addition, the liquid crystalline polyester may contain a repeating unit other than the main repeating unit as a constituent component within a range not impairing the object of the present invention, and may contain, for example, a thioester bond. Examples of the monomer that gives such a bond include mercapto aromatic carboxylic acid, aromatic dithiol, and hydroxy aromatic thiol. The amount of the monomer that gives a repeating unit other than these main repeating units is aromatic oxycarbonyl repeating unit, aromatic dicarbonyl repeating unit, aromatic dioxy repeating unit, aromatic aminooxy repeating unit, aromatic diamino repeating unit. It is preferably 10 mol% or less based on the total amount of main monomers giving the unit, the aromatic aminocarbonyl repeating unit, the aromatic oxydicarbonyl repeating unit, and the aliphatic dioxy repeating unit.

  Liquid crystal polyesters composed of these repeating units may or may not form an anisotropic melt phase depending on the constituent components, the composition ratio in the polymer, and the sequence distribution, but the liquid crystal used in the present invention. The polyester preferably forms an anisotropic molten phase.

  Specific examples of the monomer that gives an aromatic oxycarbonyl repeating unit include, for example, parahydroxybenzoic acid, metahydroxybenzoic acid, orthohydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 5-hydroxy-2-naphthoic acid. Acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, their alkyl, alkoxy or Halogen-substituted products, and ester-forming derivatives such as acylated products, ester derivatives, and acid halides thereof can be mentioned. In these, it is preferable from the point of being easy to adjust the characteristic and crystal melting temperature of liquid crystal polyester from which parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are obtained.

  Specific examples of the monomer that gives an aromatic dicarbonyl repeating unit include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1 , 4-naphthalenedicarboxylic acid, aromatic dicarboxylic acids such as 4,4′-dicarboxybiphenyl, alkyl, alkoxy or halogen-substituted products thereof, and ester-forming derivatives such as ester derivatives and acid halides thereof. . Among these, terephthalic acid, 2,6-naphthalenedicarboxylic acid is preferable because it is easy to adjust the mechanical properties, heat resistance, crystal melting temperature, and moldability of the liquid crystalline polyester from which it is obtained.

  Specific examples of the monomer that provides an aromatic dioxy repeating unit include, for example, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, Aromatic diols such as 4,4′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl ether, alkyl, alkoxy or halogen substituted products thereof, and And ester-forming derivatives such as acylated products. Among these, hydroquinone and 4,4'-dihydroxybiphenyl are preferable from the viewpoint of reactivity during polymerization and characteristics of the obtained liquid crystal polyester.

  Specific examples of the monomer that gives an aromatic aminooxy repeating unit include, for example, p-aminophenol, m-aminophenol, 4-amino-1-naphthol, 5-amino-1-naphthol, and 8-amino-2. -Aromatic amines such as naphthol and 4-amino-4'-hydroxybiphenyl, alkyl, alkoxy or halogen substituents thereof, and ester or amide-forming derivatives thereof such as acylated products thereof.

  Specific examples of the monomer that gives an aromatic diamino repeating unit include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, and alkyls thereof. , Alkoxy- or halogen-substituted products, and amide-forming derivatives thereof such as acylated products thereof.

  Specific examples of the monomer that gives an aromatic aminocarbonyl repeating unit include aromatic aminocarboxylic acids such as p-aminobenzoic acid, m-aminobenzoic acid, 6-amino-2-naphthoic acid, and alkyls thereof. , Alkoxy- or halogen-substituted products, and ester or amide-forming derivatives thereof such as acylated products, ester derivatives, and acid halides.

  Specific examples of monomers that give aromatic oxydicarbonyl repeating units include hydroxy aromatic dicarboxylic acids such as 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxyisophthalic acid, and 5-hydroxyisophthalic acid. Examples include acids, alkyl, alkoxy or halogen-substituted products thereof, and ester-forming derivatives such as acylated products, ester derivatives, and acid halides thereof.

  Specific examples of the monomer that gives an aliphatic dioxy repeating unit include aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylated products thereof. Polyesters containing aliphatic dioxy repeating units, such as polyethylene terephthalate and polybutylene terephthalate, are converted into the above aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxyamines, aromatic diamines, aromatics. A liquid crystal polyester containing an aliphatic dioxy repeating unit can also be obtained by reacting with an aminocarboxylic acid, an aromatic oxydicarboxylic acid and an acylated product, an ester derivative, an acid halide or the like thereof.

  As mentioned above, although the repeating unit contained in the liquid crystalline polyester used in this invention and the monomer which gives it were demonstrated, the liquid crystalline polyester used in this invention is represented by the following formula | equation (2)-Formula (5) as a repeating unit. The aromatic oxycarbonyl repeating unit is preferably constituted.

[In the formula, Ar ₁ is the following formula (6) or (7), Ar ₂ is the following formula (6) or (8), and p, q, r, and s are the moles of each repeating unit, respectively. The composition ratio (mol%) is shown and is a numerical value satisfying the formulas [1] to [5]. ]

In addition, it is preferable that both Ar ₁ and Ar ₂ are the above formula (6).
Examples of the monomer that gives the repeating unit represented by the formula (2) include 6-hydroxy-2-naphthoic acid and ester-forming derivatives such as acylated products, ester derivatives, and acid halides.
Examples of the monomer that gives the repeating unit represented by the formula (3) include p-hydroxybenzoic acid and ester-forming derivatives such as acylated products, ester derivatives, and acid halides.

  Examples of the monomer that gives the repeating unit represented by the formula (4) include hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 1,4- Aromatic diols such as naphthalenedicarboxylic acid, 4,4′-dihydroxybiphenyl ether, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, these Examples include alkyl-, alkoxy- or halogen-substituted products, and ester-forming derivatives such as acylated products thereof.

  Monomers that give the repeating unit represented by the formula (5) include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, Aromatic dicarboxylic acids such as 4-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, bis (4-carboxyphenyl) ether, alkyl, alkoxy or halogen substituted products thereof, ester derivatives thereof, acid halogens And ester-forming derivatives such as compounds.

  The liquid crystalline polyester of the present invention is a monomer that provides other repeating units in addition to the main monomer that provides the repeating units represented by the general formulas (2) to (5) within a range that does not impair the object of the present invention. May be copolymerized. Other monomers that give repeating units include aromatic hydroxycarboxylic acids, aromatic diols, aromatic dicarboxylic acids, aromatic hydroxydicarboxylic acids, aromatic hydroxyamines, aromatic diamines, aromatic aminocarboxylic acids, alicyclic rings Examples include aromatic dicarboxylic acids, aliphatic diols, alicyclic diols, aromatic mercaptocarboxylic acids, aromatic dithiols, and aromatic mercaptophenols. It is preferable that the monomer which gives these other repeating units is 10 mol% or less with respect to the sum total of the monomers which give the repeating unit represented by General Formula (2)-(5).

The method for producing the liquid crystalline polyester of the present invention is not particularly limited, and a known polyester polycondensation method for forming an ester bond between the monomer components, such as a melt acidification method or a slurry polymerization method, can be used.
In the melt acidosis method, a monomer is first heated to form a molten solution of a reactant, and then the reaction is continued to obtain a molten polymer. A vacuum may be applied to facilitate removal of volatiles (for example, acetic acid, water, etc.) by-produced in the final stage of condensation. This method is particularly preferably used in the present invention.
The slurry polymerization method is a method of reacting in the presence of a heat exchange fluid, and the solid product is obtained in a state suspended in a heat exchange medium.

  In both the melt acidification method and the slurry polymerization method, the polymerizable monomer component used in producing the liquid crystal polyester may be subjected to the reaction as a modified form in which a hydroxyl group is esterified, that is, a lower acyl ester. it can. The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. Particularly preferred is a method using an acetate of the monomer component in the reaction. The monomeric lower acyl ester may be separately acylated and synthesized in advance, or may be produced in the reaction system by adding an acylating agent such as acetic anhydride to the monomer during the production of the liquid crystalline polyester. .

  In either the melt acidosis method or the slurry polymerization method, a catalyst may be used as necessary. Specific examples of the catalyst include organic tin compounds such as dialkyltin oxide (for example, dibutyltin oxide) and diaryltin oxide; organic titanium compounds such as titanium dioxide, antimony trioxide, alkoxy titanium silicate, and titanium alkoxide; alkali and alkali of carboxylic acid Earth metal salts (eg, potassium acetate); inorganic acid alkali and alkaline earth metal salts (eg, potassium sulfate); gaseous acids catalysts such as Lewis acids (eg, BF3), hydrogen halides (eg, HCl), and the like . The ratio of the catalyst used is usually 10 to 1000 ppm, preferably 20 to 200 ppm, based on the total amount of monomers.

The liquid crystalline polyester of the present invention thus obtained preferably has a melting point of 190 to 250 ° C., more preferably 200 to 240, as measured by heating at 20 ° C./min with a differential scanning calorimeter (DSC). ° C, more preferably 210-230 ° C. When the melting point exceeds 250 ° C., chemical resistance may not be sufficiently exhibited. Further, when the melting point is less than 190 ° C., liquid crystal properties may not be exhibited.
The weight ratio of the A component to the B component is 50 to 95% by weight for the A component, 5 to 50% by weight for the B component, preferably 60 to 92% by weight for the A component, and 8 to 40% by weight for the B component. More preferably, the A component is 70 to 90% by weight and the B component is 10 to 30% by weight. When the B component is less than 5% by weight, the chemical resistance is insufficient. If it exceeds 50% by weight, blow molding cannot be performed.

<About component C>
The carbodiimide compound constituting the thermoplastic polyester resin composition of the present invention is a compound having a carbodiimide group (—N═C═N—) in the molecule.
Examples of the monocarbodiimide having one carbodiimide group in the molecule include N, N′-di-2,6-diisopropylphenylcarbodiimide, N, N′-diphenylcarbodiimide, and N, N′-di-2,6. -Dimethylphenylcarbodiimide, N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N-tolyl-N'-phenylcarbodiimide, N, N'-di-p-nitrophenylcarbodiimide, N, N '-Di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N, N'-di- o-Ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide N, N'-di-o-isopropylphenylcarbodiimide, N, N'-di-p-isopropylphenylcarbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenyl Carbodiimide, N, N'-di-2,6-diethylphenylcarbodiimide, N, N'-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N'-di-2-isobutyl-6-isopropylphenylcarbodiimide N, N'-di-2,4,6-trimethylphenylcarbodiimide, N, N'-di-2,4,6-triisopropylphenylcarbodiimide, N, N'-di-2,4,6-tri Isobutylphenylcarbodiimide, di-β-naphthylcarbodiimide, N, N′-di-o-tolylcarbodiimide, N -Tolyl-N'-cyclohexylcarbodiimide, N, N'-di-p-tolylcarbodiimide, N, N'-benzylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N -Aromatic monocarbodiimides such as benzyl-N'-tolylcarbodiimide, N, N'-dioctyldecylcarbodiimide, N, N'-di-cyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropyl Aliphatic / or alicyclic monocarbodiimides such as carbodiimide and di-t-butylcarbodiimide are exemplified.

  Examples of the polycarbodiimide having two or more carbodiimide groups in the same molecule include poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (4,4′-diphenylmethanecarbodiimide), and poly (methyl- Diisopropylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), poly (triylcarbodiimide), poly (diisopropylphenylenecarbodiimide), p-phenylene-bis-di-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, ethylene -Bis-diphenylcarbodiimide, hexamethylene-bis-dicyclohexylcarbodiimide and the like. Among these compounds, carbodiimides containing two carbodiimide groups are p-phenylene-bis-di-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, hexamethylene-bis-dicyclohexyl. Carbodiimide.

In the present invention, the carbodiimide compound is preferably at least one carbodiimide compound selected from the group consisting of compounds having two or more carbodiimide groups, and at least one carbodiimide compound selected from the group consisting of compounds having two carbodiimide groups. Is more preferable. In the case of having two or more carbodiimide groups, the carbodiimide group can react with the polyester and the liquid crystal polyester each not exhibiting liquid crystal, thereby improving the compatibility. Further, in the case of having two carbodiimide groups, the polyester which does not show liquid crystal and the liquid crystal polyester are connected to both ends of the carbodiimide, so that many shear alignment layers are formed on the surface of the injection-molded product, and further higher chemical resistance is obtained.
Furthermore, the carbodiimide is more preferably cyclic. By being cyclic, generation of isocyanate gas can be suppressed and the working environment is improved.
Examples of the cyclic carbodiimide compound include compounds represented by the following formula (1).

In the formula, X is a tetravalent group represented by the following formula (1-1). In the formula, Ar ^{1 to} Ar ⁴ are each independently an orthophenylene group or a 1,2-naphthalene-diyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms of the substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

The cyclic carbodiimide compound has a cyclic structure. The cyclic structure has one carbodiimide group (—N═C═N—), and the first nitrogen and the second nitrogen are bonded by a bonding group. One cyclic structure has only one carbodiimide group.
The molecular weight of the cyclic carbodiimide compound is preferably 100 to 1,000. If the molecular weight is less than 100, the structural stability and volatility of the cyclic carbodiimide compound may be a problem. On the other hand, if the molecular weight is larger than 1,000, synthesis in a diluting system is required for the production of cyclic carbodiimide, and the yield may be lowered, which may cause a problem in cost. From this viewpoint, it is more preferably 100 to 750, and further preferably 250 to 750.
Examples of the cyclic carbodiimide compound include the following compounds.

In addition, these cyclic carbodiimide compounds can be produced by various methods known in various literatures and patent publications (for example, the method described in International Publication WO 10/071213 pamphlet).
Content of C component is 0.1-5 weight part with respect to a total of 100 weight part of A component and B component, 0.2-4 weight part is preferable, and 0.3-3 weight part is more. Preferably, 0.4 to 2 parts by weight is more preferable. If the content of component C is less than 0.1 parts by weight, chemical resistance cannot be sufficiently exhibited, or blow molding cannot be performed. If it exceeds 5 parts by weight, the workability deteriorates.

<Other ingredients>
In addition, the resin composition of this invention can contain each additive, such as a heating adjuvant, antioxidant, and a mold release agent, in the range which is not contrary to the meaning of this invention.

<Heating aid>
The resin composition of the present invention can contain a heating aid for the purpose of improving the heating efficiency by an infrared (IR) heater during blow molding and shortening the heating time. Such heating aids include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide, ruthenium oxide, and immonium oxide, metals such as lanthanum boride, cerium boride, and tungsten boride. Preferable examples include various metal compounds having excellent near-infrared absorption ability, such as boride-based and tungsten oxide-based near-infrared absorbers, and carbon fillers. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene, and carbon black and graphite are preferable. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, with respect to 100 parts by weight of the total of the A component and the B component. 0.001-0.07 weight part is further more preferable. If the content is less than 0.0005 parts by weight, the effect as a heating aid may not be sufficiently obtained, and it may take a long time to heat the preform during blow molding. Moreover, when this content is more than 0.2 parts by weight, the heating aid may bleed out during blow molding overheating. The content of the metal oxide near infrared absorber, metal boride near infrared absorber, tungsten oxide infrared absorber and carbon filler is preferably in the range of 0.1 to 500 ppm (weight ratio) in the resin composition. The range of 0.5 to 300 ppm is more preferable. If the content is less than 0.1 ppm, the effect as a heating aid may not be sufficiently obtained, and it may take a long time to heat the preform during blow molding. In addition, when the content is more than 500 ppm, the resin component may be greatly decomposed.

<Antioxidant>
The resin composition of the present invention may contain at least one antioxidant selected from the group consisting of hindered phenol compounds, phosphite compounds, phosphonite compounds, and thioether compounds as an antioxidant. By blending an antioxidant, not only is the hue and fluidity at the time of molding stabilized, it is also effective in improving hydrolysis resistance.

  Examples of the hindered phenol compound include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate. 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebi (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) ) 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3- Methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- ( -Tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1 , 1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4 , 4′-di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol) ), 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy -3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl Phenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl) 4-hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane is preferably used. Particularly preferred is octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. All of these are readily available. The said hindered phenol type compound can be used individually or in combination of 2 or more types.

  Phosphite compounds include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl mono Phenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) ) Phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentae Thritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite. Furthermore, as other phosphite compounds, those that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, and the like. Suitable phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methyl). Phenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

  Also, for example, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine [commercially available as “Sumilyzer GP” (manufactured by Sumitomo Chemical Co., Ltd.). 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] dibenzo [D, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -12H Dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di -T-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8 , 10-Tetra-t-butyl-6- (3,5-di-t-butyl-4- Roxybenzoyloxy) -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t -Butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,10 -Diethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3 2] Dioxaphosphocin, 2,4,8,10-tetra-t-butyl Ru-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphine And so on. All of these are readily available. The above phosphite compounds can be used alone or in combination of two or more.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphospho Knight, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, Bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4- -Tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples include -4-phenyl-phenyl phosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenyl phosphonite. Tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite Knight and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted. The phosphonite compound is preferably tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, and stabilizers based on the phosphonite are Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos. P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) is commercially available and any of them can be used. The said phosphonite type compound can be used individually or in combination of 2 or more types.

  Specific examples of thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio) Propionate) and the like. The said thioether type compound can be used individually or in combination of 2 or more types.

The content of the antioxidant is preferably from 0.01 to 2 parts by weight, more preferably from 0.03 to 1 part by weight, and even more preferably from 0.05 to 1 part by weight based on 100 parts by weight of the total of the component A and the component B. 0.5 parts by weight. When the content of the antioxidant is less than 0.01 parts by weight, the antioxidant effect is insufficient, and not only the hue and fluidity at the time of molding become unstable, but also the hydrolysis resistance may deteriorate. . In addition, when the content is more than 2 parts by weight, the reaction component derived from the antioxidant may be deteriorated and the hydrolysis resistance may be deteriorated.
In addition, it is preferable to use a combination of two or more of the hindered phenol compounds and phosphite compounds, phosphonite compounds, and thioether compounds. By using a combination of two or more of hindered phenol compounds and phosphite compounds, phosphonite compounds, and thioether compounds, a synergistic effect as a stabilizer is demonstrated, and more hue and flow during molding. It is effective in stabilizing the properties and improving the hydrolysis resistance.

<Release agent>
The resin composition of the present invention can contain a release agent. Specific examples of release agents include fatty acids, fatty acid metal salts, oxy fatty acids, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid partial saponified esters, fatty acid lower alcohol esters, fatty acid polyvalents. Examples thereof include alcohol esters, fatty acid polyglycol esters, and modified silicones. By blending these, a molded product excellent in mechanical properties, moldability, and heat resistance can be obtained.

  Fatty acids having 6 to 40 carbon atoms are preferred. Specifically, oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montan Examples thereof include acids and mixtures thereof. The fatty acid metal salt is preferably an alkali (earth) metal salt of a fatty acid having 6 to 40 carbon atoms, and specific examples include calcium stearate, sodium montanate, and calcium montanate.

Examples of the oxy fatty acid include 1,2-oxysteric acid. Paraffin having 18 or more carbon atoms is preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like.
As the low molecular weight polyolefin, for example, those having a molecular weight of 5000 or less are preferable, and specific examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidized type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax.

Fatty acid amides having 6 or more carbon atoms are preferred, and specific examples include oleic acid amide, erucic acid amide, and behenic acid amide.
The alkylene bis fatty acid amide is preferably one having 6 or more carbon atoms, and specifically includes methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2-hydroxyethyl) stearic acid amide and the like.
As the aliphatic ketone, those having 6 or more carbon atoms are preferable, and examples thereof include higher aliphatic ketones.

Examples of the fatty acid partial saponified ester include a montanic acid partial saponified ester. Examples of the fatty acid lower alcohol ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidonic acid ester, montanic acid ester, isostearic acid ester and the like.
Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol Examples include tall monostearate, pentaerythritol adipate stearate, sorbitan monobehenate and the like. Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters, polytrimethylene glycol fatty acid esters, and polypropylene glycol fatty acid esters.

Examples of the modified silicone include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.
Of these, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferable, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferable. Of these, montanic acid ester, montanic acid partial saponified ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferable, and montanic acid partial saponified ester and ethylene bisstearic acid amide are particularly preferable. .

  A mold release agent may be used by 1 type and may be used in combination of 2 or more type. The content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight with respect to 100 parts by weight of the total of the A component and the B component.

<Preform molding>
The resin composition of the present invention is usually obtained as pellets, and a preform is molded using this as a raw material. Various molding methods such as injection molding, press molding, and extrusion molding can be selected as the molding method, but injection molding and press molding are preferred from the viewpoint of rapid cooling without crystallizing the preform. In the injection molding, not only a normal cold runner molding method but also a hot runner molding method is possible. In such injection molding, not only a normal molding method but also injection compression molding, injection press molding, foam molding (including by supercritical fluid injection), insert molding, in-mold coating molding, as appropriate, depending on the purpose. A molded product can be obtained using an injection molding method such as rapid heating / cooling die molding. For example, in the case of injection molding of a preform for blow molding, it is preferable that each pellet is preliminarily dried for 5 hours or more with a hot air dryer at 130 to 170 ° C. and then melted at a cylinder temperature of 260 to 300 ° C. and injection molded. . If the predrying temperature is less than 130 ° C, the drying becomes insufficient, the resin may be decomposed by moisture remaining in the pellets, and the intrinsic viscosity may not be stable. If the predrying temperature is higher than 170 ° C, the pellets turn yellow. The appearance of the molded body may be impaired. The mold temperature during molding is preferably 5 to 40 ° C, more preferably 10 to 30 ° C. When the mold temperature is less than 5 ° C, appearance of silver or the like may occur frequently on the molded product due to the condensation of the mold. When the mold temperature exceeds 40 ° C, the crystallization of the molded product proceeds, and at the time of blow molding Container may be damaged.

<Blow molding>
Arbitrary methods are employ | adopted for the preparation methods of the container of this invention. Examples thereof include direct blow molding, extrusion direct blow molding, one-stage biaxial stretch blow molding, and two-stage biaxial stretch blow molding. Two-stage biaxial stretch blow molding is preferable.
The container of the present invention preferably has a draw ratio of 2 times or more in the vertical direction and 2 times or more in the horizontal direction, more preferably a draw ratio of 2.5 times or more in the vertical direction and 2.5 times or more in the horizontal direction. When the draw ratio is less than 2 times in length and less than 2 times in width, uneven stretching may occur in the container. Furthermore, it is preferable to stretch at least 2 times in the machine direction and to start stretching at least 2 times in the transverse direction from the start to the completion of stretching in the machine direction.

  When biaxial stretching blow is performed in two stages, it is preferable to preheat (preheat) before blow molding. The preheating temperature is preferably 70 to 140 ° C, preferably 90 ° C to 130 ° C, and most preferably 100 ° C to 110 ° C. If the preheating temperature is less than 70 ° C., it takes time for the main heating time in the subsequent process. If the preheating temperature exceeds 140 ° C., the resin composition may crystallize, and the container may be damaged during blow molding. . The preheating method may be any method such as storage of a preform in a hot air dryer or heating with an infrared heater.

  Heating during blow molding (main heating) may be performed from both heating from the inside of the preform (internal heating) and heating from the outside of the preform (external heating). As the heating method, an infrared heating method is preferable since heating efficiency is good. Here, it is necessary to warm the resin temperature to about 130 to 160 ° C. By performing blow molding in such a resin temperature range, it is possible to obtain a good blow molded article with little thickness unevenness and without tearing.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples.
The physical properties were evaluated by the following methods.

(1). Evaluation of chemical resistance Standard NO. The JIS No. 3 dumbbell pieces described in JIS K 6251 were immersed in the chemical cyclopentanone for 1 week, and then evaluated as follows. The number of samples was n = 3.
(I) Appearance change A sample taken out after immersion for 1 week was observed, compared with that before immersion, and evaluated according to the following criteria.
○ ・ ・ ・ No change △ ・ ・ ・ Surface gloss slightly decreased × ・ ・ ・ No surface gloss

（式中、ｍ１、ｍ２、ｍ３は浸漬前のダンベル片の重量、Ｍ１、Ｍ２、Ｍ３は浸漬後のダンベル片の重量を表す。） (Ii) Weight change The weight of the three dumbbell pieces before and after the immersion was measured. The weight change rate was calculated by the following formula (a) using the obtained weight.

(In the formula, m1, m2, and m3 represent the weight of the dumbbell piece before immersion, and M1, M2, and M3 represent the weight of the dumbbell piece after immersion.)

（式中、Ｓ_１、Ｓ_２、Ｓ_３は浸漬前の最大応力値、Ｓ’_１、Ｓ’_２、Ｓ’_３は浸漬後の最大応力値を表す。） (Iii) Tensile stress reduction rate A tensile test was performed on the dumbbell pieces before and after the immersion. The test was performed under the conditions of a distance between the tension chucks of 30 mm and a tension speed of 50 mm / min. Using the maximum stress value obtained before and after the immersion, the tensile stress reduction rate was calculated by the following formula (b).

(In the formula, S ₁ , S ₂ and S ₃ represent maximum stress values before immersion, and S ′ ₁ , S ′ ₂ and S ′ ₃ represent maximum stress values after immersion.)

(2). Evaluation of blow moldability Blow molding was performed using a preform, and the following evaluation was performed.
○ ... Blow molding is possible and the bottle thickness is uniform △ ... Blow molding is possible, but the bottle thickness is not uniform × ... Blow molding is impossible

In the examples and comparative examples of the present invention, the following materials were used.
<A component>
AI: Polyethylene naphthalate resin produced in Production Example 1 below.
[Production Example 1]
Presence of 100 parts by weight of naphthalenedicarboxylic acid dimethyl ester and 60 parts by weight of ethylene glycol in the presence of 0.010 parts by weight (10 mmol%) of cobalt acetate tetrahydrate and 0.030 parts by weight (30 mmol%) of manganese acetate tetrahydrate Then, the ester exchange reaction was carried out by a conventional method, 0.012 parts by weight (10 mmol%) of antimony trioxide was added after 20 minutes from the distillation of methanol, and 0.020 part by weight (50 mmol) of normal phosphoric acid before the end of the ester exchange reaction. %) And then a polycondensation reaction was carried out at 295 ° C. under high vacuum to obtain a polyethylene naphthalate resin having an intrinsic viscosity of 0.51 dl / g. Next, the polyethylene naphthalate resin was subjected to solid phase polymerization for 8 hours under the conditions of a temperature of 227 ° C. and a vacuum degree of 0.5 Torr, to obtain a polyethylene naphthalate resin (AI). The intrinsic viscosity of the obtained polyethylene naphthalate resin (AI) was 0.65 dl / g.

A-II: Polyethylene naphthalate resin produced in Production Example 2 below.
[Production Example 2]
The polyethylene naphthalate resin (AI) obtained in Production Example 1 was subjected to solid phase polymerization for 24 hours under the conditions of a temperature of 227 ° C. and a degree of vacuum of 0.5 Torr. The intrinsic viscosity of the obtained polyethylene naphthalate resin (A-II) was 0.79 dl / g.
A-III: TRN-8550FF manufactured by Teijin Limited [polyethylene terephthalate produced from 100 mol% terephthalic acid and 100 mol% ethylene glycol, intrinsic viscosity 0.77 dl / g]

<B component>
In the production examples, the following abbreviations represent the following compounds.
BON6: 6-hydroxy-2-naphthoic acid POB: p-hydroxybenzoic acid
HQ: hydroquinone BP: 4,4′-dihydroxybiphenyl TPA: terephthalic acid NDA: 2,6-naphthalenedicarboxylic acid

[Production Example 3]
BON6, POB, HQ and TPA were charged in a reaction vessel equipped with a stirrer with a torque meter and a distillation tube so that the composition ratio shown in Table 1 was 5 mol in total. To this, 0.05 g of potassium acetate and 1.025 moles of acetic anhydride with respect to the amount of hydroxyl groups (mole) of all monomers were charged, and deacetic acid polymerization was carried out under the following conditions. The temperature was raised from room temperature to 150 ° C. over 1 hour in a nitrogen gas atmosphere, and the temperature was maintained for 30 minutes. Next, while acetic acid produced as a by-product was distilled off, the temperature was quickly raised to 210 ° C. and kept at that temperature for 30 minutes. Then, after heating up to 335 degreeC over 3 hours, it pressure-reduced to 20 mmHg over 30 minutes. When the predetermined torque was exhibited, the polymerization reaction was terminated, the reaction vessel contents were taken out, and liquid crystal polyester pellets were obtained using a pulverizer. The obtained liquid crystal polyester (BI) had a melting point of 221 ° C. measured by DSC.

[Production Example 4]
Liquid crystal polyester pellets were obtained in the same manner as in Production Example 3 except that the monomer composition ratio was changed to the composition ratio shown in Table 2. The obtained liquid crystal polyester (B-II) had a melting point of 255 ° C. measured by DSC.

Ｂ−ＩＩＩ：上野製薬（株）製 ＵＥＮＯ ＬＣＰ Ａ−５０００ ［融点：２８０℃］

B-III: UENO LCP A-5000 manufactured by Ueno Pharmaceutical Co., Ltd. [melting point: 280 ° C.]

<C component>
CI: Each value in the cyclic carbodiimide production example produced in the following production example was determined by the following method.
(1) Identification of cyclic carbodiimide structure by NMR Identification by NMR was confirmed by ¹ H-NMR and ¹³ C-NMR using JNREX270 manufactured by JEOL Ltd. In addition, deuterated chloroform was used as a solvent.
(2) Identification of carbodiimide skeleton by IR The identification of the carbodiimide skeleton is performed by using Magna-750 manufactured by Nicorey and confirming the absorption peak at 2100-2200 cm ⁻¹ characteristic of carbodiimide by FT-IR. It was.

[Production Example 5]
o- nitrophenol (0.11 mol) and pentaerythrityl tetra bromide (0.025 mol), potassium carbonate (0.33mol), _N, N ₂ N- dimethylformamide 200ml in reactor installed with a stirrer and a heating device After charging in an atmosphere and reacting at 130 ° C. for 12 hours, DMF was removed under reduced pressure, and the resulting solid was dissolved in 200 ml of dichloromethane and separated three times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and dichloromethane was removed under reduced pressure to obtain an intermediate product D (nitro form).
Next, intermediate product D (0.1 mol), 5% palladium carbon (Pd / C) (2 g), and 400 ml of ethanol / dichloromethane (70/30) were charged into a reactor equipped with a stirrer, and 5 hydrogen substitution was performed. The reaction was performed in a state where hydrogen was constantly supplied at 25 ° C., and the reaction was terminated when there was no decrease in hydrogen. When Pd / C was recovered and the mixed solvent was removed, an intermediate product E (amine body) was obtained.

Next, triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane were charged and stirred in a reactor equipped with a stirrer, a heating device, and a dropping funnel in an N2 atmosphere. A solution prepared by dissolving the intermediate product E (0.025 mol) and triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane was gradually added dropwise thereto at 25 ° C. After completion of dropping, the reaction is carried out at 70 ° C. for 5 hours. Thereafter, the reaction solution was filtered, and the filtrate was separated 5 times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and 1,2-dichloroethane was removed under reduced pressure to obtain an intermediate product F (triphenylphosphine compound).
Next, in a reactor equipped with a stirrer and a dropping funnel, di-tert-butyl dicarbonate (0.11 mol), N, N-dimethyl-4-aminopyridine (0.055 mol), and dichloromethane 150 ml under N2 atmosphere. Were charged and stirred. Thereto, 100 ml of dichloromethane in which the intermediate product F (0.025 mol) was dissolved was slowly added dropwise at 25 ° C. After dropping, the reaction was allowed to proceed for 12 hours. Then, the B-1 component represented by a following formula was obtained by refine | purifying the solid substance obtained by removing dichloromethane. The structure of the B-1 component was confirmed by NMR and IR.

C-II: Carbodilite HMV-8CA [aliphatic polycarbodiimide] manufactured by Nisshinbo Co., Ltd.
C-III: Stabaxol-I [biscarbodiimide] manufactured by Rhein Chemie Japan
C-IV: Nagase ChemteX Corporation EX-711 [bifunctional aromatic epoxy resin]

<Examples 1 to 11 and Comparative Examples 3 to 6>
(Adjustment of composition)
The components shown in Table 3 were uniformly premixed by dry blending using the A component, the B component, and the C component, and then the premixed mixture was supplied from the first supply port, melt-extruded, and pelletized. Here, the first supply port is a base supply port. The melt extrusion was carried out using a vent type twin screw extruder (TEX30α-38.5BW-3V manufactured by Nippon Steel Works, Ltd.) having a diameter of 30 mmφ equipped with a side screw. The extrusion temperature is C1 / C2 / C3 / C4 to D = 50 ° C./120° C./280° C./300° C., the main screw rotation speed is 200 rpm, the side screw rotation speed is 50 rpm, the discharge rate is 20 kg / h, The degree of vent pressure reduction was 3 kPa.

(JIS No. 3 dumbbell piece molding)
The obtained pellets were dried at 160 ° C. for 5 hours with a hot air dryer, and then using Nissei 50T (NEX50-5E manufactured by Nissei Plastic Industries Co., Ltd.), cylinder temperature 290 ° C., mold temperature 80 ° C., cooling time 20 seconds. Was molded. Using the obtained JIS No. 3 dumbbell piece, the above-mentioned chemical resistance test was conducted. The results are shown in Table 3.

(Blow molding)
After drying the obtained pellets at 160 ° C. for 5 hours with a hot air dryer, using EC160NII-4Y manufactured by Toshiba Machine Co., Ltd., molding at a cylinder temperature of 295 ° C., a mold temperature of 20 ° C., and a cooling time of 20 seconds. And a preform with a thickness of 4.2 mm was obtained. Next, using the FDB-1D manufactured by Frontier Co., Ltd. as a blower, using a 1.5 L container-shaped blow mold (vertical 2.3 times × horizontal 3.4 times), the preform as described below. The biaxial stretch blow molding was performed. The preform preliminarily heated in a hot air dryer at 100 ° C. for 1 hour was set in a blow molding machine, the output of the IR heater was set so that the preform surface temperature was 150 ° C., and the main heating was performed. Subsequently, rod stretching speed 80%, primary blow delay time 0.28 seconds, primary blow time 0.3 seconds, primary blow pressure 1.2 MPa, secondary blow time 1.2 seconds, secondary blow pressure 3 Molding was performed under conditions of 0.4 MPa and a mold temperature of 20 ° C., and blow molding was performed. The aforementioned blow moldability was evaluated. The results are shown in Table 3.

<Comparative Examples 1-2>
JIS No. 3 dumbbell piece molding and blow molding were carried out in the same manner as in Example 1 using the A component and the B component. The results are shown in Table 3.

<Examples 1 to 11>
The resin composition within the scope of the present invention can be stretch blow molded, has a low weight change rate and a low tensile stress reduction rate, and is excellent in chemical resistance.
<Comparative Examples 1-2>
Since no C component was contained, the chemical resistance was poor. Also, blow molding was not possible.
<Comparative Example 3>
The chemical resistance was inferior due to the small amount of component B added.
<Comparative Example 4>
Blow molding was not possible due to the large amount of component B added.
<Comparative Example 5>
Since the C component outside the specified range was used, blow molding could not be performed.
<Comparative Example 6>
Extrusion was not possible due to the large amount of component C added.

Claims (10)

  100 parts by weight of a resin component comprising (A) 95 to 50% by weight of a thermoplastic polyester resin (component A) not exhibiting liquid crystallinity, and (B) 5 to 50% by weight of a thermoplastic polyester resin (component B) exhibiting liquid crystallinity On the other hand, (C) a resin composition containing 0.1 to 5 parts by weight of a carbodiimide compound (component C).   The A component is composed of a dicarboxylic acid component (A-1 component) and a diol component (A-2 component), at least 50 mol% of the dicarboxylic acid component is naphthalenedicarboxylic acid, and at least 50 mol% of the diol component. The resin composition according to claim 1, wherein is ethylene glycol.   3. The resin composition according to claim 1, wherein the component C is at least one carbodiimide compound selected from the group consisting of compounds having two or more carbodiimide groups.   The resin composition according to claim 3, wherein the component C is at least one carbodiimide compound selected from the group consisting of compounds having two carbodiimide groups. C component is a cyclic carbodiimide compound represented by following formula (1), The resin composition in any one of Claims 1-4 characterized by the above-mentioned.

(In the formula, X is a tetravalent group represented by the following formula (1-1). Ar ^{1 to} Ar ⁴ are each independently substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group. Or an orthophenylene group or a 1,2-naphthalene-diyl group.)

  The resin composition according to any one of claims 1 to 5, wherein the melting point of the component B measured by heating at 20 ° C / min with a differential scanning calorimeter is in the range of 190 to 250 ° C. . B component is comprised by the repeating unit shown by following formula (2)-(5), The resin composition in any one of Claims 1-6 characterized by the above-mentioned.

(In the formula, Ar ₁ is the following formula (6) or (7), Ar ₂ is the following formula (6) or (8), and p, q, r, and s are the molar compositions of the respective repeating units. (The ratio (mol%) is a numerical value that satisfies the formulas [1] to [5].)

Ar ₁ and Ar ₂ are the said Formula (6), The resin composition of Claim 7.   The molded object formed by blow molding or injection molding from the resin composition in any one of Claims 1-8.   A preform is molded using the resin composition according to any one of claims 1 to 8, and then the preform is stretched at least twice in the longitudinal direction and is completed from the start of stretching in the longitudinal direction. A method of obtaining a molded article by stretch blow molding, characterized by starting stretching at least twice in the transverse direction.