JP2023076854A - Blow molding composed of polyethylenenaphthalate resin composition - Google Patents

Abstract

To provide a blow molding composed of a resin composition, having excellent transparency and heat resistance, with suppressed necking phenomenon in a drawing process.SOLUTION: A blow molding comprises a blow-molded resin composition. Relative to 100 pts.wt. of (A) polyethylenenaphthalate resin (A component), the resin composition comprises (B) polyether imide resin (B component) 60-150 pts.wt.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a blow-molded article made of a polyethylene naphthalate resin composition which is excellent in transparency and heat resistance and in which the necking phenomenon during stretching is suppressed.

Polyethylene naphthalate resin has been used for various purposes due to its excellent mechanical properties, heat resistance and chemical resistance. In addition, since polyethylene naphthalate resin has a slower crystallization rate in a still place than polyethylene terephthalate resin, it has the characteristic that transparent molded articles can be easily obtained by injection molding, and is used for transparent injection molded articles. In addition, since the polyethylene naphthalate resin is highly oriented and crystallized by stretching, the mechanical strength and heat resistance are improved while maintaining transparency. However, the oriented crystallization of polyethylene naphthalate resin grows rapidly starting from the plane orientation of the naphthalene rings of the main chain, so that a local constriction called necking phenomenon tends to occur. This necking phenomenon is directly linked to unevenness in the thickness of the container in blow-molded containers, making it difficult to mold containers with no unevenness in thickness. There was a problem that there were many restrictions in terms of product design. In addition, increasing the draw ratio causes a large amount of residual strain to remain in the container.

Regarding suppression of the necking phenomenon of polyethylene naphthalate resin, Patent Document 1 exemplifies a resin composition comprising polyethylene naphthalate resin and a thermoplastic polyester resin exhibiting liquid crystallinity having a specific structure. Patent Document 2 exemplifies a resin composition comprising a polyethylene naphthalate resin, a liquid crystalline thermoplastic polyester resin having a specific structure, and a compound having a reactive functional group. However, although the wall thickness of the container was improved due to the necking phenomenon, the improvement was limited to areas where the draw ratio was large, and the improvement effect was limited. In addition, since the thermoplastic polyester resin and the polyethylene naphthalate resin exhibiting liquid crystallinity are incompatible, there is also a problem that the transparency is remarkably lowered. Patent Document 3 discloses a resin composition comprising a copolymer polyester resin containing ethylene terephthalate units and ethylene naphthalate units and a polyetherimide resin. Patent Document 4 discloses a method for preventing fluorescence from a polyalkylene naphthalate resin, which comprises adding a polyetherimide resin to the polyalkylene naphthalate resin. Further, Patent Document 5 exemplifies a photographic film base made of a blend of polyethylene naphthalate resin and polyetherimide resin, but none of them have been verified for suppressing the necking phenomenon.

JP 2017-222794 A JP 2018-188547 A JP-A-7-228761 JP-A-10-101916 JP-A-9-179242

An object of the present invention is to provide a blow-molded article made of a resin composition which is excellent in transparency and heat resistance and in which the necking phenomenon during stretching is suppressed.

The present inventors have made intensive studies to achieve the above object, and found that by adding a specific amount of polyetherimide resin to polyethylene naphthalate resin, excellent transparency and heat resistance can be obtained, and necking during the stretching process can be prevented. The present inventors have found that a blow-molded article made of a resin composition in which the phenomenon is suppressed can be obtained, and have solved the above problems.

That is, the object of the present invention is a resin characterized by containing 60 to 150 parts by weight of (B) a polyetherimide resin (component B) with respect to 100 parts by weight of (A) a polyethylene naphthalate resin (component A). This is achieved by a blow-molded article obtained by blow-molding the composition.

According to the present invention, it is possible to provide a blow-molded article made of a resin composition that is excellent in transparency and heat resistance and that suppresses the necking phenomenon during the stretching process. , pharmaceutical bottles and vials.

Further details of the present invention will be described below.

<About A component>
The polyethylene naphthalate resin, which is component A of the present invention, is produced using a dicarboxylic acid component mainly composed of naphthalenedicarboxylic acid and/or an ester-forming derivative of naphthalenedicarboxylic acid, and a glycol component mainly composed of ethylene glycol. can be done.

As the naphthalenedicarboxylic acid component, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid are used as main components, but other dicarboxylic acids may be used in combination as long as the properties are not impaired. Other dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenyl ether-4, Aromatic dicarboxylic acids such as 4'-dicarboxylic acid, adipic acid, sebacic acid, succinic acid, aliphatic dicarboxylic acids such as oxalic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and the like, one or Two or more kinds may be used, and can be arbitrarily selected depending on the purpose. The amount of the other dicarboxylic acid used is preferably 30 mol % or less, more preferably 20 mol % or less, based on the total acid components. As the ester-forming derivative of naphthalenedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylate and dimethyl 2,7-naphthalenedicarboxylate are used as main components, but esters of other dicarboxylic acids are used as long as the properties are not impaired. Formable derivatives can be used in combination. Other ester-forming derivatives of dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid. acids, lower dialkyl esters of aromatic dicarboxylic acids such as diphenyl ether-4,4′-dicarboxylic acid, lower dialkyl esters of alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, adipic acid, sebacic acid, succinic acid, oxalic acid, etc. Lower dialkyl esters of aliphatic dicarboxylic acids and the like can be mentioned, and one or more of these may be used and can be arbitrarily selected depending on the purpose. The amount of other ester-forming derivative of dicarboxylic acid to be used is preferably 30 mol % or less, more preferably 20 mol % or less, relative to the total dicarboxylic acid ester-forming derivative component.

Also, a small amount of a tri- or higher functional carboxylic acid component such as trimellitic acid may be used, and a small amount of an acid anhydride such as trimellitic anhydride may be used. In addition, a small amount of hydroxycarboxylic acid such as lactic acid and glycolic acid or an alkyl ester thereof may be used, and can be arbitrarily selected depending on the purpose.

As the glycol component, ethylene glycol is used as the main component, but other glycol components can be used together as long as the properties are not impaired. Other glycol components include, for example, 1,4-butanediol, 1,3-propylene glycol, 1,2-propylene glycol, neopentylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexanedimethanol, diethylene glycol, and triethylene. One or two or more of alkylene glycols such as glycol, poly(oxy)ethylene glycol, poly(oxy)tetramethylene glycol, poly(oxy)methylene glycol, etc. may be used, and can be arbitrarily selected depending on the purpose. In addition, small amounts of polyhydric alcohol components such as glycerin may be used. A small amount of epoxy compound may also be used. The amount of other glycol components used is preferably 30 mol % or less, more preferably 20 mol % or less, based on the total glycol components.

Said polyethylene naphthalate resin can be manufactured by a conventionally well-known manufacturing method. That is, a direct esterification method in which a dicarboxylic acid component and a diol component are directly reacted to distill off water and esterify, followed by polycondensation under reduced pressure, or a dicarboxylic acid dimethyl ester and a diol component are reacted to form methyl alcohol. is distilled off, transesterified, and then polycondensed under reduced pressure. Solid state polymerization can be carried out to further increase the intrinsic viscosity.

It is preferable to use a catalyst and a stabilizer during the above transesterification, esterification and polycondensation reactions. Mg compounds, Mn compounds, Ca compounds, Zn compounds and the like are used as transesterification catalysts, and examples thereof include acetates, monocarboxylates, alcoholates and oxides thereof. The esterification reaction can be carried out using only a dicarboxylic acid and a diol without adding a catalyst, but it can also be carried out in the presence of a polycondensation catalyst, which will be described later. As polycondensation catalysts, Ge compounds, Ti compounds, Sb compounds, etc. can be used, and examples thereof include germanium dioxide, germanium hydroxide, germanium alcoholates, titanium tetrabutoxide, titanium tetraisopropoxide, and titanium oxalate. . Phosphorus compounds are preferably used as stabilizers. Preferred phosphorus compounds include phosphoric acid and its esters, phosphorous acid and its esters, and hypophosphorous acid and its esters. Further, during 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 in order to suppress diethylene glycol by-production. Various stabilizers and modifiers can be added to the obtained polyester resin.

The intrinsic viscosity of component A is preferably 0.5 to 1.0 dl/g, more preferably 0.55 to 0.85 dl/g, still more preferably 0.60 to 0.68 dl/g. . If the intrinsic viscosity of component A is less than 0.5 dl/g, the effect of suppressing necking may be poor. Sometimes.

<About B component>
The polyetherimide resin, which is the component B of the present invention, is a resin containing a cyclic imide structure, and is not particularly limited as long as it can be used for the purpose of the present invention. Polyetherimide resins containing imide groups as repeating units are preferred. Further, structural units other than cyclic imide and ether units, such as aromatic and aliphatic ester units, oxycarbonyl units, etc., may be contained in the main chain of the polyimide as long as the effects of the present invention are not impaired.

Specific examples of polyetherimide resins that can be preferably used in the present invention include polyetherimide resins represented by the following formula (1).

(In formula (1), n is an integer of 2 or more, R ₁ is a divalent aromatic or aliphatic group containing 6 to 30 carbon atoms, R ₂ is 6 to 30 carbon atoms, , alkylene groups with 2 to 20 carbon atoms, cycloalkylene groups with 2 to 20 carbon atoms, and alkylene groups with 2 to 8 carbon atoms. is a divalent organic group selected from the group consisting of polydiorganosiloxane groups selected from
Examples of R ₁ and R ₂ include aromatic residues and alkylene groups represented by the following formulas (2) to (8).

(In formula (8), n is an integer of 2 or more.)
In the present invention, a polyetherimide resin represented by the following formula (9) is preferable from the viewpoint of compatibility with polyethylene naphthalate resin.

(In formula (9), n is an integer of 2 or more.)
Examples of this polyetherimide resin include "ULTEM1010" manufactured by SABIC Japan LLC.

The content of component B is 60 to 150 parts by weight, preferably 65 to 120 parts by weight, more preferably 70 to 100 parts by weight, per 100 parts by weight of component A. If the content of component B is less than 60 parts by weight, the heat resistance and necking are not improved, and the heat resistance of the blow-molded article is not improved. On the other hand, when the content exceeds 150 parts by weight, the transparency is lowered.

(About other additives)
The resin composition of the present invention can contain various additives such as antioxidants and release agents within the scope of the present invention.

<Antioxidant>
The resin composition of the present invention may contain, as an antioxidant, at least one antioxidant selected from the group consisting of hindered phenol compounds, phosphite compounds, phosphonite compounds and thioether compounds. The addition of an antioxidant not only stabilizes the hue and fluidity during molding, but also has the effect of improving hydrolysis resistance.

Examples of hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylfer)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'-methylenebis(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-methyl phenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl 6-(3- 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-butylphenyl)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 etc. are illustrated. 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 utilized. Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is particularly preferred. All of these are readily available. The above hindered phenol compounds can be used alone or in combination of two or more.

Phosphite compounds include triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl mono Phenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 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, distearylpentaerythritol 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 pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like. Furthermore, as other phosphite-based compounds, those having a cyclic structure that react with dihydric phenols can also 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 and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite. Suitable phosphite compounds include distearylpentaerythritol 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] dioxaphosphepine [commercially available as "Sumilizer 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]dioxaphosphosine, 2,4,8,10-tetra-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]dibenzo [d,f][1,3,2]dioxaphosphepin, 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]dioxaphosphosine, 2,10-dimethyl-4,8-di-t-butyl-6-[3 -(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, 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]di Oxaphosphosine, 2,4,8,10-tetra-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-dibenzo[d,f][ 1,3,2]dioxaphosphepine, 2,10-dimethyl-4,8-di-t-butyl-6-(3,5-di-t-butyl-4-hydroxybenzoyloxy)-12H- Dibenzo[d,g][1,3,2]dioxaphosphosine, 2,4,8,10-tetra-t-butyl-6-(3,5-di-t-butyl-4-hydroxybenzoyloxy )-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, 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]dioxaphosphosine, 2,4,8,10-tetra-t-butyl- 6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, 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]di Oxaphosphosine, 2,4,8,10-tetra-t-butyl-6-[2,2-dimethyl-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-dibenzo[ d,f][1,3,2]dioxaphosphepin and the like can be mentioned. All of these are readily available. The above phosphite compounds can be used alone or in combination of two or more.

Phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenyl diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite night, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6- Di-n-butylphenyl)-3-phenyl-phenylphosphonite, Bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, Bis(2,6-di-tert-butylphenyl) )-3-phenyl-phenylphosphonite and the like. Tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite Night, bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite is more preferred. Such a phosphonite-based compound can be used in combination with a phosphite-based compound having an aryl group substituted with two or more alkyl groups, and is therefore preferable. Tetrakis (2,4-di-tert-butylphenyl)-biphenylene diphosphonite is preferable as the phosphonite compound, and the stabilizer containing the phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos. It is commercially available as P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and any of them can be used. The above phosphonite compounds can be used alone or in combination of two or more.

Specific examples of thioether compounds include dilaurylthiodipropionate, ditridecylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, pentaerythritol-tetrakis(3-laurylthiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio propionate) and the like. The above thioether compounds can be used alone or in combination of two or more.

The content of the antioxidant is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, and still more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of component A. be. 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 during molding become unstable, but also the hydrolysis resistance may deteriorate. . On the other hand, if the content is more than 2 parts by weight, the reactive components derived from the antioxidant may rather deteriorate the hydrolysis resistance.

Further, it is preferable to use a combination of two or more of the hindered phenol-based compound, the phosphite-based compound, the phosphonite-based compound, and the thioether-based compound. By using a combination of two or more types of hindered phenol-based compounds and phosphite-based compounds, phosphonite-based compounds, and thioether-based compounds, a synergistic effect as a stabilizer is exhibited, resulting in better color and fluidity during molding. It is effective in stabilizing properties and improving 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, oxyfatty acids, paraffins, low-molecular-weight polyolefins, fatty acid amides, alkylenebis fatty acid amides, aliphatic ketones, fatty acid partially saponified esters, fatty acid lower alcohol esters, and fatty acid polyvalents. Examples include alcohol esters, fatty acid polyglycol esters and modified silicones. By blending these, a molded article having excellent mechanical properties, moldability and heat resistance can be obtained.

Fatty acids preferably have 6 to 40 carbon atoms, and specific examples include oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, and montan. Acids and mixtures thereof and the like. 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, calcium montanate and the like.

Oxy fatty acids include 1,2-oxysteric acid and the like. As the paraffin, those having 18 or more carbon atoms are preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, and petrolactam.

Low-molecular-weight polyolefins preferably have a molecular weight of 5,000 or less, and specific examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidized-type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax.

As the fatty acid amide, those having 6 or more carbon atoms are preferable, and specific examples include oleic acid amide, erucic acid amide, and behenic acid amide.

The alkylenebis fatty acid amide preferably has 6 or more carbon atoms, and specific examples include methylenebisstearic acid amide, ethylenebisstearic 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.

Partially saponified fatty acid esters include partially saponified montanic acid esters. Examples of fatty acid lower alcohol esters include stearates, oleates, linoleates, linolenates, adipates, behenates, arachidonates, montanates and isostearates.

Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimilystate, and pentaerythritol. Toll 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, polypropylene glycol fatty acid esters, and the like.

Modified silicones include polyether-modified silicones, higher fatty acid alkoxy-modified silicones, higher fatty acid-containing silicones, higher fatty acid ester-modified silicones, methacryl-modified silicones, and fluorine-modified silicones.

Of these, fatty acids, fatty acid metal salts, oxyfatty acids, fatty acid esters, partially saponified fatty acid esters, paraffins, low molecular weight polyolefins, fatty acid amides, and alkylenebis fatty acid amides are preferred, and partially saponified fatty acid esters and alkylenebis fatty acid amides are more preferred. Among them, montanic acid ester, partially saponified montanic acid ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylenebisstearic acid amide are preferred, and partially saponified montanic acid ester and ethylenebisstearic acid amide are particularly preferred. .

The release agent may be used alone or in combination of two or more. The content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of component A.

<Method for producing resin composition>
Any method may be employed to produce the resin composition of the present invention. For example, a method of premixing each component and optionally other components, followed by melt-kneading and pelletizing can be mentioned. Means for premixing include a Nauta mixer, a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, and the like. In the pre-mixing, granulation can be performed by an extrusion granulator, a briquetting machine, or the like. After pre-mixing, the mixture is melt-kneaded by a melt-kneader typified by a vented twin-screw extruder, and pelletized by a device such as a pelletizer. Other examples of the melt-kneader include a Banbury mixer, a kneading roll, a constant temperature stirring vessel and the like, but a vented twin-screw extruder is preferred. Alternatively, each component and, optionally, other components may be supplied independently to a melt-kneader typified by a twin-screw extruder without being premixed.

<Preform molding>
The resin composition of the present invention is usually obtained as pellets, which are used as raw materials to form preforms. As the molding method, various molding methods such as injection molding, press molding, and extrusion molding can be selected, but injection molding and press molding are preferable from the viewpoint of rapid cooling without crystallizing the preform. In injection molding, not only the usual cold runner molding method but also the hot runner molding method is possible. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, foam molding (including injection of supercritical fluid), insert molding, in-mold coating molding, Molded articles can be obtained using injection molding techniques such as rapid heat and cool mold molding. For example, in the case of injection molding of a preform for blow molding, each pellet is pre-dried in a hot air dryer at 130-150°C for 7 hours or more, melted at a cylinder temperature of 280-310°C, and injection-molded. preferable. If the pre-drying temperature is less than 130°C, drying will be insufficient, and moisture remaining in the pellets will cause the resin to decompose, and the intrinsic viscosity may not be stable. and weighing during injection molding may become unstable. The mold temperature during molding is preferably 40 to 140°C, more preferably 60 to 120°C. If the mold temperature is less than 40°C, appearance such as flow marks may occur on the surface of the molded product. Molding may not be possible.

<Blow molding>
Any method is adopted as the method for producing the blow-molded article of the present invention. Examples include direct blow molding, extrusion direct blow molding, one-stage biaxial stretch blow molding, and two-stage biaxial stretch blow molding. When biaxial stretch blowing is performed in two stages, it is preferable to preheat (preheat) before blow molding. The preheating temperature is preferably 70 to 140°C, more preferably 90 to 130°C, and particularly preferably 100 to 110°C. If the preheating temperature is less than 70°C, the main heating time in the post-process takes time, and if the preheating temperature exceeds 140°C, the resin composition is softened and the preform is deformed, resulting in a uniform blow-molded container. There is a risk that it will not be possible. Any preheating method can be used, such as storing the preform in a hot air dryer or heating with an infrared heater. The heating (main heating) at the time of blow molding may be performed by both heating from the inside of the preform (internal heating) and heating from the outside of the preform (external heating). As for the heating method, the infrared heating method is preferable because of its high heating efficiency. Here, it is necessary to warm the resin temperature to about 150 to 200°C. By performing blow molding within such a resin temperature range, it is possible to obtain a good blow molded article with less thickness unevenness and no breakage.

<Blow molding>
The blow-molded article of the present invention has a container shape consisting of a mouth serving as an opening, a body and a bottom, and has a draw ratio (A) of 1.1 at an intermediate point of the body calculated by the following formula (1). ∼4 is preferable, and 1.1 to 3 is more preferable. If the draw ratio exceeds 4, the container may be deformed when filled with high-temperature contents or by heat treatment such as heat sterilization. On the other hand, if the draw ratio is less than 1.1, the adhesion to the mold may be insufficient, resulting in poor shaping.

A=T0/T1 (1)
(In formula (1), T0 represents the thickness (mm) at the center of the preform body, and T1 represents the thickness (mm) at the center of the container body after blow molding.)

[EXAMPLES] Hereafter, although the form which implements this invention is demonstrated by an Example, this invention is not limited to these. Moreover, evaluation of various physical properties was carried out by the following methods.

[Evaluation of Resin Composition]
(1) Transparency After drying the pellets obtained by the following method at 140 ° C. for 7 hours, an injection molding machine (EC130SXII-4Y manufactured by Toshiba Machine Co., Ltd.) was used with a cylinder temperature of 310 ° C. and a mold temperature of 90 ° C. A test piece having a length of 25 mm, a width of 50 mm, and a thickness of 1 mm was molded with a UV-visible spectrophotometer V-560 manufactured by JASCO Corporation, and the light transmittance at a wavelength of 450 nm was measured. The light transmittance should be 60% or more.

(2) Heat resistance After drying the pellets obtained by the following method at 140 ° C. for 7 hours, an injection molding machine (EC130SXII-4Y manufactured by Toshiba Machine Co., Ltd.) was used at a cylinder temperature of 310 ° C. and a mold temperature of 90 ° C. A test piece was prepared and the deflection temperature under load was measured according to ISO75-1 and 75-2. The deflection temperature under load must be 120° C. or higher under a load condition of 1.8 MPa.

(3) Glass transition temperature Using a pellet obtained by the following method, a differential scanning calorimeter (manufactured by TA Instruments Japan Co., Ltd.: DSC-2910) was used at a temperature increase rate of 20 ° C. / min. The glass transition temperature (Tg) was measured.

(4) Degree of necking After drying the pellets obtained by the following method at 140 ° C. for 7 hours, an injection molding machine (EC130SXII-4Y manufactured by Toshiba Machine Co., Ltd.) was used at a cylinder temperature of 310 ° C. and a mold temperature of 90 ° C. Dumbbell pieces were made according to ISO 527-1 and 527-2. The tensile test conditions were set at a tensile speed of 1000 mm/min to simulate blow molding, and the tensile temperature was set at a temperature 25° C. higher than the glass transition temperature of the resin composition, and the tensile test was performed until the nominal tensile strain reached 100%. The degree of necking was calculated from the cross-sectional area of the necking portion and the theoretical cross-sectional area by the following formula. The theoretical cross-sectional area referred to here is the cross-sectional area when the volume is assumed to be constant without considering the volume shrinkage. A smaller degree of necking means that the necking phenomenon is suppressed, and it is necessary to be 20% or less.
Degree of necking (%) = [(theoretical cross-sectional area - cross-sectional area of necking portion) / theoretical cross-sectional area] x 100

(5) Heat resistance of blow molded container After drying the pellets obtained by the following method at 140 ° C. for 7 hours with a hot air dryer, use EC 160NII-4Y manufactured by Toshiba Machine Co., Ltd., cylinder temperature 310 ° C. Molding was carried out at a mold temperature of 90° C. to obtain a preform having a thickness of 2.5 mm. Next, using FDB-1D manufactured by Frontier Co., Ltd. as a blow machine, a 300 ml container-shaped blow mold (length 1.0 times, width 2.2 times) was used to blow the preform in the following manner. Axial stretch blow molding was performed. First, a preform preheated in a hot air dryer at 100°C for 1 hour is set in a blow molding machine, and the output of the IR heater is set so that the surface temperature of the preform is 25°C higher than the glass transition temperature. Main heating was performed. Subsequently, the rod stretching speed was 60%, the primary blow delay time was 1 second, the primary blow time was 0.3 seconds, the primary blow pressure was 3.4 MPa, the secondary blow time was 5 seconds, and the secondary blow pressure was 3.4 MPa. Blow molding was performed under conditions of 4 MPa and a mold temperature of 70°C. The thickness of the central portion of the body of the blow-molded container was measured, and the draw ratio (A) was calculated from the following formula (1).

A=T0/T1 (1)
(In formula (1), T0 represents the thickness (mm) at the center of the preform body, and T1 represents the thickness (mm) at the center of the container body after blow molding.)

The resulting blow-molded container was immersed in boiling water for 10 hours, and the rate of change in content before and after immersion was calculated by the following formula. The rate of change in content is preferably 3% or less.
Content volume change rate (%) = [(volume before boiling water treatment - volume after boiling water treatment) / volume before boiling water treatment] x 100

[Example 1-6, Comparative Example 1-3]
According to the contents shown in Table 1, the A component and the B component were supplied separately from the first supply port to a twin-screw extruder and melt-kneaded and extruded at a temperature of 310° C. to form pellets. Here, the first supply port is the root supply port. The twin-screw extruder used was a vented twin-screw extruder with a diameter of 30 mmΦ (manufactured by Japan Steel Works, Ltd.: TEX30α-31.5BW-2V).

The following materials were used in the examples and comparative examples of the present invention.
(A component)
AI: Polyethylene naphthalate resin obtained in Production Example I <Production Example I>
100 parts by weight of naphthalene dicarboxylic acid dimethyl ester and 51 parts by weight of ethylene glycol were mixed with 0.003 parts by weight (0.012 mmol) of cobalt acetate tetrahydrate, 0.014 parts by weight (0.08 mmol) of calcium acetate monohydrate and acetic acid. Using 0.044 parts by weight (0.0205 mmol) of manganese tetrahydrate as a transesterification catalyst, transesterification was carried out by a conventional method, and 1.5 parts by weight (0.14 mmol) of ethylene glycol 1% solution of amorphous germanium dioxide was obtained. ), 0.0057 parts by weight (0.41 mmol) of trimethyl phosphate was added to terminate the transesterification reaction. Solid phase polymerization was then carried out for 8 hours at a temperature of 227° C. and a degree of vacuum of 0.5 Torr to obtain a polyethylene naphthalate resin having an intrinsic viscosity of 0.60 dl/g.

(B component)
BI: ULTEM1010 (trade name) manufactured by SABIC Japan LLC

<Examples 1 to 6>
Since the composition is within the scope of the claims, it is possible to obtain a blow-molded article having excellent transparency and heat resistance, improved necking, and excellent heat resistance.

<Comparative Examples 1 and 2>
Since the content of component B was low, heat resistance and necking were not improved, and no improvement in heat resistance of the blow-molded product was observed.

<Comparative Example 3>
Since the content of component B exceeded the upper limit, the result was poor transparency.

Claims (4)

(A) polyethylene naphthalate resin (component A) 100 parts by weight, (B) polyetherimide resin (component B) containing 60 to 150 parts by weight of the resin composition is blow-molded. Blow molding. It has a container shape consisting of a mouth portion that serves as an opening, a body portion, and a bottom portion, and is characterized in that the stretch ratio (A) at the midpoint of the body portion calculated by the following formula (1) is 1.1 to 4. The blow molded article according to claim 1.
A=T0/T1 (1)
(In formula (1), T0 represents the thickness (mm) at the center of the preform body, and T1 represents the thickness (mm) at the center of the container body after blow molding.) 3. The blow-molded article according to claim 1, which is a pharmaceutical storage container. 3. The blow molded article according to claim 1, which is a vial bottle.