JP2021152133A - Molding composed of polyethylenenaphthalate resin composition - Google Patents

Abstract

To provide a molding composed of a resin composition that has excellent flowability and heat resistance and, when a limiting gate is used, prevents a whitening phenomenon occurring at a gate part of an injection molded article, and a method for reducing the whitening phenomenon.SOLUTION: A molding composed of a resin composition has 10-90 pts.wt. (B) polyether imide resin (B component) relative to 100 pts.wt. (A) polyethylenenaphthalate resin (A component).SELECTED DRAWING: None

Description

The present invention relates to a molded product made of a polyethylene naphthalate resin composition in which the whitening phenomenon at the gate portion that occurs when a restricted gate is used is suppressed, and a method for suppressing the whitening phenomenon.

Conventionally, polyethylene naphthalate resin has excellent mechanical properties, heat resistance, and chemical resistance, and has been used for various purposes. Further, since polyethylene naphthalate resin has a slower crystallization rate in a standing place than polyethylene terephthalate resin, it has a feature that a transparent molded product can be easily obtained by injection molding, and is also used for transparent injection molded products. However, unlike polyethylene terephthalate resin, polyethylene naphthalate resin has a problem that it is oriented, crystallized and whitened by shearing in a rapidly shrinking flow path such as a gate portion of an injection molded product. Therefore, it has not been widely used for thin-walled and small transparent injection molded products. Further, even for a large molded product, an unrestricted gate typified by a sprue direct gate must be used in order to suppress the whitening phenomenon at the gate portion, which makes it difficult to seal the gate and lengthens the molding cycle. , There was a problem in mass productivity because a post-process for removing the gate part was required.

Regarding the suppression of the whitening phenomenon at the gate portion of the polyethylene naphthalate resin, Patent Document 1 exemplifies a resin composition composed of a polyethylene naphthalate resin and an amorphous copolymer polyester resin having a glass transition temperature of 80 ° C. or higher. .. However, although the effect of suppressing the whitening phenomenon at the gate portion was observed by mixing the amorphous copolymer polyester resin at 80 ° C. or higher, the obtained resin composition had lower heat resistance than the polyethylene naphthalate resin. The original characteristics of the polyethylene naphthalate resin were impaired. Patent Document 2 exemplifies a resin composition containing a copolymerized polyester resin and a polyetherimide resin composed of an ethylene terephthalate unit and an ethylene naphthalate unit. However, the study was conducted in a region where the ethylene naphthalate unit was as small as 5 to 30 in terms of molar ratio, there was no description of a homopolyethylene naphthalate resin, and no study was made on suppressing the whitening phenomenon at the gate portion. Patent Document 3 exemplifies a method for preventing fluorescence of a polyalkylene naphthalate resin, which comprises adding a polyetherimide resin to the polyalkylene naphthalate resin. Further, Patent Document 4 exemplifies a photographic film base made of a blend of a polyethylene naphthalate resin and a polyetherimide resin. It wasn't done.

JP-A-2018-104654 Japanese Unexamined Patent Publication No. 7-228761 Japanese Unexamined Patent Publication No. 10-101916 Japanese Unexamined Patent Publication No. 9-179242

An object of the present invention is to reduce a molded product made of a resin composition having excellent fluidity and heat resistance and reducing the whitening phenomenon that occurs in the gate portion of an injection molded product when a limiting gate is used, and reducing the whitening phenomenon. It is to provide a way to make it.

As a result of diligent studies to achieve the above object, the present inventors improved fluidity and heat resistance by adding a specific amount of polyetherimide resin to polyethylene naphthalate resin, and used a limiting gate. It has been found that the whitening phenomenon that occurs in the gate portion of the injection-molded product is reduced in this case, and the above-mentioned problems have been solved.

That is, the subject of the present invention is molding of a resin composition containing 10 to 90 parts by weight of (B) polyetherimide resin (B component) with respect to 100 parts by weight of (A) polyethylene naphthalate resin (A component). Achieved by the body.

According to the present invention, it is possible to provide a molded product made of a resin composition having excellent fluidity and heat resistance and reducing the whitening phenomenon that occurs in the gate portion of an injection molded product when a limiting gate is used. The injection-molded article obtained by the present invention can be suitably used for a thin-walled molded member on the exterior of an electric / electronic device, a small molded article such as a temple portion of eyeglasses or a button of a game machine.

Hereinafter, the details of the present invention will be further described.

<About component A>
The polyethylene naphthalate resin which is the component A of the present invention is produced by using a dicarboxylic acid component mainly composed of a naphthalene dicarboxylic acid and / or an ester-forming derivative of naphthalene dicarboxylic acid and a glycol component containing ethylene glycol as a main component. Can be done.

As the naphthalene dicarboxylic acid component, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid are the main components, but other dicarboxylic acids can be used in combination as long as the characteristics are not impaired. Other carboxylic acids include, for example, terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyetane-4,4'-dicarboxylic acid, diphenylsulfon-4,4'-dicarboxylic acid, diphenylether-4, Examples thereof include aromatic dicarboxylic acids such as 4'-dicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid and oxalic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Two or more kinds may be used, and can be arbitrarily selected depending on the purpose. The amount of the other carboxylic acid used is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total acid component. The ester-forming derivative of naphthalenedicarboxylic acid contains dimethyl 2,6-naphthalenedicarboxylic acid and dimethyl 2,7-naphthalenedicarboxylic acid as main components, but esters of other dicarboxylic acids as long as the characteristics are not impaired. A forming derivative can be used in combination. Examples of other dicarboxylic acid ester-forming derivatives include terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyetane-4,4'-dicarboxylic acid, and diphenylsulfon-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 and the like Examples thereof include lower dialkyl esters of aliphatic dicarboxylic acids, and one or more of these may be used, which can be arbitrarily selected depending on the purpose. The amount of the ester-forming derivative of the other dicarboxylic acid used is preferably 30 mol% or less, more preferably 20 mol% or less, based on the ester-forming derivative component of the total dicarboxylic acid.

Further, a small amount of a trifunctional or higher carboxylic acid component such as trimellitic acid may be used, or a small amount of an acid anhydride such as trimellitic anhydride may be used. Further, a small amount of hydroxycarboxylic acid such as lactic acid or glycolic acid or an alkyl ester thereof may be used, and it can be arbitrarily selected depending on the purpose.

Ethylene glycol is the main component of the glycol component, but other glycol components can be used in combination as long as the characteristics are not impaired. Examples of other glycol components include 1,4-butanediol, 1,3-propylene glycol, 1,2-propylene glycol, neopentylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexanedimethanol, diethylene glycol, and tri. One or more of alkylene glycols such as ethylene glycol, poly (oxy) ethylene glycol, poly (oxy) tetramethylene glycol, and poly (oxy) methylene glycol may be used, and can be arbitrarily selected depending on the intended purpose. Further, a small amount of a polyhydric alcohol component such as glycerin may be used. Moreover, you may use a small amount of epoxy compounds. The amount of the other glycol component used is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total glycol component.

The above-mentioned polyethylene naphthalate resin can be produced by a conventionally known production method. That is, a direct esterification method in which the dicarboxylic acid component and the diol component are directly reacted to distill off water to esterify and then polycondensation is performed under reduced pressure, or the dicarboxylic acid dimethyl ester and the diol component are reacted to methyl alcohol. Is distilled off and ester-exchanged, and then polycondensation is carried out under reduced pressure to produce an ester exchange method. Further, solid phase polymerization can be carried out in order to increase the number of ultimate viscosities.

It is preferable to use a catalyst and a stabilizer during the transesterification reaction, esterification reaction and polycondensation reaction described above. As the ester exchange catalyst, Mg compounds, Mn compounds, Ca compounds, Zn compounds and the like are used, and examples thereof include acetates, monocarboxylates, alcoholates and oxides thereof. The esterification reaction can be carried out only with a dicarboxylic acid and a 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, and examples thereof include germanium dioxide, germanium hydroxide, germanium alcoholate, titanium tetrabutoxide, titanium tetraisopropoxyside, and titanium oxalate. .. It is preferable to use a phosphorus compound as a stabilizer. Preferred phosphorus compounds include phosphoric acid and its esters, phosphorous acid and its esters, hypophosphoric acid and its esters, and the like. 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 the by-product of diethylene glycol. Further, 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 0.6 to 0.95 dl / g, and even more preferably 0.65 to 0.85 dl / g. .. If the intrinsic viscosity of component A is less than 0.5 dl / g, the toughness may be inferior, and if it exceeds 1.0 dl / g, the effect of suppressing whitening of the gate portion when a limiting gate is used may be insufficient.

<About B component>
The polyetherimide resin which is the B component 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, but is cyclic to an aliphatic or aromatic ether unit. A polyetherimide resin containing an imide group as a repeating unit is preferable. Further, as long as the effect of the present invention is not impaired, the main chain of the polyimide may contain structural units other than cyclic imide and ether units, for example, aromatic, aliphatic ester units, oxycarbonyl units and the like.

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

（式中、ｎは２以上の整数を表す。）

(In the formula, n represents an integer of 2 or more.)

In formula (1), R ₁ is a divalent aromatic or aliphatic group containing 6 to 30 carbon atoms, and R ₂ is a divalent aromatic residue having 6 to 30 carbon atoms, 2 Selected from the group consisting of an alkylene group having up to 20 carbon atoms, a cycloalkylene group having 2 to 20 carbon atoms, and a polydiorganosiloxane group chain-terminated with an alkylene group having 2 to 8 carbon atoms. It is a divalent organic group.

Examples of R ₁ and R ₂ include aromatic residues and alkylene groups represented by the following formulas (2) to (8).

（式（８）中、ｎは２以上の整数を表す。）

(In equation (8), n represents an integer of 2 or more.)

In the present invention, the polyetherimide resin represented by the following formula (9) is preferable from the viewpoint of compatibility with the polyethylene naphthalate resin.

（式（９）中、ｎは２以上の整数を表す。）

(In equation (9), n represents an integer of 2 or more.)

Examples of this polyetherimide resin include "ULTEM1010" manufactured by SABIC Japan LLC.

The content of the B component is 10 to 90 parts by weight, preferably 15 to 70 parts by weight, and more preferably 25 to 45 parts by weight with respect to 100 parts by weight of the A component. When the content of the B component is less than 10 parts by weight, the effect of suppressing whitening and the heat resistance at the gate portion when the limiting gate is used are insufficient, and when it exceeds 90 parts by weight, the fluidity decreases.

<About C component>
The fibrous filler as the C component of the present invention is preferably at least one fibrous filler selected from the group consisting of glass fibers and carbon fibers. As the glass fiber, a glass fiber having a round cross section, a flat fiber having an average major axis of 5 to 50 μm and an average major axis to minor axis ratio (major axis / minor axis) of 1.5 to 8 Cross-section glass fibers and glass milled fibers are preferably exemplified, but in particular, the average value of the major axis of the fiber long section is 10 to 40 μm, and the average value of the ratio of the major axis to the minor axis (major axis / minor axis) is 1.5 to 8. The flat cross-section glass fiber is more preferable in terms of tensile strength and dimensional accuracy.

The glass composition of the above glass fibers is not particularly limited as various glass compositions typified by A glass, C glass, E glass and the like are applied. Such glass fibers may contain components such as _{TiO 2} , SO ₃ , and P ₂ O _{5, if necessary.} Among these, E glass (non-alkali glass) is more preferable. Such glass fibers are preferably surface-treated with a well-known surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent from the viewpoint of improving mechanical strength. Further, those which have been focused with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin or the like are preferable, and the epoxy resin and the urethane resin are particularly preferable from the viewpoint of mechanical strength. preferable. The amount of the focusing agent adhered to the focused glass fiber is preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, based on 100% by weight of the glass fiber.

Examples of carbon fibers include carbon fibers such as metal-coated carbon fibers, carbon milled fibers, and vapor-grown carbon fibers, and carbon nanotubes. The fiber diameter of the carbon nanotubes is preferably 0.003 to 0.1 μm, and may be single-walled, two-walled, or multi-walled, but multi-walled (so-called MWCNT) is preferable.

Among these, carbon fiber is preferable in terms of excellent mechanical strength. As the carbon fiber, any of cellulosic type, polyacrylonitrile type, pitch type and the like can be used. Further, it is obtained by spinning or molding a raw material composition consisting of a polymer and a solvent by a methylene-type bond of aromatic sulfonic acids or salts thereof, and then spinning without undergoing an infusibilization step represented by a method such as carbonization. Can also be used. Further, any of a general-purpose type, a medium elastic modulus type and a high elastic modulus type can be used. Among these, a polyacrylonitrile-based high elastic modulus type is particularly preferable.

Further, the surface of the carbon fiber is preferably oxidized for the purpose of improving the adhesion with the matrix resin and improving the mechanical strength. The oxidation treatment method is not particularly limited, and for example, (1) a method of treating carbon fibers with an acid or an alkali or a salt thereof, or an oxidizing gas, and (2) carbon fibers that can be converted into carbon fibers or carbon fibers are oxygen-containing. Preferable examples thereof include a method of firing at a temperature of 700 ° C. or higher in the presence of an inert gas containing a compound, and (3) a method of oxidizing carbon fibers and then heat-treating in the presence of an inert gas.

Metal-coated carbon fiber is a carbon fiber coated with a metal layer on the surface. Examples of the metal include silver, copper, nickel, and aluminum, and nickel is preferable from the viewpoint of corrosion resistance of the metal layer. Examples of the metal coating method include known methods such as a plating method and a vapor deposition method, and among them, the plating method is preferably used. Further, also in the case of such a metal-coated carbon fiber, the carbon fiber mentioned above can be used as the original carbon fiber. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm. More preferably, it is 0.2 to 0.35 μm.

The carbon fiber and the metal-coated carbon fiber are preferably those which have been focused with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like. In particular, urethane-based resin and carbon fiber treated with epoxy-based resin are suitable in the present invention because of their excellent mechanical strength.

The content of the C component is preferably 10 to 170 parts by weight, more preferably 20 to 140 parts by weight, and further preferably 40 to 130 parts by weight with respect to 100 parts by weight of the component composed of the A component and the B component. be. If the content is less than 10 parts by weight, the strength may be inferior, and if it exceeds 170 parts by weight, extrusion may become difficult.

(About other additives)
The resin composition of the present invention may contain various additives such as an antioxidant and a mold release agent within a range not contrary to the gist of the present invention.

<Antioxidant>
The resin composition of the present invention can contain at least one antioxidant selected from the group consisting of hindered phenol-based compounds, phosphite-based compounds, phosphonite-based compounds and thioether-based compounds as antioxidants. By blending an antioxidant, not only the hue and fluidity during molding are stabilized, but also the hydrolysis resistance is improved.

Examples of hindered phenolic compounds include α-tocopherol, butylhydroxytoluene, cinapyl 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'-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-butylpheno) , 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-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3', 3',) 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like are exemplified. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane and 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. In particular, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferable. All of these are readily available. The above hindered phenolic compounds can be used alone or in combination of two or more.

Phenylphosphite compounds include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmono. Phenyl Phenyl Phenyl Phenyl, Monobutyl Diphenyl Phenyl Phenyl, Monodecyl Diphenyl Phenyl Phenyl, Monooctyl Diphenyl Phenyl Phenyl, Tris (diethylphenyl) Phenyl Phenyl, Tris (di-iso-propylphenyl) Phenyl Phenyl, 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 Examples thereof include diphosphite and dicyclohexylpentaerythritol diphosphite. Further, as another phosphite compound, a compound which reacts with divalent phenols and has a cyclic structure 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-). Examples thereof include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite. 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] Dioxaphosfepine [Commercially available as "Smilizer 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] dioxaphosphepine, 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-t-butyl-4-hydroxyphenyl) propionyloxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 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 Oxaphosphocin, 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] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) ) -12-Methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3- (3- (3-) Methyl-4-hydroxy-5-t-butylphenyl) 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] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 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 Oxaphosphocin, 2,4,8,10-tetra-t-butyl Lu-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphosfepine And so on. All of these are readily available. The phosphite compound can be used alone or in combination of two or more.

Phenylnite compounds include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphospho Nite, 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 is preferable, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonate is preferable. Nite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferable. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which the alkyl group is substituted by 2 or more, and is preferable. Tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizers containing the phosphonite as a main component are 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), and the like. Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthionate) 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 further preferably 0.05 to 0.5 part by weight with respect to 100 parts by weight of the component A. be. If 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 may become unstable, but also the hydrolysis resistance may deteriorate. .. Further, when the content is more than 2 parts by weight, the reaction component derived from the antioxidant may rather deteriorate the hydrolysis resistance.

Further, it is preferable to use any two or more of the hindered phenol-based compound, the phosphite-based compound, the phosphonite-based compound, and the thioether-based compound in combination. By using a combination of two or more of hindered phenol-based compounds, phosphite-based compounds, phosphonite-based compounds, and thioether-based compounds, a synergistic effect as a stabilizer is exhibited, and the hue and flow during molding are more effective. It is effective in stabilizing the properties and improving the hydrolysis resistance.

<Release agent>
The resin composition of the present invention can contain a mold release agent. Specifically, as a release agent, fatty acid, fatty acid metal salt, oxyfatty acid, paraffin, low molecular weight polyolefin, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid partially saponified ester, fatty acid lower alcohol ester, fatty acid polyvalent Examples thereof include alcohol esters, fatty acid polyglycol esters and modified silicones. By blending these, a molded product having excellent mechanical properties, moldability, and heat resistance can be obtained.

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

Examples of the oxyfatty acid include 1,2-oxysteric acid and the like. The paraffin preferably has 18 or more carbon atoms, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, and petrolactam.

As the low molecular weight polyolefin, for example, a polyolefin having a molecular weight of 5000 or less is preferable, and specific examples thereof include polyethylene wax, maleic acid-modified polyethylene wax, oxidation type polyethylene wax, chlorinated polyethylene wax, polypropylene wax and the like.

The fatty acid amide preferably has 6 or more carbon atoms, and specific examples thereof include oleic acid amide, erucic acid amide, and bechenic acid amide.

The alkylene bis fatty acid amide preferably has 6 or more carbon atoms, and specific examples thereof include methylene bisstearic acid amide, ethylene bisstearic acid amide, and N, N-bis (2-hydroxyethyl) stearic acid amide.

The aliphatic ketone is preferably one having 6 or more carbon atoms, and examples thereof include higher aliphatic ketones.

Examples of the fatty acid partially saponified ester include a montanic acid partially 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, bechenic 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 dimillistate, and pentaerythryl. Examples thereof include tall monostearate, pentaerythritol adipate stearate, and sorbitan monobehenate. Examples of the fatty acid polyglycol ester include polyethylene glycol fatty acid ester, polytrimethylene glycol fatty acid ester, and polypropylene glycol fatty acid ester.

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 acids, fatty acid metal salts, oxyfatty acids, fatty acid esters, fatty acid partially saponified esters, paraffins, low molecular weight polyolefins, fatty acid amides, and alkylene bis fatty acid amides are preferable, and fatty acid partially saponified esters and alkylene bis fatty acid amides are more preferable. Of these, montanic acid ester, montanic acid partially 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 partially saponified ester and ethylene bisstearic acid amide are particularly preferable. ..

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, based on 100 parts by weight of the component A.

<Manufacturing method of resin composition>
Any method is adopted for producing the resin composition of the present invention. For example, a method in which each component and optionally other components are premixed, then melt-kneaded and pelletized can be mentioned. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. In the premixing, granulation can be performed by an extrusion granulator, a briquetting machine, or the like, depending on the case. After pre-mixing, melt-kneading is performed by a melt-kneader typified by a bent twin-screw extruder, and pelletization is performed by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant heat stirring vessel, but a vent type twin-screw extruder is preferable. Alternatively, a method of independently supplying each component and optionally other components to a melt kneader typified by a twin-screw extruder can also be adopted.

<About molded products>
A molded product using the resin composition of the present invention can be obtained by molding pellets produced as described above. Preferably, it is obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, and heat insulating metal. Examples thereof include mold molding, rapid heating and cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultra-high-speed injection molding. Further, either a cold runner method or a hot runner method can be selected for molding. When a molded product is obtained using a cold runner, the gate portion that is the inlet to the molded product may be either a restricted gate or an unrestricted gate, but the restricted gate is preferable from the viewpoint of post-workability. The unrestricted gate is a gate in which the cross-sectional area of the flow path is not reduced at the gate portion, and the restricted gate is a gate in which the cross-sectional area of the flow path is reduced at the gate portion. The limiting gate preferably satisfies the following formula (1).

（式中、Ｓ_Ｇはランナー断面積（ｍｍ^２）、Ｓ_Ｌはゲート部断面積（ｍｍ^２）を表す。）

(In the formula, _SG represents the runner cross-sectional area (mm ² ), and _SL represents the gate cross-sectional area (mm ² ).)

Examples of the unrestricted gate include a sprue gate, and examples of the restricted gate include a pinpoint gate, a side gate, a tab gate, an overlap gate, a film gate, a fan gate, a disc gate, and a submarine gate.

Hereinafter, embodiments of the present invention will be described with reference to Examples, but the present invention is not limited thereto. In addition, the evaluation of various physical properties was carried out by the following method.

[Evaluation of resin composition]
(1) Whitening suppression effect After the pellets obtained by the following method were dried at 120 ° C. for 5 hours, the cylinder temperature was 310 ° C. and the mold temperature was 90 ° C. by an injection molding machine (EC130SXII-4Y manufactured by Toshiba Machine Co., Ltd.). Injection molding was performed with a gate simulated mold. The gate simulated mold is a mold composed of a runner simulated portion and a gate simulated portion.
The runner simulated portion has a height of 6 mm, a width of 13 mm, and a length of 5 mm, and the gate simulated portion has a width of 13 mm and a length of 125 mm, and the height can be arbitrarily changed. Gate simulating unit height arbitrarily selected, and were evaluated for S _{G /} S _L numerical Change whitening effect of inhibiting according to the following equation (1).

（式中、Ｓ_Ｇはランナー断面積（ｍｍ^２）、Ｓ_Ｌはゲート部断面積（ｍｍ^２）を表す。）

(In the formula, _SG represents the runner cross-sectional area (mm ² ), and _SL represents the gate cross-sectional area (mm ² ).)

The whitening suppressing effect was evaluated as follows by measuring the whitening length L generated when the resin was filled up to the end of the gate simulated portion of 125 mm.
⊚: L = 0 mm
〇: 0 mm <L ≤ 50 mm
Δ: 50 mm <L ≦ 100 mm
X: 100 mm <L ≦ 125 mm

(2) Fluidity The fluidity was evaluated using an Archimedes-type spiral flow mold having a flow path thickness of 2 mm and a flow path width of 8 mm. The spiral flow length is measured by drying the pellets obtained by the following method at 120 ° C. for 5 hours and then using an injection molding machine (SG150U manufactured by Sumitomo Heavy Industries, Ltd.) to inject at a cylinder temperature of 310 ° C. and a mold temperature of 90 ° C. The evaluation was performed under the condition of a pressure of 98.1 MPa. The spiral flow length needs to be 90 mm or more.

(3) Heat resistance The pellets obtained by the following method are dried at 120 ° C. for 5 hours and then tested by an injection molding machine (EC130SXII-4Y manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 310 ° C. and a mold temperature of 90 ° C. Pieces were made and the deflection temperature under load was measured according to ISO75-1 and 75-2. The heat resistance needs to be 100 ° C. or higher under a load condition of 1.8 MPa.

(4) Tensile strength The pellets obtained by the following method were dried at 120 ° C. for 8 hours and then tested by an injection molding machine (EC130SXII-4Y manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 320 ° C. and a mold temperature of 80 ° C. Pieces were prepared, and a tensile test was carried out under the conditions of a test temperature of 85 ° C. and a test speed of 5 mm / min according to ISO527-1 and 527-2, and the tensile strength was measured. The tensile strength needs to be 50 MPa or more.

[Example 1-17, Comparative Example 1-2]
According to the contents shown in Table 1, the A component and the B component are separately supplied from the first supply port, and the C component is supplied from the second supply port to the twin-screw extruder using a side feeder, and the screw rotation speed is 200 rpm. The volume was 20 kg / h, the degree of vacuum of the vent was 3 kPa, and the mixture was melt-kneaded and extruded at a temperature of 310 ° C. to pelletize it. Here, the first supply port is a supply port at the root, and the second supply port is a supply port located between the die of the extruder and the first supply port. As the twin-screw extruder, a vent-type twin-screw extruder having a diameter of 30 mmΦ (manufactured by Japan Steel Works, Ltd .: TEX30α-31.5BW-2V) was used.

The following materials were used in Examples and Comparative Examples of the present invention.
(Component A)
AI: Polyethylene naphthalate resin obtained in Production Example I <Production Example I>
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 in 100 parts by weight of naphthalenedicarboxylic acid dimethyl ester and 60 parts by weight of ethylene glycol Below, the ester exchange reaction was carried out by a conventional method, 0.012 parts by weight (10 mmol%) of antimony trioxide was added 20 minutes after distillation of methanol, and 0.020 parts by weight (50 mmol) of orthophosphate was added before the completion of the ester exchange reaction. %) Was added, and then a polycondensation reaction was carried out at 295 ° C. under high vacuum to obtain a polyethylene naphthalate resin (a) having an intrinsic viscosity of 0.51 dl / g. The obtained polyethylene naphthalate resin (a) 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 having an intrinsic viscosity of 0.68 dl / g.
(B component)
BI: ULTEM1010 manufactured by SABIC Japan GK
(C component)
CI: Glass fiber: Flat cross-section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd .: CSG 3PA-830 (product name), major axis 28 μm, minor axis 7 μm, cut length 3 mm, epoxy-based focusing agent)
C-II: Glass fiber: Round cross-section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd .: CSG 3PE-941 (product name), cut length 3 mm, epoxy-based focusing agent)
C-III; Carbon fiber: PAN-based carbon fiber (IM P303 (trade name) manufactured by Teijin Limited, fiber diameter 7 μm, cut length 3 mm, epoxy-based sizing agent)
(Other ingredients)
Stabilizer-I: Phosphorus-based stabilizer (SONGNOX6260PW (trade name) manufactured by Songwon International Japan Co., Ltd. (bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite))
Stabilizer-II: Hindered phenolic stabilizer (Adeka Stub AO-50 (trade name) manufactured by ADEKA Corporation (Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate))

<Examples 1 to 17>
Since the composition is within the scope of the present claim, it was possible to obtain a molded product having excellent fluidity and heat resistance and suppressing the whitening phenomenon at the gate portion that occurs when the limiting gate is used.

<Comparative example 1>
Since it does not contain the B component, the effect of improving the heat resistance and suppressing the whitening phenomenon in the gate portion that occurs when the limiting gate is used was not observed.

<Comparative example 2>
Since the content of the B component exceeds the upper limit, the result is that the fluidity is inferior.

Claims (7)

A molded product composed of a resin composition containing 10 to 90 parts by weight of (B) polyetherimide resin (B component) with respect to 100 parts by weight of (A) polyethylene naphthalate resin (A component). The molded product according to claim 1, wherein the fibrous filler (C component) is contained in an amount of 10 to 170 parts by weight with respect to 100 parts by weight of the component A. The molded product made of the resin composition according to claim 2, wherein the C component is at least one fibrous filler selected from the group consisting of glass fibers and carbon fibers. The C component is a flat cross-section glass fiber in which the average value of the major axis of the fiber cross section is 10 to 50 μm and the average value of the ratio of the major axis to the minor axis (major axis / minor axis) is 1.5 to 8. A molded product made of the resin composition according to claim 3. The molded product according to any one of claims 1 to 4, wherein the resin composition is molded by passing through a limiting gate in which the flow path is reduced and flowing into the cavity. The molded product according to any one of claims 1 to 5, wherein the restriction gate satisfies the following formula (1).

(In the formula, _SG represents the runner cross-sectional area (mm ² ), and _SL represents the gate cross-sectional area (mm ² ).) A method of reducing the whitening phenomenon at the gate by adding a polyetherimide resin to the polyethylene naphthalate resin.