JP2000044812A - Production of resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having a good moldability, capable of providing a molding product excellent in strength and thermal stability by melting and mixing a crystallizable polymer with a fiber, and further melting and mixing the mixed product with a polymer containing an alicyclic structure. SOLUTION: This composition is obtained by melting and mixing a melted mixture obtained by melting and mixing (A) a crystallizable polymer preferably having the melting point higher than the glass transition temperature of the component C, with (B) a fiber preferably having 0.1-100 μm diameter and 10 μm-40 mm length, with (C) an alicyclic structure-containing polymer preferably having <=2 yellowness obtained by dissolving the polymer in a soluble solvent so as to form 15 wt.% concentration and measuring the yellowness at 10 mm optical path. A polybutylene terephthalate, a polypropylene or the like is preferable as the component A. An inorganic fiber such as a glass fiber and a carbon fiber, and an organic high molecular fiber such as a polyethylene fiber and a polyamide fiber can be used as the component B. A norbornene-based polymer (hydrogenated) or the like is preferable as the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resin composition, a resin composition produced by the method, and a molded article containing the resin composition. In particular, the present invention
Production of a resin composition having high heat resistance and high strength, characterized by adding, for example, an alicyclic structure-containing polymer containing a thermoplastic norbornene-based polymer to a molten mixture of fibers and a high-melting crystalline resin. The present invention relates to a method and a molded article thereof.

[0002]

2. Description of the Related Art High-melting crystalline polymers such as polyethylene terephthalate, polybutylene terephthalate and polyphenylene sulfide, which have been widely used in the past, are inherently heat-resistant.
Further, it is known that by mixing fibers such as glass fiber, more excellent heat resistance is exhibited. On the other hand, when fibers such as glass fibers are added to such a high-melting crystalline polymer, the fluidity during melt molding is reduced, so that moldability is deteriorated, and fibers are also present near the molded product surface. However, there have been problems such as irregularities on the surface of the molded product. In order to solve such problems, for the purpose of improving the moldability of the high-melting crystalline polymer, for example, JP-A-2-
No. 180945 (Mitsui Petrochemical Co., Ltd.), a composition comprising a combination of a high-melting crystalline polymer / glass fiber / polymer having an alicyclic structure, to which an alicyclic structure-containing polymer is added. Was developed. However, the composition described in this publication is a production method in which three components of a high-melting crystalline polymer / glass fiber / polymer having an alicyclic structure are kneaded at the same time, and the resin composition obtained by this method is kneaded. The molded product had inadequate moldability, and the strength and heat resistance of the obtained molded product were insufficient, and further, there were inconveniences such as the unevenness of the surface of the molded product. The present invention comprises a high-melting crystalline polymer, a fiber and an alicyclic structure-containing polymer, and a method capable of producing a resin composition having good moldability, produced from the resin obtained by the method. It is an object of the present invention to provide a molded article having high strength, and high heat resistance.

[0003]

As a result of research for solving the above-mentioned problems, as a result of kneading three components of a high-melting crystalline polymer, a fiber such as glass fiber, and an alicyclic structure-containing polymer at the same time, Since the alicyclic structure-containing polymer melts at a lower temperature than the high-melting crystalline polymer, the fiber and the alicyclic structure-containing polymer are mixed first, and the surface of the fiber is alicyclic. It has been found that the structure-containing polymer has a structure to cover, and this structure is in a form dispersed in the high-melting crystalline polymer. And the obtained resin composition has insufficient moldability,
It was also found that the molded product had insufficient strength and heat resistance, and that the surface of the molded product was uneven. In order to solve such a problem, the present inventors conducted further research. First, the crystalline polymer and the fiber were sufficiently melt-mixed at a relatively high temperature to obtain a fiber coated with the crystalline polymer. To form
After that, the alicyclic structure-containing polymer is added and mixed to form a sea-island structure in which the fibers covered with the high-melting crystalline polymer are uniformly dispersed in the alicyclic structure-containing polymer matrix. As a result, the resin composition exhibits excellent moldability, and the molded article has high strength and heat resistance, and a molded article having a smooth upper surface (no irregularities) can be obtained. Obtained knowledge. The present invention has been made based on such findings.

Accordingly, the present invention first provides a method for producing a resin composition in which a crystalline polymer and a fiber are melt-mixed, and the obtained molten mixture and a polymer having an alicyclic structure are melt-mixed. Is what you do. In addition, the present inventors have the effect that the electrical properties (physical quantity) can be adjusted by suppressing the yellowness of the alicyclic structure-containing polymer to 2 or less;
In order to improve the moldability of the obtained resin composition and improve the strength of the molded body, it has been found that it is preferable to combine a crystalline polymer having a high melting point with the molded body as a crystalline polymer. . Therefore, the present invention relates to a molded article containing an alicyclic structure-containing polymer which is dissolved in a soluble solvent at a concentration of 15% by weight and has a yellowness of 2 or less as measured at an optical path length of 10 mm, and Provided is a method for producing a resin composition by mixing and heat-melting and kneading.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, the alicyclic structure-containing polymer refers to a polymer having an alicyclic structure in a main chain and / or a side chain.
The alicyclic structure of the polymer constituting the alicyclic structure-containing polymer used in the present invention includes a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon structure such as cycloalkene. The alicyclic structure-containing polymer used in the present invention is preferable to include a large amount of the alicyclic structure-containing polymer having a cycloalkane structure because of its excellent mechanical strength and heat resistance. Further, the polymer preferably has 4 to 30, preferably 5 to 20, and more preferably 5 to 15 carbon atoms constituting the alicyclic structure. When the number of carbon atoms is in this range, the molded article of the resin composition of the present invention is provided with good balance of mechanical strength, heat resistance, and moldability. The alicyclic structure-containing polymer used in the present invention has a proportion of the repeating unit having an alicyclic structure of 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more. When the proportion of the repeating unit having an alicyclic structure in the polymer is in this range, the heat resistance of the obtained resin composition and molded article is preferably increased. The remainder other than the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer does not need to be particularly limited.

The alicyclic structure-containing polymer used in the present invention is:
It is appropriately selected according to the purpose of use based on the characteristics. The criterion for selecting the polymer does not need to be particularly strictly defined, but a molecular weight, a glass transition temperature and the like can be used. For example, the molecular weight of an alicyclic structure-containing polymer is determined by gel permeation chromatography of a cyclohexane solution (a toluene solution when the polymer resin does not dissolve) (polystyrene conversion when toluene is used. 5,000 to 500,
Suitably, it is 000, preferably 8,000 to 200,000, particularly preferably 10,000 to 100,000. When the molecular weight is in the range, the obtained resin composition and molded product have excellent mechanical strength. When the heat resistance of the molded article of the alicyclic structure-containing polymer is increased, the glass transition temperature (Tg) is preferably higher.
For example, usually 50 to 400 ° C, preferably 70 to 300
C., more preferably 100 to 250C. When the Tg is in this range, the moldability of the resin composition is favorable, and the heat resistance of the molded article is kept high. The 5% loss on heating of the polymer having an alicyclic structure is preferably 280 ° C. or higher, more preferably 350 ° C. or higher, as measured at a heating rate of 5 ° C./min in a nitrogen atmosphere. Is appropriate. When the 5% heating loss temperature is lower than 280 ° C., decomposition occurs when the temperature is increased to improve the fluidity of the resin composition, and molding defects such as formation of bubbles due to decomposition occur inside the molded product. There is a problem that it is easy. When the 5% heating loss temperature is in the above range, even if the temperature of the resin composition is raised, molding defects such as generation of bubbles are unlikely to occur. The melt viscosity of the polymer at a temperature of 260 ° C. is usually 1 × 10 ¹ to 1 × 10 ⁵ poise, preferably 1 × 10 ² to 1 × 10 ³ poise. When the melt viscosity is in this range, excellent moldability is imparted to the resin composition, and the mechanical strength of the molded product is improved.

Specific examples of the alicyclic structure-containing polymer used in the present invention include (1) vinyl alicyclic hydrocarbon polymer,
There are (2) monocyclic cycloolefin polymers, (3) cyclic conjugated diene polymers, (4) norbornene polymers, and hydrogenated products thereof. Among these polymers, norbornene-based polymers and hydrogenated products thereof, cyclic conjugated diene-based polymers and hydrogenated products thereof are preferable, and norbornene-based polymers and hydrogenated products thereof are particularly preferable. The respective polymers are described below. (1) Specific examples of the vinyl alicyclic hydrocarbon polymer include vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane disclosed in JP-A-51-59989. And hydrogenated products thereof, JP-A-63-43910 and JP-A-64-17
No. 06, etc., such as hydrogenated aromatic ring portions of polymers of vinyl aromatic monomers such as styrene and α-methylstyrene. (2) Specific examples of the monocyclic cycloolefin polymer include monocyclic cycloolefin monomers such as cyclolohexene, cycloheptene and cyclooctene disclosed in JP-A-64-66216. There are addition polymers in the body. (3) Specific examples of the cyclic conjugated diene-based polymer,
JP-A-6-136057 and JP-A-7-25831
No. 8 discloses a cyclic conjugated diene-based monomer such as cyclopentadiene or cyclohexadiene,
Or a polymer obtained by 1,4-addition polymerization and a hydrogenated product thereof. (4) Specific examples of the norbornene-based polymer include a ring-opened polymer of a norbornene-based monomer and a hydrogenated product thereof, an addition polymer of a norbornene-based monomer, and an addition-type polymer of a norbornene-based monomer and a vinyl compound. is there. In order to obtain a regenerated resin having a good balance of heat resistance and dielectric properties, a hydrogenated ring-opening polymer of a norbornene-based monomer, an addition polymer of a norbornene-based monomer, and a vinyl compound copolymerizable with a norbornene-based monomer It is preferable to recycle the addition polymer of the above, and a hydrogenated open polymer of a norbornene monomer is particularly preferable.

The norbornene-based monomer used in the present invention can be produced using the following norbornene-based monomer. For example, bicyclo [2.2.1] hepta
2-ene (common name norbornene), 5-methylbicyclo [2.2.1] hepta-2-ene, 5,5-dimethylbicyclo [2.2.1] hepta-2-ene, 5-ethylbicyclo [ 2.2.1] Hept-2-ene, 5-butylbicyclo [2.2.1] hept-2-ene, (5-methylidenebicyclo [2.2.1] hept-2-ene, 5- Vinylbicyclo [2.2.1] hept-2-ene), 5-
Ethylidenebicyclo [2.2.1] -hepta-2-ene,
5-propenylbicyclo [2.2.1] hepta-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hepta-2-ene, 5-cyanobicyclo [2.2.1] hepta-2- Ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hepta-2-ene; tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name dicyclopentadiene ), Tricyclo [4.3.0.1
^2,5 ] dec-3-ene; tricyclo [4.3.0.1
^2,5 ] undeca-3,7-diene or tricyclo [4.3.0.1 ^2,5 ] undeca-3,8-diene or a partially hydrogenated product thereof (or an adduct of cyclopentadiene and cyclohexene) Some tricyclo [4.
4.0.1 ^2,5 ] undec-3-ene; tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dode-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-Dodeca-
3-ene, 8-ethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-Dodeca-
3-ene, 8-ethylidenetetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -dodec-3-ene, 8-vinyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodeca-3
-Ene, 8-methoxycarbonyltetracyclo [4.
4.0.1 ^2,5 . ^1,7,10 ] -dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.
0.1 ^2,5 . Tetracyclo [4.4.0.1 ^2,5 ..., Such as 1 ^7,10 ] -dodec-3-ene. 1 ^7,10 ] -dodeca-3-
Enes; tetracyclo [7.4.0.1 ^10,13.
0 ^2,7 ] trideca-2,4,6,11-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [8.4.0.1
^11,14 . 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (1,4-methano-1,4,4a, 5,10,1
0a-hexahydroanthracene), pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, pentacyclo [7.4.0.1
^3,6 . 1 ^10,13 . 0 ^2,7 ] pentadeca-4,11-diene; and tetramers of cyclopentadiene. These norbornene monomers can be used alone or in combination of two or more.

When the alicyclic structure-containing polymer is a ring-opening (co) polymer of a norbornene-based monomer, examples of the vinyl compound copolymerizable with these norbornene-based monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-
Hexene, 4,4-dimethyl-1-hexene, 4,4-
Dimethyl-1-pentene, 4-ethyl-1-hexene,
C2-C2-, such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene
20 ethylene or α-olefins; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene;
3a, 5,6,7a-tetrahydro-4,7-methano-
Cycloolefins such as 1H-indene; and non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene; These copolymerizable vinyl compounds can be used alone or in combination of two or more. Further, examples of the copolymerizable vinyl compound include a cyclic olefin. Examples of such a cyclic olefin include cyclobutene, 1-methylcyclopentene, 3-methylcyclobutene, 3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene, cyclohexene,
Monocyclic cycloolefins such as cyclooctene, 1-methylcyclooctene, 5-methylcyclooctene, cyclooctatetraene, cyclododecene and the like and monomers having a norbornene ring having one unsaturated bond can be mentioned.

In accordance with a conventional method, a ring-opened (co) polymer may be hydrogenated by hydrogenation in the presence of a hydrogenation catalyst to obtain a hydrogenated norbornene polymer. In addition, the alicyclic structure-containing polymer (unused product) obtained as described above can be used as it is, and the molded product obtained by molding the unused product once is pulverized as necessary. It may be reused as an alicyclic structure-containing polymer. Examples of such molded articles include various molded articles for optics, medical treatment, and the like, and waste materials such as sprues, runners, and mimi generated during molding. The alicyclic structure-containing polymer is preferably dissolved in a soluble solvent at a concentration of 15% by weight and has a yellowness of 2 or less as measured at an optical path length of 10 mm. The yellowness (ΔYI value) was measured by dissolving the molded body in a soluble solvent to a solid concentration of 15% by weight, and using the soluble solvent as a control solution in a cell having an optical path length of 10 mm. And measured at room temperature (25 ° C.) using a color difference meter and refers to a value obtained as a difference between the yellowness YI of the solution and the control solution. In addition, as the soluble solvent, for example, toluene can be used, and when the molded article containing the alicyclic structure-containing polymer does not dissolve in toluene, another solvent such as decalin, cyclohexane, THF, or dichloroethane is used. Can be. In addition, when the molded article once molded is reused, or when the alicyclic structure-containing polymer contains various filler components, such as when a solvent-insoluble component is contained, the insoluble component is separated by filtration or the like. What is necessary is just to measure separately. In the molded article to be reused in the present invention, the range of ΔYI is 2 or less, usually 1 to −0.5, preferably 0.5 to −0.
2, the closer to zero in this range, the better the electrical properties can be given to the resin composition and the molded article obtained in the present invention. Incidentally, by suppressing the yellowness to 2 or less, the electrical characteristics of the alicyclic structure-containing polymer are improved,
The reason has not been elucidated. Possibly, components that increase the degree of yellowness, such as its oxides and trace elements, contained in the polymer decrease the electrical characteristics. In order to keep ΔYI of the alicyclic structure-containing polymer at 2 or less, the temperature at the time of drying after synthesizing the polymer is not increased, and when the molded body once molded is reused, the temperature at the first molding is not increased. The drying and molding may be performed in the presence of an inert gas such as nitrogen purge, or a method using an alicyclic structure-containing polymer having no polar group may be used.

(2) Crystalline polymer Next, the crystalline polymer used for producing the resin composition of the present invention will be described. Examples of such crystalline polymers include high melting point polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyphenylene sulfide (PBS), polyethylene (LDPE, HEPE), polyamide, polypropylene, poly Examples include ether ether ketone and aromatic polyester. The melting point (Tm) of the crystalline polymer is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and particularly preferably 50 ° C., higher than the glass transition point (Tg) of the alicyclic structure-containing polymer resin. It is appropriate to be higher than this. When the Tm of the high-melting crystalline polymer is in the above range, the moldability of the obtained resin composition is improved, and excellent heat resistance and mechanical strength are imparted to the molded article. Such a crystalline polymer resin having a high Tm is preferably a crystalline polymer in which the melting point of the crystalline polymer is equal to or higher than the glass transition point of the alicyclic structure-containing polymer. Examples of the crystalline polymer include polybutylene terephthalate, polyphenylene sulfide, and polypropylene. The fibers used in the present invention are not particularly limited as long as they are fibrous additives used as additives for plastics. Specific examples of the fiber include inorganic fibers such as glass fiber, boron fiber, silicon carbide fiber and carbon fiber; and organic polymers such as polyethylene fiber, polypropylene fiber, polyester fiber, aromatic polyester, aromatic polyamide and polyamide fiber. There are fibers, which can be used alone or in combination.

Although the diameter of these fibers varies depending on the use of the molded article to be produced, it is usually 0.1 to 100 μm.
m, preferably 0.2 to 50 μm, particularly preferably 0.5 to 20 μm.
μm is appropriate. The length also varies depending on the use of the molded article to be produced.
It is suitably 0 mm, preferably 100 μm to 20 mm, particularly preferably 1 mm to 10 mm. The surface of the fiber is preferably surface-treated in accordance with the type of the high-melting crystalline polymer to be used. Examples of the surface treatment agent include a silane coupling agent treatment and an acid treatment. Such surface treatment has the effect of improving the mechanical strength of the obtained resin composition and its molded product. The mixing ratio of the fiber and the high melting crystalline polymer is usually 1 to 80/99 to 20, preferably 5 to 6 by weight ratio of the fiber and the high melting crystalline polymer.
0 / 95-40, more preferably 10-40 / 90-6
It is in the range of 0. The reason for limiting the mixing ratio in this way is that
When the ratio of the fiber and the high-melting crystalline polymer is in this range, the mechanical strength is enhanced by the fiber blending,
This is because melt kneading is good and the balance between the two is excellent. The mixing ratio of the melt mixture of the fiber and the crystalline polymer and the alicyclic structure-containing polymer is 5 to 95 by weight.
/ 95-5, preferably 10-90 / 90-10, more preferably 20-80 / 80-20. The reason for limiting the mixing ratio in this manner is that when the ratio of the molten mixture is within this range, the mixture is excellent in mechanical strength, precision moldability, electrical insulation, low moisture absorption, and the like.

[0013] The resin composition of the present invention comprises
A polymer other than the high melting crystalline polymer, various compounding agents, and fillers may be used alone or in combination of two or more.
In general, examples of other polymers that may be added to or included in the resin composition of the present invention as needed include the following. For example, polybutadiene, polyisoprene, styrene / butadiene / styrene block copolymer (SBS), styrene / isobutene / styrene block copolymer (SIS), hydrogenated SBS (SEB)
S), rubbers such as SIS hydrogenated products (SEPS); polystyrene, poly (meth) acrylate, polycarbonate, polyester, polyether, polyamide, polyimide, polysulfone, and the like. In the present invention, one or more of these polymers may be contained in the resin composition, and the ratio thereof can be appropriately adjusted within the range of the purpose of using the molded article.

Examples of compounding agents which may be added to the resin composition of the present invention include compounding agents generally used in thermoplastic resin materials, such as antioxidants, ultraviolet absorbers, and the like.
Light stabilizers, near infrared absorbers, coloring agents such as dyes and pigments,
There are compounding agents such as lubricants, plasticizers, antistatic agents, and optical brighteners. As the antioxidant, it is preferable to add a phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like, and a phenol-based antioxidant, particularly an alkyl-substituted phenol-based antioxidant, is preferable.
Examples of this phenolic antioxidant include 2-t-
Butyl-6- (3-tert-butyl-2-hydroxy-5-
Methylbenzyl) -4-methylphenyl acrylate,
2,4-di-t-amyl-6- (1- (3,5-di-t
Acrylate compounds such as -amyl-2-hydroxyphenyl) ethyl) phenyl acrylate; octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis (4 -Methyl-6-t-butylphenol), 1,1,
3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3-
(3 ′, 5′-di-tert-butyl-4′-hydroxyphenylpropionate) methane [namely, pentaerythrimethyl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionate) Nate)], triethylene glycol bis (3- (3-t-butyl-4-
Alkyl-substituted phenolic compounds such as hydroxy-5-methylphenyl) propionate); 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-
Bisoctylthio-1,3,5-triazine, 4-bisoctylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-
(Oxyanilino) -1,3,5-triazine and the like.

As the phosphorus-based antioxidants, those generally used in the general resin industry can be used. Examples thereof include triphenyl phosphite, diphenyl isodecyl phosphite, and phenyl diisodecyl phosphite. , Tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,
4-di-t-butylphenyl) phosphite, 10-
(3,5-di-t-butyl-4-hydroxybenzyl)
Monophosphite compounds such as -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; 4,4′-butylidene-bis (3-methyl-6-t-butylphenyl-di- Diphosphite compounds such as tridecyl phosphite) and 4,4 ′ isopropylidene-bis (phenyl-di-alkyl (C12 to C15) phosphite). Among these, monophosphite compounds, especially tris (nonylphenyl) phosphite and tris (dinonylphenyl)
Phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are preferred. Examples of more preferred sulfur antioxidants include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3. -Thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate, 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane These antioxidants may be used alone or in combination of two or more.The amount of the antioxidants is not particularly limited, but the polymer component 100 may be used.
Usually 0.001 to 5 parts by weight, preferably 0.1 to 5 parts by weight, per part by weight.
It is appropriate that the content is in the range of 01 to 1 part by weight.

Examples of the ultraviolet absorber used in the present invention include 2- (2-hydroxy-5-methylphenyl) 2H-benzotriazole and 2- (3-t-butyl-2-hydroxy-5-). Methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-
Butyl-2-hydroxyphenyl) -5-chloro-2H
-Benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 5-chloro-2- (3,5-di-tert-butyl-2-)
(Hydroxyphenyl) -2H-benzotriazole, 2
Benzotriazole ultraviolet absorbers such as-(3,5-di-t-amyl-2-hydroxyphenyl) -2H-benzotriazole; 4-t-butylphenyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate, 2,4-di-t-butylphenyl-3,5-
Di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3, 4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octylphenyl) -2H-benzo Bezoate UV absorbers such as triazole; 2,4-dihydroxybenzophenone;
-Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4-dodecaroxy-2-fodroxybenzophenone, 4-benzyloxy Benzophenone-based ultraviolet absorbers such as -2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; ethyl-2-cyano-3, Acrylic UV absorbers such as 3-diphenyl acrylate, 2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate; [2,2'-thiobis (4-t-octylphenolate)]-2-ethylhexylamine Metal complex UV absorbers such as nickel There is.

Further, examples of light stabilizers include 2, 2,
6,6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl)- 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy ) -1- (2-
(3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2,6,6
Hindered amine light stabilizers such as tetramethylpiperidine. Examples of near-infrared absorbers include cyanine-based near-infrared absorbers; pyrylium-based infrared absorbers; squarylium-based near-infrared absorbers; croconium-based infrared absorbers; azurenium-based near-infrared absorbers; There are dithiol metal complex-based near infrared absorbers; naphthoquinone-based near-infrared absorbers; anthraquinone-based near-infrared absorbers; indophenol-based near-infrared absorbers; and azimuth-based near-infrared absorbers. -103, SIR-114, SIR-128, SIR-130,
SIR-132, SIR-152, SIR-159, SIR-162 (all made by Mitsui Toatsu Dye), Kayasorb IR-750, Kayasorb IRG-002, Ka
yasorb IRG-003, IR-820B, Kayasorb IRG-022, Kayaso
rb IRG-023, Kayasorb CY-2, Kayasorb CY-4, Kayasorb
CY-9 (above, manufactured by Nippon Kayaku). In the present invention, any dye can be used without particular limitation as long as it can be uniformly dispersed and dissolved in the regenerated resin. However, oil-soluble dyes having excellent compatibility (various CI solvent dyes) are preferable. Specific examples of this oil-soluble dye include The Society of Diyes a
Various C.Is described in Color Index vol.3 published by nd Colorists. I. There are solvent dyes.

Specific examples of pigments include diarylide pigments such as Pigment Red 38; Pigment Red 48: 2, Pigment Red 53, and Pigment Red 5;
Azo lake pigments such as 7: 1; Pigment Red 14
4, Pigment Red 166, Pigment Red 22
0, Pigment Red 221, Pigment Red 248
Pigment imidazolone pigments such as Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, and Pigment Red 208; Quinacridone pigments such as Pigment Red 122; Pigment Red 149, Pigment Red 178 And perylene pigments such as CI Pigment Red 179; and anthraquinone pigments such as CI Pigment Red 177. Further examples of the lubricant include an organic compound such as an ester of an aliphatic alcohol, an ester or a partial ester of a polyhydric alcohol, and inorganic fine particles. Examples of the organic compound include glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. Examples of the inorganic fine particles include oxides, sulfides, and the like of elements belonging to Groups 1, 2, 4, and 6 to 14 of the periodic table.
Hydroxides, nitrides, halides, carbonates, sulfates,
Examples thereof include acetate, phosphate, phosphite, organic carboxylate, silicate, titanate, borate and hydrates thereof, composite compounds mainly containing them, and particles of natural compounds.

Examples of plasticizers include tricresyl phosphate, trixylyl phosphate, triphenyl phosphate, triethyl phenyl phosphate, diphenyl cresyl phosphate, monophenyl dicresyl phosphate, and diphenyl monoxylenyl. Triester phosphate plasticizers such as phosphate, monophenyldixylenyl phosphate, tributyl phosphate, and triethyl phosphate; dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-phthalyl phthalate -2-ethylhexyl, diisononyl phthalate, octyldecyl phthalate,
Phthalate ester plasticizers such as butyl benzyl phthalate; fatty acid monobasic ester plasticizers such as butyl oleate and glycerin monooleate; dihydric alcohol ester plasticizers; oxy acid ester plasticizers . Among these, a phosphoric acid triester plasticizer,
Particularly, tricresyl phosphate and trixylyl phosphate are preferred. Further, the resin composition of the present invention may contain a softening agent or a plasticizer. For example, a hydrocarbon polymer which is liquid at room temperature and whose main skeleton is mainly a CC or C = C structure is preferable. . Among these liquid hydrocarbon polymers, a linear or branched liquid hydrocarbon polymer having no hydrocarbon ring in the main chain is preferable, but in order to improve weather resistance and the like, a CＣC structure is required. Those that do not substantially have are preferred. The weight average molecular weight of the liquid hydrocarbon polymer is preferably 10,000 or less, more preferably 200 to 8,000, and particularly preferably 300 to 4,000. Specific examples of the liquid hydrocarbon polymer include squalane (C30H6).
2, Mw = 422.8), liquid paraffin (white oil, ISO VG1 specified in JIS K2231)
0, ISO VG15, ISO VG32, ISO V
G68, ISO VG100, VG8 and VG21), polyisobutene, hydrogenated polybutadiene, hydrogenated polyisoprene, and the like, with squalane, liquid paraffin and polyisobutene being particularly preferred.

Examples of antistatic agents include long-chain alkyl alcohols such as stearyl alcohol and behenyl alcohol, and fatty acid esters of polyhydric alcohols such as glycerin monostearate and pentaerythritol monostearate. Behenyl alcohol is particularly preferred. In addition, these compounding agents may be used alone or in combination of two or more, and the ratio is appropriately selected within a range according to the purpose of a molded article produced from the resin composition. The amount is usually 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the polymer component. Furthermore, in the present invention, the recycled resin may include a filler. Examples of the organic or inorganic filler include, for example, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, dowamite, calcium oxide, calcium carbonate, calcium sulfate. , Potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos and other minerals;
Examples include glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, and antimony oxide. These fillers may be used alone or in combination of two or more. The mixing ratio of the filler can be appropriately selected within a range depending on the use of the molded article of the present invention, and is not particularly limited in the present invention. The resin composition of the present invention is manufactured as follows. Preferably, a step of melt-kneading the crystalline polymer and the fiber to obtain a melt mixture, and a step of melt-kneading the melt-kneaded body and the alicyclic structure-containing polymer to obtain a resin composition. Do. First, fibers sized to a predetermined size are melt-mixed with a high melting crystalline polymer. At this time, the melting temperature varies depending on the characteristics of the high-melting crystalline polymer.
The temperature is preferably 200 ° C., preferably Tm to Tm + 150 ° C., particularly preferably Tm + 10 to Tm + 120 ° C. Such molten mixtures are commercially available from various companies,
It may be used. Then, to the obtained molten mixture,
The alicyclic structure-containing polymer and various additives, if necessary, other polymers, compounding agents, fillers and the like are added. The melting temperature at this time is preferably Tg to Tg + 200 ° C., more preferably Tg + 30 to Tg + 170 ° C., and particularly preferably Tg + 60 to Tg + 140 ° C.

Incidentally, in order to perform the melt mixing, a usual method for producing a usual thermoplastic resin can be used without any particular limitation. For example, there is a method in which fibers and respective polymers are kneaded in a molten state by a mixer, a kneader, a single-screw kneader, a twin-screw kneader, or the like. It is preferable that the resin composition of the present invention is usually extruded into a rod shape in a molten state, cut into an appropriate length by a strand cutter, and used as pellets. Also,
In order to produce a molded article from the resin composition of the present invention, a melt molding method can be used without any particular limitation. Specific examples of the melt molding method include injection molding, extrusion molding, extrusion blow molding, injection blow molding, multilayer blow molding, connection blow molding, double wall blow molding, stretch blow molding, vacuum molding, rotational molding and press. Molding. When performing the melt molding, the melting temperature of the resin at the time of molding varies depending on the components of the resin composition such as the alicyclic structure-containing polymer, but is usually from 200 to 380 ° C, preferably from 240 to 3 ° C.
It is suitable to carry out at 50 ° C, more preferably at 26-429 ° C, and even more preferably at 260-320 ° C. Various molded articles can be manufactured using the resin composition of the present invention. Specific examples of the molded article include molded articles for automobiles such as room mirrors, door mirrors, fender mirrors, lamp reflectors, extension reflectors, mirrors for head-up displays, wheel caps and bumpers, syringes, connectors, multi-way plugs, and the like. Medical molded products such as syringe rods; flexible printed wiring boards, printed wiring boards, film molded products, antenna components, exterior materials for communication equipment, and insulators for connectors, electric wire coatings, wafer shippers, capacitor films, copper with resin Molded articles for tube electric or electronic use; optical molded articles such as polygon mirrors, roof mirrors, light reflection sheets, and optical scales; building materials, stationery, and the like. Among these applications, in particular, applications requiring heat resistance, for example,
Suitable for the manufacture of automotive parts, especially lamp reflectors. When a molded article is produced from an alicyclic structure-containing polymer by an injection molding method, a sprue or a runner of a regenerated resin, which is generated as a waste material, and a resin obtained by cutting out a desired shape after extrusion molding or solution casting. Waste material of the cyclic structure-containing polymer can also be used for producing the resin composition of the present invention.

[0022]

According to the present invention, a high heat resistance is obtained by adding an alicyclic structure-containing polymer such as a thermoplastic norbornene polymer to a molten mixture of fibers and a high melting crystalline resin. And a method for producing a resin composition having high strength, and a molded article thereof.

[0023]

EXAMPLES The present invention will be described more specifically with reference to the following Reference Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. Various physical properties in the following Reference Examples, Examples and Comparative Examples were evaluated according to the following evaluation methods. (1) Hydrogenation rate Measured by ¹ H-NMR. (2) Glass transition temperature Measured according to JIS K7121 (DSC method). (3) Weight average molecular weight It was measured as a value in terms of polystyrene by gel permeation chromatography (GPC) using toluene as a solvent or a value in terms of polyisoprene by GPC using cyclohexane as a solvent. (4) Yellowness (ΔYI) The molded product was dissolved in decalin to a concentration of 15% by weight, placed in a quartz cell having an optical path length of 10 mm, and measured with a color difference meter. (5) Mechanical strength Using an injection-molded test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 3 mm (hereinafter referred to as a test piece A), the ASTM was used.
A bending test was performed based on D790 and evaluated.
Evaluation is ○ when there is a yield point, × when there is no yield point
And (6) Heat resistance Using test piece A, ASTM D648 (18.6 kg
f / cm ² ). In the evaluation, the case where the heat deformation temperature was higher than the heat deformation temperature of the alicyclic structure-containing polymer containing no high melting point crystalline resin by 5 ° C. or more was evaluated as ×, and the case where it was less than 5 ° C. as X.

(7) Moldability Injection molding machine (Roboshot α, 100, manufactured by FANUC)
Using B), at a resin temperature of 290 to 320 ° C., a mold temperature of 100 to 120 ° C., a test piece A, and a length of 90 m
m, an injection test piece B having a width of 55 mm and a thickness of 2 mm,
The appearance and dimensional accuracy were measured and evaluated. The evaluation was performed as follows.・ Appearance When there are no defects such as sink marks, warping, twisting, silver and voids; ○ When there is an abnormality
× × Mold shrinkage Mold shrinkage is 7/1000 or less; ○ Mold shrinkage exceeds 7/1000; × (8) Dielectric constant and dielectric loss tangent An injection molded plate having a diameter of 100 mm and a thickness of 1.0 mm is used. And measured at 25 ° C. and 1 MHz based on JIS K6911. The evaluation was performed as follows. -Dielectric constant is less than 2.5; が Dielectric constant is 2.5 or more and less than 3.5; ○ Dielectric constant is 3.5 or more and less than 4.5; △ Dielectric constant is 4.5 × dielectric tangent is less than 0.001; dielectric tangent is 0.001 or more and less than 0.03; ○ dielectric tangent is 0.03 or more and less than 0.05; △ dielectric The tangent is 0.05 or more; ×

The polymers A and B used in the following Reference Examples, Examples and Comparative Examples mean the following. Polymer A: methyl tetracyclododecene (MTD) 8
0 part by weight and 20 parts by weight of dicyclopentadiene (DCP) of a ring-opened polymer hydride Mw: 55,000 (polystyrene conversion value by GPC analysis; solvent: toluene). As an antioxidant, tetrakis (methylene-3- (3 ′,
0.1 part by weight of 5'-di-t-butyl-4'-hydroxyphenylpropionate) methane was added to 100 parts by weight of the polymer hydride. Tg: 140 ° C., hydrogenation rate: 99.9% or more, ΔY
I: 0.1, heat distortion temperature: 123 ° C., dielectric constant: 2.3
5, dielectric loss tangent: 0.0005. Polymer B: ring-opened polymer hydride of ethyl tetracyclododecene (ETD) Mw: 60,000 (polystyrene conversion value by GPC analysis; solvent: toluene). As an antioxidant, tetrakis (methylene-3- (3 ′,
0.2 parts by weight of 5′-di-t-butyl-4′-hydroxyphenylpropionate) methane was added to 100 parts by weight of the polymer hydride. Tg: 140 ° C., hydrogenation rate: 99.9% or more, ΔY
I: 0.1, heat distortion temperature: 123 ° C., dielectric constant: 2.3
5, dielectric loss tangent: 0.0005.

Reference Example 1 Injection molded article C Material: Polymer A Molding machine: Sumitomo Heavy Industries, Ltd .; DISC-5 Molding conditions: Resin temperature: 310 ° C., mold temperature: 110 ° C.
Molding cycle time: 10 sec Injection molded body: optical disk substrate, diameter: 130 mm, thickness: 1.2 mm ΔYI: 0.4 Reference Example 2 Injection molded body D Material: Polymer B Molding machine: Toshiba Machine Co., Ltd .; IS450 Molding conditions: Resin temperature: 340 ° C, mold temperature: 130 ° C,
Molding cycle time: 30 sec Injection molded body: flat plate, length 250 mm, width 190 mm, thickness 1.5 mm ΔYI: 2.3

Example 1 Polyphenylene sulfide (manufactured by Polyplastics, unfilled PPS, melting point: 280 ° C., Fortron 02)
20A9) Glass fiber (surface having an average diameter of 13) treated with 100 parts by weight and γ-aminopropyltrimethoxysilane.
μm, average length: 8 mm), and mixed in advance with a twin-screw extruder (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 300 ° C. and 500 c of nitrogen in the hopper.
The kneaded material was extruded from a die into a strand while being supplied at c / min, and cut with a pelletizer to obtain pre-kneaded resin pellets E. The premixed resin pellets E were added at a ratio of 140 parts by weight to 100 parts by weight of the polymer A.
The kneaded product was extruded from a die into a strand at 500C while supplying nitrogen to the hopper at 500 cc / min, and cut with a pelletizer to obtain resin composition pellets. The resin composition pellets were molded at a resin temperature of 290 ° C. and a mold temperature of 110 ° C. using an injection molding machine (Roboshot α100B manufactured by FANUC CORPORATION) to form test pieces. The molded test pieces were evaluated according to the above evaluation method. Table 1 shows the results. Example 2 A resin composition pellet was obtained in the same manner as in Example 1 except that the pre-kneaded resin pellet E was 112 parts by weight based on 100 parts by weight of the polymer A. This resin composition pellet was injection-molded in the same manner as in Example 1 to form a test piece. The obtained test pieces were evaluated according to the above evaluation method. Table 1 shows the results.

Example 3 A resin composition pellet was obtained in the same manner as in Example 1 except that the injection-molded product C was crushed with a crusher instead of the polymer A. This resin composition pellet was injection-molded in the same manner as in Example 1 to form a test piece. The obtained test pieces were evaluated according to the above evaluation method. Table 1 shows the results. Example 4 A resin composition pellet was obtained in the same manner as in Example 1 except that polybutylene terephthalate (manufactured by Teijin Limited, unfilled PBT, melting point: 210 ° C, C7000) was used instead of PPS. This resin composition pellet was injection-molded in the same manner as in Example 1 to form a test piece. The obtained test pieces were evaluated according to the above evaluation method. Table 1 shows the results.

Example 5 Resin composition pellets were obtained in the same manner as in Example 1 except that Polymer B was used instead of Polymer A. This resin composition pellet was injection-molded in the same manner as in Example 1 to form a test piece. The obtained test pieces were evaluated according to the above evaluation method. Table 1 shows the results. Example 6 A resin composition pellet was obtained in the same manner as in Example 1 except that 140 parts by weight of a commercially available glass fiber-containing PPS (manufactured by Polyplastics, Fortron 1140A1) was used instead of the pre-kneaded resin pellet E. Was. This resin composition pellet was injection-molded in the same manner as in Example 1 to form a test piece. The obtained test pieces were evaluated according to the above evaluation method. The resin composition pellets were obtained in the same manner as in Example 1 except that the injection-molded article D obtained by crushing with a crusher was used instead of the polymer A in Example 7 shown in Table 1. This resin composition pellet was injection-molded in the same manner as in Example 1 to form a test piece. The obtained test pieces were evaluated according to the above evaluation method. Table 1 shows the results.

Comparative Example 1 100 parts by weight of unfilled PPS as in Example 1 and 100 parts by weight of polymer A
Parts by weight at the same time, and the same twin-screw extruder as in Example 1 was used.
The mixture was kneaded while being supplied at 00 cc / min to obtain resin composition pellets. This resin composition pellet was prepared in Example 1
Injection molding was performed in the same manner as described above to form a test piece. The obtained test pieces were evaluated according to the above evaluation method. Table 1 shows the results. Comparative Example 2 As in Comparative Example 1, 100 parts by weight of unfilled PBT and 40 parts by weight of surface-treated glass fiber as in Example 4 were simultaneously added to 100 parts by weight of polymer A and kneaded to obtain a resin composition pellet. . This resin composition pellet was injection-molded in the same manner as in Example 1 to form a test piece. The obtained test pieces were evaluated according to the above evaluation method. Table 1 shows the results.

Example 7 The resin composition pellets prepared in Example 4 were mirror-polished on both sides with the same injection molding machine as in Example 1 and had a length of 230 mm, a width of 53 mm and a thickness of 5 mm. Injection molding was performed using a mold at a resin temperature of 310 ° C. and a mold temperature of 120 ° C. to produce a molded product E. The appearance of the molded product E was good. Further, a thickness of 40 mm is formed on one surface of the molded product E by vacuum evaporation.
A mirror F was formed by forming an aluminum reflective film having a thickness of 0 nm.
The light reflectance of this mirror at a wavelength of 400 to 700 nm is 8
5-78%. Comparative Example 3 A molded product F was produced in the same manner as in Comparative Example 1 using the resin composition pellets produced in Example 7. Surface roughness was observed in the appearance of the molded product F. Further, an aluminum reflective film having a thickness of 400 nm was formed on one surface of the molded product F by a vacuum evaporation method, and a mirror F was manufactured. Wavelength 40 of this mirror
The light reflectance at 0 to 700 nm was 36 to 42%.

[0032]

[Table 1] Yellowness Fiber / Resin Kneading Method Fiber / Resin / Polymer ΔYI (Tm: ° C.) Weight Ratio Example 1 A (0.1) Glass Fiber / The Present Invention (40/100) / 100 PPS (280) Example 2 A (0.1 ) Glass fiber / The present invention (32/80) / 100 PPS (280) Example 3 C (0.4) Glass fiber / The present invention (40/100) / 100 PPS (280) Example 4 A (0.1) Glass fiber / Invention (40/100) / 100 PBT (225) Example 5 B (0.1) Glass Fiber / Invention (40/100) / 100 PPS (280) Example 6 A (0.1) GF / PPS Commercial Product Invention (40/100) / 100 Example 7 D (2.3) Glass Fiber / The Present Invention (40/100) / 100 PPS (280) Comparative Example 1 A (0.1) Glass Fiber / Simultaneous 40/100/100 PPS (280) Comparative Example 2 A (0.1) glass fiber / simultaneous 40/100/100 PBT (225) Moldability Moldability Heat resistance Mechanical permittivity Dielectric loss tangent (appearance) (dimensional accuracy) Strength Example 1 ○ ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ ○ Example 5 ○ ○ ○ ○ ○ ○ Example 6 ○ ○ ○ ○ ○ ○ Example 7 ○ ○ ○ ○ △ × Comparative example 1 × ○ ○ × △ △ Surface crack Comparative example 2 × ○ ○ × △ △ Surface crack

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 BB03X BB033 BB12X BB123 BK00W CE00W CF043 CF06X CF07X CF16X CF163 CH09X CL00X CL013 CL033 CL063 CN01X DA016 DJ006 DK006 DL006 FA046 FD010 FD013 FD016 FD020 FD040

Claims (5)

[Claims] 1. A method for producing a resin composition, comprising: melt-mixing a crystalline polymer and a fiber; and melt-mixing the obtained melt mixture and an alicyclic structure-containing polymer. 2. The method for producing a resin composition according to claim 1, wherein the melting point of the crystalline polymer is equal to or higher than the glass transition point of the polymer having an alicyclic structure. 3. A raw material for the alicyclic structure-containing polymer, which is dissolved in a soluble solvent at a concentration of 15% by weight and has an optical path length of 10 m.
The method for producing a resin composition according to claim 1 or 2, wherein a molded article containing an alicyclic structure-containing polymer having a yellowness measured by m of 2 or less is used. 4. A resin composition produced by the method according to claim 1. 5. A molded article comprising the resin composition according to claim 4.