JPH0859993A - Molded product comprising thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain a molded product such as a sheet, a film or a fiber, excellent in heat resistance and extrusion moldability, and improved in anisotropy on molding contraction constant, etc., by melt-molding a specific thermoplastic resin composition and specifying the vicat softening point. CONSTITUTION: This molded product having a vicat softening point of >=200 deg.C is produced by melt-extruding a thermoplastic resin composition containing (A) a polyarylene sulfide resin and (B) a thermoplastic norbornene resin. The component B has e.g. a norbornene skeleton of the formula (A, B, C, D are each H, a unvalent organic group), etc., in the repeating unit and a weight- average mol.wt. of 8000-200000, and the amounts of the components A and B are 95-60wt.% and 5-40wt.%, respectively, per 100 pts.wt. of their total weight.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a molded article made of a thermoplastic resin composition, which is particularly excellent in heat resistance and moldability, and is melt extruded from a thermoplastic resin composition having improved adhesion to various materials. The present invention relates to a molded article formed by

2. Description of the Related Art Polyphenylene sulfide resin (PP
S) is a thermoplastic resin with excellent heat resistance, rigidity, electrical insulation, chemical resistance, and flame retardancy, and is therefore used in a wide range of applications such as electric / electronic parts, automobile parts, and precision equipment parts. . For example, those formed into sheets or films are being considered for applications such as capacitor films, flexible printed wiring boards, and base films for magnetic recording media, and those formed into fibers are various filters and electrical insulation materials. , It is expected to be used for various purposes such as fibers for papermaking canvas. However, since PPS is a crystalline polymer, its fluidity extremely increases at a temperature above its melting point,
It is difficult to control the fluidity, and when extrusion molding is performed to obtain a sheet, film, or fiber, there is a problem that a molded product having a uniform thickness cannot be obtained. A method for obtaining high molecular weight PPS in order to increase the melt solubility is disclosed in Japanese Patent Laid-Open No. 4-2.
Although disclosed in Japanese Patent No. 55721, etc., it requires specific polymerization conditions, and in PPS obtained by these methods,
It is difficult to obtain extruded products with stable quality. Also P
Since PS is a crystalline polymer, it has anisotropy in molding shrinkage and linear expansion coefficient. Therefore, the heat-resistant material obtained by heat-treating an unstretched sheet of PPS to crystallize the sheet locally expands / contracts in the process of heat treatment, or has a small amount of low-boiling substances present inside PPS. It was often the case that the surface state was poor and the surface condition was poor due to the spouting. Several techniques for improving these problems are disclosed in Japanese Patent Laid-Open No. 59-184619,
JP-A-2-255839, JP-A-4-14891
Although disclosed in Japanese Patent Publication No. 7 and the like, it has a drawback of requiring complicated steps and being inferior in productivity. In addition, PPS is inherently inferior in adhesiveness to various materials such as metals and inorganic / organic materials due to the characteristics of its chemical structure, and a laminated body formed by laminating a PPS sheet or PPS fiber on a molded article made of another material is However, there was a problem of lack of reliability, such as the possibility of peeling during use. As a technique for improving the adhesiveness of the PPS sheet, a technique of performing corona discharge treatment or plasma treatment on the sheet surface is disclosed in JP-A-57-187327 and JP-A-2-4903.
No. 5, JP-A-2-107641 and the like are disclosed, but these techniques require a special device and require extra cost. Under these circumstances, PPS
Molding shrinkage and anisotropy of linear expansion coefficient, which are the drawbacks of the above, and adhesion to various materials are improved, and there is a demand for molded products that are sufficiently reliable even when used in applications where precision is strictly required. However, a molded product satisfying all the above demands has not been heretofore known.

DISCLOSURE OF THE INVENTION The present invention provides a molded article which solves the above problems all at once.
An object of the present invention is to provide a molded article obtained by melt-extruding a thermoplastic resin composition which has excellent melt extrudability, has improved anisotropy of molding shrinkage and linear expansion coefficient, and has improved adhesiveness with various materials. It is what

[0002]

The present invention comprises melting and extruding a thermoplastic resin composition which essentially contains a polyarylene sulfide resin and a thermoplastic norbornene resin, and has a Vicat softening temperature of 200 ° C. It is intended to provide a molded article as described above, particularly a molded article which is a sheet / film and a fiber. The thermoplastic norbornene-based resin used in the present invention has a norbornane skeleton in its repeating unit. For example, the thermoplastic resin includes a norbornane skeleton represented by any of the general formulas (I) to (IV).

[0003]

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[0004]

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[0005]

[Chemical 3]

[0006]

[Chemical 4]

(In the formula, A, B, C and D represent a hydrogen atom or a monovalent organic group.) The thermoplastic resin having a norbornane skeleton used in the present invention is required to have sufficient strength. And its weight average molecular weight is 5,000 to 1,000,000, preferably 8,000 to 20.
In many cases. Examples of the thermoplastic resin having a norbornane skeleton that can be used in the present invention include, for example, JP-A-60-168708 and JP-A-62-25240.
6, JP-A-62-252407, JP-A-2
-133413, JP-A-63-145324, JP-A-63-264626, JP-A 1-24
Examples thereof include resins described in Japanese Patent No. 0517, Japanese Patent Publication No. 57-8815, and the like. Among these resins, a resin obtained by hydrogenating a ring-opening polymer of a norbornene-based monomer is an amorphous polymer, so that P
Anisotropy in PS molding shrinkage and linear expansion coefficient can be greatly improved, which is preferable. Specific examples of this thermoplastic resin are obtained by metathesis polymerization of at least one tetracyclododecene derivative represented by the following general formula (V) or an unsaturated cyclic compound copolymerizable with the tetracyclododecene. The hydrogenated polymer obtained by hydrogenating the obtained polymer can be mentioned.

[0008]

[Chemical 5]

(In the formula, A to D are the same as above.) In the tetracyclododecene derivative represented by the general formula (V), it is possible that A, B, C and D contain a polar group. It is preferable from the viewpoints of adhesiveness with, heat resistance, and compatibility with polyarylene sulfide resin. Furthermore, it is obtained that the polar group is a group represented by-(CH ₂ ) nCOOR ³ (wherein R ³ represents a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 10). The hydrogenated polymer to be obtained is preferable because it has a high glass transition temperature. In particular, the - (CH ₂₎ a polar substituent represented by NCOOR ^3, it contained one per molecule of tetracyclododecene derivatives of general formula (V) is preferable from the viewpoint of reducing the water absorption. In the above-mentioned general formula, R ³ is a hydrocarbon group having 1 to 20 carbon atoms, but it is preferable that the hydrogen absorption of the obtained hydrogenated polymer becomes smaller as the number of carbon atoms increases, but From the viewpoint of balance with the glass transition temperature, a chain alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms is preferable, and a methyl group, an ethyl group, or a cyclohexyl group is particularly preferable. Is preferred.

Further, the carbon atom to which the group represented by-(CH ₂ ) nCOOR ³ is bonded simultaneously has 1 to 10 carbon atoms.
The tetracyclododecene derivative represented by the general formula (V) in which the hydrocarbon group is bonded as a substituent reduces hygroscopicity and is therefore preferable. Particularly, the tetracyclododecene derivative represented by the general formula (V) in which the substituent is a methyl group or an ethyl group is preferable in that the synthesis thereof is easy. Specifically, 8-methyl-8-methoxycarbonyltetracyclo [4,4,0,1 ^2.5 1 ^7.10] dodeca-8-ene are preferred. These tetracyclododecene derivatives or a mixture of unsaturated cyclic compounds copolymerizable therewith are described, for example, in JP-A-4-77520, page 4, upper right column, line 12 to page 6, lower right column, line 6. The thermoplastic resin used in the present invention can be obtained by metathesis polymerization and hydrogenation according to the method described above.

In the present invention, the thermoplastic resin having a norbornane skeleton has an intrinsic viscosity (η _inh ) measured at 30 ° C. in chloroform of 0.2 to 1.5 dl / g, preferably 0.3 to 1 It is 0.0 dl / g. Intrinsic viscosity (η
_{If the inh} ) is less than 0.2 dl / g, the mechanical properties are poor and the impact resistance is lowered, while if it exceeds 1.5 dl / g, the workability is poor and the extrusion moldability is poor. The hydrogenation rate of the hydrogenated polymer was 60 MHz, and the value measured by ¹ H-NMR was 5
0% or more, preferably 90% or more, more preferably 9
It is 8% or more. The higher the hydrogenation rate, the better the stability to heat and light. The hydrogenated polymer used as the thermoplastic resin having the norbornane skeleton of the present invention contains a gel contained in the hydrogenated polymer from the viewpoint of preventing the occurrence of defects such as surface roughness of the sheet surface in melt extrusion molding. The amount is preferably 5% by weight or less, and particularly preferably 1% by weight or less. When the softening temperature of the hydrogenated polymer is 90 ° C. or higher and the glass transition temperature is 100 ° C. or higher, particularly 130 ° C. or higher, the heat resistance of the polyarylene sulfide resin is not significantly impaired when compounded with the polyarylene sulfide resin. It is preferable above. The polyarylene sulfide resin used in the present invention is a polymer whose main constituent unit is represented by the general formula: —Ar—S— (wherein Ar represents a divalent aromatic group). Examples of the divalent aromatic group constituting the polyarylene group include p-phenylene group, m-phenylene group, 2,6-naphthalene group,
4,4'-biphenylene group, p, p'-bibenzyl group,
Typical examples thereof include those nuclear substituents. Among these, poly-p-phenylene sulfide having a p-phenylene group as a nuclear substituent is preferable in terms of moldability. In the present invention, the polyarylene sulfide resin has at least 70 mol% of the above structural units in one molecule.
It is necessary to contain the above. This main component is 70
When it is less than mol%, the crystallinity of the obtained polyarylene sulfide resin is lowered, the transition temperature is low,
Poor physical properties of the molded product result in unfavorable results. Furthermore, in the present invention, if the polyarylene sulfide resin is less than 30 mol% in one molecule, an aromatic group having a trivalent or more valent bond, such as a 1,2,4-bonded phenylene nucleus, an aliphatic group, or a hetero group, It does not matter even if it contains an atom-containing group. As the method for producing the polyarylene sulfide resin, a condensation reaction of a dihalogenated aromatic compound and a diol aromatic compound or a monohalogenated aromatic thiol, or a dihalogenated aromatic compound, an alkali sulfide or an alkali hydrosulfide and an alkali or a sulfur Examples thereof include a method utilizing a desalting condensation reaction of hydrogen and an alkali compound, but the method is not limited to these. For mixing the thermoplastic norbornene-based resin and the polyarylene sulfide resin, a compatibilizing agent can be used in order to enhance the compatibility. As one example thereof, a copolymer mainly composed of an olefin unit and an unsaturated compound unit having at least one functional group selected from a carboxyl group, an acid anhydride group, an oxazoline group and an epoxy group, and at least one vinyl When a polymer having a multilayer structure composed of a vinyl (co) polymer of a compound is used as a compatibilizing agent, the thermoplastic norbornene resin and the polyarylene sulfide resin become more compatible with each other. The proportion of the compatibilizer used is usually 0.1 to 20 parts by weight based on 100 parts by weight of the total of the thermoplastic norbornene resin and the polyarylene sulfide resin. here,
A copolymer mainly composed of an olefin unit in a polymer having a multilayer structure and an unsaturated compound unit having at least one functional group selected from a carboxyl group, an acid anhydride group, an oxazoline group and an epoxy group (hereinafter , "Copolymer I") is, for example, a binary, ternary or multi-component copolymer of an olefin and an unsaturated compound having the above-mentioned functional group and, if necessary, another unsaturated compound. . As the olefin in the above copolymer I, ethylene and propylene are preferable, and ethylene is particularly preferable.

The carboxyl group-containing unsaturated compound is acrylic acid, methacrylic acid, maleic acid or the like, and the acid anhydride group-containing unsaturated compound is maleic anhydride, itaconic anhydride or the like, and the oxazoline group-containing unsaturated compound is Examples of the epoxy group-containing unsaturated compound such as vinyl oxazoline include glycidyl methacrylate and allyl glycidyl ether. Preferred functional groups are an epoxy group and an acid anhydride group. The amount of olefin of the polymer I is usually 60 to 99.5% by weight, the amount of the unsaturated compound monomer having a functional group is usually 0.5 to 40% by weight, and the amount of the other unsaturated monomers is usually 0 to 39%. It is 0.5% by weight. Further, the vinyl-based copolymer composed of at least one vinyl compound in the multiphase structure is specifically styrene, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, α-methylstyrene, α. -Aromatic vinyl monomers such as ethylstyrene, esters of (meth) acrylic acid methyl, ethyl, dodecyl, octadecyl, etc., vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl such as acrylonitrile, methacrylonitrile, etc. The number average degree of polymerization obtained by polymerizing one or more vinyl compounds having no carboxyl group, acid anhydride group, oxazoline group, and epoxy group, such as cyanide compounds and acrylic acid amide compounds, is usually 5 to 10 Polymerization of 1,000, preferably 10 to 10,000 Body. The multi-phase structural component is a copolymer I or a vinyl-based (co) polymer matrix in which the vinyl copolymer or copolymer I, which is a different component, is uniformly dispersed in a spherical shape.
The particle diameter of the dispersed polymer is 0.001 to 10 μm,
It is preferably 0.01 to 5 μm. If the particle diameter of the dispersed polymer is less than 0.001 μm or exceeds 10 μm, the mechanical strength of the obtained composition is lowered, which is not preferable. The multiphase structural component is usually a copolymer of 5 to 95.
In order to achieve the object of the present invention, it is preferable that the content is 20% by weight, preferably 20 to 90% by weight. The method for producing the multi-phase structural component may be any method such as a well-known chain transfer method and ionizing radiation irradiation property, but the most preferable method is described in JP-A-64-48856. Is the way.

The thermoplastic resin composition of the present invention may optionally contain an inorganic filler. Examples of the inorganic filler include, for example, glass fiber, potassium titanate fiber, asbestos, silicon carbide, silicon nitride, ceramic fiber, zirconia fiber, silica fiber, alumina fiber, fibrous filler such as gypsum fiber, and barium sulfate. , Calcium sulfate, calcium sulfite, kaolin, clay,
Bylophyllite, bentonite, sericite, zeolite, mica, mica, nepheline sinite, talc, atarubulgite, wollastonite, PMF, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, antimony oxide, zinc oxide, lead oxide , Titanium oxide,
Examples thereof include inorganic fillers such as magnesium oxide, zirconium oxide, alumina, iron oxide, molybdenum disulfide, gypsum, glass beads, glass balloons, glass powder, glass flakes, silica powder, and silica beads. When a fibrous filler is used, its average diameter is preferably within the range of 0.1 to 250 μm in terms of the balance between rigidity and impact resistance.

Since the thermoplastic norbornene-based resin used in the present invention is amorphous, it does not cause an extreme increase in fluidity at the time of melting as compared with a crystalline polyarylene sulfide resin, and has a molding shrinkage ratio and a linear expansion coefficient. Small anisotropy. Therefore, by blending the thermoplastic norbornene-based resin with the polyarylene sulfide resin, the above-mentioned drawbacks of the polyarylene sulfide resin can be significantly improved, and the extrusion moldability and dimensional accuracy of the molded product are improved. Moreover, the thermoplastic norbornene-based resin is a resin having a high glass transition temperature, and even if blended with the polyarylene sulfide resin, the high heat resistance originally possessed by the polyarylene sulfide resin is not significantly impaired. However, if a molded product is molded with a resin composition containing an excessive amount of thermoplastic norbornene-based resin, the molded product may be deformed during long-term use at high temperatures, or soldering may be required as with printed wiring boards. In some applications, the high temperature heat (230-3
The molded product may be deformed or the reliability may be significantly reduced due to (about 00 ° C.). Therefore, in order for the molded article of the present invention to have sufficient heat resistance for use in various applications, the heat distortion temperature of the resin composition is preferably more than 180 ° C. under a load of 66 psi, and the Vicat softening temperature is Is 200 ° C. or higher. In the present invention, in order to obtain a thermoplastic resin composition satisfying the above-mentioned heat distortion temperature, extrusion moldability, and anisotropy in molding shrinkage, the total amount of the thermoplastic norbornene resin and the polyarylene sulfide resin is 100
The thermoplastic norbornene resin and the polyarylene sulfide resin are 1 to 60% by weight and 99% by weight, respectively.
It is desirable to be contained in the range of ˜40 wt%, preferably in the range of 5-40 wt%, 95-60 wt%, respectively. When the thermoplastic norbornene-based resin is less than 1% by weight, various defects due to the crystallinity of the polyarylene sulfide resin are not improved, and the anisotropy of the molding shrinkage rate and the linear expansion coefficient of the resin composition becomes large, and Since the fluidity of the composition becomes too large, melt extrusion molding becomes difficult, and the adhesion to various raw materials becomes poor, so that the molded product formed from such a composition becomes poor in reliability. Further, when the thermoplastic norbornene-based resin exceeds 60% by weight, the heat distortion temperature of the composition is remarkably lowered, and a molded article molded with such a composition is used for a long time at high temperature or soldered. It may be deformed by the high temperature heat applied during the process. Particularly, when the thermoplastic norbornene-based resin is a resin having no polar substituent in the norbornane skeleton, 1 to 4
It is preferably within the range of 0% by weight.

The thermoplastic resin composition used in the present invention may be blended with other thermoplastic resins or elastomers within a range not impairing the effects of the present invention. Examples of these thermoplastic resins include polyester, polyvinyl chloride, polyamide, polyimide, polyetherimide,
Polycarbonate, polyphenylene ether, polysulfone polyethersulfone, polyetheretherketone, polyetherketone, polyarylate, polytetrafluoroethylene, polydifluoroethylene, polystyrene and the like, elastomers, polyolefin rubber, fluorine Examples thereof include rubber and silicone rubber. In addition, the thermoplastic resin composition used in the present invention,
If necessary, an antistatic agent, a coloring agent, a flame retardant, an antioxidant, such as 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,2-methylene-bis- (4-ethyl-6-t-butylphenol), tris (di-nonylphenylphosphide), an ultraviolet absorber such as p-
t-Butylphenyl salicylate, 2,2'-dihydroxy-4-methoxy-benzophenone, 2- (2'dihydroxy-4'-m-octoxyphenyl) benzotriazole, "TINUVIN 320" [manufactured by Ciba Geigy], "TINUVIN 329". [Ciba Geigy], “TINUVIN 622LD” [Ciba Geigy], “CHIMASSORB 119FL” [Ciba Geigy], lubricants such as paraffin wax, stearic acid, hardened oil, stearamide, methylene bis stearamide, m-butyl stearate, Ketone wax,
Octyl alcohol, hydroxystearic acid triglyceride and the like may be added in the required amounts. In the present invention,
The melt viscosity of the thermoplastic resin composition is 1,000 to 25,000 at 300 ° C. and a shear rate of 1,000 sec ⁻¹ .
It is preferably in the range of 0 poise, particularly 3,000.
It is preferably in the range of ˜10,000 poise. If the melt viscosity is less than 1,000 poise, the fluidity becomes too large and the film-forming property is poor, so that it is difficult to stably obtain an extrusion-molded product, and the strength of the molded product decreases. On the other hand, if it exceeds 25,000 poise, the viscosity becomes too high, and it becomes difficult to form an extrusion-molded product having stable quality. The thermoplastic resin composition used in the present invention, using a mixer such as a single-screw extruder, a multi-screw extruder, a Banbury mixer, a kneader, a mixing roll, a resin composition and a filler, a flame retardant, if necessary further Obtained by mixing the additives used. An example of the method for producing the thermoplastic resin composition used in the present invention will be described. After mixing the components with a mixer, the mixture is melt-kneaded at 240 to 360 ° C. using an extruder to obtain a granulated product. Examples of a simple method include a method of directly kneading each component in a molding machine to obtain pellets. Further, there is a method in which a filler and a flame retardant are added later while kneading a resin component using a twin-screw extruder to prepare pellets. The method for extrusion-molding the molded article of the present invention is not particularly limited. For example, when molding into a sheet or film, a melt extruder is used, and the resin composition heated to a molding temperature of 260 to 380 ° C. A sheet or a film can be formed by extruding from a die of a mold or a manifold type and winding with various rolls.
It is also possible to further stretch and process the sheet-shaped molded product in the uniaxial or biaxial direction. Examples of the fiber include a method in which the resin composition heated to a melt extrusion temperature of 260 to 380 ° C. is melt extruded from a spinneret and spun. Further, these fibers may be drawn by a known method. In addition, the above-mentioned thermoplastic resin can be extruded from a suitable die to obtain various extruded products such as rods and tubes. These extruded products may be further stretched.

A colored layer may be provided on the surface of the molded article of the present invention. The coating material for forming these colored layers is not particularly limited, and a synthetic resin for coating material having a number average molecular weight of usually 1,000 to 1,000,000 in organic solvent, water, etc., and if necessary, pigment, coating material, metal, metal compound. It may be a solution or suspension of the above. Here, as the usable solvent, methanol, acetone, methyl ethyl ketone,
Examples thereof include ethyl acetate, pentane, octane and the like. Examples of paints include melamine resin-based paint, vinyl chloride resin-based paint, epoxy resin-based paint, urethane resin-based paint, polyester-based paint, acrylic resin-based paint, A
BS resin-based paint, vinyl acetate resin-based emulsion paint,
Examples thereof include acrylic resin emulsion paints, alkyd resin paints, polyamide resin paints, polyimide resin paints, polyvinylidene fluoride resin paints, silicone resin paints and polybutadiene paints. The method for applying the above-mentioned coating material to the molded article of the present invention is not particularly limited, but for example, brush coating, spraying, roll coating,
Coating means such as dipping can be mentioned. In this case, the molded article of the present invention may be subjected to surface treatment such as solvent treatment or oxidant treatment in advance before coating in order to form a stronger coloring layer. In addition, in order to make the molded product of the present invention a colored molded product, in addition to the above-mentioned methods, various paints, a method of molding using a pre-compounding pigment before molding may also be mentioned. it can. The molded article of the present invention may be printed. Here, the method for printing the molded article of the present invention is not particularly limited, and includes graphics, flexographic, silk screen,
Known methods such as dry offset, transfer and stamping can be used. When the molded product of the present invention is used in combination with another molded product, a colored layer such as a coloring agent or a coupling agent may be applied to the molded product of the present invention for the purpose of enhancing adhesiveness. As the adhesive for forming these adhesive layers, known adhesives that are generally used can be used. Epoxy adhesives, acrylic adhesives, cyanoacrylic adhesives, polyurethane adhesives, silicone adhesives A UV-curable adhesive, a hot-melt adhesive, a solution of a thermoplastic norbornene-based resin in an organic solvent, or the like can be used. Among these, a solution obtained by dissolving a thermoplastic norbornene-based resin in an organic solvent is compatible with the thermoplastic norbornene-based resin in the thermoplastic resin composition of the present invention, so that the adhesion becomes particularly high, which is preferable. . Here, when a solution obtained by dissolving a thermoplastic norbornene-based resin in an organic solvent is used as the adhesive, its structure is the same as the structure of the thermoplastic norbornene-based resin in the thermoplastic resin composition used for the molded article of the present invention. They may be present or different, but those having the same structure are preferable. In addition, the molded product of the present invention and another molded product can be bonded by using an ultrasonic welding method. The molded article of the present invention is a film for electrical insulation under high temperature, a packaging material, an interior cover film, a magnetic tape pace, a photographic film base,
Dielectric pace, base film for floppy disk,
Sheets and films for capacitors, flexible printed wiring boards, chip carriers, TAB tape, etc .; clothing, stuffed cotton, non-woven fabrics, artificial leather, artificial fur, flocking, moquette, various filters, electrical insulation materials,
It can be used in a wide range of applications such as textiles such as papermaking canvas, hot water pipes, chemical pipes for chemical plants, and other extruded products such as various electric / electronic parts, automobile parts, precision machine parts and daily necessities.

[0017]

EXAMPLES The present invention will be described in more detail with reference to the following examples.
However, the present invention is limited to the following examples.
is not. In the examples, parts and% are not particularly specified.
It is based on weight. Also, various measurements in the examples
Is as follows:Vicat softening temperature According to JIS K7206, test pieces with a thickness of 1/8 "
It was measured using a load of 1 kg and a heating rate of 50 ° C./h.Extrudability ◯: A molded product that could be stably and continuously extruded. X: A homogeneous molded product could not be extruded.Solder heat resistance Float the formed film in a solder bath at 260 ° C for 5 seconds.
Next, compare the condition of the sample before and after floating in the bath
It was judged according to. ○: No change at all Δ: The shape is retained although there is some deformation. X: Deformation was severe and the original shape was not retained.Heat shrinkage After heating at 180 ° C for 30 minutes according to ASTM D2838
In the longitudinal direction (MD) and width direction (TD) of the film
The shrinkage ratio was measured.Paintability The appearance of the coating film was visually evaluated according to the following evaluation criteria. ○: good, △: slightly inferior, ×: badAdhesion of coating film 100 pieces of 1mm x 1mm squares on the painted film
Carve with a cutter, perform a cellophane tape peeling test,
Adhesion was evaluated according to the following evaluation criteria. ◯: The number of peeled eyes is 0. Δ: The number of peeled eyes is 1 to 10. X: The number of peeled eyes exceeds 10. Reference example(A) Production of thermoplastic norbornene-based resin (A) -18-Methyl-8-methoxycarbonyltetracyclo
[4, 4, 0, 1^2.5, 1^7.10] Dodeca-3-en 10
0 g, 1,2-dimethoxyethane 60 g, cyclohexa
240 g, 1-hexene 8 g, and diethylaluminum
Dissolved 0.96 mol / l of toluene in toluene
Add 3.4 ml of the liquid to an autoclave with an internal volume of 1 liter.
I got it. On the other hand, another flask was charged with tungsten hexachloride (0.1%).
05 mol / l 1,2-dimethoxyethane solution 2
0 ml and 0.1 mol / l of paraaldehyde 1,
10 ml of 2-dimethoxyethane solution were mixed. This mixture
Add 4.9 ml of the combined solution to the mixture in the autoclave.
Added After sealing, heat the mixture to 80 ° C and stir for 3 hours
Was done. 1,2-dimethoxy was added to the obtained polymer solution.
Mixed solvent of 2/8 (weight ratio) of ethane and cyclohexane
Was added to make the polymer / solvent 1/10 (weight ratio),
Add 20 g of triethanolamine and stir for 10 minutes
It was To this polymerization solution, add 500 g of methanol to 30
Stir for a minute and let stand. Except for the upper layer separated into two layers,
And methanol were added, and the mixture was stirred and left standing, and then the upper layer was removed. As well
The above operation was performed twice more, and the resulting lower layer was cyclohexene.
Polymer diluted with sun or 1,2-dimethoxyethane
Cyclohexane-1,2-dimethoxyethane with a concentration of 10%
A tongue solution was obtained. Add 20 g of palladium / silica to this solution.
Camagnesia [manufactured by JGC Chemicals, palladium amount = 5
%] Is added, and the hydrogen pressure in the autoclave is 40 kg / c.
m²After reacting at 165 ° C for 4 hours, the hydrogenation catalyst
It was removed by filtration to obtain a hydrogenated polymer solution. Also,
Into this hydrogenated polymer solution, pentaeryth
Lytyl-tetrakis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate]
After adding 0.1% to the body, dissolve at 380 ° C under reduced pressure
The medium was made. Next, melt the resin under a nitrogen atmosphere.
Pelletized with an extruder at an intrinsic viscosity of 0.55 dl /
g (30 ° C., in chloroform), weight average molecular weight 8.0
× 10 ^Four, Hydrogenation rate 99.5%, glass transition temperature 168 ° C
The thermoplastic resin (a) -1 of was obtained. (A) -2 The same as (a) -1 except that the polymerization time was changed to 4 hours.
Metathesis Ring-opening polymerization, hydrogenation, pelletization
Viscosity 0.68 dl / g (30 ° C, in chloroform), water
Thermoplastic norbo with an addition rate of 99% and a glass transition temperature of 166 ° C
Runne resin (a) -2 was obtained. (A) -3 6-Ethylindene 2-tetracyclododecene Reference Example 1
Metathesis ring-opening polymerization similar to the above, followed by hydrogenation and pelletization
And an intrinsic viscosity of 0.50 dl / g (30 ° C, chloroform
Medium), weight average molecular weight 6.2 × 10^Four, Hydrogenation rate 99%,
A thermoplastic resin (a) -3 having a glass transition temperature of 140 ° C. is obtained.
It was (A) -4 55 mol% ethylene and 2-methyl-1,4,5,8-di
Methano-1,2,3,4,4a, 5,8,8a-octa
Pellets obtained by addition-polymerizing 45 mol% of hydronaphthalene
Intrinsic viscosity 0.62 dl / g (35 ° C, decalin
Medium), weight average molecular weight 9.5 × 10^Four,Glass-transition temperature
The thermoplastic resin (a) -4 of 140 degreeC was obtained.(B) Polyarylene sulfide (B) -1: polyphenylene sulfide LA-4X (re
Near type) manufactured by Topren Co., Ltd. (b) -2: polyphenylene sulfide T-4 (semi-crosslinked)
Type) Topren Co., Ltd. Compatibilizer: Modiper A4101 NOF CORPORATION

Examples 1 to 7 and Comparative Examples 1 to 4 The thermoplastic norbornene resins, polyarylene sulfide resins and compatibilizers of Reference Examples were blended as shown in Table 1 and melted at 300 ° C. using a twin-screw extruder. The mixture was mixed to produce a pellet-shaped thermoplastic resin composition. The Vicat softening temperature was measured for these resin compositions. Further, using these resin compositions, the resin temperature was raised to 310 ° C. to be heated and melted, and extrusion-molded from a T-die to obtain a width of 20 cm and a thickness of 10
A 0 μm film was obtained. These films were evaluated for extrusion moldability, solder heat resistance, and heat shrinkage. Further, an acrylic paint (manufactured by NOF Corporation, Nissan Candy Tone R4C) and a thinner (manufactured by NOF Corporation, Nissan High Plus No. 3) were added to the obtained film.
00) and a resin paint mixed in a weight ratio of 75/25 were applied using an air spray gun. 80 drying
It was carried out at 30 ° C. for 30 minutes to obtain a coating having a dry film thickness of 25 μm.
The paintability and coating adhesion of this coated film were evaluated. Table 1 shows the above evaluation results.

[0019]

[Table 1]

As is apparent from Table 1, the thermoplastic resin compositions (Examples 1 to 7) used in the molded articles of the present invention were excellent in heat resistance and moldability, and the anisotropy in heat shrinkage was improved. It is also excellent in paintability. On the other hand, in Comparative Example 1, a thermoplastic norbornene-based resin was not blended, and such a composition could not be stably extruded, had a large anisotropy in heat shrinkage, and was not compatible with a coating film. It also has poor adhesion. Further, Comparative Examples 2 to 4 are those in which the thermoplastic norbornene-based resin is excessively contained, and these have a Vicat softening temperature of less than 200 ° C., and thermal deformation is observed in solder heat resistance, etc. Is inferior in heat resistance. Example 8 Using the resin composition of Example 1, melt spinning was performed from a die having a die diameter of 2.8 mm at an extrusion temperature of 320 ° C., cooled in hot water at 80 ° C., and obtained as undrawn. There was no yarn breakage and stable continuous extrusion was possible. This unstretched yarn was stretched 3.5 times in a 90 ° C. stretching bath to obtain a good quality fiber.

[0021]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition used in the present invention is excellent in heat resistance and extrusion moldability, has improved anisotropy such as molding shrinkage, and has excellent adhesion to various materials. As a result, a molded product extruded from such a resin composition has a uniform thickness and an excellent appearance, and is extremely resistant to deformation and performance deterioration due to long-term use during the soldering process or in a high temperature environment. It will be reliable. Further, since the molded product of the present invention is excellent in paintability and printability, various colors and patterns can be formed, and a molded product having an excellent appearance can be obtained.

Claims (3)

[Claims] 1. A molded article obtained by melt-extruding a thermoplastic resin composition containing a polyarylene sulfide resin and a thermoplastic norbornene-based resin as essential components, and having a Vicat softening point temperature of 200 ° C. or higher. 2. The molded article according to claim 1, which is a sheet or a film. 3. The molded article according to claim 1, which is a fiber.