JP5365055B2 - Molded body and molding method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded body in which a molding base material composed of polyarylene sulfide resin composition and an orientation layer are integrated without using an adhesive. <P>SOLUTION: A molded film is a molded body in which a molding base material (A) made of the polyarylene sulfide resin composition and an orientation layer (B) composed essentially of the polyarylene sulfide resin composition are integrated without using an adhesive. On at least one side of a biaxial orientation polyphenylene sulfide film composed essentially of p-phenylene sulfide, the orientation layer (B) of a laminated biaxial orientation polyphenylene sulfide film in which a copolymerized polyphenylene sulfide layer having at least one or more copolymerized components other than the p-phenylene sulfide is laminated, is preliminarily shaped. Then, the orientation layer (B) is arranged in a metallic die and, on the side of the copolymerized polyphenylene sulfide layer of the orientation layer (B), the molding base material (A) made of resin composition composed essentially of polyarylene sulfide is integrated by injection molding. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a molded body in which a molded substrate made of a resin composition and an alignment layer are integrated without using an adhesive, and more specifically, a molded substrate made of a polyarylene sulfide resin composition, and a polyarylene. The present invention relates to a molded body in which an alignment layer composed of a resin composition containing sulfide as a main component is integrated without an adhesive.

  Conventionally, polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) has excellent properties such as heat resistance, flame retardancy, rigidity, chemical resistance, electrical insulation and low hygroscopicity. It is suitably used for electrical / electronic equipment, machine parts, automobile parts and the like. For example, (1) a resin composition of polyphenylene sulfide is disclosed (Patent Document 1). Further, (2) a polyphenylene sulfide biaxially oriented film is disclosed (Patent Document 2). PPS can be molded into various shapes by a melt molding method such as injection molding, but it has been necessary to increase the thickness in order to maintain strength. Polyphenylene sulfide, on the other hand, can improve toughness and strength by being biaxially oriented, and can reduce wall thickness. However, since the film thickness is constant and there is an upper limit for the thickness, it has a complicated shape. There were restrictions on processing. And, taking advantage of both, when trying to heat-seal a biaxially oriented PPS film and a PPS base material, heat is insufficient if the appearance (smoothness) of the film and mechanical properties (toughness, strength) are maintained. However, sufficient adhesive strength cannot be obtained. On the other hand, if the film is sufficiently heated until it can be heat-sealed, the properties and appearance of the film may be impaired.

Conventionally, as a method for improving the adhesiveness, (3) corona treatment has been disclosed (Patent Document 3), but a slight improvement was observed compared to untreated, but almost no improvement was observed. . Furthermore, although it has also been proposed to apply (4) an adhesive (Patent Document 4), when the adhesive is inferior in heat resistance and hydrolysis resistance, for example, it may not be used with a compressor motor insulating material or the like. It was. In addition, there are cases where the adhesive cannot be used, such as the use in oil or in a solvent, and the use has been limited.
JP 2007-246883 A JP 54-142275 A JP-A-2-228333 JP 62-292431 A

  It is an object of the present invention to provide a molded body in which a molding substrate made of a polyarylene sulfide resin composition and an alignment layer are integrated without using an adhesive, and a molding method thereof.

The molded film of the present invention comprises a molded substrate (A) comprising a resin composition containing polyarylene sulfide subjected to deionization treatment, and an orientation layer comprising a resin composition comprising p-phenylene sulfide as a main component ( B), and the alignment layer (B) has at least one type other than p-phenylene sulfide on at least one side of the biaxially oriented polyphenylene sulfide film layer (B1) whose main component is p-phenylene sulfide. A copolymerized polyphenylene sulfide layer (B2) having a copolymer component is laminated, the elongation at break is 100% or more and 150% or less, and the orientation parameter obtained by laser Raman spectroscopy of the orientation layer (B) is 2.0 to 8. consists .0 a is laminated biaxially oriented polyphenylene sulfide film, via an adhesive molding substrate (a) and an orientation layer (B) is A molded body characterized by comprising integrated by Rukoto without insert molding method. Further, a copolymerized polyphenylene sulfide layer (B2) having at least one copolymer component other than p-phenylene sulfide on at least one side of the biaxially oriented polyphenylene sulfide film layer (B1) mainly composed of p-phenylene sulfide. Is a laminated biaxially oriented polyphenylene sulfide film in which the elongation at break is 100% or more and 150% or less, and the orientation parameter obtained by laser Raman spectroscopy of the orientation layer (B) is 2.0 to 8.0. An alignment layer (B) is shaped in advance and then placed in a mold, and a molding substrate (A) made of a resin composition containing polyarylene sulfide on the copolymerized polyphenylene sulfide layer side of the alignment layer (B) is injection molded. It is an insert molding method that integrates.

According to the present invention, as will be described below, a molding substrate made of a polyarylene sulfide resin composition and a molding in which an alignment layer containing the polyarylene sulfide resin composition as a main component is integrated without an adhesive. You can get a body.

  The molded product of the present invention can be widely used for electrical insulation, circuit boards, general industrial use, and the like, and the effect is more prominent when used especially for electrical insulation.

  The polyarylene sulfide constituting the molding substrate (A) and the alignment layer (B) of the present invention is a homopolymer or copolymer having a repeating unit of-(Ar-S)-. Ar includes structural units represented by the following formulas (A) to (K).

(R1 and R2 are substituents selected from hydrogen, an alkyl group, an alkoxy group, and a halogen group, and R1 and R2 may be the same or different.)
As the repeating unit of polyarylene sulfide used in the present invention, the structural formula represented by the above formula (A) is preferable, and representative examples thereof include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, and random thereof. Examples thereof include copolymers, block copolymers, and mixtures thereof. Particularly preferred polyarylene sulfide is preferably polyphenylene sulfide (PPS) from the viewpoint of heat resistance and economy. The polyarylene sulfide used in the resin composition constituting the molded substrate (A) of the present invention is preferably a p-phenylene sulfide unit represented by the following structural formula as the main structural unit of the polymer, more preferably 80 mol% or more. Is preferably a PPS resin containing 90 mol% or more. When the p-phenylene sulfide unit is less than 80 mol%, the crystallinity and glass transition temperature of the polymer are low, and the heat resistance, dimensional stability, mechanical properties, dielectric properties, etc., which are the characteristics of PPS, may be impaired.

The alignment layer (B) of the present invention is preferably a biaxially oriented polyarylene sulfide film containing p-phenylene sulfide as a main component.
The alignment layer (B) further has at least one copolymer component other than p-phenylene sulfide on at least one side of the biaxially oriented polyphenylene sulfide film layer (B1) containing p-phenylene sulfide as a main component. A laminated biaxially oriented polyphenylene sulfide film in which the sulfide layer (B2) is laminated is preferred. The PPS resin of the alignment layer (B1) constituting the biaxially oriented polyphenylene sulfide film containing p-phenylene sulfide as a main component or the laminated biaxially oriented polyphenylene sulfide film is less than 8 mol% of the repeating unit in the PPS resin, preferably If it is less than 5 mol%, it does not matter even if units containing other sulfide bonds capable of copolymerization are contained. Further, in the copolymerized polyphenylene sulfide layer (B2) constituting the laminated biaxially oriented polyphenylene sulfide film, other sulfides that can be copolymerized are used as long as they are 8 mol% or more and 20 mol% or less of the repeating units in the PPS resin. Units containing bonds may be included. Examples of units containing a copolymerizable sulfide bond include trifunctional units, ether units, sulfone units, ketone units, meta bond units, aryl units having substituents such as alkyl groups, biphenyl units, terphenylene units, Examples include vinylene units and carbonate units. One or more of these can coexist. In this case, the structural unit may be either a random type or a block type copolymerization method.

  The melt viscosity of the PPS resin is not particularly limited as long as melt kneading is possible, but it is preferably in the range of 100 to 2000 Pa · s at a temperature of 315 ° C. and a shear rate of 1,000 (1 / sec). More preferably, it is in the range of 200 to 1,000 Pa · s.

  The PPS resin obtained above is subjected to crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, washing with an organic solvent, hot water and an aqueous acid solution, an acid anhydride, It can also be used after various treatments such as activation with functional group-containing compounds such as amines, isocyanates and functional group disulfide compounds.

  Next, although the manufacturing method of PPS resin is illustrated, in this invention, it is not limited to this in particular. For example, sodium sulfide and p-dichlorobenzene are reacted in an amide polar solvent such as N-methyl-2-pyrrolidone (NMP) at high temperature and high pressure. If necessary, a copolymer component such as trihalobenzene can be included. Caustic potash or alkali metal carboxylate is added as a polymerization degree adjusting agent, and a polymerization reaction is performed at 230 to 280 ° C. After the polymerization, the polymer is cooled, and the polymer is filtered as a water slurry through a filter to obtain a granular polymer. This is stirred in an aqueous solution such as acetate at 30 to 100 ° C. for 10 to 60 minutes, washed several times with ion exchange water at 30 to 80 ° C. and dried to obtain a PPS powder. The powder polymer is washed with NMP at an oxygen partial pressure of 10 torr or less, preferably 5 torr or less, then washed several times with ion exchange water at 30 to 80 ° C., and dried under a reduced pressure of 5 torr or less.

  As a specific method for crosslinking / high molecular weight by heating PPS resin, under an oxidizing gas atmosphere such as air or oxygen or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. A method of heating until a desired melt viscosity is obtained at a predetermined temperature in a heating container can be exemplified. The heat treatment temperature is usually selected from 170 to 280 ° C, more preferably from 200 to 270 ° C, and the heat treatment time is usually selected from 0.5 to 100 hours, more preferably from 2 to 50 hours. However, by controlling both of these, a target viscosity level can be obtained. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade, but in order to efficiently and uniformly perform the treatment, use a heating apparatus with a rotary type or a stirring blade. Is preferred.

  As a specific method for heat-treating the PPS resin under an inert gas atmosphere such as nitrogen or under reduced pressure, a heat treatment temperature of 150 to 280 ° C., preferably 200 to 200 ° C. under an inert gas atmosphere such as nitrogen or under reduced pressure. A method of heat treatment at 270 ° C. and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours can be exemplified. The heat treatment apparatus may be a normal hot air drier or a heating apparatus with a rotary or stirring blade, but it is preferable to use a heating apparatus with a rotary or stirring blade for efficient and more uniform treatment. . The PPS resin used in the present invention is preferably a substantially linear PPS that does not undergo high molecular weight by thermal oxidative crosslinking treatment in order to achieve the goal of improving tensile elongation at break.

The PPS resin used in the present invention needs to contain at least a PPS resin that has been subjected to deionization treatment. Specific examples of the deionization treatment include an acid aqueous solution washing treatment, a hot water washing treatment, and an organic solvent washing treatment, and these treatments may be used in combination of two or more methods.

  The following method can be illustrated as a specific method for the organic solvent cleaning treatment of the PPS resin. That is, the organic solvent is not particularly limited as long as it does not have an action of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, Sulfoxide / sulfone solvents such as dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane, Halogen solvents such as tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, Phenol, cresol, alcohol phenol based solvents such as polyethylene glycol, benzene, and aromatic hydrocarbon solvents such as toluene and xylene. Among these organic solvents, N-methylpyrrolidone, acetone, dimethylformamide and chloroform are particularly preferably used. These organic solvents are used alone or in combination of two or more.

  As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and it is possible to appropriately stir or heat as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning PPS resin with an organic solvent, Arbitrary temperature can be selected in the range of normal temperature-300 degreeC. As the cleaning temperature increases, the cleaning efficiency tends to increase, but usually a sufficient effect is obtained at a temperature of room temperature to 150 ° C. The PPS resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

  The following method can be illustrated as a specific method of the hot water washing process of PPS resin. That is, it is preferable that the water to be used is distilled water or deionized water in order to exhibit a preferable chemical modification effect of the PPS resin by hot water washing. The operation of the hot water treatment is usually performed by adding a predetermined amount of PPS resin to a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the PPS resin to water is preferably larger, but usually a bath ratio of 200 g or less of PPS resin is selected for 1 liter of water.

  The following method can be illustrated as a specific method of the acid aqueous solution washing treatment of the PPS resin. That is, there is a method of immersing the PPS resin in an acid or an acid aqueous solution, and it is possible to appropriately stir or heat as necessary. The acid to be used is not particularly limited as long as it does not have an action of decomposing PPS resin. For example, aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halogen-substituted fatty acids such as chloroacetic acid and dichloroacetic acid. Saturated carboxylic acids, aliphatic unsaturated monocarboxylic acids such as acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid And inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid and silicic acid. Of these, acetic acid and hydrochloric acid are preferably used. It is preferable to wash the acid-treated PPS resin several times with water or warm water in order to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin is not impaired by the acid treatment.

  The molded substrate (A) constituting the present invention is preferably composed of a resin composition containing the PPS resin, and preferably contains 30% by weight or more of the PPS resin. If it is less than 30% by weight, polymers other than PPS resin, inorganic fillers, and the like can be included. Examples of the polymer other than the PPS resin include various polymers such as polyetherimide, polyethersulfone, polysulfone, polyphenylene ether, polyester, polyarylate, polyamideimide, polycarbonate, polyolefin, and polyetheretherketone, and at least one of these polymers. Can be mentioned.

  Moreover, as inorganic fillers other than PPS resin, a fibrous form, plate shape, powder form, granular form etc. can be used, for example. Specifically, for example, fibrous fillers such as carbon fiber, potassium titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, and stone fiber, wollastonite, phlogopite, muscovite, zeolite Swellable layered silicate such as sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, montmorillonite, synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, Non-fibrous fillers such as metal compounds such as iron oxide, carbonates such as calcium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, ceramic beads, boron nitride, silicon carbide, graphite, pyrophyllite and calcium phosphate Can be mentioned. These may be hollow, and two or more of these fillers may be used in combination.

  In the molded product of the present invention, the molded substrate (A) composed of the PPS resin composition and the alignment layer (B) composed of the resin composition containing polyarylene sulfide as a main component are integrated without using an adhesive. This is a molded product. The adhesive has a composition other than the polyarylene sulfide resin and is not particularly limited, and examples thereof include polyurethane, epoxy, polyester, and silicone.

Orientation layer (B) of the present invention is composed of two or more layers, and the orientation layer biaxially oriented polyphenylene sulfide film layer (B) constituting the p- phenylene sulfide as a main component (B1) is, p- A film obtained by melt-molding a polyphenylene sulfide resin composition containing a phenylene sulfide unit as a main component to form a sheet, stretching at least uniaxially, preferably biaxially, and then heat-treating. The p-phenylene sulfide unit contained is preferably 92 mol% or more, more preferably 95 mol% or more. When the p-phenylene sulfide unit is less than 92 mol%, the crystallinity of the biaxially oriented polyphenylene sulfide film is lowered, and the heat resistance and thermal dimensional stability of the film may be impaired. The polyphenylene sulfide resin composition containing p-phenylene sulfide as a main component preferably contains 90% by weight or more of a polyphenylene sulfide resin containing p-phenylene sulfide as a main component. Other polymers can be included. Examples of the polymer other than the polyphenylene sulfide resin include various polymers such as polyetherimide, polyethersulfone, polysulfone, polyphenylene ether, polyester, polyarylate, polyamideimide, polycarbonate, polyolefin, polyetheretherketone, and at least one of these polymers. Mention may be made of blends containing seeds. In the present invention, polyetherimide is preferred from the viewpoint of improving moldability.

The polyetherimide used in the present invention is a polymer containing an aliphatic, alicyclic or aromatic ether unit and a cyclic imide group as repeating units, and is particularly limited as long as it is a polymer having melt moldability. Not. For example, U.S. Pat. Nos. 4,141,927, 2,262,678, 2,606,912, 2,606,914, 2,596,565, 2,596,566 and 2,598,566, polyether imide, 2,259,536, 2,599,171. No. 9, JP-A-9-48852, Japanese Patent No. 2565556, Japanese Patent No. 2564636, Japanese Patent No. 2564737, Japanese Patent No. 2563548, Japanese Patent No. 2563547, Japanese Patent No. 2558341, Japanese Patent No. 2558339, Japanese Patent No. 2835580 The described polymer. As long as the effect of the present invention is not impaired, the main chain of polyetherimide contains a structural unit other than cyclic imide and ether units, for example, aromatic, aliphatic, alicyclic ester units, oxycarbonyl units, and the like. May be. In the present invention, a condensate of 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride and m-phenylenediamine or p-phenylenediamine is used from the viewpoint of melt moldability and the like. preferable. This polyetherimide is available from General Electric under the trade name “Ultem” ®.

  Further, when adding polyetherimide to the polyphenylene sulfide resin, it is preferable to add a compatibilizing agent. Examples of preferable compatibilizing agents are selected from, for example, an epoxy group, an amino group, and an isocyanate group. And alkoxysilanes having one or more functional groups. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds, ureido group-containing alkoxysilane compounds such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane Γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanate pro Isocyanate group-containing alkoxysilane compounds such as ruethyldiethoxysilane, γ-isocyanate-propyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltri Examples include amino group-containing alkoxysilane compounds such as methoxysilane and γ-aminopropyltrimethoxysilane. Among them, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyl The use of an isocyanate group-containing alkoxysilane compound such as dimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanate-propyltrichlorosilane is preferable because the dispersibility of the polyetherimide can be improved. Used.

  Moreover, additives, such as an inorganic or organic filler, a lubricant, a coloring agent, a ultraviolet absorber, a compatibilizing agent, can also be included.

In the present invention, a copolymerized polyphenylene sulfide layer (B2) in which at least one copolymer unit other than the p-phenylene sulfide unit is copolymerized on at least one side of the biaxially oriented polyphenylene sulfide film layer (B1). Are stacked . This is a preferred embodiment from the viewpoint of improving adhesiveness with the molding substrate. The copolymerized polyphenylene sulfide used in the present invention is preferably composed of p-phenylene sulfide units having 80 to 92 mol% of repeating units as a main component. When the main component is less than 80 mol%, the heat resistance of the film may be significantly reduced, and when it exceeds 92 mol%, the adhesiveness with the molded body made of the resin composition may not be sufficiently improved.

  As the copolymer unit, m-phenylene sulfide unit represented by the following formula,

(Here, X represents an alkylene, CO, or SO ₂ unit.)

(Wherein R represents an alkyl, nitro, phenylene, or alkoxy group), and these complex units may be present. Preferred copolymerized units are m-phenylene sulfide units. The copolymerization amount of these units is preferably 8 mol% or more and 20 mol% or less, more preferably 10 mol% or more and 18 mol% or less. If the copolymerization component is less than 8 mol%, the adhesiveness with the resin composition may not be sufficiently improved during integral molding with the resin composition, and if it exceeds 20 mol%, the heat resistance of the alignment layer is reduced. There is a case.

  The mode of copolymerization of the above-mentioned main component and copolymer component of the copolymerized polyphenylene sulfide used in the present invention is not particularly limited, but is preferably a random copolymer.

  In the present invention, the remaining part of the repeating unit of the copolymer constituting the copolymerized polyphenylene sulfide may be composed of other copolymerizable structural units. For example, it is represented by the following formula: The trifunctional phenyl sulfide is preferably 1 mol% or less of the entire copolymer.

  The melting point of the copolymer polyphenylene sulfide constituting the copolymer polyphenylene sulfide layer (B2) of the present invention is preferably 1 to 100 ° C. lower than the melting point of the polyarylene sulfide constituting the biaxially oriented polyphenylene sulfide film layer (B1). More preferably, it is 10-50 degreeC, More preferably, it is 20-40 degreeC. When the difference between the melting point of the copolymerized polyphenylene sulfide and the melting point of the polyarylene sulfide constituting the biaxially oriented polyphenylene sulfide film layer (B1) is less than 1 ° C., the adhesiveness with the biaxially oriented polyphenylene sulfide film layer (B1) is The alignment layer (B) may not be sufficiently enhanced, or the planarity of the alignment layer (B) may deteriorate or heat shrink. The melting point of the copolymerized polyphenylene sulfide and the melting point of the polyarylene sulfide constituting the biaxially oriented polyphenylene sulfide film layer (B1) If the difference exceeds 100 ° C., the heat resistance of the alignment layer (B) may be significantly reduced. The melting point of the copolymerized polyphenylene sulfide can be appropriately adjusted depending on the molar ratio of the copolymerization components. For example, when the melting point of the copolymerized polyphenylene sulfide is 210 ° C., it can be obtained by setting the molar ratio of the copolymer components to 20 mol%.

  In the present invention, the copolymerized polyphenylene sulfide is preferably melt-molded into a sheet, biaxially stretched and heat-treated. By biaxially orienting the copolymerized polyphenylene sulfide layer, heat resistance and toughness can be improved. A method of laminating the copolymerized polyphenylene sulfide layer is not particularly limited, but a method of co-extrusion with a polyphenylene sulfide resin composition containing a p-phenylene sulfide unit as a main component is preferably used.

  The thickness of the copolymer polyphenylene sulfide layer (B2) is not particularly limited, but is preferably 5 μm or more and 50 μm or less. More preferably, they are 10 micrometers or more and 30 micrometers or less. When the thickness of the copolymerized polyphenylene sulfide layer is less than 5 μm, the adhesion to the molded body made of the resin composition may not be sufficiently improved, and when it exceeds 50 μm, the heat resistance of the alignment layer may be lowered.

  The alignment layer (B) of the present invention may be subjected to any processing such as heat treatment, molding, surface treatment, laminating, coating, printing, embossing and etching, as necessary.

The orientation of the biaxially oriented polyphenylene sulfide film layer (B1) or copolymerized polyphenylene sulfide layer (B2) constituting the orientation layer (B) of the present invention can be confirmed by orientation parameters that can be measured by laser Raman spectroscopy. it can. In the present invention, when the alignment parameter of the alignment layer (B) is 1.1 or more, it is determined that the alignment layer (B) is aligned. When the alignment layer (B) is composed of (B1) and (B2), it is determined that the alignment layer (B) is oriented if at least one of the orientation parameters is 1.1 or more. . Orientation parameter obtained by laser Raman spectroscopy, area by der of 2.0 to 8.0. A more preferable range of the orientation parameter is 2.5 to 6.0. Orientation parameters by laser Raman spectroscopy reflect molecular orientation and crystal content. When the orientation parameter exceeds 8.0, the molecular chain orientation is excessively advanced or crystallization is excessively advanced, and the tensile elongation at break is reduced. Or may not be able to withstand On the other hand, when the orientation parameter is less than 2.0, the molecular chain orientation may be insufficient or the progress of crystallization may be insufficient, which may reduce the heat resistance of the alignment layer. The alignment parameters of the alignment layer B1 or B2 by laser Raman spectroscopy include, for example, the stretching temperature and stretching ratio in longitudinal stretching, the preheating temperature before transverse stretching, the stretching temperature and stretching ratio in transverse stretching, and the heat setting temperature after stretching. By making it the preferred range of the present invention, it can be made the range of the present invention.

  The measurement method by the laser Raman spectroscopy is not particularly limited. For example, a laser Raman apparatus (PDP320 (manufactured by Photon Design)) is used, the microprobe objective lens is 100 times, and the objective lens is in the near infrared region (1064 to 1300 nm). ) Having transparency, NA of 0.95, and chromatic aberration correction can be used. Cross slit 1 mm, spot diameter 1 μm, light source Nd-YAG (wavelength 1064 nm, output: 1 W), diffraction grating Spectrograph 300 g / mm, slit: 100 μm, detector InGaAs (Roper Scientific 512) is preferably used.

The film used for measurement was sampled and embedded in an epoxy resin, and then the film cross section was taken out with a microtome. The film cross-section was adjusted to be parallel to the film longitudinal direction or width direction, and the average value was obtained by measuring 5 samples for each of the longitudinal direction and width direction with the central point of each sample as the measurement point. . The measurement is performed through a polarizer placed in a polarization direction parallel to the polarization direction of incident light, the sample is rotated, and a polarization direction perpendicular to the polarization direction parallel to the film surface is displayed with respect to the polarization direction of the laser light. A spectrum was obtained. The orientation parameter is
(Orientation parameter) = (I1575 / I740) (Parallel) / (I1575 / I740) (Vertical)
I1575 / I740 (parallel): In the Raman spectrum measured in the polarization direction parallel to the film surface, the Raman band near 1575 cm-1 is divided by the Raman band intensity near 740 cm-1.
I1575 / I740 (perpendicular): A Raman spectrum measured in the polarization direction perpendicular to the film surface, obtained by dividing the Raman band near 1575 cm-1 by the Raman band intensity near 740 cm-1.

Elongation at break of the oriented layer (B) of the present invention, it is necessary from the viewpoint of mold-like shaping in insert molding of the present invention is 150% or more and 100% or less. More preferably, they are 120% or more and 150% or less, More preferably, they are 130% or more and 150% or less. If the elongation at break is less than 100%, film cracking may occur during mold shaping, and there is no particular upper limit on the elongation at break, but in order to exceed 150%, the area stretch ratio in film formation must be increased. It is necessary to reduce, and the flatness and film forming stability of the film may deteriorate. In order to make the breaking elongation within the above range, it can be obtained by setting the film-forming stretching condition and the heat setting condition defined in the present application.

  The thickness of the alignment layer (B) of the present invention is preferably 5 μm or more and 1000 μm or less. More preferably, they are 10 micrometers or more and 500 micrometers or less, More preferably, they are 20 micrometers or more and 300 micrometers or less. When the thickness is less than 5 μm, the mechanical strength may not be sufficient, and when the thickness exceeds 1000 μm, the insert moldability may deteriorate.

  The method for integrating the orientation layer (B) and the molded base material (A) comprising the polyarylene sulfide resin composition is not particularly limited, but the orientation layer shaped on the surface of the molded base material (A) that has been molded in advance. (B) is heated to a melting point of the copolymerized polyphenylene sulfide layer (B2) —20 ° C. or higher and below the melting point of the biaxially oriented polyphenylene sulfide film layer (B1), and heated to such an extent that the flatness of the B1 layer is not impaired. The method of thermocompression bonding by applying or the method of integration by injection molding method in which a pre-shaped film is inserted into a mold is preferably used, and the latter method is particularly preferably used from the economical viewpoint.

  In the present invention, it is preferable from the viewpoint of improving the adhesion between the molding substrate and the alignment layer that injection molding is performed so that the molding substrate (A) is in contact with the copolymerized polyphenylene sulfide layer (B2).

  In the present invention, it is important that the molding substrate (A) composed of the polyarylene sulfide resin composition and the alignment layer (B) are integrated, but the molding substrate (A) and the alignment layer ( B) being integrated means that the alignment layer B is adhered to the base material A with a strength higher than that of material destruction. When the alignment layer B is peeled off, the surface of the alignment layer B is If it appears as the original surface, it is considered unintegrated.

  Subsequently, although the method to manufacture the molded object of this invention is demonstrated, it cannot be overemphasized that this invention is not limited to the following description.

  Examples of the method for producing the polyphenylene sulfide resin (PPS) include the following methods. Sodium sulfide and p-dichlorobenzene are reacted in an amide polar solvent such as N-methyl-2-pyrrolidone (NMP) under high temperature and high pressure. If necessary, a copolymer component such as trihalobenzene may be included. As a polymerization degree adjusting agent, caustic potash or alkali metal carboxylate is added, and a polymerization reaction is performed at a temperature of 230 to 280 ° C. After the polymerization, the polymer is cooled, and the polymer is filtered as a water slurry through a filter to obtain a granular polymer. This is stirred in an aqueous solution such as acetate at a temperature of 30 to 100 ° C. for 10 to 60 minutes, washed several times with ion exchange water at a temperature of 30 to 80 ° C. and dried to obtain a PPS granular polymer. The obtained granular polymer was washed with NMP at an oxygen partial pressure of 10 torr or less, preferably 5 torr or less, and then washed several times with ion-exchanged water at a temperature of 30 to 80 ° C. to form a by-product salt, a polymerization aid, and Unreacted monomers and the like are separated to obtain a PPS resin. If necessary, another polymer, an inorganic or organic additive, or the like is added to the PPS resin obtained as described above to the extent that the object of the present invention is not hindered to obtain a PPS resin composition.

  Examples of the method for producing the copolymerized polyphenylene sulfide resin include the following methods. Sodium sulfide, p-dichlorobenzene, and the accessory component monomer are blended in the ratios referred to in the present invention, and in the presence of a polymerization aid in an amide polar solvent such as N-methyl-2-pyrrolidone (NMP) under high temperature and high pressure. React. As an accessory component monomer,

(Here, X represents an alkylene, CO, or SO ₂ unit.)

(Wherein R represents an alkyl, nitro, phenylene, or alkoxy group), and a plurality of these subcomponent monomers may be present. A preferred accessory component monomer is

  A copolymerized polyphenylene sulfide resin is obtained by adding an inorganic or organic additive or the like to the above-obtained polymer as necessary or to the extent that does not interfere with the object of the present invention.

  Next, the manufacturing method of the orientation layer (B) of this invention is demonstrated. The PPS resin composition and the copolymerized polyphenylene sulfide resin are supplied to separate melt extrusion apparatuses and heated to the melting point or higher of each raw material. Each raw material melted by heating is laminated in two or three layers in a molten state by a merging device provided between the melt extrusion device and the die outlet, and is extruded from the slit-like die outlet. Such a molten laminate is cooled on the cooling drum to below the glass transition point of the PPS resin to obtain a substantially amorphous two-layer laminate sheet. Although a well-known apparatus can be applied to the melt extrusion apparatus, a uniaxial or biaxial extruder is simple and preferably used.

  Next, this unstretched film is uniaxially stretched and uniaxially oriented or biaxially stretched to be biaxially oriented. Stretching methods include sequential biaxial stretching methods (stretching methods that combine stretching in each direction, such as a method of stretching in the width direction after stretching in the longitudinal direction), and simultaneous biaxial stretching methods (in the longitudinal direction and the width direction). The method of extending | stretching simultaneously), or the method which combined them can be used. Here, a sequential biaxial stretching method in which stretching in the longitudinal direction and then in the width direction is performed first is used.

  An unstretched polyphenylene sulfide film is heated with a heated roll group, and the stretching ratio is 3 to 4 times in the longitudinal direction (MD direction), preferably 3.0 to 3.5 times, preferably 1 or 2 steps from the viewpoint of improving electrical properties. Stretching in the above multistage (MD stretching). The stretching temperature is in the range of Tg (glass transition temperature) to (Tg + 40) ° C., preferably (Tg + 5) to (Tg + 30) ° C. Here, Tg represents the glass transition temperature of polyphenylene sulfide, but when the alignment layer (B) is a laminated film, that is, when it is composed of (B1) and (B2) layers, Tg is high (B1). It is preferable to stretch in the above range according to the layer. Thereafter, it is cooled by a cooling roll group of 20 to 50 ° C.

  As a stretching method in the width direction (TD direction) following MD stretching, for example, a method using a tenter is common. The both ends of this film are gripped with clips, guided to a tenter, and stretched in the width direction (TD stretching). The stretching temperature is preferably Tg to (Tg + 40) ° C., more preferably (Tg + 5) to (Tg + 30) ° C. From the viewpoint of improving the elongation at break, the draw ratio is 3 to 4 times, preferably 3.0 to 3.5 times, and stretched in one or more stages (TD stretching).

  Next, this stretched film is heat-set under tension. The preferred heat setting temperature in the case of one-stage heat setting is 240 to 280 ° C., and the total time of the heat setting process and the relaxation treatment process is 1 to 10 seconds, preferably 3 to 8 seconds. A more preferable heat treatment is multistage heat setting. In this case, the heat setting temperature at the first stage is 160 to 220 ° C., preferably 180 to 220 ° C., and the treatment time is 1 to 15 seconds, preferably 1 to 8 seconds. Subsequently, the maximum temperature of the subsequent heat setting is 240 to 280 ° C, preferably 260 to 280 ° C. Furthermore, this film is subjected to a relaxation treatment in the width direction at 240 to 280 ° C, more preferably 260 to 280 ° C. The relaxation rate is preferably 0.1 to 8%, more preferably 2 to 5%. The total time of the subsequent heat setting step and the relaxation treatment step at 240 ° C. or higher is preferably 1 to 15 seconds, and more preferably 2 to 10 seconds.

  Further, the film is cooled and rolled up to room temperature, if necessary, in the longitudinal and width directions, if necessary, to obtain the desired biaxially oriented polyphenylene sulfide film.

  From the viewpoint of imparting stronger adhesiveness to the biaxially oriented polyphenylene sulfide film used in the present invention, a preferred embodiment of the present invention includes subjecting the copolymerized polyphenylene sulfide layer to corona discharge treatment or plasma treatment.

  The biaxially oriented polyphenylene sulfide film obtained above was cut into a circle according to the mold and inserted into a disk-shaped mold (center, direct gate) having a diameter of 150 mm and a thickness of 3 mm. Next, a molding base material (A) made of a pellet-like polyarylene sulfide resin composition is introduced into an injection molding machine (SE-100DU manufactured by Sumitomo Heavy Industries), injection molding is performed on the mold, and the film and the injection molding resin are made. A composite was obtained (mold temperature, 130 ° C., molding machine resin temperature 300-350 ° C.).

[Measurement method of characteristics]
(1) Melting temperature of resin and film Using a differential scanning calorimeter DSC (RDC220) manufactured by Seiko Instruments Inc. according to JIS K7121-1987 and a disk station (SSC / 5200) manufactured by the same company as a data analysis device, 5 mg of a sample was made of aluminum. The temperature was raised from room temperature to 340 ° C. at a heating rate of 20 ° C./min on a tray, melted and held at 340 ° C. for 5 minutes, rapidly solidified and held for 5 minutes, and then from room temperature at a heating rate of 20 ° C./min. The temperature rose. At that time, the peak temperature of the endothermic peak of melting observed was defined as the melting temperature (Tm).
(2) Glass transition temperature It was measured according to JIS K7121-1987. Using a differential scanning calorimeter DSC (RDC220) manufactured by Seiko Instruments Inc. and a disk station (SSC / 5200) manufactured by Seiko Instruments Inc. as a data analysis device, 5 mg of the sample was melted and held at 350 ° C. for 5 minutes on an aluminum tray, and rapidly cooled and solidified. The temperature was raised from room temperature at a heating rate of 20 ° C./min. The glass transition temperature (Tg) was calculated by the following formula.
Glass transition temperature = (extrapolated glass transition start temperature + extrapolated glass transition end temperature) / 2
(3) Melt Viscosity Melt viscosity was measured using Capillograph 1C (manufactured by Toyo Seiki Co., Ltd., die length 10 mm, hole diameter 0.5 to 1 mm) under the conditions of 310 ° C. and shear rate 1000 / sec.
(4) After washing the ash platinum dish with pure water, it is fired at 700 ° C. for 1 hour and dried in a desiccator. The weight of the platinum dish is precisely weighed to 0.1 mg using an analytical balance, and this value is defined as Ag. Next, about 5 g of the polymer sample was taken in a platinum dish, and the total amount of the platinum dish and the sample was precisely weighed to 0.1 mg with an analytical balance. This value is Bg. After that, place a platinum dish containing a polymer sample on a stainless steel bat and place it in a high-temperature oven set at 440 ° C. and bake for 5 hours, then raise the high-temperature oven setting to 500 ° C. and bake for 5 hours after reaching 500 ° C. did. After the treatment, it was cooled until the high-temperature oven temperature became 300 ° C. or lower, and after reaching 300 ° C. or lower, the stainless steel vat on which the platinum plate was placed was taken out, and the treated platinum plate was stored in a desiccator for 12 hours. Thereafter, the platinum dish was taken out from the desiccator and placed in a muffle furnace stable at 538 ° C. and baked for 6 hours. After the treatment, the platinum dish was taken out of the muffle furnace, and it was confirmed that the carbide (black) was completely eliminated in the sample. If even a small amount of carbide is observed, firing is further performed. After the completion of firing, the platinum dish was taken out of the muffle furnace, placed on a clean stainless steel bat and cooled in a desiccator for 30 minutes, and then the weight of the platinum dish was precisely weighed to 0.1 mg with an analytical balance. This value is Cg. Using weights A, B, and C measured by the above method, ash content was calculated according to the following formula.
Ash content (% by weight) = (C−A) / (B−A) × 100
(5) After washing the sodium-plated platinum dish with pure water, it was fired at 700 ° C. for 1 hour and dried in a desiccator. The weight of the platinum dish was precisely weighed to 0.1 mg using an analytical balance. This value is Ag. Next, about 5 g of the polymer sample was taken in a platinum dish, and the total amount of the platinum dish and the sample was precisely weighed to 0.1 mg with an analytical balance. This value is Bg. After that, place a platinum dish containing a polymer sample on a stainless steel bat and place it in a high-temperature oven set at 440 ° C. and bake for 5 hours, then raise the high-temperature oven setting to 500 ° C. and bake for 5 hours after reaching 500 ° C. did. After the treatment, it was cooled until the high-temperature oven temperature became 300 ° C. or lower, and after reaching 300 ° C. or lower, the stainless steel vat on which the platinum plate was placed was taken out, and the treated platinum plate was stored in a desiccator for 12 hours. Thereafter, the platinum dish was taken out from the desiccator and placed in a muffle furnace stable at 538 ° C. and baked for 6 hours. After the treatment, the platinum dish was taken out of the muffle furnace, and it was confirmed that the carbide (black) was completely eliminated in the sample. If even a small amount of carbide is observed, firing is further performed. After firing, the platinum dish was taken out of the muffle furnace, placed on a clean stainless steel bat and cooled in a desiccator for 30 minutes. Next, about 2 ml of pure water: hydrochloric acid = 1: 1 (hereinafter referred to as 1: 1 hydrochloric acid) liquid was added to the platinum dish. Hydrochloric acid was a special grade product. Thereafter, a platinum dish containing 1: 1 hydrochloric acid was heated using a hot plate. Heating was performed to such an extent that the solution boiled gently. When it was nearly evaporated to dryness, the heating was stopped and the platinum dish was cooled to room temperature. Thereafter, the contents of the platinum dish were washed with ion-exchanged water using a TPX funnel in a TPX-made 50 ml volumetric flask in several times while being placed in the volumetric flask, and the marked line of the volumetric flask was aligned with ion-exchanged water. Using the sample solution thus adjusted, measurement is performed using an atomic absorption measuring apparatus with ion-exchanged water as a blank. Specifically, prepare a calibration curve using a standard solution containing sodium before measurement, collect Xml of the sample solution, dilute with ion-exchanged water to make Yml, adjust the concentration so that it falls within the range of the calibration curve, Measurement was performed using the sample solution. Let the obtained value be Cppm. Using the above numerical values, the metal concentration was calculated according to the following.
Concentration [ppm] = C / (BA) × 50 × Y / X
(6) Insert injection moldability Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.), processing was performed at an injection / cooling rate of 12/15 seconds using a disk mold having a diameter of 150 mm, and the resulting integral molding was obtained. When the orientation layer (B) of the product is peeled off and the orientation layer (B) is peeled off with the original surface without material destruction, the interface between the molding substrate (A) and the orientation layer (B) When bubbles of 1 mm or more existed in the surface, blistering and peeling occurred, and the interface peeled, it was regarded as a defective product. The defect rate was evaluated according to the following criteria. The number of processed samples is 100 for each sample.
○: The defect rate exceeds 0% and 5% or less. Δ: The defect rate exceeds 6% and 20% or less. X: The defect rate exceeds 20%.

Reference Example 1 Molded Substrate (A) Production Method of PPS Resin Composition [Raw Materials Used] (A) PPS-1: In a 70 liter autoclave with a stirrer and a bottom plug valve, 47.5% sodium hydrosulfide 8 .27 kg (70.00 mol), 96% sodium hydroxide 2.94 kg (70.63 mol), N-methyl-2-pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 0.513 kg ( 6.25 mol), and 3.82 kg of ion-exchanged water, and gradually heated to 245 ° C. over about 3 hours through nitrogen at normal pressure to distill water 8.09 kg and NMP 0.28 kg, followed by reaction. The vessel was cooled to 200 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide. Thereafter, the mixture was cooled to 200 ° C., 10.34 kg (70.32 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min, and reacted at 270 ° C. for 140 minutes. Thereafter, 2.67 kg (148.4 mol) of water was injected while cooling from 270 ° C. to 250 ° C. over 15 minutes. Next, the mixture was gradually cooled from 250 ° C. to 220 ° C. over 75 minutes, and then rapidly cooled to near room temperature, and the contents were taken out. The contents were diluted with about 35 liters of NMP, stirred as a slurry at 85 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh (aperture 0.175 mm) to obtain a solid. The obtained solid was similarly washed and filtered with about 35 liters of NMP. The operation of diluting the obtained solid with 70 liters of ion-exchanged water, stirring at 70 ° C. for 30 minutes, and filtering through an 80 mesh wire net to collect the solid was repeated a total of 3 times. The obtained solid and 32 g of acetic acid were diluted with 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, filtered through an 80 mesh wire mesh, and further obtained solids were diluted with 70 liters of ion exchange water. The mixture was stirred at 70 ° C. for 30 minutes and then filtered through an 80 mesh wire net to collect a solid. The solid material thus obtained was dried at 120 ° C. under a nitrogen stream to obtain dry PPS. The obtained PPS had a melt viscosity of 45 Pa · s, an ash content of 0.02% by weight, and a sodium concentration of 85 ppm.
67 parts by weight of glass fiber was blended with 100 parts by weight of the polymerized PPS resin and melt kneaded / pelletized with a twin screw extruder.
Reference Example 2 Production of Copolymerized Polyphenylene Sulfide Resin Autoclave with 100 moles of sodium sulfide nonahydrate, 45 moles of sodium acetate and 25 liters of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) Was gradually heated to a temperature of 220 ° C. while stirring, and the contained water was removed by distillation. In the system after dehydration, 5 liters of 91 mol of p-dichlorobenzene as a main component monomer, 10 mol of m-dichlorobenzene as a secondary component monomer, and 0.2 mol of 1,2,4-trichlorobenzene were added. It was added together with NMP, nitrogen was pressurized and sealed at 3 ° C./cm ² at a temperature of 170 ° C., the temperature was raised, and polymerization was carried out at a temperature of 260 ° C. for 4 hours. After completion of the polymerization, the mixture was cooled, the polymer was precipitated in distilled water, and a small block polymer was collected with a wire mesh having a 150 mesh opening. The small block polymer thus obtained was washed five times with distilled water at 90 ° C. and then dried under reduced pressure at a temperature of 120 ° C. to obtain a melt viscosity of 100 Pa · s and a melting point of 250 ° C. A polymerized polyphenylene sulfide resin was obtained. Next, 0.3% by weight of calcium carbonate powder having an average particle size of 1.2 μm was added, uniformly dispersed and blended, and extruded into a gut shape at a temperature of 320 ° C. with a 30 mmφ twin-screw extruder, to produce copolymer polyphenylene sulfide pellets. Obtained.
Reference Example 3 Production of PPS Resin A PPS resin mainly composed of a p-phenylene sulfide unit uses 101 moles of p-dichlorobenzene as a main component monomer, except that no secondary component monomer is used. The PPS resin was produced in the same manner as in the production of the copolymer polyphenylene sulfide resin. The PPS resin had a melt viscosity of 300 Pa · s and a melting point of 283 ° C.
Example 1
The copolymerized polyphenylene sulfide resin and PPS resin obtained in Reference Examples (2) and (3) were each dried at a temperature of 180 ° C. for 3 hours under a reduced pressure of 1 mmHg, and then supplied to separate extruders in a molten state. The double pipe type laminating device at the top of the die is led to have two layers, then discharged from the T-die die provided, rapidly cooled with a cooling drum at a temperature of 25 ° C., and substantially copolymerized polyphenylene A two-layer laminate sheet of sulfide / PPS was obtained. Next, each obtained laminated sheet is caused to travel in contact with a plurality of heating rolls having a surface temperature of 95 ° C., and in the longitudinal direction between 30 ° C. cooling rolls having different peripheral speeds provided next to the heating roll. Stretched 5 times. The uniaxially stretched sheet thus obtained was stretched 3.7 times at a temperature of 100 ° C. in a direction perpendicular to the longitudinal direction using a tenter, and subsequently heat treated at 200 ° C. for 4 seconds (first stage heat treatment). Followed by heat treatment (second-stage heat treatment) at 260 ° C. for 4 seconds. Subsequently, after 5% relaxation treatment in the transverse direction for 4 seconds in a 260 ° C. relaxation treatment zone, the film edge was removed after cooling to room temperature, and biaxial orientation of copolymerized polyphenylene sulfide / PPS (10/65 μm) A polyarylene sulfide film was obtained.

Insert the copolymer polyphenylene sulfide side of the obtained biaxially oriented polyarylene sulfide film so as to be on the injection molding side, and inject the PPS resin obtained in Reference Example 1 at an injection temperature of 330 ° C. and an injection pressure of 40 MPa. An integral molded body of a mold at 80 ° C. and a PPS resin composition molded substrate-film was produced. The defective rate of the obtained molded body was 3 out of 100 molded bodies, and the defective rate was less than 5%.
(Example 2)
The biaxially oriented polyarylene sulfide film of copolymerized polyphenylene sulfide / PPS (10/65 μm) used in Example 1 was applied to the surface of the molding substrate obtained by injection molding in the same manner as in Example 1 at 260 ° C. The PPS resin composition molded substrate-film integral molded body was produced by hot pressing under a pressure of 300 kg / cm 2. The defective rate of the obtained molded body was 10 out of 100 molded bodies, and the defective rate was 10%.
(Example 3)
A biaxially oriented polyphenylene sulfide film was obtained in the same manner as in Example 1 except that only the PPS resin of Reference Example 3 was used. The obtained biaxially oriented polyphenylene sulfide film was subjected to insert injection molding in the same manner as in Reference Example 5 to prepare a PPS resin composition molded body-film molded body. The defective rate of the obtained molded body was 50 out of 100 molded bodies, and the defective rate was 50%.
(Comparative Example 1)
Adhesive: Urethane adhesive, “Ad Coat” 76P1
The mixing ratio of the main agent and the curing agent of the above-mentioned adhesive was adjusted so that the main agent / curing agent = 100/8, and the solid content concentration was adjusted to 32% with ethyl acetate. It applied to the corona discharge treatment surface of the axially oriented polyphenylene sulfide film. The drying conditions were 80 ° C. for 3 minutes, and the coating thickness was adjusted to 8 μm after drying. Moreover, what was produced by injection-molding only the PPS resin composition molded substrate in Example 1 was placed so that the adhesive layer side was the molded substrate side, and the PPS resin composition molded article-adhesive film was molded. The body was produced by press-bonding at 80 ° C. and 10 MPa. The obtained molded body was heated at a temperature of 60 ° C. for 50 hours to cure the adhesive. The defective rate of the molded body was 100 out of 100 molded bodies, and the defective rate was 100%.
(Comparative Example 2)
Adhesive: “Chemit Epoxy” TE5920 (manufactured by Toray Industries, Inc.) Solid content concentration 30 wt%
Adhesive formulation: Agent A / Agent B = 15/100
The PPS resin composition was molded in the same manner as in Comparative Example 1 except that it was applied to the corona discharge-treated surface of the biaxially oriented polyphenylene sulfide film by the gravure roll method in the same manner as in Comparative Example 1, and then the drying conditions were 100 ° C. and 3 minutes. A body-film compact was produced. The obtained molded body was heated at a temperature of 150 ° C. for 1 hour to cure the adhesive. The defective rate of the molded body was 100 out of 100 molded bodies, and the defective rate was 100%.

  The molded article of the present invention is a molded article in which the resin composition molding substrate and the film are integrated without using an adhesive, and can be widely used for electrical insulation, circuit boards, general industrial use, etc. It is particularly suitable for electrical insulation and is industrially useful.

Claims (2)

A molded body comprising a molding group (A) comprising a resin composition containing polyarylene sulfide subjected to deionization treatment and an alignment layer (B) comprising a resin composition comprising p-phenylene sulfide as a main component. Copolymer polyphenylene in which the alignment layer (B) has at least one copolymer component other than p-phenylene sulfide on at least one side of the biaxially oriented polyphenylene sulfide film layer (B1) mainly composed of p-phenylene sulfide. Laminated biaxial orientation in which the sulfide layer (B2) is laminated, the elongation at break is 100% or more and 150% or less, and the orientation parameter obtained by laser Raman spectroscopy of the orientation layer (B) is 2.0 to 8.0. It is made of polyphenylene sulfide film, and the molding substrate (A) and orientation layer (B) are insert molded without any adhesive. Molded body characterized by comprising integrated by. A copolymer polyphenylene sulfide layer (B2) having at least one copolymer component other than p-phenylene sulfide is laminated on at least one side of a biaxially oriented polyphenylene sulfide film layer (B1) mainly composed of p-phenylene sulfide. An alignment layer which is a laminated biaxially oriented polyphenylene sulfide film having a fracture elongation of 100% or more and 150% or less and an alignment parameter obtained by laser Raman spectroscopy of the alignment layer (B) of 2.0 to 8.0 (B) is pre-shaped and then placed in a mold, and a molding substrate (A) made of a resin composition containing polyarylene sulfide on the copolymer polyphenylene sulfide layer side of the orientation layer (B) is injection molded. Integrated insert molding method.