TW201313430A - Polyarylene sulfide film for mold-release and method for preparing thermosetting resin molded body using the same - Google Patents

Abstract

The subject of present invention is to provide a polyarylene sulfide film having excellent mold releasability. The solution of present invention is a polyarylene sulfide film for mold-release, which is a film formed by polyarylene sulfide film, and at least one side of the film satisfies the following (1) and (2) simultaneously. (1): The average roughness to centreplane (Sra) is 70 nm and less. (2): The hardness in depth of 10 nm measured by the nanoindentation method is 4.0 GPa and more.

Description

Poly-arylene sulfide film for mold release and method for producing thermosetting resin molded body using the same

The present invention relates to a polycondensation aryl sulfide film for mold release, which is used for molding a thermosetting resin, and a method for producing a thermosetting resin molded body using the same.

In the process of resin molding, a mold release film can be used for the purpose of facilitating the hot rolling of the hot-rolled molded body from the metal mold and preventing the metal mold from being contaminated by a hot press.

In the past, a release film has been a fluorine-based film, a polymethylpentene film, a polypropylene film, a polyethylene terephthalate film, or the like. However, the fluorine-based film is excellent in mold release property, but the problem is that it is a high-priced article and is difficult to burn at the time of waste incineration treatment after use, and a toxic gas is generated at the time of combustion. Since the polymethylpentene film has a low softening temperature, there is a problem that the film is likely to wrinkle during the molding. A polypropylene film or a polyethylene terephthalate film is relatively inexpensive, and has poor heat resistance, and is insufficient in mold release property at a high temperature. In order to improve the mold release property, an example of a surface layer of these films or a release layer formed of, for example, a thermosetting polyoxymethylene type release agent is known, but there is a case where the polyfluorene component is transferred to There is a concern that the surface of the body is molded to impair the quality of the product.

On the other hand, a polyphenylene sulfide film (hereinafter abbreviated as a PPS film) is excellent in heat resistance and chemical resistance, and exhibits good mold release property over a wide temperature range, and thus, in recent years, it has been expected to be a general-purpose release. The mold film can replace the expensive fluorine-based film. For example, there has been proposed a PPS film for mold release which adjusts the particle addition concentration to improve surface smoothness and reduce surface defects (see Patent Documents 1 and 2).

Further, in recent years, there have been many cases in which productivity is improved by setting the hot rolling temperature to a high temperature of 180 ° C or higher to shorten the rolling time, and it is highly desirable to develop a release film having a higher mold release property. In the case of high-temperature molding as described above, the conventional PPS film may have insufficient mold release property. For example, when the PPS film described in Patent Documents 1 and 2 is rolled at a temperature of 180 ° C or higher, the film may be When the molded body is in close contact, the film may be broken or broken at the time of peeling, and the molded body may not be obtained.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Publication No. 9-300365

Patent Document 2 Japanese Patent Laid-Open Publication No. 2008-110549

Patent Document 3 Japanese Patent Laid-Open Publication No. 2001-154198

An object of the present invention is to provide a polycondensation aryl sulfide film for mold release which is excellent in mold release property.

In order to solve the above problems, the polyarylene sulfide film of the present invention mainly has the following constitution. that is:

(I) a film of a poly(arylene sulfide) for demolding, which is a film composed of a poly(arylene thioether) resin, and satisfies the following (1), (2) at least one side of the film; 1): The center plane average roughness (SRa) is 70 nm or less, and (2): the hardness at a depth of 10 nm measured by a nanoimprint method is 4.0 GPa or more.

(II) The polyarylene sulfide film for mold release according to (I), wherein the film has a tensile modulus in the longitudinal direction and the width direction of 4.0 GPa or less.

(III) A method for producing a thermosetting resin molded body, which comprises placing a thermosetting resin preform on one surface of the film (1) and satisfying the surfaces of (1) and (2) And a step of shaping the thermosetting resin preform by hot calender molding using a metal mold.

(IV) The method for producing a thermosetting resin molded body according to (III), wherein the thermosetting resin is an epoxy resin.

According to the present invention, the release property of the poly(arylene sulfide) film can be greatly improved, and even if the film is formed by hot rolling at a high temperature of 180 ° C or higher, the film does not crack or break, and the film can be removed. The mold film is peeled off, and a thermosetting resin molded body is efficiently obtained.

[Formation for implementing the invention]

The invention is described below.

The poly-aryl aryl sulfide used in the present invention means that the main constituent unit is an -(Ar-S)-repeating unit, and it is preferred to contain a homopolymer or copolymer having more than 80% by mole of the repeating unit. Ar is a repeating unit represented by the following formula (A) to formula (L), and the like, and the repeating unit represented by the formula (A) is particularly preferable.

(However, R1 and R2 in the formula are hydrogen, an alkyl group selected from carbon atoms of 1 to 6, an alkoxy group having 1 to 6 carbon atoms, a substituent of a halogen group, and R1 and R2 may be the same or different).

On the premise that the repeating unit is the main constituent unit, a small number of branching units or crosslinking units represented by the following formulas (M) to (P) and the like may be contained. The amount of copolymerization of these branching units or crosslinking units is preferably in the range of 0 to 1 mol% with respect to -(Ar-S)-unit 1 molar.

Further, the poly-aryl aryl sulfide used in the present invention may be any of a random copolymer, a bulk copolymer and a mixture thereof having the above-mentioned repeating unit.

Representative examples of the poly(arylene sulfide) include polyphenylene sulfide, polyphenylene sulfide, polyphenylene sulfide, these random copolymers, bulk copolymers, and the like. . A particularly suitable poly(arylene sulfide) is a polyphenylene sulfide (hereinafter also referred to as PPS), which contains a p-phenylene sulfide unit represented by the following formula as a main constituent unit of the polymer. The content is preferably 80 mol% or more, preferably 90 mol%, more preferably 95 mol% or more. When the p-phenylene sulfide unit is less than 80 mol%, the crystallinity of the polymer is low or the heat transfer temperature is low, and the heat resistance and dimensional stability of the polyarylene sulfide film are impaired. The case of mechanical characteristics, etc.

The melt viscosity of the poly(arylene sulfide) in the present invention is not particularly limited, but is preferably in the range of 100 to 2,000 Pa s at a temperature of 310 ° C and a shear rate of 1,000 (1/sec), more preferably Range of 200~1,000Pa‧s. Further, the molecular weight of the poly(arylene sulfide) is not particularly limited, and a general poly(aryl) sulfide can be used. The weight average molecular weight of the poly(arylene sulfide) can be exemplified by 5,000 to 1,000,000, and 7,500 to 500,000. 10,000 to 100,000 is preferred.

The method for producing the poly(arylene sulfide) is not particularly limited, and an aromatic compound containing at least one core-substituted halogen or thiophene and an alkali metal monosulfide represented by JP-A-5-163349, for example, can be used. The method of reacting in a polar organic solvent at a high temperature is preferably obtained by bringing a vulcanizing agent into contact with a dihalogenated aromatic compound in an organic polar solvent.

In the present invention, the obtained polycondensation aryl sulfide may be subjected to heating in air for crosslinking/high molecular weight; heat treatment in an inert gas atmosphere such as nitrogen or under reduced pressure; The solvent, hot water, aqueous acid solution, and the like are washed, and various treatments such as activation of a functional group-containing compound such as an acid anhydride, an amine, an isocyanate, and a functional disulfide are used.

In the present invention, the poly(arylene sulfide) may be blended with a resin other than the poly(aryl sulfide) (heteropolypolymer) as long as it does not inhibit the characteristics of the present invention, and an antioxidant or a heat stabilizer may be added. Additives such as lubricants, UV absorbers, etc.

Further, in the present invention, the polyarylsulfide may contain organic or inorganic particles. Examples of such particles include inorganic particles such as calcium carbonate, cerium oxide, titanium oxide, aluminum oxide, kaolin, calcium phosphate, barium sulfate, talc, zinc oxide, and metal, or polytetrafluoroethylene particles and polyfluorinated particles. For example, cross-linked polystyrene particles to 300 ° C will not melt organic particles. Calcium carbonate or cerium oxide is preferred, and these particles are suitable because they have good affinity with the polymer and are less likely to form voids around the particles during film formation. The shape of the particles is not particularly limited, and particles of a spherical shape, a rectangular shape, a monodisperse form, and agglomerated shape may be used. These particles may be used alone or in combination of two or more. The amount of the particles added is less than 5% by weight based on the entire film, and is preferable from the viewpoint of ensuring high mold release property. In the case where the particle content is 5% by weight or more, because it is thin When the surface roughness of the film is increased, the release film and the molded body are firmly adhered to each other, and the mold release property may be deteriorated.

The thickness of the poly(arylene sulfide) film for mold release of the present invention is not particularly limited, and is preferably in the range of 1 to 500 μm, preferably 3, from the viewpoint of workability when using the release film. The range of ~250 μm, more preferably in the range of 5 to 100 μm.

Further, the polyarylene sulfide film for mold release of the present invention may be a stretched film or an unstretched film, and a film of an appropriate elongation condition may be used depending on the application.

It is important that the surface average roughness (SRa) of the surface of the polyarylene sulfide film for mold release of the present invention is 70 nm or less (conveniently referred to as surface physical property (1)). It is preferably 50 nm or less, more preferably 30 nm or less. When the average surface roughness of the center surface exceeds 70 nm, the adhesion between the unevenness on the surface of the film and the molded body is improved, and when the film is hot rolled at a high temperature of 180 ° C or higher, the mold release property may be insufficient. The lower limit of the center plane average roughness of the industrially film-formable poly-arylene sulfide film is 0.5 nm. In order to set the center surface average roughness to the above range, as described in the specific examples exemplified in the examples, the content of the particles, the average particle diameter of the particles, the stretching ratio at the time of film formation, the heat treatment temperature, and the like may be appropriately Adjustment.

From the viewpoint of improving mold release property, the polyaryl aryl sulfide film for mold release of the present invention is important in that the hardness at a depth of 10 nm from the surface is 4.0 GPa or more as measured by a nanoimprint method. It is called surface physical property (2)). It is preferably 4.2 GPa or more, more preferably 4.5 GPa or more. When the hardness is less than 4.0 GPa, the hot press delay at a high temperature of 180 ° C or higher may cause insufficient mold release property. On the other hand, the upper limit of the hardness It is not particularly limited, and the upper limit is substantially about 10 GPa. In order to achieve such a hardness, for example, a rubbing treatment or the like is applied to the surface of the film as will be described later.

In the case where the surface hardness is to be achieved by subjecting the surface of the poly(arylene sulfide) film to rubbing, the method of rubbing is not particularly limited, and for example, a known rubbing device can be used (see, for example, Patent Document 3). In this case, it is necessary to adjust the rubbing conditions so that the hardness value measured on the surface of the rubbed film by the nanoimprint method is within the aforementioned range.

In this case, it is preferable to rub the friction density (mm) represented by the following formula M to a condition of 300 mm or more, preferably 500 mm or more, and more preferably 700 mm or more. In the case where the friction density does not satisfy 300 mm, the hardness value measured by the nanoimprint method on the surface of the rubbed film may be out of the above range.

M=NL(1+2 π Rn/60V)

N in the above formula is the number of rubbing times, L is the length (mm) of the rubbing cloth in contact with the surface of the film, R is the radius (mm) of the rubbing roll including the thickness of the rubbing cloth, and n is the rotating speed of the rubbing roll (rprn ), V is the moving speed (mm/s) of the film.

The time for performing the rubbing treatment on the surface of the film is not particularly limited, and may be exemplified by, for example, a biaxially stretched film, rubbing the unstretched film before stretching; rubbing after extending in one direction; and winding after biaxial stretching Friction is performed before; after the winding, post-processing friction is performed.

The polyarylene sulfide film for mold release of the present invention is important in that at least one side of the film satisfies both surface physical properties (1) and surface physical properties (2). The surface satisfying these surface physical properties (1), (2) is suitable for use as a release surface, and the opposite side table The surface physical properties of the surface are not particularly limited. Therefore, the particle addition concentration on both surfaces may be different depending on the application, and a film different from the resin may be formed on the surface layer opposite to the surface having the surface physical properties satisfying (1) and (2).

Further, the stretched aryl sulfide film for mold release of the present invention preferably has a tensile modulus in the longitudinal direction and the width direction of the film of 4.0 GPa or less, preferably 3.7 GPa or less, more preferably 3.4GPa or less. When either of the tensile modulus in the longitudinal direction or the width direction of the film exceeds 4.0 GPa, the moldability of the film may be insufficient because the rigidity of the film is too high.

The polyarylene sulfide film for mold release of the present invention can be suitably used as a release film at the time of hot calender molding using a metal mold. For example, when manufacturing a printed circuit board, an IC wafer (wafer mold), a ceramic electronic component, a thermosetting resin product, a cosmetic board, or the like, the metal plates are sandwiched between the metal plates or between the resins at the molding step to make the metal When the board is made of a resin board, when manufacturing a flexible printed circuit board, when making a flexible printed circuit board, when manufacturing a fiber-reinforced composite material, when manufacturing a fiber-reinforced composite material, when manufacturing a sports and leisure product A film suitable for use. The release film used in the production of the laminate is specifically referred to, for example, in the calender molding at the time of manufacturing a multilayer printed circuit board, in order to prevent the subsequent connection between the printed circuit board and the separator or other printed circuit board. The film in between. In addition, the release film used in the manufacture of the flexible printed circuit board specifically refers to, for example, etching of the base film when manufacturing a movable portion and a deformable flexible printed circuit board in an electrical product. Thereby forming a circuit in order to protect the circuit The coating resin is used to cover the film used for coating the resin in order to cause the coating resin to adhere to the uneven portion of the circuit. The release film used for molding the epoxy resin composition for semiconductor encapsulation is specifically, for example, a powder or an ingot of an epoxy resin material by a known molding method such as a transfer mold or a compression mold. In the case of hardening molding, a film is present between the metal mold and the epoxy resin to prevent adhesion therebetween. The release film used in the production of the fiber-reinforced composite material is specifically, for example, a method in which a base material resin is molded by using a carbon fiber prepreg of an epoxy resin to produce various products, in order to prevent the metal mold and the epoxy resin. The film used for the adhesion. The release film used in the manufacture of sports and leisure articles is, for example, a carbon fiber pre-rolled in a cylindrical shape in an autoclave, for example, in the manufacture of a fishing rod, a golf club rod, a windsurfing rod, or the like. When the dip is hardened, the film used to prevent adhesion to the mold is used.

The present invention is particularly suitable for use in preventing the adhesion of a metal mold and a prepreg when a prepreg obtained by impregnating a base resin with a reinforcing fiber base is formed by a calender molding die. Examples of the structure of the prepreg to be used include high-strength fibers such as carbon fibers, glass cloths, and aramid fibers, and examples of the base resin impregnated include an epoxy resin, an unsaturated polyester resin, and an acryl. A thermosetting resin such as a base resin, a phenol resin, a melamine resin, or a polyamide resin, and an epoxy resin is preferred.

Next, for the method for producing the polyarylene sulfide film for demolding of the present invention, a method for producing a biaxially oriented polyphenylene sulfide film of polyphenylene sulfide by using polyphenylene sulfide is exemplified. However, the explanation of the present invention is not limited thereto.

(1) Polymerization method of polyphenylene sulfide

Sodium sulfide and p-dichlorobenzene are reacted in a guanamine-based polar solvent such as N-methyl-2-pyrrolidone (NMP) under high temperature and high pressure. It is also possible to include a copolymerization component such as trihalogenated benzene as necessary. Potassium hydroxide or an alkali metal carboxylate or the like may be added as a polymerization degree adjuster, and it may be polymerized at 230 to 280 °C.

After the polymerization, the polymer was cooled, the polymer was slurried with water, and filtered through a filter to obtain a particulate polymer. This is stirred in an aqueous solution of acetate or the like at 30 to 100 ° C for 10 to 60 minutes, washed with ion-exchanged water at 30 to 80 ° C several times, and dried to obtain a PPS powder. The powder polymer is washed with NMP at a partial pressure of oxygen of 10 torr or less, preferably 5 torr or less, and then washed with ion-exchanged water at 30 to 80 ° C for several times, and dried under reduced pressure of 5 torr or less. The powder polymer obtained by these is substantially a linear PPS polymer, and thus the film can be stably stretched.

(2) Method for preparing particle dispersed particles

The polyphenylene sulfide powder obtained as described above is mixed with a slurry obtained by dispersing particles in a liquid, and the mixture is supplied to a ventilating extruder, melt-kneaded, and the liquid is removed, and the phenyl group is dispersed. Particles are dispersed in the thioether. A suitable dispersion method is to first make the particles finely dispersed in a liquid having a boiling point of 90 to 290 ° C to form a slurry (hereinafter referred to as a particle slurry). It is desirable here to remove coarse or fine particles by filtration or decanter. The average particle diameter of the particles is preferably in the range of 0.5 to 3.0 μm in the particle slurry, and from the viewpoint of preventing secondary aggregation, the particle concentration in the slurry is based on the weight of the entire particle slurry. It is preferably 80% by weight or less in terms of the amount. The liquid may, for example, be water, ethylene glycol, triethylene glycol, NMP, diphenyl ether or the like, and water, ethylene glycol or triethyl glycol which does not dissolve the polyphenylene sulfide at a boiling point or higher of the liquid. A diol is preferred.

Next, by mixing the above-mentioned particle slurry to the polyphenylene sulfide powder, supplying it to an extruder having a vent hole, or supplying the polyphenylene sulfide powder to an extruder having a vent hole a method of forcibly injecting the particle slurry before or during melting of the polymer, and kneading the particle slurry into a polyphenylene sulfide in a molten state while removing the liquid component by a vent hole, thereby dispersing the particles In the polyphenylene sulfide. Here, from the viewpoint of dispersibility and removal efficiency of the liquid component, the ratio of the liquid component is preferably 30% by weight or less based on the polyphenylene sulfide powder, and more preferably 20% by weight or less. The gut-like polymer discharged from the extruder is cooled by a water bath or the like by a usual method, and is cut into particles in which particles are dispersed in the polymer (hereinafter referred to as particle particles).

Further, only the phenylene sulfide powder obtained in (1) is granulated (hereinafter, this granule is referred to as a non-particle granule). When a film is produced, it can be used in combination with the above particles.

(3) Manufacture of biaxially oriented polyphenylene sulfide film

After the particle particles and/or the non-particle particles obtained as described above are dried under reduced pressure, they are introduced into a melting portion of the extruder and heated to a temperature of 300 to 350 ° C, preferably an extruder of 310 to 340 ° C. . Then, the molten polymer passing through the extruder was passed through a filter, and the molten polymer was discharged into a film shape using a metal nozzle of a T die. This filter part or gold The set temperature of the nozzle is preferably set to a temperature of 3 to 20 ° C higher than the temperature of the melting portion of the extruder, preferably 5 to 15 ° C. The film was adhered to a cooling drum having a surface temperature of 20 to 70 ° C, and solidified by cooling to obtain an unstretched film having substantially no alignment.

Next, the unstretched film is biaxially stretched to have a biaxial alignment. The extension method may be a sequential biaxial stretching method (an extension method in which a method of extending in the longitudinal direction and extending in the width direction is sequentially extended in a single direction); and a biaxial stretching method (simultaneously toward the long side) A method of extending in the width direction) or a method of combining the same. Here, a sequential biaxial stretching method in which the first longitudinal direction is extended and then the width direction is extended will be described as an example.

After the unstretched polyphenylene sulfide film is heated by the heating roller group, it is 2.5 to 4.5 times, preferably 3.0 to 4.0 times, more preferably 3.1 to 3.4 times, and 1 stage in the longitudinal direction (MD direction). Or multi-stage extension (MD extension) performed in 2 or more stages. In the case where the stretching ratio is less than 2.5 times, there is a case where the planarity of the film is remarkably deteriorated in the course of the subsequent heat treatment. The elongation temperature is preferably from 70 to 130 ° C, preferably from 80 to 110 ° C. It is then cooled by a cooling roller set of 20 to 50 °C.

After the MD extension, the extension method in the width direction (TD direction) is generally a method using, for example, a tenter. The two ends of the film were clamped by a jig and guided to a tenter to extend in the width direction (TD extension). The elongation temperature is preferably from 70 to 130 ° C, preferably from 80 to 110 ° C. The stretching ratio is 2.5 to 4.5 times, preferably 3.0 to 4.0 times, and more preferably 3.1 to 3.4 times.

Next, the biaxially stretched film is subjected to heat treatment under tension. The heat treatment temperature is preferably in the range of 160 to 280 ° C, and is preferably carried out in a plurality of stages of one stage or two stages or more. At this time, from the viewpoint of the dimensional stability of the heat, it is preferable to carry out the relaxation treatment in the range of 0 to 10% in the film width direction at the heat treatment temperature. In the case of the second-stage heat treatment, the first-stage heat treatment temperature is set in the range of 160 to 220 ° C, and the second-stage heat treatment temperature is set in the range of 230 to 280 ° C and higher than the temperature in the first stage. The film is suitable for film formation or stable film formation. The film was cooled to room temperature after heat treatment.

(4) Friction treatment

The biaxially oriented polyphenylene sulfide film obtained as described above was subjected to a rubbing treatment using a rubbing device. The friction device can also be used by a well-known person. The outline is obtained by pressing a roller wound with a rubbing cloth against the film, and rotating the roller while relatively moving it to rub. The direction of rotation of the roller is preferably along the direction in which the rubbing cloth is wound, and it is preferable to rotate in the opposite direction to the moving direction of the film. Further, the direction of movement of the roller shaft and the film may be at a certain angle θ. The strength of the friction can be appropriately changed in accordance with the rotation speed ratio, the amount of pressing, and the like. The rotational speed ratio refers to the value obtained by dividing the relative linear velocity of the roller by the relative moving speed of the film. The pressing amount generally refers to pressing the rubbing cloth (roller) into the film from the position where the surface of the film meets the surface of the rubbing cloth. The length of the surface. The material of the rubbing cloth is suitable for cellulose acetate, cotton, ray, polyamide, acrylic, aramid and the like. The form of the rubbing cloth is preferably a non-woven fabric, a woven fabric, or a woven fabric. From the viewpoint of improving productivity, the rubbing direction is preferably such that the direction of rotation of the rubbing roller is parallel to the longitudinal direction (MD direction) of the film. In addition, From the viewpoint of preventing dust or the like from adhering to the film, it is preferable to perform static elimination after rubbing. As described above, the obtained polyphenylene sulfide film is suitably used as a film for mold release.

[Examples]

The method for measuring the physical property value and the method for evaluating the effect are as follows.

(1) Center plane average roughness (SRa)

Using the SURF CORDER ET 4000A manufactured by Otaru Research Institute, the surface center plane average roughness (SRa) was obtained in accordance with the following conditions.

Contact lens radius of curvature: 2μm

Cut-off point: 0.25mm

Measuring length: 0.5mm

Measurement interval: 5μm

Number of measurements: 80 times.

(2) Nano imprint hardness

The measurement was carried out by a nanoimprint method using a nanometer hardness tester "Nano Indenter DCM" manufactured by MTS Systems. The load-bearing/de-loading test was carried out using a diamond-shaped triangular pyramid indenter to obtain a load-pressing depth map. At this time, the hardness H at the maximum load Pmax is calculated by the following formula.

H=Pmax/A

A in the above formula is the indentation projected area, which is a value calculated using the effective contact depth calculated from the load-press depth map. The measurement was carried out 10 times in accordance with the following conditions, and the average value of the hardness at a press-in depth of 10 nm was obtained.

Measuring condition

Measuring device: Nano Indenter DCM made by MTS Systems

Determination method: nanoimprint method (continuous rigidity measurement method)

Using the indenter: a diamond-shaped triangular pyramid indenter

Maximum indentation depth: about 3μm

Measurement environment: 25 ° C ‧ atmosphere.

(3) Tensile modulus

An Instron type tensile tester was used in accordance with the method specified in ASTM-D882 and measured according to the following conditions. The sample was changed and the longitudinal direction and the width direction of the film were measured 10 times, and the average value was obtained.

Measuring device: "Tensilon AMF/RTA-100" automatic measuring device for film elongation of ORIENTEC Co., Ltd.

Sample size: width 10mm × test length 100mm

Stretching speed: 300mm/min

Measurement environment: 25 ° C, 65% RH.

(4) Film thickness

The average value was determined by a 10-point measurement using a Dial Gauge thickness meter (manufactured by Mitutoyo Co., Ltd.).

(5) Demoulding evaluation by metal mold forming test

A prepreg (made by Toray Industries, product model: 3252S-15) composed of carbon fiber and epoxy resin and cut into a size of 29 cm × 29 cm was sandwiched between two sample film sheets cut into a size of 30 cm × 30 cm. At this time, lamination is performed so that the rubbed surface is in contact with the prepreg. By warming the metal mold The calendering machine (plate metal mold) at 200 ° C was applied to apply a pressure of 2 MPa for 5 minutes, and then the laminate was taken out, and after sufficiently cooling at room temperature, the prepreg and the sample film were torn by hand. The release property at the time of peeling was judged by the following criteria. C is unqualified.

Mold release

A: The film is not broken and is easily peeled off from the prepreg.

B: Part of the film is broken and peeled off by the prepreg

C: Firmly adhered and not peeled off from the prepreg.

(6) Moldability evaluation by metal mold forming test

A projection having a right-cylindrical shape having a diameter of 5 cm and a height of 7 mm at the center portion was formed, and a vent hole for a vacuum suction (a hole diameter of 1 mm) was opened at six intervals along the circumference of the bottom portion of the projection portion. A metal mold (having a size of 15 × 25 cm) was attached to a vacuum forming machine (device name: Forchem 300 type) manufactured by Chengguang Industry Co., Ltd. The sample film was cut into an A4 size and mounted on a device, and the sample film was preheated for 10 seconds using a ceramic heater attached to a device heated to 350 ° C, and then the unheated metal mold was pressed against the sample film. After pressing, vacuum suction was performed through the vent hole for 30 seconds to form a film. At this time, since the sample film could not sufficiently conform to the protrusion shape of the metal mold, the metal mold was attracted obliquely with the upper end portion of the protrusion as a starting point. The linear distance between the two points on the plane projected by the circle at the top of the protrusion on the start point and the end point of the inclined portion (the contact point between the film and the protrusion and the contact point on the bottom side of the protrusion) (It is observed that the starting point and the ending point are approximately concentric circles.) 10 points are measured by a vernier scale (10 points are uniformly taken from the entire circumference), and the average value is defined as the width of the 裾. The moldability at the time of molding was judged by the following criteria. C is unqualified.

Formability

A: 裾 width is less than 1cm

B: 裾 width is 1cm or more and 2cm or less

C: The width of the crucible is 2 cm or more.

(1) Production of polyphenylene sulfide powder

The autoclave was charged with 47% sodium hydrogen sulfide (9.44 kg (80 mol), 96% sodium hydroxide 3.43 kg (82.4 mol), N-methyl-2-pyrrolidone (NMP) 13.0 kg (131 m). Sodium acetate 2.86kg (34.9 mol) and ion-exchanged water 12kg, nitrogen gas is passed under normal pressure, and it takes about 3 hours to slowly heat to 235 ° C, and water 17.0 kg and NMP 0.3 kg (3.23 mol) After the reaction, the reaction vessel was cooled to 160 °C. Next, add 11.5 kg (78.4 mol) of p-dichlorobenzene (p-DCB), 0.007 kg (0.04 mol) of 1,2,4-trichlorobenzene, and 22.2 kg (223 mol) of NMP under nitrogen. The reaction vessel was sealed and stirred at 400 rpm while raising the temperature from 200 ° C to 270 ° C at a rate of 0.6 ° C / minute. After 30 minutes at 270 ° C, 1.11 kg (61.6 mol) of water was injected into the system over 10 minutes, and the reaction was continued at 270 ° C for another 100 minutes. Then, 1.60 kg (88.8 mol) of water was again injected into the system, and after cooling to 240 ° C, it was cooled at a rate of 0.4 ° C / min, cooled to 210 ° C, and then quenched to near room temperature. The contents were taken out, diluted with 32 liters of NMP, and the solvent and solid were filtered through a sieve (80 mesh). The obtained particles were again washed with 38 liters of NMP at 85 °C. Then, it was washed 5 times with 67 liters of warm water and filtered, washed 5 times with 70,000 g of 0.05% by weight aqueous calcium acetate solution and filtered to obtain PPS polymer particles. It was dried by hot air at 60 ° C, and dried under reduced pressure at 120 ° C for 20 hours, whereby a white polyphenylene sulfide powder was obtained.

(2) Production of particle-free particles

The polyphenylene sulfide powder obtained in (1) was supplied to a ventilating extruder having a biaxial screw having a diameter of 30 mm, and was melted at a temperature of 320 °C. This melt was filtered through a 95% cut-off filter made of metal fibers and having a pore size of 10 μm, and then extruded through a die having a pore diameter of 2 mm to obtain a gut-like resin composition. Further, the composition was cut into a length of about 3 mm to obtain a particle-free particle of polyphenylene sulfide.

(3) Production of particle particles

Calcium carbonate particles having an average particle diameter of 1.2 μm were dispersed in 50% by weight of ethylene glycol to prepare a slurry. After filtering the slurry with a filter, it was mixed with the obtained polymer (1) using a Henschle mixer. At this time, mixing was carried out so that the weight of calcium carbonate became 20 weight% with respect to the weight of the polymer obtained by (1). The obtained mixture was supplied to a ventilating extruder having a biaxial screw having a diameter of 30 mm, and melted at a temperature of 320 °C. This melt was filtered through a filter made of metal fibers and having a 95% cut-off pore diameter of 10 μm, and then extruded through a die having a pore diameter of 2 mm to obtain a gut-like resin composition. Further, the composition was cut into a length of about 3 mm to obtain particle particles having a particle content of 20% by weight.

(Example 1)

The particle-free particles obtained above were mixed with the particle particles so that the content of calcium carbonate became 0.5% by weight based on the weight of the polyphenylene resin, and then the pressure was reduced at 3 mmHg and at a temperature using a rotary vacuum dryer. Dry at 180 ° C for 4 hours. The obtained dried wafer was supplied to a full-thread single-axis extruder heated to 310 ° C in the melting section, and filtered at a temperature of 320 ° C after the filter was set, and the temperature was set at 310 ° C. The metal nozzle of the mold was melt-extruded, and an electrostatic charge was applied to the casting drum having a surface temperature of 25 ° C while being tightly cooled and solidified to produce an unstretched film.

This unstretched film was preheated by a longitudinal stretching machine composed of a plurality of heated roller groups, and then stretched in the longitudinal direction of the film at a film temperature of 101 ° C at a magnification of 3.5 times by the difference in rotation speed of the rolls. Then, the two ends of the film were clamped by a jig, and guided to a tenter, and extended at a stretching temperature of 101 ° C at a stretching ratio of 3.7 times in the width direction of the film, followed by heat treatment at a temperature of 260 ° C. Seconds. Between the heat treatments, a 5% relaxation treatment was performed in the film width direction. After the film was cooled to room temperature, the edge of the film was removed to prepare a biaxially oriented PPS film having a thickness of 25 μm.

One side of the produced film was uniformly rubbed using a friction device manufactured by Newtom. The rubbing cloth was made of a tanned woven fabric and rubbed under conditions of a friction density of 1000 mm. The center surface average roughness and the nanoimprint hardness of the friction surface were measured as described in Table 1. As a result of evaluation of mold release property using this film, as shown in Table 1, excellent mold release property was exhibited.

(Example 2)

In the same manner as in Example 1, except that the particle-free particles were mixed with the particles in the first embodiment, and the content of the calcium carbonate was 2.0% by weight based on the weight of the polyphenylene resin. PPS film. The physical properties and mold release properties of the film were as described in Table 1. Although film breakage occurred, the adhesion resistance was small, and the mold release property was not problematic.

(Example 3)

Except that in Example 1, the amount of extrusion of the melt extrusion and the speed of the casting drum were adjusted, and the thickness of the unstretched film was set to 25 μm, and then, the film was not subjected to stretching, and the surface was subjected to rubbing treatment, in addition to the examples. 1 A PPS film for mold release was produced in the same manner. The physical properties and mold release properties of the film were as described in Table 1, and exhibited excellent mold release properties.

(Example 4)

Except that in Example 1, the stretching ratio of the longitudinal stretching was set to 3.2 times, the stretching ratio in the width direction was set to 3.1 times, the first stage was 190 ° C (5 seconds), and the second stage was 260 ° C (5 seconds). A PPS film for mold release was produced in the same manner as in Example 1 except that the heat setting was carried out in two stages. The physical properties and mold release properties of the film were as described in Table 1, and exhibited excellent mold release properties.

(Example 5)

A PPS film for mold release was produced in the same manner as in Example 1 except that the stretching ratio of the longitudinal stretching was 4.1 times and the stretching ratio in the width direction was 4.0 times. The physical properties and mold release properties of the film were as described in Table 1, and exhibited excellent mold release properties.

(Comparative Example 1)

A PPS film for mold release was produced in the same manner as in Example 1 except that the film was not subjected to rubbing treatment in Example 1. The physical properties and mold release properties of the film were as described in Table 1, and the film was firmly adhered and could not be peeled off.

(Comparative Example 2)

A PPS film for mold release was produced in the same manner as in Example 1 except that the amount of pressing at the time of rubbing was set to 0.1 mm in Example 1. The physical properties and mold release properties of the film were as described in Table 1, and the film was firmly adhered and could not be peeled off.

(Comparative Example 3)

A PPS film for mold release was produced in the same manner as in Example 2 except that the film was not subjected to rubbing treatment in Example 2. The physical properties and mold release properties of the film were as described in Table 1, and the film was firmly adhered and could not be peeled off.

(Comparative Example 4)

A PPS film for mold release was produced in the same manner as in Example 1 except that the non-particle particles and the particles were mixed to have a calcium carbonate content of 5.0% by weight. The physical properties and mold release properties of the film were as described in Table 1, and the film was firmly adhered and could not be peeled off.

[Industrial availability]

The polyarylene sulfide film for mold release of the present invention can be used as a release film which is used for mold release from a metal mold in a molding process such as molding of a carbon fiber-epoxy prepreg. get on.

Claims (4)

A film of a poly(arylene sulfide) for demolding, which is a film composed of a poly(arylene sulfide) resin, and satisfies the following (1), (2) at least one side of the film; (1): The center plane average roughness (SRa) is 70 nm or less, and (2): the hardness at a depth of 10 nm measured by a nanoimprint method is 4.0 GPa or more. The polyaryl aryl sulfide film for mold release according to the first aspect of the invention, wherein the film has a tensile modulus in the longitudinal direction and the width direction of 4.0 GPa or less. A method for producing a thermosetting resin molded article, comprising: placing a thermosetting resin preform on one surface of the film satisfying (1) and (2) at the same time as the film of the first aspect of the patent application; And a step of shaping the thermosetting resin preform by hot calender molding using a metal mold. The method for producing a thermosetting resin molded article according to claim 3, wherein the thermosetting resin is an epoxy resin.