JP2841561B2 - Laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a laminate. More specifically, the present invention relates to a laminate which is lightweight and / or rich in cushioning properties and has a high-dimensional balance of properties such as tear strength, tensile strength and heat resistance.

[Prior Art] Conventionally, an oriented film obtained by stretching and heat-treating a resin composition containing polyphenylene sulfide as a main component is disclosed in
205119 and JP-A-57-205445. Since the above-mentioned film is excellent in heat resistance and dielectric properties, it is expected to be applied to various uses including electric insulating materials, dielectrics for capacitors, heat-resistant packaging materials and heat-resistant labels.

In particular, a biaxially oriented polyphenylene sulfide film having a thickness of 12 μm or more has attracted attention as an application as an electrical insulating material for a class F heat-resistant type transformer or motor.

Unstretched polyphenylene sulfide sheets are also known in JP-A-56-34426 and JP-A-57-121052. On the other hand, a laminate obtained by laminating biaxially oriented PPS films via an adhesive is also known in JP-A-61-241142.

[Problems to be Solved by the Present Invention] However, the conventional polyphenylene sulfide film has a disadvantage that the polyphenylene sulfide polymer itself is expensive, so that the film cost per unit volume is higher than the conventional general-purpose film. . In addition, the film has poor tear strength compared to general-purpose films such as polyester film, and has high rigidity, so it can be used when slitting films or winding flat copper wires used for motors, transformers, etc. There was also a problem in safety during handling such as tearing or cutting a hand at the edge of the film.

Further, when the polyphenylene sulfide film is used as a heat-resistant printing substrate, the cushioning property is poor,
There is a problem that print suitability at the time of printing is poor, the print becomes unclear, or ink is poorly loaded, that is, so-called dropout occurs.

On the other hand, the unstretched sheet has a problem that the tear strength is high but the mechanical properties and heat resistance are inferior.

Further, in the laminate of JP-A-61-241142, since the adhesive is interposed, there is a danger that various properties such as excellent heat resistance and humidity dimensional stability of the polyphenylene sulfide film are hindered by the adhesive. is there.

The present invention solves such a problem and provides a laminate that is not only lightweight and / or rich in cushioning properties but also has excellent heat resistance and mechanical properties.

[Means for Solving the Problems] In order to solve the above problems, the present invention provides at least one surface of an unstretched polyphenylene sulfide sheet (A) (hereinafter sometimes simply referred to as sheet (A) or PPS-NO). A polyphenylene sulfide film (B) mainly composed of the following formula and a composition containing external particles so as to satisfy the formula and being at least uniaxially stretched (hereinafter simply referred to as film (B)) ) May be laminated without an adhesive.

0.4 ≤ Y ≤ 2.5 ... X ≤ 40 ... (13-5Y) ≤ X ≤ (100-35Y) ... Y: Average particle size of external particles (unit: μφ) X: Addition amount of external particles (Unit:% by weight) In the present invention, polyphenylene sulfide (hereinafter referred to as PP)
S may be abbreviated as S) when 70 mol% or more (preferably 85 mol% or more) of the repeating unit has a structural formula Means a polymer comprising the structural unit represented by Such components
If it is less than 70 mol%, the crystallinity and the heat transition temperature of the polymer will be low, and the heat resistance, dimensional stability, mechanical properties and the like, which are the characteristics of a film composed of a resin composition containing PPS as a main component, will be impaired.

If the amount of the repeating unit is less than 30 mol%, preferably less than 15 mol%, a unit containing a copolymerizable sulfide bond may be contained. As the repeating unit of less than 30 mol%, preferably less than 15 mol% of the repeating unit, for example, a trifunctional unit, an ether unit, a sulfone unit, a ketone unit, a meta bonding unit, an aryl unit having a substituent such as an alkyl group, Specific examples include a biphenyl unit, a terphenylene unit, a vinylene unit, and a carbonate unit, and one or two or more of these units can be used. In this case, the structural unit may be in any form of random copolymerization or block copolymerization. Also, the main structural unit of the polymer at or near the end of the polymer There can be no problem with the presence of other structural units.

The unstretched polyphenylene sulfide sheet (A) referred to in the present invention is a general term for a film, sheet and plate, preferably obtained by melt-molding the above-mentioned composition containing 50% by weight or more of PPS and preferably having a thickness of 1 mm or less. , Substantially non-oriented.

In the present invention, the external particles are organic polymer particles and / or inorganic particles made of oxides, carbides, nitrides or inorganic salts of elements of Groups II, III and IV of the periodic table.

Examples of the organic polymer particles include divinylbenzene /
Examples include styrene copolymerized (crosslinked) products, polyimides, and silicone resin particles. Furthermore, the temperature at the time of 10% weight loss in the heating weight loss curve is 370 ° C (more preferably 390 ° C,
More preferably, the temperature is 420 ° C. or higher in terms of foaming during extrusion and the like. The upper limit of the temperature at the time of 10% weight loss is not particularly limited, but usually about 600 ° C. is a manufacturing limit.

Examples of the inorganic particles include synthetic calcium carbonate, heavy calcium carbonate, carbon black, titanium monoxide, titanium dioxide, CaF ₂ , LiF, MgF ₂ , wet silica, colloidal silica, dry silica, aluminum silicate, and calcium silicate. , Barium sulfate, aluminum oxide, aluminum hydroxide, calcium phosphate and the like.

In the present invention, the true density of the external particles is preferably 4.5 or less, more preferably 3.5 or less.
If the density exceeds the above range, it is difficult to achieve the weight reduction characteristic of the present invention.

Furthermore, the wear resistance of the blade during slitting and the film (B)
External particles having a Moh's hardness of 4 or less are preferred from the viewpoint of weight reduction and the like. Among these, calcium carbonate, particularly heavy carbon dioxide, is preferred because of the low cost of the external particles per unit weight and the lightening effect of the film (B) due to the ease of forming voids around the external particles in the film (B). Calcium is preferred.

Further, two or more kinds of external particles satisfying the patent requirements of the present invention may be mixed and used.

Average particle diameter Y of external particles in the present invention (unit: μφ)
Further, it is necessary that the addition amount X (unit:% by weight) of the external particles satisfies the formula, the formula and the range of the formula described in claim (1) at the same time. If the average particle diameter Y is less than the range defined by the formula (1), the effect of reducing the weight of the present invention is hardly obtained. When the average particle diameter Y and the addition amount X exceed the formulas and formula ranges described in claim (1), the film is likely to be broken at the time of film formation or the filter of the extruder used at the time of casting film production. It is not preferable because film productivity is deteriorated such as clogging is likely to occur, and film abrasion is deteriorated. When the average particle diameter Y and the amount of addition X exceed the ranges of the formulas described in claim (1), the specific gravity increase by the external particles is superior to the weight reduction effect by void formation, so that the weight reduction effect of the film is not obtained. Expression becomes extremely difficult, and the shaving property of the film deteriorates. If the value is less than the range of the above formula, the effect of reducing the weight of the film hardly appears because the total volume of the voids in the film due to the formation of voids is small.

Mainly composed of the composition containing the external particles according to claim (1) of the present invention means a composition containing 50% by weight or more of polyphenylene sulfide. When the content of polyphenylene sulfide is less than 50% by weight, the heat resistance, temperature characteristics, and the like, which are characteristics of a film made of the composition, are impaired. In particular, the weight ratio of PPS in the remaining composition obtained by subtracting the weight of the external particles of the present invention from the weight of the composition is preferably 90% by weight or more. The melt viscosity of the PPS is preferably in the range of 500 to 12,000 poise at 300 ° C. and a shear rate of 200 sec ⁻¹ . Further, as long as the content of the external particles of the present invention satisfies the patent requirements of the present invention, other resin compositions and various additives can be included.

The film (B) of the present invention is characterized by blending the above-mentioned polyphenylene sulfide and external particles so as to satisfy the patent requirements of the present invention. In order to obtain it, it is essential that the film be further stretched in at least one axial direction.

That is, the non-oriented sheet obtained by simply extrusion-molding the composition is almost the same as a conventional polyphenylene sulfide film in terms of lightness and cushioning property, and the weight and weight are not obtained by stretching the non-oriented sheet for the first time. Cushioning properties develop. About this, fine closed cells (voids) are formed at the interface between PPS and external particles during the stretching process.
Is estimated to be generated. In addition, the combination of PPS and external particles according to the requirements of the present invention more clearly demonstrates the lightness and cushioning effect than the combination of other general-purpose resins, such as polyethylene terephthalate, and external particles. Although the reason for this is not clear, it is thought that the affinity between the resin and the external particles is affecting.

The apparent specific gravity of the polyphenylene sulfide film (B) of the present invention is in the range of 0.50 to 1.30 (preferably 0.50 to 1.30).
1.10) is desirable. If it is less than the above range, the strength of the film (B) itself is small and practical handling becomes difficult. If it exceeds this range, the effect of cost reduction by reducing the apparent specific gravity of the film (B) and reducing the amount of raw materials is sufficient. No longer.

The cushion ratio of the laminate of the present invention is preferably in the range of 9 to 50% (preferably 12 to 35%). When the cushioning ratio is within the above range, the printability when printed as a printing substrate is improved. In particular, it is desirable that the content is within the upper limit of the above range, because the roll form of the long film is also improved.

In the present invention, the polyphenylene sulfide film (B) is a uniaxially oriented film or a biaxially oriented film of a composition comprising polyphenylene sulfide and the external particles of the present invention as main components.
Although the film is an axially-oriented film, a biaxially-oriented film is more preferable for more clearly expressing the effects of the present invention. The thickness of the film is preferably in the range of 0.3 to 150 μm, but the effect is large in the range of 8 to 125 μm. The average surface roughness Ra (cutoff value 0.25 μm) of the film is not particularly limited, but from the viewpoint of workability at the time of winding and the like, 0.02 to 0.2.
30 μm (cutoff value 0.25 μm), preferably 0.03 to
A range of 0.10 μm is desirable. Further, it is preferable that the film is a crystallized film having a crystallinity of 25% to 45% by an X-ray diffraction method. Further, the orientation degree OF obtained for the crystal peak at 2θ = 20 to 21 ° by wide-angle X-ray diffraction was different in the End direction and Edge direction.
It is preferable that the film is a biaxially oriented film in the range of 0.07 to 0.5 and in the range of 0.6 to 1.0 in the through direction.

 Next, a method for producing the laminate of the present invention will be described.

First, as a polymerization method of PPS used in the present invention, a method of reacting alkali sulfide and p-dihalobenzene in a polar solvent under high temperature and high pressure is used.

In particular, sodium sulfide and p-dichlorobenzene
The reaction is preferably performed in an amide polar solvent such as methyl-2-pyrrolidone. In this case, in order to adjust the degree of polymerization, it is most preferable to add a so-called polymerization aid such as a caustic alkali or an alkali metal carboxylate and react at 230 to 280 ° C. The pressure and the polymerization time in the polymerization system are appropriately determined depending on the type and amount of the auxiliary agent used, the desired degree of polymerization, and the like.

After completion of the polymerization, the system is gradually cooled to precipitate the polymer, and then the slurry formed in water is filtered off with a filter to obtain a granular polymer. The obtained granular polymer is optionally agitated in an aqueous solution of acetate or the like at a temperature of 30 to 100 ° C for 10 to 60 minutes, and then washed several times with ion-exchanged water at a temperature of 30 to 80 ° C. And then dried to obtain polyphenylene sulfide (PPS) powder.

Further, after the powdery and / or granular polymer obtained as described above is washed with NMP under an atmosphere having an oxygen partial pressure of 30 torr, preferably 10 torr, more preferably 5 torr or less,
It is effective to repeat the washing several times at a temperature of 30 to 80 ° C. with ion-exchanged water in order to more clearly bring about the effects of the present invention. The weight of NMP with respect to the weight of the polymer at this time is
The washing temperature is preferably twice or more, and the washing temperature is preferably 60 to 150 ° C., but is not limited thereto. For example, under an inert gas atmosphere where the oxygen partial pressure is in the above range, NM is measured using a Soxhlet extractor.
After extraction with P, a method of repeating washing several times with ion-exchanged water at a temperature of 30 to 80 ° C. is also effective. When the polymer thus obtained is dried, the oxygen partial pressure in the drying atmosphere needs to be 30 torr, preferably 10 torr, more preferably 5 torr, as described above. Here, if the oxygen partial pressure deviates from the above range at the time of washing with NMP, the melt crystallization temperature Tmc of the obtained polymer increases, and the film-forming property of the film is significantly deteriorated. The Tmc of the polymer washed by NMP with the oxygen partial pressure within the above range is usually in the range of 160 to 190 ° C., and the film forming property is good.

In order to form this polymer into an unstretched sheet, it is supplied to a melt extruder represented by an extruder, heated to a temperature equal to or higher than the melting point of the polymer, melted, continuously extruded from a slit-shaped die, and formed into a film. The non-oriented unstretched polyphenylene sulfide sheet (A) is obtained by rapidly cooling to a temperature below the glass transition point.

Further, the external particles of the present invention, if necessary, other polymers, additives and the like are mixed and added to the obtained PPS polymer so as to satisfy the requirements of the claims of the present invention. A composition is made.

At this time, a slurry (hereinafter, sometimes referred to as a fine particle slurry) is prepared by dispersing the external particles of the present invention in a liquid having a boiling point of 180 ° C to 290 ° C (more preferably 180 to 250 ° C) with a ball mill vibration mill or the like. Then, after the slurry and PPS are uniformly mixed by high-speed stirring such as a Henschel mixer or the like, the obtained mixture is supplied to an extruder having at least one vent hole. After the melt-kneading, a method of removing the liquid component from the vent hole and extruding the liquid component from an appropriate die to produce a resin composition containing polyphenylene sulfide as a main component is desirable for clearly exhibiting the effects of the present invention.

Here, the mixture obtained after uniformly mixing by high-speed stirring such as a Henschel mixer is supplied to an extruder having at least one vent hole, and is first melt-kneaded in the extruder. The resin component is obtained by removing the liquid component from the vent hole and extruding through a suitable die. However, even when an extruder having two or more vent holes is used, the final vent is in a molten state. Even when a part of the liquid component in the unmelted mixture is removed from some of the vent holes, the proportion should be 50% by weight or less of the liquid component. In any case, it is essential to create a state in which the liquid, the external particles, and the polymer in the molten state coexist in the cylinder of the extruder. In this way, the liquid component in the polymer is removed to such an extent that there is no drawback associated with vaporization of the liquid such as foaming as compared with the case where the finally obtained resin composition is processed by an extruder without vent holes. Is done.

Examples of the liquid include ethylene glycol, triethylene glycol, N-methylpyrrolidone, diphenyl ether, and the like.
Those which do not dissolve polyphenylene sulfide at a temperature higher than the boiling point are preferred. The content of the external particles in the slurry is preferably in the range of 10 to 70% by weight.

The PPS-based composition obtained in this manner is described in JP-A-55-111.
235 and the like, melted by supplying to an extruder or the like by a known method, extruded from a T-die onto a cooling drum to form an unstretched sheet, stretched the sheet vertically at a temperature of 95 to 115 ° C. A uniaxially oriented film is obtained by performing a heat treatment at a temperature of not less than ℃ and not more than the melting point. Alternatively, the sheet
Simultaneously or sequentially biaxially stretched vertically or horizontally at a temperature of ~ 115 ° C, and further heat-treated at a temperature of 200 ° C or higher and a melting point or lower.
Obtain an axially oriented film.

Further, in order to obtain a polyphenylene sulfide film having an apparent specific gravity or a preferable cushion rate described in claim (3) of the present invention, the polyphenylene sulfide film is obtained by the centrifugal sedimentation method of the external particles according to claim (1) or (2). When the cumulative distribution curve of the Stokes diameter is represented by a rosin-Lambert distribution, the uniform number N (see “Powder Engineering Handbook” p44, Asakura Shoten, published in 1972) is 5 or more, preferably 6 or more. If the equal number N is within the above range, it is easy to achieve the patent requirement described in claim (3).

When the unstretched sheet of the PPS containing the external particles is stretched to produce the polyphenylene sulfide film (B) of the present invention, the temperature is 95 to 115 ° C, preferably 95 to 105 ° C.
The film according to claim (3), wherein the film is preferably stretched at a temperature of at least 8 times, preferably at least 10 times at the same time in the vertical and horizontal directions or sequentially in the biaxial system. This is effective for obtaining (B).

As described above, the polyphenylene sulfide film (B) of the present invention is obtained.

The present invention relates to an unstretched polyphenylene sulfide sheet (A) and a polyphenylene sulfide film (B).
It is laminated without using an adhesive. Prior to lamination, the sheet (A) may be subjected to heat treatment or oxidative crosslinking. Further, the present invention also includes performing a corona discharge treatment or a plasma treatment on the surfaces of the sheet (A) and the film (B).

A first embodiment of a possible laminate configuration of the laminate of the present invention has a two-layer structure in which a sheet (A) and a film (B) are laminated, and the thickness ratio A / B of A and B is The range of 0.1 to 10 is preferable in terms of balance of heat resistance, light weight, cushioning property and mechanical properties when heat is applied. The thickness of the entire laminate is preferably in the range of 20 to 700 μm.

The second embodiment of the laminate structure which can be considered as the laminate of the present invention is a film (B), a sheet (A), a film (B ').
Are laminated in this order, and that the thickness of B, A, B 'satisfies the formula 0.1 ≦ (B + B ′) / A ≦ 10, the heat resistance when heat is applied, the light weight,
It is preferable in terms of balance with cushioning properties and mechanical properties, particularly tear strength. The thickness ratio B / B 'of B and B' is 0.5
The range of -2.0 is preferable from the viewpoint of workability during processing. Further, the thickness of the entire laminate is preferably in the range of 30 to 1000 μm.

Next, the method of laminating the sheet (A) and the film (B) is performed by thermocompression bonding under high temperature and high pressure, or
A method in which PPS is directly melt-extruded on the substrate and laminated.

In the former method, the temperature is 180 to 270 ° C and the pressure is 1 to 20.
It is performed by a roll press, a hot press, etc. under the condition of kg / cm ² .

When three layers are laminated, a two-layer body is first prepared under the above conditions, and a film (B) is further added to the sheet (A) side of the two-layer body.
Or three layers can be laminated at the same time.

On the other hand, when the PPS is directly melt-extruded and laminated on the film (B), the PPS is supplied to an extruder, heated to a temperature equal to or higher than the melting point, continuously extruded from a slit die, and a press provided below. It laminates while pressing on the film (B) on a roll.

In the case of laminating three layers, PPS can be extruded between the two layers of the film (B) under the above conditions and laminated. In still another method, another film (B) can be laminated by thermocompression bonding on the sheet (A) side of the two-layer laminate obtained by the above method.

Next, methods for measuring and evaluating characteristic values of polymers, films, and the like used in the description of the present invention will be described.

(1) Average particle size of external particles External particles are added to a dispersion medium such as methanol or ethanol and dispersed by an ultrasonic dispersion method. The obtained diluted dispersion of external particles is dropped on a smooth sample stage and dried sufficiently to prepare a sample for measuring the average particle size. Or,
PPS is removed from the film by a plasma low-temperature incineration method (for example, model PR-503 manufactured by Yamato Scientific Co., Ltd.) to expose external particles, thereby preparing a sample for measuring the average particle size. Processing conditions are PP
Select a condition where S is incinerated but external particles are not damaged. This is observed with a scanning electron microscope (SEM),
The image of the particles (shading of the light produced by the particles) is linked to an image analyzer (for example, QTM900 manufactured by Cambridge Instrument). D was the average particle size.

 D = ΣDi / N Here, Di is the equivalent circle diameter of the particle, and N is the number.

(2) the film and the apparent specific gravity light liquid of the laminate, n- heptane (0.68 g / cm ^3), the heavy liquid, using carbon tetrachloride (1.59 g / cm ^3), was determined by ASTM-D1505.

(3) Suitability for printing at the time of printing After coating the ink receiving layer on the laminate at 3 μm, printing was performed with a video printer GZ-P10B / W made by Sharp, and the printing condition was observed and judged.

 ：: Printing and image are good.

X: The print and the image are unclear and partially missing.

(4) Cushion rate Dial gauge made by Mitoyo (No.2109-10, probe: 3mmφ
Attach a 10g pedestal to the upper part of the spindle of the hard ball), lift the spindle and lower it on the sample set on the measuring table. A weight of 50 g is placed on the pedestal, the thickness after 5 seconds is read, and the value at this time is defined as a μm. In addition, replace the weight of the pedestal with that of 500 g, read the thickness after 5 seconds,
The value at this time is assumed to be b μm. From these values, the cushion ratio C was calculated by the following equation.

C = 100 × (ab) / a (Unit:%) (5) Sharpness Using a Gakushin-type dyeing abrasion fastness tester manufactured by Daiei Kagaku Seiki Seisakusho, with a load of 216 g / 20 mm, dry cloth Was rubbed 30 times, and evaluated by the presence or absence of white powder attached to the silk fabric. The white powder was indicated by x and the white powder was not indicated by o.

(6) Tear strength Measured according to JIS-P8116-1960 and expressed in g / mm.

(7) Breaking strength Measured according to the ASTM-D-638-72 method.

(8) True density of external particles Determined by a pycnometer method using xylene or an aqueous solution of sodium hexametaphosphate (0.003 mol / L) as a solvent.

[Use] The laminate of the present invention has good heat resistance and cushioning properties, and is therefore most suitable as a printing base material for a printer or a material for image formation.

It is also ideal as an insulating material for motors and transformers. For example, it can be used as an insulating material for various motors such as hermetic motors, servo motors, and vehicle motors, various transformers such as gas transformers, oil transformers, and mold transformers, and generators.

It is also suitable for interior materials such as electric wire covering materials, printed circuit boards, belts, diaphragms, acoustic diaphragms, flame-retardant and lightweight wallpapers, and heat-resistant labels.

Further, the laminate of the present invention may be bonded to another film, for example, a heat-sealable film, a heat-resistant fiber sheet, a metal, or coated with another resin.

[Example] Next, an example of the present invention will be described in more detail.

Examples 1-2 In a stainless steel autoclave, sodium sulfide 32.6 was added.
kg (250 mol, containing 40 wt% of water of crystallization), 100 g of sodium hydroxide, 36.1 kg (250 mol) of sodium benzoate, and 79.2 kg of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) After dehydration at 205 ° C, 37.5 kg (255 mol) of 1,4-dichlorobenzene (abbreviated as p-DCB) and 20.0 kg of NMP were added and reacted at 265 ° C for 4 hours, and then the system was cooled to room temperature. The resulting polymer slurry in water
After pouring into 200 mol and stirring at 70 ° C. for 30 minutes, the polymer is separated. This polymer was further washed 5 times while stirring with ion exchanged water (9 times the weight of the polymer) at about 70 ° C., and then stirred for about 1 hour with a 5% by weight aqueous solution of calcium acetate at about 70 ° C. under a nitrogen stream. . Further, after washing three times with ion-exchanged water at about 70 ° C., it was separated and dried at 120 ° C. under an atmosphere of 0.8 to 1 torr for 20 hours to obtain a white PPS powder. Furthermore, this PPS powder was mixed with NMP at 90 ° C in a commercially available nitrogen gas atmosphere.
(3 times the weight of the PPS polymer), the mixture was stirred 1 to 5 times for 5 minutes to 1 hour, washed with water and dried as described above to obtain a white PPS powder.

(1) Preparation of unstretched PPS sheet This powder was melted at 310 ° C. with a 40 mm extruder and filtered with a 95% cut pore diameter 10 μm filter using metal fibers. It was extruded from a T-die having a lip, cast on a metal drum whose surface was kept at 25 ° C., solidified by cooling, and an unstretched film having a thickness of 50 μm was obtained. (Referred to as PPS-NO-1).

(2) Preparation of Biaxially Oriented PPS Film Ethylene glycol slurry (solid content concentration: 50%) of heavy calcium carbonate having a uniform number N of 8.3 and an average particle diameter of 0.6 μm in a rosin-ramler distribution was added to 100 parts by weight of this powder.
The mixture was stirred at 50 ° C. at a high speed using a Henschel mixer.

This mixture was supplied to a counter-rotating twin-screw extruder having a single-stage vent hole, melted at 310 ° C., and polyethylene glycol was removed from the molten resin at the vent portion.
Thereafter, the molten polymer was extruded from a 3φ die, quenched, and then cut into pellets to obtain a resin composition mainly containing polyphenylene sulfide of the present invention containing 16.7% by weight of calcium carbonate based on the polymer (resin A). And).

Resin A is melted at 310 ° C with an extruder having a diameter of 40 mm, filtered through a filter having a 95% cut hole diameter of 10 µm using metal fibers, and then extruded from a T-die having a linear lip with a length of 400 mm and a gap of 1.5 mm. Was cast on a metal drum kept at 25 ° C. and solidified by cooling to obtain an unstretched film having a thickness of 300 μm. The film was stretched at a film temperature of 100 ° C. and a stretching speed of 300
The film is stretched 3.7 times at 00% / min.
The film was stretched 3.4 times at 00 ° C. and a stretching speed of 1000% / min, and further heat-treated under tension at 270 ° C. for 10 seconds in a subsequent heat treatment chamber in the same tenter to obtain a biaxially oriented PPS film having a thickness of 25 μm. (Referred to as film 1).

Similarly, a biaxially oriented PPS film having a thickness of 25 μm was obtained using heavy calcium carbonate having an average particle size of 1.1 μm (the uniform number N = 7.5) instead of heavy calcium carbonate having an average particle size of 0.6 μm. (Referred to as film 2).

(3) Preparation of laminate The PPS-NO-1 and the film 1 were heated at a temperature of 230 ° C and a pressure of 10 kg / cm ^2.
The three layers were superposed and laminated so as to form a film 1 / PPS-NO-1 / film 1 by the press roll of Example 1 (Example 1).

Similarly, lamination was performed using the film 2 (Example 2).

Example 3 The same method as in Examples 1 and 2 except that the content of heavy calcium carbonate having an average particle size of 2.4 μm (the uniform number N = 6.9) with respect to the PPS polymer was set to 15.0% by weight, was used. A biaxially oriented PPS film was obtained (referred to as film 3). Film 3 was laminated as in Examples 1-2.

Comparative Examples 1-2 Light calcium carbonate having an average particle size of 0.2 μm (the uniform number N = 7.9) instead of heavy calcium carbonate having an average particle size of 0.6 μm, and an average particle size of 4.0 μm (the uniform number N = 4.8) A biaxially oriented PPS film having a thickness of 25 μm was obtained in the same manner as in Example 1 except that heavy calcium carbonate was used (hereinafter referred to as film 4 and film 5).

Further, lamination was performed in the same manner as in Examples 1 and 2 (Comparative Examples 1 and 2).

Examples 4 to 6 The same procedure as in Example 2 was carried out except that the content of heavy calcium carbonate having an average particle size of 1.1 μm was 8% by weight, 30% by weight, 38% by weight and 50% by weight based on the PPS polymer. 25μm thick
Was obtained (hereinafter referred to as film 6, film 7, and film 8). In addition, heavy calcium carbonate 50
In the case of containing by weight, stretchability was poor and a stretched film was not obtained.

Film 6, film 7, and film 8 were obtained in Examples 1 to
(Examples 4, 5 and 5)
Example 6).

Example 7 A method similar to that of Example 2 was used except that aluminum silicate (Georgiakaolin) having an average particle size of 1.1 μm (the uniform number N = 6.1) was used instead of heavy calcium carbonate having an average particle size of 1.1 μm. Thus, a biaxially oriented PPS film having a thickness of 25 μm was obtained (referred to as film 9). Film 9 was prepared as in Examples 1-2.
Laminated in the same manner as described above.

Example 8 The thickness was determined in the same manner as in Example 2 except that heavy calcium carbonate having an average particle size of 1.1 μm (the uniform number N = 6.1) was used instead of heavy calcium carbonate having an average particle size of 1.1 μm. 25μ
m was obtained as a biaxially oriented PPS film (film 10). Film 10 was laminated as in Examples 1-2.

Comparative Example 3 The thickness was determined in the same manner as in Example 2 except that JIS No. 1 zinc white having an average particle size of 0.27 μm (the uniform number N = 7.3) was used instead of heavy calcium carbonate having an average particle size of 1.1 μm. A 25 μm biaxially oriented PPS film was obtained (referred to as film 11). Film 11 was laminated as in Examples 1-2.

Comparative Example 4 An unstretched PPS sheet having a thickness of 100 μm was produced in the same manner as in Examples 1 and 2 (referred to as PPS-NO-2).

Comparative Example 5 A 100 μm thick film of “Torelina” type 3000 manufactured by Toray Industries, Inc. was used.

(Evaluation) Tables 1 and 2 show the evaluation results of the obtained samples.

It can be seen that the laminate of the present invention that satisfies the patent requirements of the present invention is lightweight and rich in cushioning properties, and also has excellent printability, sharpness, and mechanical properties.

Examples 9 to 11 In the same manner as in Example 2, an unstretched sheet having a different film thickness and a biaxially oriented PPS film containing heavy calcium carbonate having an average particle size of 1.1 μm were prepared, and each layer as shown in Table 3 was prepared. To produce a three-layered laminate having different thickness configurations. Table 3 shows the results.

When the thickness composition ratio (B + B ') / A decreases, the tear strength increases, but the lightness, cushioning properties, and rupture strength tend to deteriorate. Conversely, when the composition ratio increases, the tear strength tends to decrease. is there.

[Effects of the Invention] As a result of the above-described structure, the laminate of the present invention not only has excellent properties such as heat resistance, flame retardancy and wet heat resistance, but also has a higher tear strength than a conventional oriented PPS film. It has excellent pod weight and good cushioning properties. Further, the film of the present invention can reduce the cost of the film because the amount of the raw material polymer per unit volume can be reduced as compared with the conventional oriented PPS film.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) B32B 1/00-35/00

Claims (3)

(57) [Claims] 1. An unstretched polyphenylene sulfide sheet (A) comprising, on at least one side thereof, a composition comprising external particles so as to satisfy the following formula, the formula, and the formula, and being stretched in at least one axial direction. Wherein the polyphenylene sulfide film (B) is laminated without an adhesive. 0.4 ≦ Y ≦ 2.5 X ≦ 40 (13−5Y) ≦ X ≦ (100−35Y) where Y: average particle diameter of external particles (unit: μφ) X: amount of external particles added (Unit: wt%) 2. The laminate according to claim 1, wherein the true density of the external particles is 4.5 or less. 3. Polyphenylene sulfide film (B)
3. The laminate according to claim 1, wherein the apparent specific gravity is 0.50 to 1.30.