JPH0353934A - Press-molding laminate constituted of polyphenylene sulfide and metallic plate, case molded with this laminate and manufacture of laminate and case - Google Patents

Abstract

PURPOSE:To make a polyphenylene sulfide layer hard to crack at the time of draw processing or bend processing, by a method wherein the title laminate is comprised by sticking a sheet consisting mainly of the polyphenylene sulfide and a metallic plate to each other and the sheet consists mainly of the polyphenylene sulfide having specific crystallinity. CONSTITUTION:This is a laminate comprised by sticking a sheet consisting mainly of polyphenylene sulfide and a metallic plate to each other and the sheet consists mainly of the polyphenylene sulfide whose crystallinity is 14% or less. The polyphenylene sulfide is of high-molecular-weight one whose melt viscosity is 1000-25000 poise to make the same into a sheetlike state by consisting mainly, for example, of high-polymerization-degree poly-p-phenylene sulfide. The sheet consisting mainly of the polyphenylene sulfide is used under a state where the crystallinity is 14% or less and breaking extension in accordance with D-638 of ASTM at 23 deg.C becomes at least 200%.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a product in which a sheet mainly made of polyphenylene sulfide and a metal plate are laminated, and the sheet is laminated with a metal plate, which is subjected to mechanical processing such as drawing or press forming. A laminate for press molding that does not cause damage such as cracks or crazing on a sheet mainly made of polyphenylene sulfide when subjected to this process, and a laminate that is formed into a concave shape and used as, for example, cases for electrolytic capacitors or dry batteries. Regarding a case that satisfies the conditions, a method for manufacturing this laminate, and a method for manufacturing the case, [Background of the Invention] Various uses can be considered for a laminate in which a resin and a metal plate are stacked, but in particular, it is used only for insulation purposes. When forming cases that require chemical resistance and heat resistance, it is necessary to use a resin that satisfies these requirements. When molding, for example, a case for an electrolytic capacitor using the above-mentioned laminate, it is necessary that the resin layer forming the inner surface of the case does not swell or dissolve due to chemicals such as electrolyte. Polyphenylene sulfide is a resin that meets the above requirements. As is well known, this polyphenylene sulfate (hereinafter sometimes referred to as PPS) is composed of alternating bonds of benzene rings and carbon atoms. This PP. S resin not only has good properties in terms of chemical resistance and heat resistance, but also good mechanical properties.

However, conventionally, PPS has been considered to be a material with poor workability, and when PPS and a metal plate are pasted together and then drawn or bent, damage such as cracks or cracks may occur in the PPS layer. will be born.

The present invention solves the above problems by laminating a sheet mainly made of PPS on a metal plate in a state with good workability.
An object of the present invention is to provide a laminate for press molding in which cracks are less likely to occur in the PPS layer during drawing or bending.

Another object of the present invention is to provide a case that is less susceptible to the effects of chemicals and is suitable for use as, for example, a case for an electrolytic capacitor or a dry battery.

Furthermore, it is an object of the present invention to provide a method for manufacturing a laminate in which PPS can be maintained in a state that is easy to process when laminating a sheet mainly composed of PPS and a metal plate.

[Means for Solving the Problems 1] The present invention is a laminate consisting of a sheet mainly made of polyphenylene sulfide and a metal plate, the sheet being made of polyphenylene sulfide having a crystallinity of 14% or less. and polyphenylene having a crystallinity of 14% or less as described above and a breaking elongation of 200% or more according to ASTM D=638 at 23°C. It is a laminate consisting of a sheet mainly composed of sulfide and a metal plate.

Further, the present invention is a case in which any of the above laminates is press-molded into a concave shape.6 Furthermore, the present invention provides a case in which a metal plate is roughened by surface treatment, and polyphenylene is applied to the treated surface of the metal plate. A method of manufacturing the above-mentioned laminate by thermocompression bonding of sheets mainly composed of nylene sulfide, and a method of roughening a metal plate by surface treatment and extrusion laminating a sheet mainly composed of polyphenylene sulfide on the treated surface of the metal plate. This is a method of manufacturing the above-mentioned laminate.

Furthermore, by laminating a sheet mainly composed of polyphenylene sulfide with a crystallinity of 14% or less and a metal plate via an adhesive layer, the elongation at break according to ASTM D-638 at 23°C is 200% or more. This is a method for producing a laminate in which a sheet mainly made of polyphenylene sulfide and a metal plate are thermally bonded together by curing the adhesive at a heating temperature within a range that maintains the following state.

The present invention is a method for producing a case in which the laminate produced by the above method is press-molded into a concave shape, and after this press-molding, the adhesive is further cured by heating to a temperature higher than the temperature of the hot pasting process.

The PPS resin used in the present invention is mainly composed of high polymerization degree polyphenylene sulfide. Specifically, for example, it is mainly composed of high polymerization degree poly p-phenylene sulfide. . In addition, in order to form a sheet, the melt viscosity is 1.
000-25. 000 poise (melt viscosity is temperature 310
It has a high molecular weight of 6.degree. C./shear rate of 200 seconds (the same applies hereinafter). If the melt viscosity is less than 1000 voids, the film forming properties will be poor, the sheet cannot be stably molded, and the bending resistance of the sheet will be low. Also, the melt viscosity is 25. If it exceeds 000 poise, stable melt extrusion becomes difficult.

The above PPS is produced by combining an alkali metal sulfide and a dihaloaromatic compound in the presence of water in an organic amide solvent such as N-methylpyrrolidone, as described in JP-A No. 61-7332. can be obtained by a specific two-step temperature-programmed polymerization method.

Alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof.

Examples of dihaloaromatic compounds include p-dichlorobenzene,
m-dichlorobenzene, 2,5-dichlorotoluene, p
-Dibromobenzene etc. are the main ones.

The PPS used in the present invention is substantially linear, preferably poly p-phenylene sulfide or m-
It is a poly p-phenylene sulfide copolymer containing phenylene sulfide units as a minor component. Also,
A poly p-phenylene sulfide copolymer having a slightly branched structure introduced by copolymerizing a small amount of polyhalobenzene such as trichlorobenzene can also be suitably used.

In order to have a crystallinity of 14% or less and to be able to process such as drawing together with a metal plate, it is not preferable that the crystallization rate is too high. The crystallization temperature (Tc,) is preferably 120°C or higher.

The method of measuring the crystallization temperature (T c + ) referred to here is the exothermic peak temperature of crystallization that appears when the humidity is raised from 23°C at a rate of 10°C/min using a differential scanning calorimeter.

In addition, the melt crystallization temperature (TC2), which is the crystallization temperature at the time of temperature cooling after melting, does not directly limit the PPS used in the present invention, but the sheet with a low crystallinity is
It is easier to obtain a lower power. Moreover, if this TC2 is too low, mechanical properties and heat resistance may be insufficient during use after processing. Normally TC2 is 170”C~2
The temperature is about 40°C. The value of TC2 mentioned here is determined using a differential scanning calorimeter at a rate of 380 °C from 23 °C at a rate of 1O °C/min.
This is the exothermic peak temperature of crystallization that appears when the temperature is raised to 38°C, held for 3 minutes, and then lowered at a rate of 10°C/min.

In addition, in order to obtain sufficient elongation, polyphenylene sulfide that is too highly crosslinked is not preferred.

In addition, optional components include small amounts of polyethylene, polypropylene, polyolefins such as poly-4-methylbentene-1, rubbers such as polyisoprene, polyethylene terephrate, polycarbonate, tetrafluoroethylene resin, polyether ether, etc. Thermoplastic resins such as ketones and boriketone sulfides may also be blended.

Further, organic or inorganic fillers such as glass fiber, carbon black, talc, clay, mica, titanium oxide, molybdenum disulfide, carbon fiber, calcium carbonate, kaolin, and alumina may be added. Titanium oxide is used as a white pigment. Examples of other pigments include carbon as a black pigment, cobalt as a green pigment, copper cyanine as a blue pigment, and iron oxide as a red pigment.

Furthermore, additives such as antioxidants, heat stabilizers, lubricants, and colorants may be added.

The above composition is used as a sheet having a thickness of 15 to 250 LLm. In addition, the metal plate is, for example, an aluminum plate (
Annealed product 1/2H material or 0 material) with thickness 100~5
00 μm is used.

As a method for laminating a sheet mainly made of highly polymerized polyphenylene sulfide and a metal plate, the surface of the metal plate is first subjected to chemical etching or mechanical treatment (for example, sand blasting, shot blasting, etc.), electrolytic etching treatment, or anodizing. The etched surface is formed by surface treatment such as treatment, chemical conversion treatment, painting treatment, or a combination thereof, and a sheet mainly composed of polyphenylene sulfide is laminated on this etched surface by thermocompression bonding, extrusion lamination, or the like. The sheet mainly composed of polyphenylene sulfide is fixed to the above-mentioned treated surface of the metal plate by an anchor effect without using an adhesive.

Alternatively, a sheet mainly composed of polyphenylene sulfide and a metal plate are stacked on top of each other and fixed with an adhesive.

In order to easily deform the sheet and metal plate laminated together, the sheet mainly composed of polyphenylene sulfide has a crystallinity of 14% or less, or has a crystallinity of 14% or less and is heated at 23°C. It is used in a state where the elongation at break according to ASTM D-638 is 200% or more.

The relationship between crystallinity and elongation of a PPS sheet is not necessarily uniform, but may vary depending on the chemical structure of PPS or the presence or absence of additives. Therefore, in order to obtain the effects of the present invention, the sheet laminated with the metal plate only needs to have a crystallinity of 14% or less, but a sheet with a breaking elongation of 200% or more to obtain a favorable effect during actual processing. It can also be referred to as a state with a low degree of crystallinity.

The relationship between crystallinity and elongation of PPS used in the present invention is typically as shown in Table I.

(Table 1l) shows the crystallinity (xe
) and elongation at break (%). This applies to a PPS sheet with a thickness of 25 μm, but it can be seen that if the degree of crystallinity (XC) is about 14% or less, the elongation can be increased to 200% or more.

1 2 (table 1) Also, Figure 6 is above (table Crystallinity shown in l) This is a graph that shows the relationship between the tensile strength and the elongation at break.

In Table 1, the samples were formed as follows.

It is produced by the water addition two-stage polymerization method described in JP-A No. 61-7332 and explained above, and has a melt viscosity of 5900 poise (310°C/shear rate 200°C).
A PPS resin (measured at -1 seconds) was heated and melted at 310°C using a 50 mm extruder, and the molten resin extruded through a 5 mm diameter nozzle was cooled and cut with a pelletizer to create pellets. This pellet was crystallized at 150° C., then heated and melted using an extruder with a diameter of 50 mm, and a sheet with a thickness of 25 μm was produced using a T-guidance with a clearance of 0.5 mm. The extrusion speed was 12 m/min, and the temperature of the cooling roll at this time was 40°C.
I was able to obtain an S sheet. The rightmost column in the above (Table 1l) shows the conditions for crystallizing the above 0% amorphous sheet. For example, a sheet with a crystallinity of 3% has a crystallinity of 3% obtained as described above. 1 2 sheets with 0%
It was heated in an oven at 0''C for 25 minutes.

In addition, the measurement conditions for yield point strength and elongation at break are ASTM
No. 4 dumbbells (gauge length 25 mm, gauge width 6 mm) were prepared as tensile test specimens from PPS sheets of each of the above-mentioned crystallinity degrees. The testing machine used for the tensile test was a Tensilon UTM-11+ model manufactured by Toyo Baldwin.

Using this testing machine, the dumbbell was subjected to a bow tension test at a pulling speed of 50 mm/min until it broke. Measured environmental temperature 23°C. The humidity was 50%.

In the case of a laminate made of a PPS sheet with a crystallinity (Xc) of approximately 14% or less, or a breaking elongation of 200% or more, and a metal plate such as aluminum, press processing such as squeezing or bending is required. When subjected to processing, PPS can expand or contract following this processing, and PPS
Damage such as cracks and cracks is less likely to occur in sheets mainly made of .

Note that since the present invention aims at producing a 5-layer structure that can be machined into a concave shape, etc., the PPS used is preferably 6, which has good thermal stability.

In other words, in the presence of oxygen, PPS resin crosslinks and thickens at high temperatures, increasing its storage modulus. In a nitrogen stream, this degree decreases, but the storage modulus changes over time during heating. It is preferable to use a material with a small increase in processability. The following (Table 2) is an example in which the storage modulus initially decreases as the heating time progresses.
3 shows the change over time in the storage modulus of PPS resin preferably used in the present invention, measured in a nitrogen atmosphere.

(The following is a blank space) l 6 (Table 2) The method for measuring the storage elastic modulus in the above is as follows. In the above table, the rate of change refers to the 0 minute value of storage modulus and l
Rate of change from O minute value (10 minute value/0 minute value) XIOO (%)
It shows.

Weighed 40g of Polymer and placed it on a chrome-plated ferro plate, measuring 10cm x 12cm square and 3mm thick.
The sample was placed in a frame plate, the top surface was covered with a chrome-plated ferro plate, and the sample was placed in a press heated to 315°C. Allow 2 minutes for preheating, repeat deaeration during that time, then 80kg
/cm2 and pressed for 3 minutes. Cooling is 25℃
It was carried out for 3 minutes at 90 kg/cm2, and the thickness was 3 mm.
A press sheet of the polymer was created.

The storage modulus is measured using a Rheometrics Dynamic Spectometer (RDS).
- II) was used.

First, the diameter of 25 mm facing each other was preheated to 300℃.
A 3 mm thick sample cut into 25 mm x 25 mm was placed between the flat plates. This sample was heated and melted in a nitrogen atmosphere, and after 2 minutes, the plate spacing was adjusted to 2.5 mm.
Remove excess sample that has melted and dripped out of the plate. After an additional 3 minutes, the plate spacing was adjusted to 2 mm, excess sample was removed, and the sample was allowed to equilibrate for 5 minutes.

The strain applied to the sample was set to 1O%, the sample was vibrated at 1O radian/second, and the time dependence of the storage modulus was measured.

Melt viscosity shown in (Table-1) 5. 900 poise PP
Measured values for the S resin and the PPS resin with a melt viscosity of 7.400 voids produced by the same two-stage water addition polymerization method are shown in Table 2. In this way, in a nitrogen atmosphere, PPS resin whose storage modulus increases little or tends to decrease over time has good thermal stability and excellent processability, and is therefore preferable for application to the laminate according to the present invention. It's Chino.

[Example] Examples of the present invention will be described below.

Figure 1 shows an embodiment of the laminate according to the present invention, and shows a sectional view of the laminate.

In this example, a sheet 1 mainly made of PPS and an aluminum plate 2 were joined by an anchor effect. In the manufacturing process, the joint surface of the aluminum plate 2 was roughened by a chemical etching process. This chemical etching step was performed on the aluminum plate 2 using a 10% aqueous solution of sodium hydroxide (NaOH) or a 98% aqueous solution of phosphoric acid (H.PO4).

1 9 Through this chemical etching process, the surface of the aluminum plate 2 has a roughness of 2. The surface was uneven to the extent of um or more. PP
Sheet 1 containing S as a main component had a crystallinity of 14% or less as measured by the density gradient tube method. This has a melt viscosity of 5. The raw material with 900 voids was melt-extruded at a temperature of about 310°C and cast using a cast roll at 40°C. The sheet produced under these conditions had a crystallinity of approximately 0%. The above PPS sheet 1 with a crystallinity of approximately 0% and the aluminum plate 2 are
A laminate was obtained by thermocompression bonding and solidification using a hot roll at 70''C.

Here, in the laminate formed by thermocompression bonding, the degree of crystallinity of PPS changes depending on the surface temperature of the thermo roll used during the thermocompression bonding. The following (Table 3) shows that when the sheet 1, which is mainly made of PPS, and the aluminum plate 2 are thermocompression bonded with a heat roll, the surface temperature of the heat roll is changed, and the PPS crystals are crystallized at each roll surface temperature. It shows the measured value of the degree of oxidation. In this measurement, the feeding speed by the hot roll was 1
．． The speed is 5m/min. In Table 3), Xc indicates the degree of crystallinity. This crystallinity Xc was measured by the density gradient tube method, and was calculated from the following formula based on the measured value of density ρ.

Xc=(ρJρ)・{(ρ−ρ6)/(ρ0−ρ.)}
However, crystal density; ρ. = 1.4300 amorphous density: ρ
．． =1.3125 Here, the crystal density is European Polymer
Journal (1971) vol. 7 P112
B. described in 7. J. The X-ray analysis value of Talor et al. was used, and the amorphous density was determined by measuring the density of a non-oriented sheet that had been rapidly cooled and confirmed to be amorphous by X-rays. In addition, if additives are present, the density of the additives is generally subtracted from the calculation.

(The following is a margin) cTable-3) As shown in (Table-3), when thermocompression bonding was carried out using a roll whose surface temperature was 160°C or less, crystallization of PPS sheet 1 hardly progressed. Since the PPS sheet is in a low crystallization state, the elongation at break can be increased to over 200% (see (Table 1)), and when subjected to processing such as drawing, the PPS sheet is We were able to obtain a product with no cracks or damage.

In the above embodiment, the bonding surface of the aluminum plate 2 is surface-treated by chemical etching, but mechanical treatment (e.g., sand blasting, shot blasting, etc.), electrolytic etching treatment, anodizing treatment, chemical conversion treatment, painting, etc. A laminate equivalent to that of the above embodiment can be obtained by surface treatment such as surface treatment or a combination thereof.

The laminate shown in FIG. 1 could also be produced by extrusion lamination. In this method, similarly to the thermocompression bonding described above, the bonding surface of the aluminum plate 2 is roughened by a chemical etching process. 2 3 sheet 1 of PPS contains about 3 ml of raw material with a melt viscosity of 5.900
The PPS was melt-extruded at a temperature of 10°C, laminated on the joint surface of the aluminum plate 2, and pressed with a cooling press roll at 40°C, while cooling the PPS. As a result, it was possible to obtain a laminate of the PPS sheet 1 and the aluminum plate 2 in an amorphous state (crystallinity measured by density gradient tube method: approximately 0%). Incidentally, the temperature of the above-mentioned cooling pressure roll is generally 80°C or lower, preferably 60°C or lower.

Since no adhesive is used in the laminate manufactured by the above-mentioned hot pressing (Example 1) or extrusion lamination (Example 2), there is no need to consider the chemical resistance of the adhesive. For example, PPS using epoxy adhesive
When bonding a sheet of aluminum to an aluminum plate, some chemicals may dissolve the adhesive. When adhesive is used, there is a risk that the adhesive may be affected by chemicals at the joint end surface between the PPS sheet and the aluminum plate, and the adhesive may be extracted. The above embodiment in which no adhesive is used is effective.

FIG. 3 shows a cross-sectional view of a cylindrical case molded using the laminate obtained in Example 1 or Example 2. This case was manufactured by drawing and molding the above-mentioned laminate obtained by thermocompression bonding or extrusion lamination. This drawing process is carried out by a step-by-step press operation using a mold, which allows the PPS to
A cylindrical case was formed in which the seat 1 was on the inner side. As mentioned above, PPS sheet 1 has a crystallinity of 14% or less and a breaking elongation of 200% or more. There were no cracks, and cylindrical cases could be easily created by deep drawing. In this drawing process, by heating the mold to about 120 to 130'' C as necessary, the PPS sheet 1 can easily follow the deformation of the aluminum plate 2 in the drawing process.

In FIG. 3, the PPS seat 1 is on the inner side of the case, but it is also possible to have the PPS seat 1 only on the outer side.

Comparative Example 1 for comparison with Example 1 and Example 2 described so far will now be described. As a result of trying to thermocompress sheets with crystallinity degrees of 21% and 31% shown in Table 1 above to chemically etched aluminum in the same manner as in the above example, the adhesive strength was weak and the sheets easily peeled off. A good laminate could not be obtained.

FIG. 2 shows another embodiment of the laminate according to the invention.

The symbol l is a sheet of PPS. The PPS sheet has a melt viscosity of 5. A raw material having a weight of 900 poise was melt-extruded at a temperature of about 310°C and cast using a cast roll at a temperature of 40°C. The sheet produced under these conditions has a crystallinity of approximately 0%. Note that the thickness of the PPS sheet 1 is approximately 25 μm.

Reference numeral 2 is an aluminum plate (annealed 1/2 11 material or 0 material) and has a thickness of about 300 Ltm.

Reference numeral 3 is an adhesive. As the adhesive 3, epoxy, polyester, phenol, etc. can be used, but in this example, a modified epoxy adhesive is used.
Specifically, the product name "ThreeBond 1570" manufactured by ThreeBond Co., Ltd. was used.

The specific manufacturing method is as follows: First, the adhesive surface of the above-mentioned amorphous PPS sheet 1 is surface-treated by corona treatment.
Apply the above adhesive 3 to the adhesive surface of the PS sheet 1,
An adhesive layer with a thickness of approximately 10 μm was obtained. After about 30 minutes had passed, the PPS sheet 1 and the aluminum plate 2 were placed on top of each other with the adhesive 3 in between, and bonded together using hot rolls. The temperature conditions for this bonding are approximately 100°C and the feed speed is 1.5m/min.
And so. Thereafter, the adhesive was heat-cured using a press. The temperature conditions for this thermosetting treatment were approximately 100°C for 2 hours.

In this completed laminate, it was confirmed that the PPS sheet 1 remained almost transparent, and the crystallinity of the PPS sheet 11 was approximately 3% or less.

Next, the laminate of Example 3 obtained in the above bonding process was deep drawn to form a cylindrical case having the same shape as shown in FIG. This cylindrical case was intended to be used, for example, as a case for an electrolytic capacitor or a dry battery, and was manufactured with dimensions of 10 mm in outer diameter and 10 mm in height. This was produced by pressing and drawing the laminate in stages. This cylindrical case is
It was confirmed that there were no cracks or cracks in the PPS sheet l on the inner surface, and that it could function satisfactorily as an insulating film. PPS is DMF (N.N. dimethylformamide)
When the cylindrical case described above is used as a case for an electrolytic capacitor, it will not swell or dissolve due to the electrolyte inside the capacitor.

Tsujizuma0eZ 2 8 Here, Comparative Example 2 will be described for comparison with the laminate of Example 3 obtained by the bonding process. This comparative example 2
has a crystallinity of 21% and 3l% shown in Table 1 above.
The sheet was used and bonded to an aluminum plate using the same bonding method as in the above example to form a laminate. When this was drawn and bent, cracks appeared.

A sheet with a crystallinity of 3% shown in Table 1) is heated to a surface temperature of 1.
0.0 with roll at 80℃. When molded by thermocompression bonding at 3 m/min, the laminate sheet had a crystallinity of 20%, and when it was drawn, cracks occurred.

Jitsuma 9 4 The laminate shown in FIG. 2 was manufactured by a process different from that of Example 3 above. In this example, corona-treated P
A PS sheet and an aluminum plate were laminated. The steps up to this point are the same as in the third embodiment. In this example, after laminating a PPS sheet and an aluminum plate with an adhesive and bonding them with a hot roll under the same conditions as in Example 3 above, the adhesive is not heat-cured using a press machine. A laminate was produced. The laminate bonded at 100°C and 1.5 m/min can obtain sufficient adhesive strength even if the heat curing treatment is omitted, and the peel strength is approximately 4.
It was about kgf/25mm. However, the measurement conditions are based on JIS K6854, and the peeling speed is 50 mm/min with peeling in a 90 degree direction. In addition, the case shown in Fig. 3 was deep-drawn using this laminate.
No cracks or cracks were found in PS sheet 1.

By using the same bonding process as shown in Example 4 above, a laminate was produced without heat curing of the adhesive, and as a result,
The case shown in FIG. 3 was drawn, and after the drawing process, the adhesive was hardened in a heating furnace. The curing conditions were 150°C for 2 hours. With this process, PP
It was confirmed that S turned white and crystallization was progressing. In this example, the PPS sheet 1 remains in an amorphous state in the laminate state. Therefore, when deep drawing the case, the elongation of the PPS sheet is sufficiently high.
The PPS layer was able to follow the drawing process.

After the case was manufactured, the adhesive strength was sufficiently increased by heat curing the adhesive. Note that after the above-mentioned adhesive was heat-cured, there were no problems with properties such as insulation.

Figure 4 shows the laminate of Example 6 in cross section. In this Example 6, the amorphous PPS sheet 1 was bonded to both sides of the aluminum plate 2 without using an adhesive. This joining method is the same as in Example 1 or 2, in which PPS sheets 1 are laminated by thermocompression bonding or extrusion lamination on both sides of an aluminum plate 1 whose surfaces have been roughened by chemical etching. The sheet 1 and the aluminum plate 2 were joined by an anchor effect. If the laminate of Example 6 is molded into a concave shape to manufacture a case as shown in FIG.
You can get a case covered with.

Figure 5 shows a cross section of the laminate of Example 7. In this example, a PPS sheet 1 having a crystallinity of 14% or less was bonded to both the front and back surfaces of an aluminum plate 2 via an adhesive 3. This bonding method is the same as in Example 3. When a case as shown in FIG. 3 is manufactured using the laminate of Example 7, both the inside and outside surfaces are covered with the PPS sheet 1. When used as a case for an electrolytic capacitor, both the inside and outside surfaces are insulated with sheets mainly made of PPS. In addition, when the PPS-based sheet is directed toward the outside of the case, the outside of the case can be made white or another color by adding titanium oxide, a white pigment, or other pigments as a filler to the PPS. becomes possible.

A cylindrical case shown in FIG. 3 was drawn and formed using the laminated body produced in Example 1 or Example 2. As mentioned above, since the PPS in the laminate of Example 1 or Example 2 has a crystallinity of 14% or less and a breaking elongation of 200% or more, the PPS sheet portion is sufficient during drawing forming. No elongation cracks occur. In this example, the drawn cylindrical case was further heat treated in a heating furnace at 160°C for 1 hour to promote crystallization of PPS. This made it possible to obtain a case having a PPS layer with even higher heat resistance. In this way, the case after molding is heat-treated for a certain period of time to increase the degree of crystallinity, as necessary.

Note that the case according to the present invention is not limited to use for electrolytic capacitors or dry batteries, but can also be used as a medicine case, etc.

Further, the metal plate is not limited to an aluminum plate, and may be a zinc plate, a copper plate, or the like.

[Effect] As described above, according to the inventions described in claims 1 and 2, since the sheet of PPS with low crystallinity and high elongation at break is laminated on a metal plate, it is possible to The PPS sheet can follow the deformation of the metal plate during processing and bending, resulting in good workability. It is possible to obtain flexible laminated materials. Further, according to the third aspect of the invention, the case has a surface layer with excellent insulation properties and chemical resistance, and is suitable as a case for, for example, an electrolytic capacitor or a dry battery.

According to the invention described in claims 4 and 5, PP with low crystallinity and high elongation at break can be produced without using an adhesive.
It becomes possible to produce a laminate of a sheet mainly composed of S and a metal plate.

According to the invention described in claim 6, it is possible to fix a sheet mainly made of PPS, which has a low degree of crystallinity and a high elongation at break, to a metal plate made of aluminum or the like using an adhesive. You will be able to maintain it in a low state.

According to the seventh aspect of the invention, when the case is drawn, the PPS has a low crystallinity so that it is suitable for processing, and the adhesive is further hardened after being processed into the case. A case with high peel strength of the PPS layer can be obtained.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing a laminate according to the present invention, FIG. 2 is a sectional view showing a laminate according to another embodiment of the invention, and FIG. 3 is a sectional view showing an embodiment of a case according to the invention. 4 and 5 are cross-sectional views showing a laminate according to still another example, and FIG. 6 is a diagram showing the relationship between the degree of crystallinity and elongation at break of PPS. 1...PPS sheet, 2...aluminum plate, 3...
glue. 3 5 Ward Ward N Ward N 217

Claims (1)

[Scope of Claims] 1. A laminate consisting of a sheet mainly composed of polyphenylene sulfide and a metal plate, which sheet is mainly composed of polyphenylene sulfide with a crystallinity of 14% or less. A laminate for press molding 2, according to claim 1, wherein the sheet has an A at 23°C.
A laminate for press molding 3 mainly composed of polyphenylene sulfide having a breaking elongation of 200% or more according to STM D-638, a laminate for press molding according to claim 1 or claim 2, which is formed into a concave shape. The laminate according to claim 1 or claim 2 is manufactured by press-molding the case 4, roughening the metal plate by surface treatment, and bonding a sheet mainly composed of polyphenylene sulfide by thermocompression to the treated surface of the metal plate. Method 5: A method 6 of manufacturing a laminate according to claim 1 or 2 by roughening a metal plate by surface treatment and extrusion laminating a sheet mainly composed of polyphenylene sulfide on the treated surface of the metal plate. A range in which a state in which the elongation at break according to ASTM D-638 at 23°C can be maintained at 200% or more when a sheet mainly composed of polyphenylene sulfide of 14% or less and a metal plate are laminated via an adhesive layer. Method 7 for producing a laminate, in which a sheet mainly composed of polyphenylene sulfide and a metal plate are thermally bonded together by curing the adhesive at a heating temperature of A case manufacturing method in which the adhesive is molded and then heated above the temperature of the hot pasting process after this press molding to further harden the adhesive.