JP3425375B2 - Manufacturing method of chemical resistant sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to lining materials such as reaction towers, reaction tanks, storage tanks, transportation and storage tanks, liquid containers, containers for chemicals and electronic parts, and vehicles, ships. The present invention relates to a method for producing a chemical resistant sheet having weather resistance, heat resistance and the like suitable as an interior material for aircraft, public facilities, houses and the like.

[0002]

2. Description of the Related Art Fluorine-based resins are excellent in chemical resistance, heat resistance, non-adhesiveness, electrical characteristics, etc., and are therefore used in various industries such as chemicals, petroleum, paints, inks, industrial chemicals, pharmaceuticals and semiconductors. Widely used in the field. However, polytetrafluoroethylene resin (hereinafter abbreviated as PTFE), which is a typical fluorine-based resin, has poor surface activity, cannot be bonded by ordinary means, and does not melt and fluidize. When used for the interior of tanks, etc., in the past, so-called loose lining method of simply interposing the sheet between the vessel wall and the contents, or the surface on the adhesive side of the sheet was activated by mechanical or chemical treatment. Although the method of lining it through an adhesive after applying it was adopted, the former method has large application restrictions, and the latter method also has insufficient adhesive strength and the fragility of the sheet itself. There was a problem in use and processing due to.

Therefore, the present applicant has previously developed a laminated chemical resistant sheet using PTFE, and continuously obtains this chemical resistant sheet as a long product by thermocompression bonding with a heat roll. Established manufacturing method
No. 18410). This chemical resistant sheet is made of PTF
A thermoplastic fluororesin film is interposed between a sheet base material made of E and a glass cloth, and this is thermocompression bonded to form an integrated laminate. The glass cloth side is used as an adhesive surface to form an ordinary adhesive. It has already been used in a wide range of industrial fields because of its excellent advantages such as high strength adhesion to the wall surfaces of various materials and the fact that the sheet itself is strong due to the laminated structure with the glass cloth. In particular, the long product produced by the above-described manufacturing method can be cut into an appropriate length according to the size of the portion to be lined, etc., and therefore, a large amount of unused short material due to an excess portion does not occur, resulting in waste. Less economical.

[0004]

By the way, in recent years, along with the expansion of applications of chemical-resistant lining, various characteristics required from the lining specifications and processing, that is, mechanical characteristics such as bending and tension, Thermal and electrical characteristics and other necessary characteristics are diversified, and the above-mentioned PTFE
In order to deal with the field in which the chemical resistant sheet using the is not suitable in terms of characteristics, the demand for a lining material in which a sheet of a fluororesin having melt fluidity and a glass cloth are laminated is rapidly increasing.

However, a conventional chemical-resistant sheet using a melt-flowable fluororesin is a product having a certain size by laminating and integrating the fluororesin sheet and glass cloth by a badge type hot press. In addition, since the excess part when cut according to the size of the part to be lined is all unused short material, it is wasteful and uneconomical, and the manufacturing efficiency is poor and the cost is high. there were.

Regarding the production of a chemical resistant sheet using such a melt flowable fluororesin, the above-mentioned P is conventionally used.
The reason why the continuous method using a heat roll such as the chemical resistant sheet using TFE is not adopted is as follows. That is, when the melt flowable fluororesin sheet and the glass cloth are thermocompression bonded through a pair of heat rolls, it is necessary to heat the resin sheet to a temperature higher than the melting point. Generally, the melt flowable fluororesin has a melting point. And the pour point are close to each other, the transfer of the melt-fluidized resin to the roll surface cannot be avoided even if the conditions such as heating temperature and running speed are strictly controlled. This is because there is a possibility that not only the thickness uniformity is impaired and the quality is deteriorated, but also the resin sheet is torn to cause a product defect, or the resin transferred to the roll surface is accumulated and the operation becomes impossible.

In view of the above-mentioned circumstances, the present invention provides a chemical resistant sheet in which a sheet of fluororesin having melt fluidity and a glass cloth are laminated, but the chemical resistant sheet is By establishing a means to easily manufacture with high efficiency by a continuous method, it is possible to commercialize the chemical resistant sheet as a long product, and contribute to resource saving by reducing the generation of wasteful unused short materials. , The aim is to reduce the manufacturing cost and achieve a stable supply of products.

[0008]

In order to achieve the above object, the method for producing a chemical resistant sheet according to claim 1 of the present invention has a melt fluidity, as indicated by the reference numerals in the drawings. Resin sheet 1 made of fluorine resin and glass cloth 2
And a continuous roll-out from each winding roll R1, R2, while continuously running the superposed sheet 10, one high temperature roll having a roll surface temperature higher than the melting point of the fluororesin, An unheated roll that forms a nip for each hot roll and that does not have a heating mechanism.
And the two low temperature rolls 4A and 4B each having a roll surface temperature lower than the same melting point are made to come into contact with the surface 2a of the glass cloth 2 on the surface of the high temperature roll 3 for heating. By press-bonding, the resin sheet 1 and the glass cloth 2
The laminated sheet 11 is characterized by being integrated with.

According to the above structure, the continuously running laminated sheet 10 includes the high temperature roll 3 and the two low temperature rolls 4.
The surface 2a on the glass cloth 2 side is in contact with the peripheral surface of the high-temperature roll 3 between the two nip portions 8 and 8 before and after the resin sheet 1 at positions of both the nip portions 8 and 8.
The side surface 1a comes into contact with the surfaces of the low temperature rolls 4A and 4B. In this process, the inner surface 1 of the resin sheet 1
Since the b side is heated by the high temperature roll 3 through the glass cloth 2, the temperature becomes higher than the melting point and the surface layer portion thereof melts and fluidizes, but the outer surface 1a of the resin sheet 1 absorbs heat by the low temperature rolls 4A and 4B. Since the temperature is kept lower than the melting point by the melting point, the melted and fluidized resin does not transfer to the surfaces of the low temperature rolls 4A and 4B, and especially the low temperature roll 4B on the rear side is formed from the laminated sheet 11 immediately after thermocompression bonding. It will absorb heat evenly and rapidly over the entire sheet width to cool it, and the shrinkage degree due to the temperature gradient in the sheet width direction (cooling on both sides faster than the center side) in the case of natural cooling will occur. The occurrence of waviness and wrinkles due to the difference can be avoided, and the resin sheet 1 side of the resulting laminated sheet 11 has excellent flatness.

On the other hand, the interface portion between the resin sheet 1 and the glass cloth 2 in the superposed sheet 10 contacts the peripheral surface of the high temperature roll 3 between the nip portions 8 at two front and rear portions, and the resin sheet 1 Since it is possible to secure a time margin for the melted and fluidized fluororesin to enter the fiber structure of the glass cloth 2, the glass cloth 2 bites into the layer of the resin sheet 1 in the laminated sheet 11 after thermocompression bonding and is completely integrated. There is no peelable interface.

However, when the number of low-temperature rolls is one, the superposed sheet 10 is heated and pressure-bonded at the nip portion 8 at one place, and the sheet 10 comes into contact with the high-temperature roll 3 within an extremely short time. In melting the fluorine-based resin of the resin sheet 10 with the glass cloth 2 with
Since it is necessary to set the heating temperature by the high-temperature roll 3 to be very high, even if the low-temperature roll is in contact with the surface 1a on the resin sheet 1 side, as long as the thickness of the resin sheet 1 is not so large, high-temperature heating is possible. The entire resin layer is instantly melted and fluidized, and the surface layer portion thereof is transferred to the low temperature surface of the low temperature roll and solidified, so that the adhesion and accumulation tend to make the operation rather difficult. Further, the thickness of the sheet may change, and it is difficult to obtain a satisfactory pressure-bonding strength.

As described above, in order to surely exhibit the melting action of the fluororesin by the high temperature roll 3 and the heat absorbing action by the low temperature rolls 4A and 4B, the high temperature roll 3 of the invention can be used. It is recommended that the roll surface temperature is 50 ° C. or more higher than the melting point of the fluororesin, and the roll surface temperature of the low temperature rolls 4A and 4B is set to 50 ° C. or more lower than the melting point . Further, the from the viewpoint of the melting action and the heat absorbing action of the sheet properties and the as chemical resistance sheet, as in the invention of claim 3, the thickness of the resin sheet 1 is 0.05 to 3 mm, the glass cloth 2 Thickness Is 0.2-2
A configuration of mm is preferred.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION A method for producing a chemical resistant sheet according to the present invention will be specifically described below with reference to the drawings. FIG. 1 shows a continuous manufacturing apparatus to which the manufacturing method of the present invention is applied. In the figure, R1 is a winding roll of a fluororesin sheet 1 having melt fluidity, R2 is a winding roll of glass cloth 2, and 3 is a roll. The high temperature rolls 4A and 4B whose surface temperatures are set higher than the melting point of the fluororesin sheet 1 are low temperature rolls whose surface temperatures are set lower than the melting point of the fluororesin sheet 1 and 5A and 5B are roll pairs. Is a front guide roll, 6 is a rear guide roll, and 7 is a take-up roll. The low-temperature rolls 4A and 4B are arranged back and forth with the high-temperature roll 3 to form nip portions 8 and 8.

In order to manufacture a chemical resistant sheet, the fluororesin sheet 1 and the glass cloth 2 which are respectively wound as long materials on the winding rolls R1 and R2 are continuously fed out in synchronization with each other. Part rolls 5A and 5B to form a superposed sheet 10, and while the superposed sheet 10 is continuously run, the high temperature roll 3 and the low temperature roll 4
The surface 2a on the glass cloth 2 side (see FIG. 2) is passed between the nip portions 8 and 8 in front of and behind A and 4B in a state of being in contact with the peripheral surface of the high temperature roll 3 to perform thermocompression bonding. As shown in FIG. 3, the rear guide roll 6 is used as the laminated sheet 11 in which the fluororesin sheet 1 and the glass cloth 2 are integrated.
It is continuously wound around the winding roll 7 via.

According to this manufacturing method, the continuously running laminated sheet 10 includes the high temperature roll 3 and the two low temperature rolls 4.
In the process of passing between A and 4B, the inner surface 1b side of the resin sheet 1 is heated by the high-temperature roll 3 through the glass cloth 2, so that the temperature becomes higher than the melting point, and the surface layer portion thereof is melted and fluidized and the glass cloth 2 However, the outer surface 1a of the resin sheet 1 is kept at a temperature lower than the melting point by heat absorption by the low temperature rolls 4A and 4B. Therefore, the melted and fluidized fluororesin is not transferred to the surfaces of the low temperature rolls 4A and 4B, and the chemical resistant sheet can be manufactured in a stable continuous process.

By the way, generally, when a resin sheet and another material are continuously thermocompression-bonded through a heating roll, the laminated sheet which has been heated to a high temperature by this thermocompression-bonding is naturally left to cool until it is wound up. In this case, both sides are cooled faster than the center side in the sheet width direction, and the temperature gradient can cause a difference in the shrinkage degree in the sheet width direction, so that waviness and wrinkles of the sheet easily occur. However, in the above-mentioned manufacturing method, the low temperature roll 4B on the rear side is the laminated sheet 11 immediately after thermocompression bonding.
The laminated sheet 11 is cooled by uniformly and rapidly absorbing heat over the entire sheet width.
The resin sheet 1 of the obtained laminated sheet 11 is in a state in which the shrinkage property is almost lost at a stage away from the sheet, and thus the occurrence of waviness and wrinkles due to the difference in expansion and contraction in the sheet width direction is avoided.
The side has excellent flatness.

On the other hand, at the interface between the resin sheet 1 and the glass cloth 2 in the superposed sheet 10, the resin sheet 1 is formed in the process of contacting the peripheral surface of the high temperature roll 3 between the nip portions 8 at the front and rear. Since there is time to allow the melted and fluidized fluororesin to enter the fiber structure of the glass cloth 2, even if the low temperature roll 4B on the rear side comes into contact with the laminated sheet 11 immediately after thermocompression bonding as described above, the resin sheet 1
The fusion property between the glass cloth 2 and the glass cloth 2 is not hindered. Therefore,
In the obtained laminated sheet 11, the glass cloth 2 bites into the layer of the resin sheet 1 and is completely integrated, and there is no peelable interface.

As described above, the roll surface temperature of the high temperature roll 3 constitutes the resin sheet 1 in order to surely exhibit the melting action of the fluorine resin by the high temperature roll 3 and the heat absorbing action by the low temperature rolls 4A and 4B. It is preferable that the melting point of the fluororesin is set to 50 ° C. or higher, and the roll surface temperatures of the low temperature rolls 4A and 4B are set to 50 ° C. or lower than the melting point. The press nip pressure in both nip portions 8 and 8 may be about 1 to 5 Kg / cm.

[0019] Incidentally, cold roll 4A, 4B, since it is warm due to heat transfer from the hot roll 3, shall be the non-heated roll with no heating mechanism. Therefore, the roll surface temperature of the unheated low temperature rolls 4A and 4B can be set only by radiating heat from the entire roll during continuous operation and exhausting heat by heat conduction through the bearing portion, but it is necessary. If necessary, an appropriate cooling mechanism may be provided to positively exhaust heat.

As a constituent material of the resin sheet 1, a molten flow is used.
Any fluorinated resin having mobility can be used, and it is not particularly limited.
No, but for example CF₂= CF₂And CF₂= CF-CF₃
Copolymer (commercially available from EI DuPont
Product name Teflon FEP), CF ₂= CF₂And CF₂= CF
-ORf copolymer (Rf is a perfluoroalkyl group:
Teflon PFA), CH₂= CH₂And CF₂= CF₂
Copolymer (Teflon ETFE, Mitsui DuPont Flo
Product name of Rochemical Co., Tefzel), CH₂= CF₂The weight of
Combined (polyvinylidene fluoride resin: Teflon PVD)
F, Pennwalt's trade name Kainer), CH₂=
CH₂And CF₂= CClF copolymer (Teflon EC
TFE), CHF = CH₂Polymer of Teflon PV
F) and the like, among which CF is particularly preferable.₂= CF₂
And CF₂= CF-CF₃Copolymer of Teflon FE
P) and CF₂= CF₂And CF₂= CF-ORf
The copolymer (Teflon PFA) of is preferable.

The thickness of the resin sheet 1 is 0.05-5 mm
Is preferred. That is, when the thickness is too thin, it becomes extremely difficult to melt and fluidize the inner surface 1b side while the outer surface 1a side is not melted during thermocompression bonding with the glass cloth 2, and the sheet 1 during running is subjected to the thermocompression bonding portion. There is a concern that it may break or the stacking may not be possible. On the contrary, if the thickness is too thick, it is necessary to slow down the feed rate in order to compensate for the decrease in thermal conductivity, which leads to a decrease in manufacturing efficiency, and it is difficult to wind it around a roll due to its large rigidity. It becomes difficult to apply the manufacturing method, and the rigidity and the material cost increase, so that the application restriction as a chemical resistant sheet becomes large.

The glass cloth 2 has a thickness of 0.2 to
A thickness of 2 mm is suitable. That is, if this thickness is too thin, the strength as a chemical resistant sheet becomes insufficient, and the fluorine-based resin melted and fluidized at the time of thermocompression bonding penetrates to the surface 2a of the glass cloth 2 and the surface 2a.
It will hinder the adhesiveness on the side. On the other hand, if it is too thick, the heat conduction through the glass cloth 2 from the high-temperature roll 3 at the time of thermocompression bonding deteriorates, the fusion of the resin sheet 1 becomes difficult, and it is suitable for use as a chemical resistant sheet. Greater constraints.

The laminated sheet 11 thus obtained, that is, the chemical resistant sheet, can be easily provided with an adhesive lining on the wall surface of the tower tanks or tanks using a general adhesive on the glass cloth 2 side. Along with the resin sheet 1
On the side surface, the very high chemical resistance, heat resistance, non-adhesiveness, electrical characteristics, etc. inherent to the fluororesin can be exhibited, and the surface 1a on the resin sheet 1 side is smooth and wavy and wrinkle free. In addition to the quality, since the resin sheet 1 and the glass 2 are completely integrated without a peelable interface, there is no concern that the resin sheet 1 will peel off even under severe usage conditions. Also, since this chemical resistant sheet is obtained as a long product,
It can be used by cutting it to an appropriate length according to the size of the part to be lined, etc., and produces a large amount of unused short material due to excess parts like a chemical resistant sheet of a certain size manufactured by the badge method. It is very economical with no waste. In addition, especially the resin sheet 1 is 0.05 to 0.3 mm
The extremely thin chemical resistant sheet is extremely useful as an interior material for vehicles, ships, aircraft, public facilities, houses and the like.

[0024]

[0025]

EXAMPLE 1 In the apparatus configuration of FIG. 1, a high-temperature roll 3 having a diameter of 250 mm whose surface is made of hard chrome and a non-heated low-temperature roll 4A having a diameter of 220 mm whose surface is made of hard chrome, 4B and both low temperature rolls 4A,
The inter-axis distance of 4B is set to 380 mm, the press nip pressure of the nip portions 8 and 8 is set to 2.5 Kg / cm, and the roll surface temperature of the high-temperature roll 3 during continuous operation is set to 380 mm.
C., the resin surface 1 made of Teflon PFA (described above) having a thickness of 0.2 mm and glass having a thickness of 0.65 mm while controlling the roll surface temperature of both low temperature rolls 4A and 4B to 180 to 190 ° C. The cloth 2 is continuously fed from the winding rolls R1 and R2 having the same width, and the cloth is passed through between the front guide rolls 5A and 5B to be overlapped.
Both the nip portions 8 and 8 with the surface of the glass cloth 2 contacting the peripheral surface of the high temperature roll 3 while continuously feeding at 0 mm / min.
Through hot pressing to continuously produce a long chemical resistant sheet. This chemical-resistant sheet has excellent flatness without waviness or wrinkles, and according to a microscopic observation of the cross section,
The glass cloth 2 bites into the layer of the resin sheet 1 and is completely integrated without a peelable interface, and has properties suitable as a lining material or a corrosion resistant fabric.

Example 2 Teflon FEP having a thickness of 0.1 mm as the resin sheet 1
A glass cloth 2 having a thickness of 0.
The roll surface temperature of the high temperature roll 3 during continuous operation is 300 ° C., and the roll surface temperature of both low temperature rolls 4A and 4B is 180 to 200.
℃, press nip pressure of the nip portion 8, 8 is 2.0 Kg / c
A long chemical resistant sheet was continuously manufactured in the same manner as in Example 1 except that m and the feed rate were set to 250 mm / min. This chemical resistant sheet is excellent in flatness without waviness and wrinkles, and the resin sheet 1 and the glass cloth 2 are completely integrated, and are thin and highly flexible, which makes them particularly suitable as interior materials. there were.

[0027]

According to the method of manufacturing a chemical resistant sheet according to the first aspect of the present invention, the chemical resistant sheet has a laminated form of a resin sheet made of a fluororesin having a melt fluidity and a glass cloth. Despite this, they are heated and pressure-bonded to each other through two nip portions before and after, which are formed between one high-temperature roll whose surface temperature is higher than the melting point of the fluororesin and two low-temperature rolls whose melting point is lower than the same melting point. By the continuous method, it is possible to easily and reliably produce a long product with high efficiency. Moreover, the obtained chemical resistant sheet is excellent in strength because the resin sheet and the glass cloth are completely integrated in a state where there is no peelable interface and is excellent in flatness without waviness or wrinkles and is of very high quality. In addition, since it is a long product, it is possible to reduce the generation of wasteful unused short material and contribute to resource saving. Furthermore, the low-temperature roll does not have a heating mechanism.
Since a non-heated roll is used, the device configuration can be simplified.
The advantage is that the equipment cost can be reduced accordingly.
It

According to the second aspect of the present invention, in the above manufacturing method, since the roll surfaces of the high temperature roll and the low temperature roll are set to have a specific temperature difference with respect to the melting point of the fluororesin, the chemical resistant sheet is obtained. Has the advantage that it can be produced more reliably by a continuous method.

[0029]

According to the second aspect of the invention, in the above manufacturing method, since the thickness of the resin sheet and the glass cloth is within the specific range, the reliability of the chemical resistant sheet by the continuous method is increased, and There is an advantage that suitable properties can be imparted as a chemical resistant sheet.

[Brief description of drawings]

FIG. 1 is a schematic side view of a continuous manufacturing apparatus to which a method for manufacturing a chemical resistant sheet according to the present invention is applied.

FIG. 2 is a sectional view of the same chemical resistant sheet.

[Explanation of symbols]

1 resin sheet 1a outer surface 1b Inner surface 2 glass cloth 2a Glass cloth side surface 3 high temperature roll 4A, 4B low temperature roll 5A, 5B guide roll 6 guide rolls 7 winding roll 8 Nip part 10 stacked sheets 11 laminated sheets R1, R2 winding roll

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-227449 (JP, A) JP-A-8-99389 (JP, A) JP-A-48-73564 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 B29C 63/00-65/82

Claims (3)

(57) [Claims] 1. A resin sheet made of a fluorine-based resin having melt fluidity and a glass cloth are continuously fed out from respective winding rolls and overlapped with each other. One high-temperature roll having a melting point higher than that of the fluororesin , and a nip portion for each high-temperature roll , and a heating mechanism
Between the two low-temperature rolls whose roll surface temperature is lower than the same melting point and which consist of non-heated rolls, the surface of the glass cloth is brought into contact with the surface of the high-temperature rolls and thermocompression-bonded to obtain the resin sheet. A method for producing a chemical resistant sheet, comprising: a laminated sheet in which a glass cloth and glass cloth are integrated. 2. The resistance according to claim 1, wherein the roll surface temperature of the high temperature roll is set to be 50 ° C. or more higher than the melting point of the fluororesin, and the roll surface temperature of the low temperature roll is set to be 50 ° C. or more lower than the melting point. Method for manufacturing chemical sheet. 3. A resin sheet having a thickness of 0.05 to 5 mm,
Method for producing a chemical-resistant sheet according the thickness of the glass cloth to claim 1 or 2 Ru 0.2~2mm der.