TWI468288B - Multilayer sheet, endless belt and method for manufacturing endless belt - Google Patents

Description

Method for manufacturing multi-layer thin material, endless belt and endless belt

The present invention relates to a method for producing a laminated thin material, an endless belt, and an endless belt. More specifically, the present invention relates to, for example, a multi-layered thin material which is useful for industrially relevant heat resistance, non-adhesiveness, abrasion resistance, and slip resistance, and an endless belt composed of the laminated thin material and A method of manufacturing an endless belt.

In the heat-resistant composite thin material which has been known, a heat-resistant resin having good heat resistance or non-adhesiveness is combined with a heat-resistant fiber woven fabric having excellent heat resistance and tensile strength, and these heat-resistant composite thin materials are used as industrial Relevant heat-resistant, non-adhesive thin materials or heat-resistant, non-adhesive conveyor belts.

The heat-resistant fiber woven fabric used for the heat-resistant composite thin material is, for example, a woven fabric such as glass fiber or aromatic polyamide fiber which is formed by plain weave, diagonal weave or the like.

Moreover, as the heat resistant resin used for the above heat-resistant composite thin material, for example, a fluororesin such as tetrafluoroethylene resin (PTFE) is used.

However, in general, fluororesin has good heat resistance, cold resistance, non-adhesiveness, chemical resistance, flame resistance, weather resistance, electrical insulation, and low friction. Etc. However, due to lack of wear reisistance and good low friction, it is easy to slip.

The abrasion resistance is superior to that of the fluororesin, and the low friction is inferior to the fluororesin, the grip is superior to the fluororesin, and the heat resistant material which is difficult to slide is, for example, a polyimide resin.

As a manufacturing method for improving the abrasion resistance of a thin material, for example, the proposed method is a method in which a heat-resistant fiber woven fabric is impregnated and adhered to a mixture of a polyimine-based resin dispersed in an aqueous suspension of a fluororesin, and dried. A method of re-baking (Japanese Patent Laid-Open Publication No. 2006-21403 (Patent Document 1)).

However, the thin material of the above-mentioned Patent Document 1 is a mixed material of a polyimine-based resin and a fluororesin. Therefore, both properties are averaged, and it seems difficult to obtain a good abrasion resistance of the polyimide resin. . It is important for the endless belt for conveyance to have an appropriate slip-resistance and wear resistance on the contact surface with the drive roller, that is, the inner side surface of the belt body, but the mixture of the polyimide resin and the fluororesin seems to be mixed. It’s hard to make it both.

In the case of a mixture of a polyimine-based resin and a fluororesin, a layer of a polyimine-based resin and a fluororesin is formed into a tubular endless belt (Japanese Patent Laid-Open No. Hei 7-106032 (Patent Document 2) Japanese Laid-Open Patent Publication No. H7-178741 (Patent Document 3) and JP-A-2002-178422 (Patent Document 4) are also proposed. However, the manufacturing method thereof is press-formed by a cylindrical metal mold, and it seems to increase the equipment cost in order to correspond to various sizes.

[Patent Document 1] JP-A-2006-21403

[Patent Document 2] JP-A-7-110632

[Patent Document 3] Japanese Patent Publication No. 7-187741

[Patent Document 4] JP-A-2002-178422

The present invention has been made in consideration of the above matters, and an object of the invention is to provide a laminated thin material, an endless belt composed of the composite thin material, and a method for producing an endless belt, which can provide good heat resistance and non-adhesiveness. And a thin material having the required abrasion resistance or slip resistance, which is obtained by cutting a thin material into a desired size and using a mold to manufacture various sizes without using a mold. Looped belt.

In order to achieve the above object, a multi-layered thin material according to the present invention comprises at least one composite layer composed of a fluororesin and a heat-resistant fiber cloth and a surface layer composed of a polyimide pigment. Wherein, the surface layer is formed by a processing surface formed by surface-activation of the composite layer.

As a preferred aspect of the multi-layered thin material of the present invention, the surface activation treatment includes an inorganic particle adhesion firing treatment, a metal sodium etching treatment, a plasma discharge treatment, or a corona discharge treatment.

Further, the endless belt of the present invention comprises an annular body formed of the above-mentioned multi-layered thin material.

Next, in the method for producing an endless belt according to the present invention, the multi-layered thin material is cut into a strip shape; and the opposite ends of one of the multi-layered thin materials are joined to obtain an annular body.

Further, in another method of manufacturing the endless belt of the present invention, a strip of the laminated thin material and a further thin material is laminated, and the opposite ends of the laminated thin material of the strip are And the opposite ends of the other thin material of the ring are respectively joined or arranged in close proximity to obtain an annular body.

According to the present invention, a laminated thin material having excellent heat resistance, non-adhesiveness, abrasion resistance, and slip resistance can be obtained.

Since the surface layer of the multi-layered thin material is a polyimide-based resin, it is possible to obtain non-adhesiveness, abrasion resistance, or slip resistance suitable for the intended use, required properties, and the like.

Then, according to the present invention, the multi-layer thin material is directly laminated or another thin material is laminated, and then the multi-layer thin material is cut into strips or the laminate of another thin material is cut into strips. In the form of an endless belt having a desired width and length, an endless belt can be obtained. Therefore, an endless belt having a desired width, length, and layer configuration for the purpose can be easily produced. Further, the width and length of each layer can be prepared before lamination, and these layers are laminated to produce an endless belt.

Further, depending on the case, the same multi-layered thin material is not cut, and after forming an endless belt having a wide width, the wide-width endless belt is cut into a desired width, whereby a plurality of sheets can be simultaneously manufactured. An endless belt of the same length. Further, when the endless belt having the wide width is cut, by adjusting the width, it is easy to create and distinguish the endless belts having different widths.

On the other hand, since the surface layer of the multi-layered thin material can be formed by coating the polyimide-based resin, the surface layer portion is obtained in a thin material in advance, and the surface is laminated as compared with the case of laminating by an adhesive or the like. Since the bonding strength of the layer is high, a multi-layered thin material and an endless belt having good strength and durability can be obtained, and the production of the multi-layered thin material or the endless belt can be easily and efficiently performed.

The multi-layered thin material of the present invention has at least one composite layer composed of a fluororesin and a heat-resistant fiber woven fabric and a surface layer composed of a polyimide-based resin, wherein the surface layer is passed through a processing surface Forming, the treated surface is formed by surface-activation of the composite layer.

Preferred examples of the multi-layered thin material of the present invention are, for example, the examples described in Figs.

The multi-layered thin material 10 of the present invention shown in Fig. 1 has a composite layer 2 composed of a fluororesin 2a and a heat-resistant fiber woven fabric 2b, and a surface layer 3a composed of a polyimide-based resin. The multi-layered thin material is formed by a treatment surface 4a formed by surface-activation of the composite layer 2, wherein the surface layer 3a is formed by a treatment surface 4.

The multi-layered thin material 11 of the present invention shown in Fig. 2 has a surface layer composed of a polyimide resin on both surfaces thereof, and has a layer composed of a fluororesin 2a and a heat-resistant fiber woven fabric 2b. a composite layer 2 and a composite layer 3a of a surface layer 3a composed of a polyimide-based resin, wherein the surface layer 3a is formed by a processing surface 4 by which the composite layer 4 is formed The material layer 2 is formed by surface activation treatment.

<Composite layer>

The composite layer of the multi-layered thin material of the present invention is composed of a fluororesin and a heat-resistant fiber woven fabric.

The fluororesin of the present invention is not limited and may be selected from polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP). A heat resistant resin selected from the group consisting of. Among them, polytetrafluoroethylene is particularly preferred.

The fluororesin can be blended with a conductive powder as needed. Thereby, conductivity or electrical conductivity can be imparted, and the abrasion resistance can be improved. Preferred specific examples of the conductive powder are carbon black and titanium oxide (Titanium Oxide). The amount thereof is preferably from 1 to 20 parts by mass relative to the fluororesin.

In the present invention, the heat-resistant fiber woven fabric is not limited, and is, for example, a glass fiber or an aromatic polyamide fiber. The thickness of the heat-resistant fiber woven fabric is generally 30 to 1000 μm, particularly preferably 30 to 700 μm.

The composite material layer is preferably formed by, for example, impregnating an aqueous suspension of fluororesin particles with a heat-resistant fiber woven fabric, and drying it, followed by firing. The solvent used in the preparation of the aqueous suspension is, for example, water, and particularly preferably pure water. The number of fluororesin particles in the aqueous suspension is 20 to 60 parts by mass, particularly preferably 30 to 60 parts by mass, per 100 parts by mass of the solvent.

The composite layer-based fluororesin of the present invention is sufficiently impregnated into the interior of the heat-resistant fiber woven fabric, and preferably the surface of the heat-resistant fiber woven fabric is covered with a fluororesin. Therefore, the total amount of the heat-resistant fiber woven fabric and the fluororesin is set to 100 parts by mass, and the application amount of the fluororesin is 30 to 70 parts by mass, particularly preferably 40 to 60 parts by mass.

<surface layer>

The multi-layered thin material of the present invention has a surface layer composed of a polyimide pigment.

In the present invention, the polyimide-based resin is not limited, and is preferably, for example, a polyimide and a polyimide imide, and particularly preferably a polyimide.

When the present invention is formed by coating a surface layer, a liquid polyimide varnish can be used for easy coating, and a solvent can be used as needed. Thereby, the viscosity can be lowered to improve the coating efficiency.

Further, the polyimide resin can be used in combination with a conductive powder as needed. Thereby, for example, conductivity or thermal conductivity or electrical conductivity or thermal conductivity is imparted, and the abrasion resistance can be improved.

In the formation of the surface layer, the polyimine-based resin may be applied to the surface-activated surface of the composite layer, dried, and then fired. The firing temperature of the polyimine-based resin is preferably from 300 to 400 ° C, particularly preferably from 330 to 370 ° C.

The thickness of the surface layer can be appropriately determined according to the specific use or purpose of the multi-layered thin material and the endless belt of the present invention. For example, the composite thin material used in the production of the endless belt which is particularly suitable for transporting purposes means that the thickness of the surface layer of the polyimide resin is preferably from 1 to 50 μm, particularly preferably from 5 to 20 μm.

<Surfacting treatment>

In the multi-layered thin material of the present invention, the surface layer is formed by a treatment surface formed by surface-activation of the composite layer. Here, the surface activation treatment refers to the surface tension of the fluororesin on the surface of the composite layer of the present invention, so that the fluororesin of the composite layer and the surface layer as the composite thin layer are formed. The polyimine-based resin is a process which can be joined and produces sufficient joint strength. If the surface activation treatment is not carried out, a surface layer composed of a polyimide pigment can not be formed on the composite layer, and the object of the present invention cannot be achieved.

Preferred surface activation treatments of the present invention include, for example, silica particle adhesion baking treatment, sodium metal etching (Natrium etching) surface treatment, plasma discharge treatment, and corona discharge ( Corona discharge), etc., among which, in particular, the cerium oxide particle adhesion baking treatment is preferred.

Here, the surface activation treatment of the present invention is as follows in detail.

The cerium oxide particle adhesion baking treatment is a method in which a mixed aqueous suspension of cerium oxide particles and fluororesin particles is applied to a composite material composed of a fluororesin and a heat-resistant fiber woven fabric, and then subjected to a baking treatment. A treatment that enhances the hydrophilicity of the surface of the composite.

Metal sodium etching surface treatment: a treatment in which a metal sodium solution is applied to a composite material composed of a fluororesin and a heat-resistant fiber woven fabric to enhance the hydrophilicity of the surface of the composite material.

Plasma discharge treatment: a treatment in which a glow discharge treatment is performed on a surface of a composite material composed of a fluororesin and a heat-resistant fiber woven fabric to enhance the hydrophilicity of the surface of the composite material.

Corona discharge treatment: a treatment in which a corona discharge treatment is performed on a surface of a composite material composed of a fluororesin and a heat-resistant fiber woven fabric to enhance the hydrophilicity of the surface of the composite material.

The surface activation treatment is preferably performed on the entire surface of the surface layer of the composite material layer, but may be performed on a part of the surface layer of the composite material layer.

By performing this surface activation treatment, the contact angle (Japanese Industrial Standard JIS, K6768) when pure water droplets are on the fluororesin on the surface of the composite layer is remarkably reduced. The contact angle is 106 degrees before the surface activation treatment, and the contact angle is 80-90 degrees by the adhesion of the cerium oxide particles, and the surface contact angle is 50-60 degrees by the metal sodium etching, by plasma The discharge treatment is reduced to 50 to 60 degrees.

<ring band>

The endless belt of the present invention is formed of an annular body of a belt formed of the above-mentioned multi-layered thin material. Therefore, the endless belt of the present invention has good characteristics of the above-mentioned multi-layered thin material, for example, the composite layer mainly formed of a fluororesin and a heat-resistant fiber woven fabric has good heat resistance, shape stability, non-adhesiveness, and durability. The properties, and the polyimide-based resin mainly based on the surface layer have various properties (for example, abrasion resistance, heat resistance, durability).

Next, in the method for producing an endless belt according to the present invention, the multi-layered thin material is cut into a strip shape, and the opposite ends of the multi-layered thin material strip are joined to obtain an annular body. Further, the annular body may be joined by, for example, (1) by overlapping the peripheral portion of one end portion of the multi-layered thin material ribbon with the other end portion (Fig. 3(A)); The two ends of the layered thin strip are firmly joined to the end section thereof (Fig. 3(B)); (3) by joining the two ends of the laminated thin strip to the same connection Obtained from the thin material (Fig. 3(C)). Further, the joining of the two ends can be carried out by heat sealing or using an adhesive.

Further, in another method of manufacturing the endless belt of the present invention, the laminated layer of the laminated thin material and the other thin material are laminated, and the opposite ends of the laminated thin material of the strip are bonded thereto. The opposite ends of the other thin material of the strip are respectively joined or closely arranged to obtain an annular body. Here, the other thin material laminated with the above-mentioned multi-layered thin material may be, for example, a thin material composed of a single layer or a plurality of layers. Moreover, this other thin material can use a single layer and a multiple layer of thin material. The other thin material also includes, for example, the above composite material 2 and the composite thin materials 10, 11, and the like.

Fig. 4 is a view showing a preferred embodiment of the endless belt of the present invention. The endless belt 12 of the present invention shown in Fig. 4 is formed on the outer peripheral side of the multi-layered thin material 10 shown in Fig. 1, and the other thin material 5 is on the inner peripheral side, and the other thin material 5 is used in combination with the above. The thin layer of the same content of the material layer 2. The endless belt 12 of the present invention is formed at the opposite ends of the laminated thin material 10 and the opposite ends of the other thin material 5 of the strip at positions 6 and 7, respectively. A ring body is an endless belt.

Further, as a preferred embodiment of the endless belt of the present invention, the multi-layered thin material 10 shown in Fig. 1 is also provided on the inner peripheral side, and the other thin material 5 is on the outer peripheral side.

The present invention differs from the method of manufacturing an endless belt by using a seamless tubular member made by a conventional mold. The present invention can easily produce an endless belt having a desired width, length, and layer configuration in accordance with the use.

Further, depending on the case, the same multi-layered thin material is not cut, and after forming an endless belt having a wide width, the wide-width endless belt is cut into a desired width, whereby a plurality of sheets can be simultaneously manufactured. An endless belt of the same length. Further, when the endless belt having the wide width is cut, by adjusting the width, it is easy to create and distinguish the endless belts having different widths.

Preferably, the laminated thin material of the present invention and the laminated thin material of another thin material are obtained by heat-sealing the double-layered thin material and another thin material, or may be a laminated thin material by an adhesive. And another thin material is joined to obtain a laminated thin material.

[Examples]

<Example A1>

(1) forming a multi-layered thin material of a surface layer of a polyimide resin on one side of a composite material

First, in order to obtain a composite material of a fluororesin and a glass fiber, an aqueous suspension of a fluororesin (PTFE) is impregnated with a continuous coating device and attached to a plain woven glass fiber (thickness: 95 μm), dried at 80 ° C, and then 350 The temperature of °C was fired to obtain a composite material (thickness: 135 μm) of a fluororesin and a glass fiber.

Then, in order to carry out the surface activation treatment of the composite material of the fluororesin and the glass fiber, 100 parts by mass of the aqueous suspension of the PTFE resin is mixed with 100 parts by mass of the aqueous suspension of cerium oxide to obtain a surface-enhanced treatment liquid.

Next, the surface active treatment liquid was applied onto one surface of the composite material of the fluororesin and the glass fiber in a continuous coating apparatus, dried at 80° C., and then fired at a temperature of 350° C. to cause the cerium oxide to adhere and burn. A surface active treatment layer is obtained.

Next, in order to obtain a liquid polyimine varnish, 100 parts by mass of a solvent (dimethylacetamide (DMAC) was mixed and sold in the market (Toray neece #3000 (trade name) manufactured by Toray Industries, Inc.) 100 parts by mass, and a liquid polyimine varnish having a viscosity of 50 Cp (centipoise).

Next, the liquid polyimine varnish was applied and adhered to the surface of the composite material (thickness: 135 μm) of the fluororesin and the glass fiber which had been surface-activated by a continuous coating apparatus, and dried at 80° C., and then The temperature was 350 ° C, and a multi-layered thin material (thickness: 140 μm) which formed a surface layer of a polyimide resin on one side of a composite of a fluororesin and a glass fiber (Fig. 1) was obtained.

The fluororesin layer of the above-obtained composite material and the polyimide layer of the multi-layered thin material were compared by the following evaluation methods. The evaluation results are shown in Table 1.

1) Abrasion test: It was carried out in accordance with JIS Japanese Industrial Standard H8682-1. (Using a SUGA abrasion tester, the speed was 2.4 m/min, the load was 350 gf, and the number of test rotations was 1000 times, and the condition of the #4000 water-resistant film was measured as an abrarating wheel (diameter 50 mm, width 12 mm) of the abrasive material. )

2) Friction coefficient: It is implemented in accordance with JIS Japanese Industrial Standard K7218. (Using the friction and wear tester manufactured by Orientec, the sliding speed was 50 mm/s, the load was 20 N, the test time was 30 minutes, and the SUS304 ring was used for the measurement.)

3) Contact angle: It is implemented in accordance with JIS Japanese Industrial Standard K6768. (The contact angle meter CA-D type manufactured by Kyowa Interface Chemical Co., Ltd. was used, and distilled water was used as the test liquid.)

According to the above evaluation results, the abrasion resistance of the polyimide resin is superior to that of the fluororesin, and the non-adhesiveness and low friction are inferior to those of the fluororesin. From the results, it was found that the polyimide resin was less likely to be worn and slipped than the fluororesin.

The structure of the embodiment A1 is preferably such that the fluororesin surface is used for the non-adhesive property and the slip-resistance is not important, and the use of the polyimide film surface for the wear resistance and the slip resistance is important. Contact side, but not limited to this.

<Example A2>

(2) forming a multi-layered thin material of the surface layer of the polyimide film on both sides of the composite material

A laminate thin material was obtained in the same manner as in Example A1. On the surface of the surface layer of the multi-layered polyimide material on which the polyimine resin was not formed, the surface activation treatment and the formation of the surface layer of the polyimide resin were carried out in the same manner as in Example A1, and a polyimine was formed. The surface layer of the resin was laminated on both sides of the composite (thickness 145 μm) (Fig. 2).

The structure of the embodiment A2 is preferably used for abrasion resistance and slip resistance, and is not intended to be used, but is not limited thereto.

<Example A3>

(3) The laminated thin material of the layer A and the thin material of the embodiment A1, and the endless belt

The composite sheet material (thickness: 140 μm) of Example A1, a composite material of fluororesin and glass fiber (thickness: 135 μm) was laminated, and the layers of the same fluororesin were laminated, and then heated at a temperature of 350 ° C by a hot press. The heat was sealed so as to be in the form of a ring, and an endless belt (thickness: 275 μm) having a surface layer of a fluororesin on one side and a surface layer of a polyimide resin on the other side (Fig. 4) was obtained.

The structure of the endless belt of this embodiment A3 is preferably such that the fluororesin surface is used for the non-adhesive property and the slip-resistance is not important, and the polyimide film surface is used for abrasion resistance and slip resistance. The important job is the drive roller side on the non-contact side, but not limited to this.

<Example A4>

(4) An annular strip of two layers of the multilayered material of the embodiment A1 and a polyimine resin on both sides

Two layers of the layered thin material (thickness: 140 μm) of Example A1 were prepared, and the layers of the same fluororesin were overlapped, and then heat-sealed and heat-sealed at a temperature of 350 ° C to laminate them. In the form of a ring, an endless belt (thickness 280 μm) having a surface layer of a polyimide resin on both sides thereof was formed (Fig. 4).

The structure of the endless belt of this embodiment A4 is preferably used for applications in which abrasion resistance and slip resistance are important, and non-adhesiveness is not important, but not limited thereto.

As in the above embodiments A1 to A4, it is possible to provide a high-functional multi-layered thin material having heat resistance, abrasion resistance, non-adhesiveness and slip resistance, and a conveyor belt composed of the laminated thin material, which is required for the corresponding Non-adhesive, abrasion-resistant, slip-resistant, cut to the required size and in an annular manner, it is possible to manufacture endless belts of various sizes without using a mold.

<Comparative Example A1>

The multi-layered thin material of Example A1 was coated with a liquid polyimine varnish without surface activation treatment, but could not be joined, and a multi-layered thin material having sufficient joint strength to be used could not be obtained.

<Examples C1 to C4>

In the examples A1 to A4, the oxidized layer of the present invention was obtained in the same manner as in the examples A1 to A4 except that the surface treatment layer was formed by the metal sodium etching treatment instead of the cerium oxide adhesion firing treatment. Thin materials C1, C2 and endless belts C3, C4.

<Examples D1 to D4>

In the examples A1 to A4, except for the cerium oxide adhesion baking treatment, the surface treatment treatment layer was formed by plasma treatment, and the others were the same as those of the examples A1 to A4, and the stratified thin film of the present invention was obtained. Materials D1, D2 and endless belts D3, D4.

<joint strength test>

The polyiminoimine surface layer of each of the multi-layered thin materials obtained by the above Examples A1 to A4, Examples C1 to C4, and Examples D1 to D4 was subjected to a cross-hatch adhesion test according to Japanese Industrial Standard JIS H5400 ( Cross cut adhesion test) (1 mm × 180.39 L), but the number of squares peeled from the stratified sheet material is zero in any of the stratified sheets. On the other hand, in Comparative Example A1 in which the surface-treated layer was not subjected to the peeling, the number of squares peeled off was 100. The evaluation results are shown in Table 2.

2. . . Composite layer

2a. . . Fluororesin

2b. . . Heat resistant fiber woven fabric

3a. . . Surface layer

4. . . Processing surface

5. . . Another thin material

6, 7. . . End joint position

10, 11. . . Multi-layer thin material

12. . . Annular band

Figure 1 is a cross-sectional view showing the construction of a multi-layered thin material of the present invention;

Figure 2 is a cross-sectional view showing the construction of a multi-layered thin material of the present invention;

Figure 3 is a cross-sectional view showing the structure of the endless belt of the present invention;

Figure 4 is a cross-sectional view showing the structure of an endless belt of the present invention.

2. . . Composite layer

2a. . . Fluororesin

2b. . . Heat resistant fiber woven fabric

3a. . . Surface layer

4. . . Processing surface

10. . . Multi-layer thin material

Claims (5)

A multi-layered thin material comprising: at least one composite layer composed of a fluororesin and a heat-resistant fiber cloth; and a surface layer composed of a polyimide-based resin; wherein the surface layer is The treatment surface is formed by a treatment surface formed by surface-activation of the composite layer. The multi-layered thin material according to claim 1, wherein the surface activation treatment is an inorganic particle adhesion baking treatment, a metal sodium etching treatment, a plasma discharge treatment, or a corona discharge treatment. An endless belt comprising an annular body formed of a multi-layered thin material according to claim 1 of the patent application. A method for manufacturing an endless belt, which is obtained by cutting a multi-layered thin material according to claim 1 of the patent application into a strip shape; and joining the opposite ends of one of the multi-layered thin materials to obtain a loop Shape. The invention relates to a method for manufacturing an endless belt, which is a ribbon which is laminated with a laminated thin material according to claim 1 and a thin layer, and the laminated thin material of the strip is The two ends and the opposite ends of the other thin material of the ring are respectively joined or arranged in close proximity to obtain an annular body.