JPH1158543A - Spiral tubular article with good insulating characteristics and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To allow a heater to be easily installed at the center of a tape with shape retentivity and good adhesive properties with a pipe and thermal efficiency by embedding a flexible conductive base in a groove or banks provided on both sides of a tape-like heat resistant resin film. SOLUTION: In the spiral tubular article 1, a tape-like heat resistant film 2 having a groove at the center to be an inside layer or banks on both sides or a tape-like heat resistant resin film 2 with adhesive with the groove or the banks disposed on both sides is spirally wound on a long shape-imparting member such as a heat resistant pipe or the like made of stainless steel or the like. A flexible conductive base 5 or suitablty flat base is wound on the groove or between the banks. A tape-like heat resistant resin film 4 with adhesive to become an outside layer with the adhesive disposed inside is spirally lap wound on the base 5. Then, the adhesive is cured, laminated integrally, and the shaped laminate is removed from the bar or pipe.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for applications such as heaters which have good adhesion to pipes and have good thermal efficiency, and particularly for purposes such as keeping the temperature of pipes in semiconductor manufacturing equipment and analytical equipment. The present invention relates to a shape-retaining spiral tubular article that can be used and a method for producing the same. More specifically, the present invention relates to a shape maintaining property in which a flexible conductive base material, for example, a flat base material such as a heater is sandwiched between insulating layers wound in a spiral shape. It relates to a spiral tube. The present invention also provides a flexible conductive flexible substrate between a tape-like film with an adhesive serving as an inner layer wound in a spiral shape and a heat-resistant film with an adhesive serving as an outer layer. The present invention relates to a shape-retaining spiral tubular article formed by laminating and integrating materials. Further, the present invention provides a tape-shaped heat-resistant resin film to be an inner layer wound spirally, a tape-shaped heat-resistant resin film to be an outer layer, and an adhesive and a flexible conductive base material therebetween. The present invention relates to a method for manufacturing a spiral tubular article which is arranged, cured and cured to form an integrated laminate.

[0002]

2. Description of the Related Art Conventionally, pipes have been used to prevent solidification and adhesion of substances to be transported to pipes in analytical instruments such as liquid chromatographs or mass spectrometers and pipes constituting transport paths for chemicals and the like in medical equipment. It is necessary to heat the pipe to keep it warm, and sometimes heat the pipe to evaporate the substance attached to the inner surface and secure a degree of vacuum. Furthermore, the water pipe may be kept warm and heated to prevent the water pipe from freezing. In such a case, conventionally, a flexible planar heating element such as a ribbon heater is generally wound in a band shape around a pipe.

[0003]

However, the pipe system of the above-mentioned pipe is generally provided in a narrow space between the apparatuses, and it is often necessary to wind a pipe-shaped heating element around the pipe and mount it. And the planar heating element has poor adhesion to the pipe. For this reason, the thermal efficiency is low, and the temperature cannot be controlled accurately. SUMMARY OF THE INVENTION It is an object of the present invention to provide a heater in which a flexible conductive substrate is integrally provided between both ends in a longitudinal direction, which is easy to mount on a body to be heated, has good adhesion, and a method for manufacturing the same. It is to be.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a tape-shaped heat-resistant resin film A for forming an inner layer of a spiral material, an adhesive layer for forming an intermediate layer, and a tape for forming an outer layer. A flexible conductive base material for providing conductivity is integrally provided between both ends in the longitudinal direction of any layer of the laminate having the structure of the heat-resistant resin film B. The present invention relates to a shape-retaining spiral tubular article in which the flexible conductive substrate is partially or entirely embedded in a groove provided in a central portion of a resin film A or a bank provided on both sides thereof. The invention relates to a tape-shaped heat-resistant resin film in which a spiral-shaped material is provided with a groove in a central portion serving as an inner layer, or a tape with an adhesive provided with banks on both sides.
The heat-resistant resin film A is spirally wound around a long shape-imparting member with the groove or the bank outside, and a flexible conductive base material is wound thereon such that a part or all of the flexible conductive base material is embedded therein, Further, a tape-like heat-resistant resin film B with an adhesive serving as an outer layer is wound thereon in a spiral shape with the adhesive inside, and the adhesive is cured and laminated to form a laminated body. The present invention relates to a shape-retaining spiral tubular article obtained by removing a spiral shape from a long shape imparting member. Further, the present invention provides a tape-shaped heat-resistant resin film having a groove in the center thereof serving as an inner layer wound on a long shape-imparting member having the same outer shape as the object to be heated, or a bank on both sides thereof. A flexible conductive substrate that provides conductivity between both ends in the longitudinal direction between the provided tape-shaped heat-resistant resin film A with an adhesive and the tape-shaped heat-resistant resin film B as an outer layer. And placing the adhesive such that the conductive substrate is partially or entirely buried in the groove or embankment, and curing and bonding the adhesive with the inner and outer layers of the film overlapping to laminate and integrate. And a method for manufacturing a spiral tubular article.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be listed below. 1) The above-mentioned spiral tubular article, wherein the tape-like heat-resistant resin film A forming the inner layer side of the spiral-shaped article and the tape-shaped heat-resistant resin film B forming the outer layer each have a thickness of 25 to 200 μm. 2) The spiral tubular article described above, wherein the adhesive layer is a thermosetting adhesive. 3) The spiral tubular article described above, wherein the tape-shaped heat-resistant resin film A and the tape-shaped heat-resistant resin film B are tape-shaped aromatic polyimide films.

Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a partial cross-sectional view of an example of a spiral tubular article cut in parallel with a spiral core. FIG. 2 is a partial cross-sectional view of another example of a spiral tubular article cut in parallel to a spiral core. FIG. 3 is a cross-sectional view of a tape-shaped heat-resistant resin film having a groove at the center used in the manufacturing method of the present invention. FIG. 4 is a cross-sectional view of a tape-like heat-resistant resin film having a bank provided with an adhesive on both sides used in the manufacturing method of the present invention. FIG. 5 is a perspective view showing an example of the spiral tubular article of the present invention. FIG. 6 is a partial perspective view showing an example of use of an example of a spiral tubular object.

In FIG. 1, a spiral tubular article 1 having shape retention is a tape-like heat-resistant resin film A forming an inner layer of the spiral article, an adhesive layer 3 forming an intermediate layer, and an outer layer. A flexible conductive substrate 5 that imparts conductivity between both ends in the longitudinal direction of one of the layers of the laminated body having the configuration of 4 which is the tape-shaped heat-resistant resin film B forming the layer is integrally formed. The flexible conductive base material 5 is partially or entirely embedded in a groove provided at the center of the tape-like heat-resistant resin film A.

In FIG. 2, a spiral tubular article 1 having shape retention is a tape-shaped heat-resistant resin film A forming an inner layer of the spiral article, and an adhesive layer 3 (an inner layer) forming an intermediate layer. And an adhesive layer 3b in contact with the outer layer) and a tape forming the outer layer.
A flexible conductive substrate 5 that imparts conductivity is provided integrally between both ends in the longitudinal direction of any layer of the laminate having the configuration of 4, which is the heat-resistant resin film B,
An adhesive layer 3 is provided on both sides of the tape-shaped heat-resistant resin film A.
The bank is provided by a, and the flexible conductive substrate 5 is partially or entirely embedded therein.

In FIG. 3, a groove is provided at the center of the tape-shaped heat-resistant resin film A2. In FIG. 4, a bank is provided on both sides of the tape-shaped heat-resistant resin film 2 with an adhesive 3a. In FIG. 5, a shape-retaining spiral tubular article 1 is a tape-shaped heat-resistant resin film 2 forming an inner layer spirally wound and a tape-shaped heat-resistant resin film forming an outer layer. A flexible conductive base material 5 for imparting conductivity between both ends in the longitudinal direction of the laminate having the configuration of B which is 4 has a shape that is integrally formed in a spiral shape.

In FIG. 6, the space between the spiral tubular objects having shape retention is expanded so that the object to be heated 10 can be inserted, and the object to be heated 10 is inserted between the spiral tubular objects. While maintaining the state, the spiral tubular article 1 is rotated in the direction of the arrow in the figure, and the object to be heated 10 is taken into the spiral tubular article 1 with this rotation.
The spiral tubular article 1 can be relatively easily and quickly attached to the object to be heated 10 simply by rotating the tubular article 1 in the axial direction, and the spiral tubular article 1 returns to its original shape after the attachment. , Can be evenly and orderly mounted on the object to be heated 10. Therefore, for example, even when both ends of the object to be heated are connected to a large-sized device or the like and there is little freedom, the object can be wound around the object to be heated 10 relatively easily and quickly. In addition, since the diameter of the spiral tubular object can be arbitrarily set, not only the object to be heated having a small degree of freedom but also the object to be heated having a large degree of freedom, the rod or the rod is not restricted by the size of the diameter. If it is a pipe, it can be applied to any object to be heated.

[0011] The spiral tubular article of the present invention is, for example,
A groove with a groove in the center or a bank on both sides that becomes the inner layer
The tape-shaped heat-resistant resin film A or the tape-shaped heat-resistant resin film A with the adhesive is provided with a long shape such as a heat-resistant rod or pipe made of metal, for example, stainless steel, with the adhesive outside the groove or the bank. A flexible conductive base material, preferably a flat base material, is wound around the member in a spiral shape between its grooves or banks, and a tape-like heat-resistant sheet with an adhesive layer serving as an outer layer is further wound thereon. The conductive resin film B is wound in a spiral shape with the adhesive inside, wound and cured, the adhesive is laminated and integrated, the formed laminate is removed from a long shape-imparting member such as a rod or a pipe, and the spiral is formed. It can be obtained as a molded article having a shape maintained. The spiral tubular article of the present invention has almost the same shape and uniformity as the outer diameter of the spiral article even at an ordinary temperature, preferably in an environment heated to a high temperature of about 200 ° C., and even after being attached to the object to be heated. No change in shape is maintained.

The tape-shaped heat-resistant resin film A for forming the inner layer of the spiral material in the present invention is preferably made of an aromatic polyimide or aromatic polyamide having a glass transition temperature or a melting point of 180 ° C. or more. Is a tape-like film having a thickness of 25 to 200 μm and a width of 3 to 50 mm. In particular, the coefficient of linear expansion (CTE) at 50-300 ° C. is 60 × 10 ⁻⁵ cm / cm / ° C. (p
pm).
50 × 10 ⁻⁵ cm / cm / ° C. and a tensile modulus of 2
An aromatic polyimide film or an aromatic polyamide film having a weight of 00 to 1400 kg / mm ² is preferably used. Among them, an aromatic polyimide film having a water absorption of 4% or less, particularly 3% or less is suitably used.

The aromatic polyimide is, for example, 3,
Aromatic tetracarboxylic dianhydrides such as 3 ', 4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride and 3,3', 4,4'-benzophenone tetracarboxylic dianhydride And p-phenylenediamine,
It is obtained by polymerizing and imidizing an aromatic diamine such as 4,4'-diaminodiphenyl ether. In particular, an aromatic polyimide obtained by using 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in an amount of 15 mol% or more in the aromatic tetracarboxylic acid component has heat resistance, low linear expansion coefficient, It is preferable because of its low water absorption. The aromatic polyamide is, for example, 2-chloroterephthalic acid chloride, aromatic acid chloride such as 2,5-dichloroterephthalic acid chloride and 2-chloro-p-ferylenediamine,
It is obtained by reaction with an aromatic diamine such as 4,4'-diaminodiphenyl ether.

In the present invention, the adhesive layer forming the intermediate layer comprises a heat-resistant thermoplastic adhesive, a thermosetting adhesive, preferably a thermosetting adhesive. 2-100 μm in thickness and 2-50 in width in dry state
mm. The adhesive layer may be provided as a tape-like film with an adhesive, or after the tape-like film is wound, an adhesive is applied or an adhesive sheet is adhered to the tape. -May be provided.

As the thermosetting adhesive, epoxy resin, NBR-phenol resin, phenol-butyral
Epoxy resin, epoxy-NBR resin, epoxy-phenolic resin, epoxy-nylon resin, epoxy-polyester resin, epoxy-acrylic resin, acrylic resin, polyamide-epoxy-phenolic resin,
Examples include a polyimide resin and a polyimidesiloxane-epoxy resin. The adhesive is composed of one side of the tape-shaped heat-resistant resin film A and the tape-shaped heat-resistant resin film B.
Is preferably provided on each of the two sides.

The heat-resistant resin film B for forming the outer layer in the present invention is made of aromatic polyimide, aromatic polyamide, aromatic polyester, fluororesin or aromatic polyamideimide having a glass transition temperature or melting point of 180 ° C. or higher. And preferably have a thickness of 25-200
A sheet-like film having a thickness of 3 to 50 mm is used. In particular, when the coefficient of linear expansion (CTE) at 50 to 250 ° C. is not more than 60 × 10 ⁻⁶ cm / cm / ° C. (sometimes expressed in ppm), especially at 3 to 50 × 10 ⁻⁶ cm / cm / ° C. In addition, an aromatic polyimide film or an aromatic polyamide film having a tensile modulus of 200 to 1400 kg / mm ² is preferably used. Among them, an aromatic polyimide film having a water absorption of 4% or less, particularly 3% or less is suitably used.

As the flexible conductive substrate in the present invention, a metal foil, a metal wire, or a strip-shaped metal having a conductive function between both ends in the longitudinal direction of the spiral object, preferably having a thickness of 5- A metal foil such as a copper foil or a nichrome foil having a thickness of about 100 μm and a width of about 0.4 to 40 mm is used. This flexible conductive substrate may be provided alone or in parallel, and may be provided over substantially the entire surface of the tape-like heat-resistant resin film B by the adhesive. May be
Preferably, it is provided substantially at the center. Further, a flexible conductive substrate whose surface is thinly coated with a heat-resistant resin in advance by a coating method or the like may be used.

The above-mentioned aromatic polyimide film can be produced, for example, as follows. First, the aromatic tetracarboxylic dianhydride and the aromatic diamine are polymerized in an organic polar solvent such as N, N-dimethylacetamide or N-methyl-2-pyrrolidone, and the logarithmic viscosity of the polymer (measurement temperature: 30 ° C, concentration: 0.5g / 100m
1 solvent, solvent: N-methyl-2-pyrrolidone) is 1 to 5
A polyamic acid (imidation ratio: 5% or less) solution having a polymer concentration of 15 to 25% by weight and a rotational viscosity (30 ° C.) of 500 to 4500 poise is obtained. Then, preferably 100 parts by weight of the polyamic acid is 0.0%
1 to 1% by weight of a phosphorus compound, for example an organic or inorganic phosphorus compound such as a (poly) phosphate ester and / or an amine salt of a phosphate ester, and preferably 0 to 100 parts by weight of polyamic acid. .02
To 6 parts by weight of an inorganic filler such as colloidal silica, silicon nitride, talc, titanium oxide and calcium phosphate (preferably 0.005 to 5 μm, particularly 0.005 to 2 μm
m) is added to prepare a polyamic acid solution composition.
The polyamic acid solution composition as it is or with the addition of a chemical imidizing agent is cast on a support having a smooth surface, dried to form a solidified film, and the solidified film is peeled from the support surface. Next, after one or both surfaces of the solidified film are coated with a surface treatment solution containing an aminosilane-based, epoxysilane-based or titanate-based surface treatment agent, the film can be further dried. The solidified film obtained as described above is stretched in both directions, if necessary, and then heated at a temperature within the range of 350 to 500 ° C. while holding both edges in the width direction of the dried film. After drying and imidization, it can be suitably produced as an aromatic polyimide film. The aromatic polyimide film obtained as described above is preferably heated under a low tension or no tension at a temperature of about 200 to 400 ° C., subjected to a stress relaxation treatment, and wound up. This aromatic polyimide film can be used as it is or after being subjected to a surface treatment by corona discharge treatment, plasma treatment, ultraviolet irradiation, glow discharge treatment, and flame treatment, and as an aromatic polyimide film having improved adhesion.

The above-mentioned aromatic polyamide film can be produced, for example, as follows. The aromatic acid chloride and the aromatic diamine are synthesized by solution polymerization in an organic polar solvent or by interfacial polymerization using an aqueous medium. When acid chloride and diamine are used as monomers for the polymer solution, hydrogen chloride is produced as a by-product, so that it is neutralized by using an inorganic neutralizer such as calcium hydroxide or an organic neutralizer such as ethylene oxide. Add the agent. The reaction between the isocyanate and the carboxylic acid is carried out in an aprotic organic polar solvent in the presence of a catalyst. These polymer solutions may be used directly as a stock solution for forming a film, or the polymer may be isolated once and then redissolved in the above solvent to prepare a stock solution. An inorganic salt such as calcium chloride or magnesium chloride may be added as a dissolution aid to the film forming stock solution. The polymer concentration in the film forming stock solution is preferably from 2 to 35% by weight.

The tape-shaped heat-resistant resin film provided with a groove in the center used in the present invention includes excimer laser processing, mechanical cutting, chemical etching and the like. Can be Further, it is also possible to produce the shape shown in FIG. 3 by a modified extrusion molding using a thermoplastic heat-resistant resin. Examples of the thermoplastic heat-resistant resin include thermoplastic polyimide, thermoplastic polyamide-imide, polyether-terketone, polyetherketone, polyethersulfone, and polysulfone. The method for producing a tape-like heat-resistant resin film with an adhesive provided on both sides, which is used in the present invention, includes a method in which an adhesive tape slit on a tape-like heat-resistant resin film. -A method of bonding tapes on both sides of a tape-shaped heat-resistant resin film, or an excimer laser at the center of a tape-shaped heat-resistant resin film with an adhesive.
There is a method of forming a groove by machining and mechanical cutting, and leaving a bank on both sides. Alternatively, a method in which a protective film is disposed at the center and an adhesive solution is applied to both sides and dried, and then the adhesive bank is provided on both sides of the film except for the protective film is also possible.

The shape-retaining spiral tubular article of the present invention has, for example, the same outer shape as the object to be heated.
It may have any shape such as a circular or square cross section. A) A tape-shaped heat-resistant resin to be an inner layer spirally wound around a long shape-imparting member, for example, a heat-resistant rod or pipe with a groove provided at the center thereof or a bank provided on both sides outside. Film A, preferably a tape-shaped aromatic polyimide film A, and a tape to be an outer layer having the same width or a slightly smaller width.
Tape-shaped heat-resistant resin film B, preferably tape-shaped aromatic polyimide film B, an adhesive therebetween, and a flexible conductive substrate for providing conductivity between both ends in the longitudinal direction, preferably tape-shaped. A flat conductive base material such as a heater is placed in the groove or the bank, and in the case of a thermosetting adhesive, the solvent is dried and a thermoplastic resin is formed at the B stage. In the case of adhesives, the laminate is heated by applying pressure to a temperature above the glass transition temperature or melting point, so that the inner and outer layers of the film are laminated, and in the case of thermosetting adhesives, they are cured. After heating to a temperature equal to or higher than the temperature, or cooling in the case of a thermoplastic adhesive, the adhesive is cured and laminated and integrated, and then the spiral laminate is removed from the elongated shape imparting member. can get.

The above method can be preferably carried out, for example, as follows. First, the heat-resistant resin film A serving as the inner layer is slit to 3 to 50 mm, and the center thereof is 0.3 to 40 mm in width and 2 to 50 μm in depth.
A groove is formed in the surface. On the other hand, an adhesive is applied to one side of the heat-resistant resin film B, and the dry thickness of the adhesive is 2-100 μm.
m is obtained. This film is 3-50mm
To form a tape-like heat-resistant resin film with a thermosetting adhesive. The tape-shaped film A is spirally wound around a circular rod or pipe having a diameter of 5 to 50 mm with the groove outside, and both ends are fixed. Then
A conductive base material, preferably a tape-shaped heater, having a width smaller than that of the above-mentioned groove is inserted into the groove, and spirally wound thereon. Then, a tape-shaped heat-resistant resin film B with a thermosetting adhesive as an outer layer is wound thereon so that the adhesives overlap each other, and the tape-shaped heat-resistant resin film A / thermosetting adhesive Agents, heaters / thermosetting adhesives / tapes
Heat-resistant resin film B is formed, and if necessary, the surroundings are pressed and fixed with a tape-shaped or linear-shaped material, and heated to a temperature in the range of 150 to 400 ° C. After the adhesive is hardened and laminated and integrated, and cooled, the formed laminated body is removed from a rod or a pipe, and the spiral tubular heater is removed.
Can be obtained. At the time of pressurization and fixing, a tape-shaped or linear one that pressurizes and fixes the periphery
It is preferable to use a heat-shrinkable material because pressing and fixing become uniform.

The spiral tubular article of the present invention may be applied to the object to be heated as it is, or may be used after being cut to an appropriate length. Further, the outermost layer is formed of a heat-resistant foam for heat insulation. Or a heat-resistant porous sheet. In the case of a heated body having a complicated shape, the heated body may be covered by using a combination of a spiral tubular object and a planar heater.

[0024]

Embodiments of the present invention will be described below. In each of the following examples, the physical properties of the polyimide film were measured by the following methods. Water absorption: measured according to ASTM D570-63 (23
° C × 24 hours) Tensile modulus: Measured according to ASTM D882-64T (MD) Linear expansion coefficient (50-250 ° C or 50-300 ° C):
Samples that were heated at 300 ° C for 30 minutes and relaxed
A device (tensile mode, 2g load, sample length 10mm, 2
0 ° C / min)

REFERENCE EXAMPLE 1 N, N-dimethylacetamide (54.6 kg) was added to a polymerization tank having an internal volume of 100 liters.
4,4'-biphenyltetracarboxylic dianhydride 8.8
26 kg and 3.243 kg of paraphenylenediamine are added and polymerized at 30 ° C. for 10 hours, and the logarithmic viscosity of the polymer (measuring temperature: 30 ° C., concentration: 0.5 g / 100 ml solvent, solvent: N, N-dimethyl) Acetamide)
Was 1.60, and a polyamic acid (imidization ratio: 5% or less) solution having a polymer concentration of 18% by weight was obtained. In this polyamic acid solution, monostearyl phosphate triethanolamine salt at a ratio of 0.1 part by weight to 100 parts by weight of the polyamic acid and an average particle diameter of 0 part by weight (based on solid content) of 0.5 part by weight. 0.08 μm of colloidal silica was added and uniformly mixed to obtain a polyamic acid solution composition. The rotational viscosity of this polyamic acid solution composition was 30.
It was 00 poise. This polyamic acid solution composition was continuously cast from a slit of a T-die mold.
The solution was extruded on a smooth support in a drying oven to form a thin film of the solution, dried at 130 ° C. for 10 minutes, peeled off from the support, and cured in a curing oven while holding in the width direction (200).
To 450 ° C. for about 20 minutes) to obtain an aromatic polyimide film having a thickness of 75 μm. This film has an elastic modulus of 750 kg / mm ² and a linear expansion coefficient (50-300).
C.) was 16 ppm and the water absorption was 1.5%.

Reference Example 2 Reference Example 1 was repeated, except that instead of paraphenylenediamine, 6.007 kg of 4,4'-diaminodiphenyl ether and 67.6 kg of N, N-dimethylacetamide were used.
In the same manner as in the above, an aromatic polyimide film having a thickness of 75 μm was obtained. This film has an elastic modulus of 370 kg / m.
m ² , linear expansion coefficient (50 ° C to 250 ° C) 40pp
m, and the water absorption was 2.5%.

Reference Example 3 An aromatic polyimide film having a thickness of 125 μm was obtained in the same manner as in Reference Example 1 except that the slit of the T-die mold was changed. This film had an elastic modulus of 690 kg / mm ² , a coefficient of linear expansion (50-300 ° C.) of 18 ppm, and a water absorption of 1.6%.

Example 1 A solution of a polyimidesiloxane-based thermosetting adhesive (composed of a polyimidesiloxane, an epoxy resin, a phenol resin and a curing catalyst) in a tetrahydrofuran solution (solids) was applied to the 75 μm aromatic polyimide film produced in Reference Example 1. (A concentration of 25% by weight) was applied so that the thickness after drying was 30 μm, and dried at 100 ° C. to obtain a polyimide film with an adhesive. This film is 10 mm wide and 9.
Two types of tape with an adhesive were prepared by slitting to a width of 5 mm. The width 2 is set at the center of the adhesive layer of the tape having a width of 10 mm.
A groove having a thickness of 30 mm and a depth of 30 mm was formed with an excimer laser. The tape is wound spirally around a stainless steel rod having an outer diameter of 10 mm with the groove on the outside, and then fixed at both ends. The center of the nichrome foil is 2 mm wide and 40 μm thick.
A tape having an electric resistance value of 14.7 Ω / m was wound in a groove and wound, and then both ends were fixed.
The tape with an adhesive having a width of m was wound spirally with the adhesive inside, and both ends were fixed. The laminate was placed in an oven at 100 ° C. for 1 hour without applying any pressure.
After heating at 00 ° C. for 1 hour and then at 250 ° C. for 1 hour to cure, the laminate is allowed to cool, and the spiral material as the laminate is removed from the stainless steel round bar, and the spiral tube is a 100 cm long spiral tube. A heater was obtained. When this spiral tubular heater was applied with a load of 250 g in the longitudinal direction and measured for elongation, the elongation was 48%. It was easy. At this time, the spiral tubular heater could be mounted evenly and orderly. This spiral tubular heater was placed in a high-temperature bath at 220 ° C. and heat-treated, and the outer diameter before and after the heat treatment was measured. 10.3mm before heat treatment,
After the heat treatment, it was 10.4 mm. When this spiral tubular heater was spirally wound around a stainless steel pipe having a diameter of 10 mm and the withstand voltage between the nichrome foil of the spiral tubular heater and the stainless steel pipe was measured, it was 1.5 KV / 1 minute. Test did not short circuit. When a voltage of 30 V was applied to both ends to heat the pipe, the temperature of the pipe was 140 ° C. and was uniformly maintained at that temperature.

Example 2 A spiral tube, which is a spiral tube, was produced in the same manner as in Example 1 except that the aromatic polyimide film of 75 μm produced in Reference Example 2 was used instead of the aromatic polyimide film produced in Reference Example 1. A heater was obtained. After applying a load of 250 g in the longitudinal direction, the spiral tubular heater returns to its original state after removing the load, and has an outer diameter of 10 mm.
Could be easily wound around a round bar. At this time, the spiral tubular heater could be mounted evenly and orderly. Also, the spiral tubular heater
Was placed in a 220 ° C. high-temperature bath and heat-treated, and the outer diameter before and after the heat treatment was measured. 10.3mm before heat treatment, 1 after heat treatment
0.2 mm. The spiral tubular heater was spirally wound around a stainless steel pipe having a diameter of 10 mm, and the withstand voltage between the stainless steel pipe and the nichrome foil of the spiral tubular heater was measured.
There was no short circuit in the one minute test. Also, 50V at both ends
When the pipe was heated by applying a voltage of
The temperature was kept uniformly high at ℃.

Example 3 A 6 mmφ stainless steel rod was used, the thickness of the adhesive after drying was changed to 20 μm, and 6 mm width and 5.8 mm width tapes obtained from the aromatic polyimide film according to Reference Example 2 were used. And 2mm wide and 20μm deep at the center of 6mm wide
Are formed with an excimer laser, and the heating condition is set at 250 ° C.
The procedure was carried out in the same manner as in Example 1 except that the temperature was changed to 320 ° C. for 20 minutes at 320 ° C. to obtain a spiral tubular heater having a 6 mm inner diameter and a length of 100 cm. After applying a load of 250 g in the longitudinal direction, the spiral tubular heater returns to its original state without the load, and has an outer diameter of 6 g.
It could be easily wound spirally around a round bar of mm. At this time, the spiral tubular heater could be mounted evenly and orderly. Similarly, when it was spirally wound around a pipe bent at a right angle of 15R with a diameter of 6 mm, it could be mounted evenly and orderly. The spiral tube heater was placed in a high-temperature bath at 280 ° C., and the outer diameter before and after the heat treatment was measured. It was 6.3 mm before the heat treatment and 6.2 mm after the heat treatment.

Example 4 A 10 mm wide tape obtained from the aromatic polyimide film according to Reference Example 2 was used for the inner layer, and a 2 mm wide tape was formed at the center.
Excimer laser processing of a groove having a depth of 40 μm was carried out in the same manner as in Example 3 except that a tape having a width of 9.5 mm obtained from the aromatic polyimide film according to Reference Example 1 was used for the outer layer. A spiral tubular heater having a 6 mm inner diameter and a 100 cm length was obtained. After applying a load of 250 g in the longitudinal direction, the spiral tubular heater returns to its original state without the load, and has an outer diameter of 6 mm.
Could be easily wound around a round bar. At this time, the spiral tubular heater could be mounted evenly and orderly. Also, the spiral tubular heater
Was placed in a 220 ° C. high-temperature bath and heat-treated, and the outer diameter before and after the heat treatment was measured. 5.9 mm before heat treatment, and 6.
1 mm.

Example 5 Using an 8 mmφ stainless steel rod, the aromatic polyimide film of Reference Example 3 was slit to a width of 10 mm, and the center portion was formed with a groove having a width of 2 mm and a depth of 40 μm by chemical etching. Same as in Example 1 except that the sheet was made with the adhesive inside dried and the thickness of the adhesive after drying was 30 μm on the outside, and the heating conditions were changed to 250 ° C. for 2 hours and 320 ° C. for 30 minutes. The inner diameter 8mm, length 100c
Thus, a spiral tubular heater having a spiral tubular shape of m was obtained. This spiral tubular heater has a length of 250 mm.
When a load of g was applied and the elongation was measured, it was 27%.
When the load was removed, it returned to its original state, and it could be easily wound spirally around a round bar having an outer diameter of 8 mm. At this time, the spiral tubular heater could be mounted evenly and orderly. In addition, this spiral tubular heater is
Heat treatment was performed in a high-temperature bath at 0 ° C., and the outer diameter before and after the heat treatment was measured. 8.3mm before heat treatment, 8.4mm after heat treatment
Met.

Example 6 Adhesive tape of 4 mm width was formed on both sides of a 10 mm width tape obtained from the aromatic polyimide film according to Reference Example 3 for the inner layer.
(Polyimide siloxane, thermosetting component, thickness 25 μm, one side covered with PET)
The same procedure as in Example 5 was carried out except that a tape having a width of 9 mm obtained from the aromatic polyimide film according to Reference Example 1 was used as the outer layer, and the inner diameter was 10 m.
A spiral tubular heater having a length of 100 cm and a spiral tubular shape was obtained. The spiral tubular heater was measured for elongation by applying a load of 250 g in the longitudinal direction and found to be 40%. When the load was removed, it returned to its original state, and was wound spirally around a round bar having an outer diameter of 8 mm. It was easy to turn on. At this time, the spiral tubular heater could be mounted evenly and orderly. This spiral tubular heater was placed in a high-temperature bath at 220 ° C. and heat-treated, and the outer diameter before and after the heat treatment was measured. It was 10.3 mm before heat treatment and 10.4 mm after heat treatment.

[0034]

Since the present invention is configured as described above, the following effects can be obtained. The spiral tubular article of the present invention has shape retention properties, good adhesion to pipes, good thermal efficiency, and a heater.
Since it is easy to install the tape in the center of the tape, the withstand voltage is good. In addition, it can be easily and evenly mounted on the object to be heated.

According to the production method of the present invention, it is possible to obtain a spiral tubular article having an arbitrary inner diameter and having good shape retention and heat resistance.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view of an example of a spiral tubular article of the present invention cut in parallel with a spiral core.

FIG. 2 is a partial cross-sectional view of another example of the spiral tubular article of the present invention cut in parallel with a spiral core.

FIG. 3 is a cross-sectional view of a tape-shaped heat-resistant resin film provided with a groove in the center used in the manufacturing method of the present invention.

FIG. 4 is a cross-sectional view of a tape-shaped heat-resistant resin film provided with a bank on both sides by an adhesive used in the manufacturing method of the present invention.

FIG. 5 is a perspective view showing an example of a spiral tubular article of the present invention.

FIG. 6 is a partial perspective view showing an example of use of an example of a spiral tubular object. DESCRIPTION OF SYMBOLS 1 Spiral tubular heater 2 Tape-shaped heat-resistant resin film A forming inner layer 3 Adhesive layer forming intermediate layer 3a Adhesive layer in contact with inner layer 3b Adhesive layer in contact with outer layer 4 Outer layer Tape-shaped heat-resistant resin film B5 for forming a flexible conductive substrate imparting conductivity 10 Heated body

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tadao Muramatsu 1-12-32 Nishihonmachi, Ube City, Yamaguchi Prefecture Ube Industries, Ltd. Polymer Research Laboratory (Ube) (72) Inventor Kenji Sonoyama Obe City, Yamaguchi Prefecture 10 Ube Kosan Co., Ltd., Ube Chemical Factory, 1978 Kogushi

Claims (6)

[Claims] 1. A tape forming an inner layer of a spiral material.
Heat-resistant resin film A, adhesive layer forming intermediate layer and tape-shaped heat resistant resin film B forming outer layer
A flexible conductive base material for providing conductivity is integrally provided between both ends in the longitudinal direction of one of the layers of the laminate having the structure described above, and the center of the tape-shaped heat-resistant resin film A is provided. A shape-retaining spiral tubular object, in which the flexible conductive substrate is partially or entirely embedded in a groove provided in a portion or a bank provided on both sides. 2. A spiral heat-resistant tape-like heat-resistant resin film having a groove at the center portion serving as an inner layer or a tape-like heat-resistant resin film A with an adhesive provided on both sides of a bank. Spiral winding around a long shape-imparting member with the groove or bank on the outside, wrapping it so that part or all of the flexible conductive substrate is buried, and further bonding on it as an outer layer A tape-shaped heat-resistant resin film B with an adhesive is wound in a spiral shape with the adhesive inside, wound and cured, the adhesive is laminated and integrated, and the formed laminate is removed from the long shape-imparting member. Spiral tubular article with shape retention obtained by 3. The tape-shaped heat-resistant resin film A and the tape-shaped heat-resistant resin film B each have a thickness of 25-20.
The spiral tubular article according to claim 1 or 2, which has a thickness of 0 µm. 4. The spiral tube according to claim 1, wherein the tape-shaped heat-resistant resin film A and the tape-shaped heat-resistant resin film B are each a tape-shaped aromatic polyimide film. Stuff. 5. The method according to claim 1, wherein the adhesive is a thermosetting adhesive.
A spiral tubular article according to any one of claims 1 to 4. 6. A tape-shaped heat-resistant resin film provided with a groove in the center thereof, which is an inner layer wound on a long shape-imparting member having the same outer shape as the object to be heated, or banks provided on both sides thereof. A flexible conductive substrate for providing conductivity between both ends in the longitudinal direction between the tape-shaped heat-resistant resin film A with an adhesive and the tape-shaped heat-resistant resin film B as an outer layer; The adhesive is placed so that the conductive substrate is partially or entirely buried in the groove or bank, and the adhesive is cured and laminated and integrated while the inner and outer layers of the film are stacked. A method for producing a spiral tubular article.