JPH11135236A - Spiral-tube-shaped heater - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily adhere a heater with a heated body by integrally placing a flexible conductive substrate between longitudinal both ends, on one layer of a layered product consisting of an inner side layer of tape-shaped heat- resistant polymeric material, an intermediate layer of polyimide based adhesion, and an outer side layer of tape-shaped heat-resistant polymeric material. SOLUTION: In a spiral tube-shaped heater 1 with shape keeping property, a flexible conductive substrate 5, which provides conductivity between longitudinal both ends, is integrally placed on one layer of a layered product consisting of tape-shaped heat-resistant polymeric material 2 forming an inner side layer of a spiral matter, a polyimide based adhesion layer 3 comprising of a polyimide based adhesion layer 3a in contact with the inner side layer and a polyimide based adhesion layer 3b in contact with an outer side layer, and tape-shaped heat-resistant polymeric material 4 forming the outer side layer, preferably between the polyimide based adhesion layer 3a and the polyimide based adhesion layer 3b. Therefore, this spiral tube-shaped heater 1 has shape keeping property, good tightness to a pipe, and good thermal efficiency.

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. A tape-shaped polymer material serving as an inner layer and an outer layer provided integrally with a flexible conductive base material, for example, a flat base material such as a heater, sandwiched between insulating layers that can be used. The present invention relates to a spiral tubular heater in which a flexible conductive base material is laminated and integrated with a polyimide-based adhesive between a heat-resistant polymer material with an adhesive and a layer.

[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 An object of the present invention is to provide a heater which can be easily attached to an object to be heated and has good adhesion.

[0004]

According to the present invention, a tape-shaped heat-resistant polymer material A for forming an inner layer of a spiral material is provided.
Any layer of the laminate having the structure of the polyimide-based adhesive layer forming the intermediate layer and the tape-like heat-resistant polymer material B forming the outer layer can be made conductive between both ends in the longitudinal direction. The present invention relates to a shape-retaining spiral tubular heater in which a conductive base material is integrally provided.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be listed below. 1) The above-mentioned spiral tubular heat-resistant polymer material in which the tape-shaped heat-resistant polymer material A forming the inner layer side of the spiral material and the tape-shaped heat-resistant polymer material B forming the outer layer each have a thickness of 25 to 200 μm. -Ta-. 2) The above spiral tubular heater in which the flexible conductive substrate is a planar substrate such as a tape-shaped heater. 3) The spiral tubular heater as described above, wherein the tape-shaped heat-resistant polymer material A and the tape-shaped heat-resistant polymer material B are tape-shaped aromatic polyimide films. 4) A flexible conductive substrate is integrally provided in parallel with the longitudinal direction of the laminate, and the conductive substrate is turned at least once and both ends are taken out from one of the spiral objects. The spiral tubular heater described above.

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 heater according to the present invention, which is cut parallel to a spiral core. FIG. 2 shows a spiral tubular heater of the present invention.
It is a perspective view showing an example of a tar. FIG. 3 is a partial perspective view showing an example of use of an example of the spiral tubular heater of the present invention.

In FIG. 1, a spiral tubular heater-1 having shape retention is a tape-shaped heat-resistant polymer material A for forming an inner layer of a spiral-shaped material, and a polyimide-based material for forming an intermediate layer. Adhesive layer 3 (polyimide adhesive layer 3a in contact with the inner layer and polyimide adhesive layer 3 in contact with the outer layer
b) and any layer of the laminate having the constitution of 4, which is a tape-like heat-resistant polymer material B forming an outer layer, preferably a polyimide-based adhesive layer 3a and a polyimide-based adhesive A flexible conductive substrate 5 that provides conductivity between both ends in the longitudinal direction is provided integrally with the layer 3b.

In FIG. 2, a spiral tubular heater-1 having shape retention is a tape-shaped heat-resistant polymer material A for forming an inner layer of a spiral-shaped material, and a polyimide-based material for forming an intermediate layer. It is possible to impart conductivity between both ends in the longitudinal direction to any layer of the laminate having the constitution of 4, which is the tape-like heat-resistant polymer material B forming the adhesive layer (not shown) and the outer layer. A flexible conductive substrate 5 is provided integrally.

In FIG. 3, the space between the spiral tubular heaters having a shape-retaining property 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 heaters. While maintaining the object to be heated 10 in that state, the spiral tubular heater-1 is rotated in the direction of the arrow in FIG.
As the object to be heated 10 is taken into the spiral tubular heater 1 along with this rotation, the object to be heated 10 can be relatively easily and quickly added to the object to be heated 10 simply by rotating in the axial direction of the tubular heater 1. The spiral tubular heater 1 can be returned to its original shape after the mounting, and can be uniformly and orderly mounted on the object to be heated 10. Therefore, for example, even when both ends of the body to be heated are connected to a large-sized device or the like and there is little freedom,
It can be relatively easily and quickly wound around the object to be heated 10. Further, since the diameter of the spiral tubular heater can be arbitrarily set, not only a heated object having a small degree of freedom but also a heated object having a large degree of freedom, and the diameter of the spiral tubular heater is not limited. It can be applied to any object to be heated as long as it has a rod, pipe or pipe shape.

The spiral tubular heater of the present invention is made of, for example, a tape-shaped heat-resistant polymer material A with a polyimide-based adhesive serving as an inner layer, made of a metal such as stainless steel, with the adhesive being on the outside. Spirally wound around a long shape-imparting member such as a heat-resistant rod or pipe, on which a flexible conductive substrate, preferably a substantially planar substrate, is wound around its center, Further, a tape-like heat-resistant polymer material B with an adhesive serving as an outer layer is spirally stacked and wound with the polyimide-based adhesive inside, and the adhesive is cured and laminated and integrated (this process). Medium, pressure is applied so as not to unwind the wound material around the shape-imparting member), and the formed laminate is removed from a long shape-imparting member such as a rod or a pipe to maintain a spiral shape. As a molded product It is possible to obtain. The spiral tubular heater according to the present invention has almost the same shape and uniform shape as the outer diameter of the spiral object even in an environment heated to normal temperature, preferably at a high temperature of about 200 ° C., and even after being mounted on the object to be heated.・ The shape is maintained without any change in order.

The sheet-like heat-resistant polymer material 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 to 300 ° C. is 60 × 10 ⁻⁵ cm / cm / ° C. (pp
m) (hereinafter also referred to as m).
0 × 10 ⁻⁵ cm / cm / ° C. and a tensile modulus of 20
A heat-resistant rubber such as an aromatic polyimide film or an aromatic polyamide film having a weight of 0 to 1400 kg / mm ² or a silicone rubber 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 polyimide-based adhesive layer forming the intermediate layer is made of a heat-resistant polyimide-based thermoplastic adhesive or a polyimide-based thermosetting adhesive,
Preferably, the dry thickness of the laminated adhesive layer is 2-1.
00 μm and 3-50 mm in width. 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.

Examples of the polyimide-based thermoplastic adhesive include polyimide-based polymers containing an imide bond in a polymer chain, such as polyimide, polyamideimide, polyetherimide, and polyesterimide. As the polyimide-based thermosetting adhesive, a combination of a polymer containing an imide bond in a polymer chain such as polyimide, polyamide imide, polyether imide, polyester imide, and polyimide siloxane, and a thermosetting resin are generally used. is there. Examples of the thermosetting resin include thermosetting resins such as an epoxy resin, a phenol resin, and an acrylate resin, and a polyimide oligomer having a reactive functional group at a terminal or a side chain such as a bismaleimide resin. No. The Tg of the polyimide-based thermoplastic adhesive and the cured polyimide-based thermosetting adhesive are preferably from 20 to 380 ° C, particularly preferably from 30 to 340 ° C.

The tensile elastic modulus (25) of the polyimide-based thermoplastic adhesive and the cured polyimide-based thermosetting adhesive.
It is preferable ° C.) is 5-450kg / mm ^2.
More preferably, it is 10-400 kg / mm ² . The polyimide-based thermoplastic adhesive and the cured polyimide-based thermosetting adhesive preferably use 5 to 100 parts by weight of polyimide. More preferably, the polyimide content is 10% by weight or more. The polyimide-based adhesive may include a silane coupling agent or a titanate-based coupling agent. The mixing amount of the silane coupling agent is 10
0.1-6 parts by weight is suitable for 0 parts by weight. More preferably, it is 0.3-5 weight. As the type of the silane coupling agent, aminosilane, epoxysilane, thiolsilane and the like are preferable. The polyimide adhesive is preferably provided on one side of the tape-shaped heat-resistant resin film A and on one side of the tape-shaped heat-resistant resin film B, respectively.

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 ⁻⁵ cm / cm / ° C. (may be expressed in ppm), especially at 3 to 50 × 10 ⁻⁵ 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. Only one flexible conductive base material may be provided or a plurality of flexible conductive base materials may be provided in parallel, and substantially the entire surface of the tape-like heat-resistant resin film B is formed by the polyimide adhesive. May be provided, but preferably 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 is obtained, for example, as follows. First, an aromatic tetracarboxylic dianhydride such as pyromellitic dianhydride or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and an aromatic diamine are combined with N, N-dimethylacetamide or N
-Polymerization in an organic polar solvent such as -methyl-2-pyrrolidone and the logarithmic viscosity of the polymer (measuring temperature: 30 ° C, concentration:
0.5 g / 100 ml solvent, solvent: N-methyl-2-pyrrolidone) 1-5, polymer concentration 15-40% by weight
A degree of polyamic acid solution is obtained. Next, preferably, 0.01 to 100 parts by weight of the polyamic acid is used.
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 0.02 to 100 parts by weight of polyamic acid. -6
Parts by weight of an inorganic filler such as colloidal silica, silicon nitride, talc, titanium oxide (preferably having an average particle size of 0.005
−5 μm, especially 0.005-2 μm) to prepare a polyamic acid solution composition. This polyamic acid solution composition as it is or by adding a chemical imidizing agent,
The film is cast on a surface of a support having a smooth surface, dried to form a solidified film, and the solidified film is separated from the surface of the support. 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, as it is or corona discharge treatment, plasma treatment,
After surface treatment by ultraviolet irradiation, glow discharge treatment, and flame treatment, it can be used as an aromatic polyimide film having improved adhesiveness.

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 spiral tubular heater of the present invention having a shape-retaining property has, for example, the same outer shape as the object to be heated (the shape may be any shape such as a circular or square cross section). A tape-shaped heat-resistant polymer material A to be an inner layer spirally wound around a heat-resistant rod or pipe, preferably a tape-shaped aromatic polyimide film A and the same width as the shape-imparting member. A tape-like heat-resistant polymer material B, which is a slightly narrow outer layer, preferably a tape-like aromatic polyimide film B, a polyimide-based adhesive therebetween, and conductivity between the both ends in the longitudinal direction. A flexible conductive base material, preferably a planar conductive base material such as a tape-shaped heater, is disposed. In the case of a polyimide-based thermosetting adhesive, the solvent is dried to form a B-shaped conductive base material. -In the case of polyimide-based thermoplastic adhesive, By heating the glass transition temperature or above the melting point temperature by applying pressure to the layer member,
While the inner layer and the outer layer of the film are stacked, the polyimide is heated to a temperature equal to or higher than the curing temperature in the case of a polyimide-based thermosetting adhesive, or cooled in the case of a polyimide-based thermoplastic adhesive. After the system adhesive is cured and laminated and integrated, the spiral laminate is obtained by removing it from the elongated shape imparting member.

The above method can be preferably carried out, for example, as follows. First, a polyimide-based adhesive is applied to one surface of the heat-resistant polymer material A and the heat-resistant polymer material B to be the inner layers, and a film having a dry thickness of the polyimide-based adhesive of 2 to 100 μm is obtained. This film is slit to 3 to 50 mm to produce a tape-like heat-resistant polymer material with a polyimide-based thermosetting adhesive. The tape-shaped heat-resistant polymer material A is spirally wound around a circular rod or pipe having a diameter of 5 to 50 mm with the polyimide-based adhesive surface facing outward, and both ends are fixed. Next, a conductive base material, preferably a tape-shaped heater, having a width smaller than that of the above-described tape is spirally wound thereon. Next, a tape-shaped heat-resistant polymer material B with a polyimide-based thermosetting adhesive serving as an outer layer is further wound thereon so that the polyimide-based adhesives overlap with each other. A / Polyimide thermosetting adhesive / heater
/ Polyimide thermosetting adhesive / tape heat-resistant polymer material B
Press and fix with heat-shrinkable fibers or braids such as polyimide and polyimide, heat to a temperature in the range of 150-400 ° C, cure the polyimide adhesive, laminate and integrate, cool, and form By removing the laminated body from the rod or the pipe, a spiral tubular heater can be obtained.

The spiral tubular heater of the present invention may be applied to a heated object as it is, or may be used after being cut into an appropriate length (in this case, a terminal is separately provided and used). ) Further, the outermost layer may be covered with a heat-resistant foam sheet or a heat-resistant porous sheet for the purpose of keeping heat. In the case of a heated body having a complicated shape, the heated body may be covered using a combination of a spiral tubular heater and a planar heater.

[0023]

Embodiments of the present invention will be described below. In the following description, “part” means “part by weight” and “%” means “% by weight”. In each of the following examples, physical properties of the polyimide film and the like 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,
Measured at 20 ° 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 the polyamic acid solution, monostearyl phosphate triethanolamine salt was added at a ratio of 0.1 part by weight to 100 parts by weight of the polyamic acid, and 0.5 parts by weight (based on solid content) of 0.1 parts by weight of the average particle. 08 μm colloidal silica was added and mixed uniformly 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 onto a smooth support in a drying oven to form a thin film of the solution, dried at 130 ° C. for 10 minutes, peeled from the support, and cured in a curing oven while holding in the width direction (200 ° C.).
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 coefficient of linear expansion (50-300 ° C.).
Was 16 ppm and the water absorption was 1.5%.

Reference Example 2 Reference Example 1 was repeated except that paraphenylenediamine was replaced by 6,007 kg of 4,4′-diaminodiphenyl ether and 67.6 kg of N, N-dimethylacetamide.
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 N was placed in a separable flask made of glass having a capacity of 2 liters.
-Methyl-2-pyrrolidone (NMP) (1000 g) was added, and 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) 73.56 g was added to the solution.
(250 mmol) and diaminopolysiloxane (DA
PS) (Toray Dow Corning Silicone Co., Ltd.
(BY16-853U) 88 g (100 mmol);
61.58 g (150 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) is added, and the mixture is stirred at 60 ° C. for 2 hours under a nitrogen atmosphere. Thereafter, the temperature was further raised to 200 ° C. to carry out a polymerization reaction for 3 hours while removing water. Finally, the reaction solution was added to 10 liters of water, and precipitated using a homomixer for 30 minutes, and the polymer was filtered.
The powder was isolated. The polymer powder is used at 80 DEG C. in a 5-liter 2-propanol using a homomixer.
Was performed twice for 1 hour, followed by drying with hot air at 120 ° C. for 5 hours, followed by vacuum drying at 120 ° C. for 24 hours to obtain 210 g of a polyimidesiloxane powder. This polyimide siloxane had a logarithmic viscosity (30 ° C.) of 0.32 and an imidization ratio of substantially 100%. A film was prepared from a THF solution of this polyimide siloxane powder. The tensile modulus of this film is 57 kg / mm ² and Tg is 190 ° C.
Met.

Reference Example 4 A polyimide siloxane powder was obtained in the same manner as in Reference Example 3 except that a-BPDA was changed to 450 mmol, DAPS was changed to 100 mmol, and BAPP was changed to 350 mmol. A film was prepared from a THF solution of this polyimide siloxane powder. The tensile modulus of this film is 115
kg / mm ² and Tg were 235 ° C.

REFERENCE EXAMPLE 5 N, N-dimethylacetamide (DMAc) 17 was placed in a glass separable flask having a capacity of 300 ml.
5.76 g was added, and 2,3,3 ′, 4 ′ was added to the solution.
-Biphenyltetracarboxylic dianhydride (a-BPD
A) 14.71 g (0.05 mol) of 1,3-bis (4-aminophenoxy) benzene (TPE-R) 2
9.23 g (0.1 mol) was added thereto, and the mixture was stirred at 50 ° C. for 1 hour under a nitrogen atmosphere to produce an amic acid oligomer. Then, the temperature of the reaction solution was raised to about 165 ° C. For 3 hours to produce an imido oligomer having an amino group at the terminal. After the reaction solution was cooled to 50 ° C., 11.77 g (0.12 mol) of maleic anhydride and 35 g of xylene were added, and the temperature of the reaction solution was raised to 160 ° C., while removing xylene together with generated water. After stirring for 4 hours, an imide oligomer having an unsaturated group at the terminal
Finally, the reaction solution is cooled to room temperature (about 20 ° C.) and then poured into water to precipitate a powdery imide oligomer, and the precipitated imide oligomer powder is separated by filtration. After washing twice with toluene and drying under reduced pressure, a terminal-modified imide oligomer was produced. This terminal-modified imide oligomer had an imidization ratio of 95% or more and an intrinsic viscosity of 0.04.

On the other hand, 300 g of N-methyl-2-pyrrolidone was placed in a glass flask having a capacity of 300 ml.
29.42 g (0.1 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA),
41.07 g (0.1 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP)
And stirred under a nitrogen atmosphere at 50 ° C. for 1 hour to generate a polyamic acid. The reaction solution was heated to about 190 ° C. and stirred at that temperature for 5 hours to generate an aromatic polyimide. . The reaction solution is extruded into fibers at room temperature (about 20 ° C.), fibers are formed by a wet spinning method in water at room temperature or lower, and the fibers are washed twice with methanol at 25 ° C., and then dried under reduced pressure. Dried to aromatic polyimide fiber (diameter:
200 μm). The polyimide of this aromatic polyimide fiber had an imidization ratio of 95% or more and a logarithmic viscosity of 0.41. 50 g of the imide oligomer thus obtained, 50 g of an aromatic polyimide fiber and 1,4
-400 g of dioxane was charged into a 1-liter glass container, and stirred at room temperature (about 25 ° C) for about 2 hours to prepare a thermosetting resin solution as a uniform adhesive solution. This solution composition maintained a uniform solution state even when left at room temperature for one week. After casting the above solution composition on a glass plate to form a thin film, the solution was mixed at 90 ° C. for 30 minutes and at 140 ° C. for 3 minutes.
After heating and drying for 0 minutes and peeling off from the glass plate, a dry film as a thermosetting thermosetting adhesive having a thickness of 20 μm was produced. This film had a tensile modulus of 200 kg / mm ² and a Tg of 260 ° C.

Example 1 A polyimidesiloxane-based thermosetting adhesive [85 parts of the polyimidesiloxane obtained in Reference Example 3, epoxy resin (manufactured by Yuka Shell Co., Ltd.) on the 75 μm aromatic polyimide film produced in Reference Example 1 Epicot 828) 10 parts, BT
5 parts of resin (manufactured by Mitsubishi Gas Chemical Company, BT2170)] in tetrahydrofuran (solid concentration: 25%) so as to have a thickness of 30 μm after drying, and drying at 100 ° C. to obtain a polyimide film with an adhesive. Obtained. This film was slit into 10 mm width and 9.8 mm width to produce two types of tapes with an adhesive. A 10 mm wide tape is spirally wound around a stainless steel round bar having an outer diameter of 10 mm with the adhesive layer on the outside. Then, both ends are fixed, and the nichrome width 2 mm, thickness 40 μm, electric resistance value are fixed at the center. After winding a tape of 14.7 Ω / m, both ends are fixed, and a tape with an adhesive having a width of 9 mm is further placed thereon.
The adhesive layer was wound spirally with the adhesive layer inside, and both ends were fixed. Furthermore, it is made of Tetron (made by Chugai Seimitsu Co.,
TCT-02545) Heat shrink tape (braid, width 4mm)
And spirally wound in an oven at 100 ° C for 1 hour.
After heating at 200 ° C for 1 hour, removing the tetron heat shrink tape, heating at 250 ° C for 1 hour for curing,
After cooling, the spiral material as a laminate is removed from the stainless steel round bar, and a spiral tubular heater having a length of 100 cm is provided.
I got The spiral tubular heater has a diameter of 10 m.
m of stainless steel pipe, and a voltage of 50 V was applied to both ends. The temperature of the pipe was 150 ° C. and was maintained at that temperature uniformly.

Example 2 A 75 μm aromatic polyimide film produced in Reference Example 2 was used in place of the aromatic polyimide film produced in Reference Example 1, and a polyimidesiloxane thermosetting adhesive [Reference Example] 85 parts of the polyimide siloxane obtained in Step 4, 10 parts of an epoxy resin (Epicoat 828, manufactured by Yuka Shell Co., Ltd.), BT resin (manufactured by Mitsubishi Gas Chemical Company, BT
2170) 5 parts and a silane coupling agent (manufactured by Dow Corning Silicone Toray Co., Ltd., SH6040) (1 part) except that a spiral tubular heater having a length of 100 cm was used in the same manner as in Example 1. Obtained. Further, a stainless pipe having a diameter of 10 mm was wound around the spiral tubular heater, and a voltage of 50 V was applied to both ends. The temperature of the pipe is 153 ° C,
It was maintained at that temperature uniformly.

Example 3 The adhesive solution obtained in Reference Example 5 [imide oligomer] was applied to the 75 μm aromatic polyimide film produced in Reference Example 2.
5 parts, 5 parts of an aromatic polyimide fiber, and 40 parts of 1,4-dioxane) were applied so that the thickness after drying was 25 μm, and dried at 150 ° C. to obtain a polyimide film with an adhesive. This film was slit into 10 mm width and 9.8 mm width to produce two types of tapes with an adhesive.
10mm tape with outer diameter 10m with adhesive layer outside
After spirally wrapping it around a stainless steel round bar
After fixing both ends, winding a tape made of nichrome 2 mm wide, 40 μm thick and having an electric resistance value of 14.7 Ω / m at the center thereof, fixing both ends, and further bonding a 9.8 mm wide adhesive thereon. The tape with the agent was spirally wound with the adhesive layer inside, and both ends were fixed. Furthermore, a braid of polyimide fiber (polyimide fiber P manufactured by Lenting Co.)
84, 4 mm wide) and wound in an oven at 100 ° C. for 1 hour, 200 ° C. for 1 hour, 30 ° C.
After heating at 0 ° C for 1 hour, remove the braid, and further at 340 ° C for 1 hour.
After heating and curing for a period of time, the mixture was allowed to cool and the spiral material as a laminate was removed from the stainless steel round bar, and the length was 100 c.
m spiral tubular heater was obtained. Further, a stainless pipe having a diameter of 10 mm was wound around the spiral tubular heater, and a voltage of 50 V was applied to both ends. Pipe temperature is 15
At 0 ° C., it was maintained uniformly at that temperature.

[0033]

Since the present invention is configured as described above, the following effects can be obtained. The spiral tubular heater of the present invention has shape retention properties, good adhesion to pipes, and good thermal efficiency. Furthermore, since a polyimide adhesive is used, heat resistance is high,
Spiral tubular heater with excellent electrical insulation.
In addition, it can be easily and evenly mounted on the object to be heated.

[Brief description of the drawings]

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

FIG. 2 is a perspective view showing an example of a spiral tubular heater according to the present invention.

FIG. 3 is a partial perspective view showing an example of use of an example of the spiral tubular heater of the present invention. Reference Signs List 1 spiral tubular heater 2 tape-shaped heat-resistant polymer material A forming inner layer 3 polyimide-based adhesive layer forming intermediate layer 3a polyimide-based adhesive layer in contact with inner layer 3b polyimide in contact with outer layer System adhesive layer 4 Tape-like heat-resistant polymer material B 5 forming outer layer 5 Flexible conductive base material 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 polymer material A, a polyimide-based adhesive layer forming an intermediate layer, and a tape-shaped heat-resistant polymer material B forming an outer layer. A shape-retaining spiral tubular heater in which a flexible conductive substrate for providing conductivity is integrally provided between both ends. 2. A glass transition temperature (Tg) of from 20 to 380.
The spiral tubular heater according to claim 1, which is a polyimide-based adhesive containing a polyimide-based polymer having a temperature of ° C as a main component. 3. A tensile modulus (25 ° C.) of 5-450 kg.
The spiral tubular heater according to claim 1 or 2, which is a polyimide-based adhesive containing a polyimide-based polymer having a ratio of / mm ² as a main component. 4. The spiral tubular heater according to claim 1, which is a polyimide adhesive containing 5 to 100% by weight of a polyimide polymer. 5. The spiral tubular heater according to claim 1, which is a polyimide adhesive containing a silane coupling agent. 6. A flexible conductive substrate is provided integrally and in parallel with the longitudinal direction of the laminate, and the conductive substrate is turned at least once and both ends are formed from one of the spiral members. The spiral tubular heater according to any one of claims 1 to 5, which has been taken out.