JP3525744B2 - Heat resistant polymer tape with adhesive for spiral tubular heater - Google Patents

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 having good adhesion to pipes and good thermal efficiency, and particularly for the purpose of heat insulation of pipes such as semiconductor manufacturing equipment and analytical instruments. A heat-resistant polymer tape serving as an inner layer and an outer layer, which are integrally formed by sandwiching a flexible conductive base material, for example, a flat base material such as a heater, between insulating layers that can be used. Heat-resistant adhesive with a shape-retaining spiral tubular heater, in which a flexible conductive substrate is laminated and integrated with a layer of heat-resistant polymer tape by an adhesive. It relates to a polymer tape.

[0002]

2. Description of the Related Art Conventionally, a pipe for preventing a substance to be conveyed from solidifying or adhering to a pipe in an analytical instrument such as a liquid chromatograph or a mass spectroscope or a pipe constituting a passage for conveying a liquid medicine in a medical instrument. It is necessary to heat the pipe to keep it warm, and sometimes the pipe is heated in order to evaporate the substance adhering to the inner surface and secure the degree of vacuum. Further, the water pipe may be kept warm or heated to prevent it from freezing. In such a case, for example, a flexible sheet heating element such as a ribbon heater is generally wound into a pipe and wound around a pipe.

[0003]

However, the piping system of the above-mentioned pipe is generally provided in a narrow space between the devices, and it is necessary to wind the sheet heating element around the pipe. However, the sheet heating element has poor adhesion to the pipe. Therefore, the thermal efficiency is low, and therefore the temperature cannot be controlled accurately. An object of the present invention is to provide a shape-retaining spiral tubular heater which can be easily wound around a pipe or the like, has good adhesion to the pipe, has good thermal efficiency, and can control temperature. A heat-resistant polymer tape with an adhesive is provided.

[0004]

The present invention is directed to a heat-resistant polymer tape A forming an inner layer of a spiral-shaped material, an adhesive forming an intermediate layer, and a heat-resistant polymer tape forming an outer layer. For a shape-retaining spiral tubular heater in which a flexible conductive base material that provides conductivity is integrally provided between both ends in the longitudinal direction of any of the layers having the structure of type B. A heat-resistant polymer tape is provided on one side thereof with a heat-resistant adhesive, and the adhesive can be pressure-bonded at a low pressure and has a water absorption rate of 1.8% or less. The present invention relates to a heat resistant polymer tape with an adhesive. In this specification, water absorption is room temperature (23 ° C., 50% RH, 24 hours)
Means the value obtained by the following formula. Water absorption rate = [(B−A) / A] × 100 (%) A: 120 ° C. × weight after drying for 20 minutes B: Weight after leaving at 23 ° C. and 50% RH for 24 hours

[0005]

Preferred embodiments of the present invention will be listed below. 1) Heat-resistant polymer tape A and heat-resistant polymer tape B
Is 35-200 μm in thickness, and at least one of them has a rigidity of 0.80 kg or more. The heat-resistant polymer tape with an adhesive for spiral tubular heater according to claim 1. 2) Heat-resistant polymer tape A and heat-resistant polymer tape B
Wherein each is an aromatic polyimide tape, and the heat-resistant polymer tape with an adhesive for a spiral tubular heater according to claim 1 or 2. 3) The heat-resistant polymer tape with an adhesive for a spiral tubular heater according to claim 1, wherein the adhesive can be pressure-bonded at a pressure of 10 kg / cm ² or less.

The present invention will be described below in detail with reference to the drawings. FIG. 1 shows a spiral tubular heater.
FIG. 3 is a cross-sectional view of an example of a heat-resistant polymer tape with an adhesive for use in an automobile. FIG. 2 is a partial cross-sectional view of an example of a spiral tubular heater using a heat-resistant polymer tape with an adhesive for the spiral tubular heater of the present invention, cut in parallel with a spiral core. is there. FIG. 3 shows the spiral tubular heater of the present invention.
FIG. 3 is a perspective view showing an example of a spiral tubular heater using a heat-resistant polymer tape with an adhesive for a motor.

In FIG. 1, a heat-resistant polymer tape 1 with an adhesive for a spiral tubular heater is a heat-resistant polymer tape 2 for a shape-retaining spiral tubular heater.
The heat-resistant adhesive 3 is provided on one surface of the adhesive, and the adhesive can be pressure-bonded at a low pressure and the water absorption is 1.8% or less. In FIG. 2, the shape-retaining spiral tubular heater 10 is a heat-resistant polymer tape A forming an inner layer of the spiral-shaped material 2, and an adhesive 3 forming an intermediate layer (in the inner layer, (Which is composed of the adhesive 3a in contact with the outer layer and the adhesive 3b in contact with the outer layer) and any layer of the laminate having the constitution 4 which is the heat-resistant polymer tape B forming the outer layer, preferably the adhesive 3a
A flexible conductive base material 5 that provides conductivity is integrally provided between both ends of the adhesive 3b and the adhesive 3b in the longitudinal direction. In FIG. 3, the shape-retaining spiral tubular heat
The taper 10 is a heat-resistant polymer tape A that forms the inner layer of the spiral-shaped material 2, an adhesive (not shown) that forms the intermediate layer, and a heat-resistant polymer tape that forms the outer layer. B
The flexible conductive base material 5 which provides conductivity is integrally provided between both ends in the longitudinal direction of any one of the layers having the structure of 4 above.

The heat-resistant polymer tape with an adhesive for the spiral tubular heater according to the present invention has a heat-resistant polymer tape provided on one surface thereof with a low pressure. Since the water absorption rate is 1.8% or less, preferably 1.5% or less, and particularly 1.2% or less and 0.1% or more, it can be pressure-bonded with and can be easily adhered to the object to be heated. Heater
Can be easily obtained.

The shape-retaining spiral tubular heater obtained by applying the heat-resistant polymer tape with an adhesive for the spiral tubular heater of the present invention is inserted into a heated object. Insert the heated object between the spiral tubular heaters by expanding it as much as possible, and then rotate the spiral tubular heater while keeping the heated object in that state. Since the heating element is taken into the spiral tubular heater, the spiral tubular heater can be relatively easily and quickly attached to the object to be heated simply by rotating it in the axial direction of the tubular heater.
The spiral tubular heater returns to its original shape after it is mounted, so that it can be mounted evenly and orderly on the object to be heated. 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 to be heated can be relatively easily and quickly wound around the object to be heated. Further, since the diameter of the spiral tubular heater can be arbitrarily set, not only the heated object having a small degree of freedom but also the heated object having a large degree of freedom, and the size of the diameter are not limited. If it is rod-shaped or pipe-shaped, it can be applied to any object to be heated.

The above spiral tubular heater is made of metal, for example, a heat-resistant rod such as stainless steel or the like, with a heat-resistant polymer tape A having an adhesive serving as an inner layer being the outside. A long shape-imparting member such as a pipe is wound in a spiral shape, and a flexible conductive base material, preferably a planar conductive base material, is wound around the spiral shape-applying member. A heat-resistant polymer tape B with an adhesive to be an outer layer is wound in a spiral shape with the adhesive inside, and the adhesive is cured (solidified) to be laminated and integrated to form a laminated body. It can be removed from a long shape-imparting member such as a rod or a pipe to obtain a molded product having a spiral shape. The spiral tubular heater obtained as described above has a working temperature of, for example, 20
Even after being heated to a high temperature of about 0 ° C., and even after being attached to the object to be heated, there is almost no change in the shape such as the outer diameter of the spiral shape and the shape and uniformity are maintained.

The heat-resistant polymer tape A and the heat-resistant polymer tape B forming the inner layer of the spiral-shaped material in the present invention have a glass transition temperature or a melting point of 180.
It is made of aromatic polyimide or aromatic polyamide having a temperature of ℃ or more, and preferably has a thickness of 35-200 μm and a width of 3
A -50 mm tape film is used. Especially 5
Linear expansion coefficient (CTE) at 0-300 ℃ is 60 × 10 ^-6
cm / cm / ° C (sometimes expressed in ppm) or less,
Among them, an aromatic polyidic film or an aromatic polyamide film having a tensile elastic modulus of 200 to 1400 kg / mm ² and especially 3 to 50 × 10 ^-6 cm / cm / ° C. is preferably used. Among them, the aromatic polyimide film is particularly preferably used. In particular, the rigidity (kg) defined by the following formula for the heat-resistant polymer tape A and the heat-resistant polymer tape B is 0.8 kg or more, particularly 1 k.
g or more and 25 kg or less, thickness 35-200 μm
Is preferably used. Rigidity (kg) = Tape thickness (mm) ² x Elastic modulus (kg
/ Mm ² )

The above-mentioned 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, those obtained by using 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as an aromatic polyimide in an amount of 15 mol% or more in the aromatic tetracarboxylic acid component have heat resistance, a low linear expansion coefficient, It is preferable because it has a low water absorption. Examples of the aromatic polyamides include aromatic acid chlorides such as 2-chloroterephthalic acid chloride and 2,5-dichloroterephthalic acid chloride and 2-chloro-p-phenylenediamine,
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 is made of a heat resistant thermoplastic adhesive or a thermosetting adhesive, and preferably the laminated adhesive layers have a thickness in the dry state of 2 to 100 μm. , Width is 3-50 mm. Also,
This adhesive layer may be provided as a tape with an adhesive, or after the tape is wrapped, an adhesive may be applied or an adhesive sheet may be attached to provide a tape with an adhesive. Good.

Examples of the thermosetting adhesive include epoxy resin, NBR-phenolic resin, phenol-butyric resin.
Resin, epoxy-NBR resin, epoxy-phenol resin, epoxy-nylon resin, epoxy-polyester resin, epoxy-acrylic resin, acrylic resin, polyamide-epoxy-phenol resin,
Examples thereof include polyimide resins and polyimide siloxane-epoxy resins. Examples of the thermoplastic adhesive include polyimide resins.

Examples of the polyimide-based thermoplastic adhesive include thermoplastic polyimide, thermoplastic polyamide-imide,
Preferable examples thereof include those having an imide bond in the polymer chain, such as thermoplastic polyetherimide, thermoplastic polyesterimide, and thermoplastic polyimidesiloxane. As the polyimide-based thermosetting adhesive, a polymer having an imide bond in a polymer chain such as thermoplastic polyimide, thermoplastic polyamide-imide, thermoplastic polyether imide, thermoplastic polyester imide, thermoplastic polyimide siloxane, and the like. A combination with a curable resin is common. Examples of the thermosetting resin include resins such as an epoxy resin, a phenol resin, and an acrylate resin, and a polyimide oligomer having a reactive functional group at the terminal or side chain such as a bismaleimide resin. The Tg (glass transition temperature) of the polyimide-based thermoplastic adhesive and the cured polyimide-based thermosetting adhesive is preferably 20 ° C. or higher and 380 ° C. or lower, and particularly 30
Those having a temperature of not less than 0 ° C and not more than 340 ° C are preferable.

The polyimide-based thermoplastic adhesive and the cured polyimide-based thermosetting adhesive have tensile elastic modulus (25
C) is preferably 5 kg / mm ² or more and 450 kg / mm ² or less, more preferably 10 kg / mm
² or more and 400 kg / mm ² or less. The polyimide-based thermoplastic adhesive and the cured polyimide-based thermosetting adhesive are preferably polyimide in an amount of 5% by weight or more and 100% by weight or less. Particularly, it is preferable to use polyimide in an amount of 10% by weight or more and 100% by weight or less. The polyimide adhesive may include a silane coupling agent or a titanate coupling agent. The mixing amount of these coupling agents is preferably 0.1 parts by weight or more and 6 parts by weight or less, more preferably 0.3 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the adhesive. is there.
As the kind of the silane coupling agent, aminosilane, epoxysilane, thiolsilane and the like are suitable.

As the flexible conductive base material in the present invention, a metal foil, a metal wire or a strip-shaped metal, which has a conductive function between both ends in the longitudinal direction of the spiral-shaped material, preferably has a thickness of 5 to 5. A metal foil with a thickness of 100 μm and a width of about 0.4-40 mm, preferably a nichrome foil, is used. This flexible conductive substrate may be provided only one or in parallel, and may be provided on almost the entire surface of the tape-shaped heat-resistant resin film B by the above-mentioned adhesive. It may be provided, but it is preferable to provide it at substantially the center. Alternatively, the surface of a flexible conductive substrate may be thinly coated with a heat resistant resin or a heat resistant surface treatment agent such as a silane coupling agent by a coating method or the like.

The above aromatic polyimide film can be manufactured, 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 to give a 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 (imidization 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, it is preferably 0.0 based on 100 parts by weight of the polyamic acid.
0 to 1% by weight of a phosphorus compound, for example, an organic phosphorus compound or an inorganic phosphorus compound such as a (poly) phosphate ester and / or an amine salt of a phosphate ester, and preferably 100 parts by weight of a polyamic acid. .02
~ 6 parts by weight of colloidal silica, silicon nitride, talc,
Inorganic fillers such as titanium oxide and calcium phosphate (preferably having an average particle size of 0.005 to 5 μm, especially 0.005 to 2
μm) is added to prepare a polyamic acid solution composition. This polyamic acid solution composition is cast as it is or by adding a chemical imidizing agent, cast on the surface of a support having a smooth surface, dried to form a solidified film, and the solidified film is peeled from the surface of the support. Next, a surface treatment solution containing an aminosilane-based, epoxysilane-based, or titanate-based surface treatment agent may be applied to one side or both sides of the solidified film, and then 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. in a state where both widthwise edges of the dried film are held. Then, it can be dried and imidized to be suitably manufactured as an aromatic polyimide film. The aromatic polyimide film obtained as described above,
Suitably under low tension or no tension 200-400 ℃
It is heated at about the same temperature, subjected to stress relaxation treatment, and wound up. This aromatic polyimide film can be used as an aromatic polyimide film with improved adhesiveness as it is or after being subjected to surface treatment by corona discharge treatment, plasma treatment, ultraviolet irradiation, glow discharge treatment, or flame treatment.

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

The method for producing a shape-retaining spiral tubular heater using the heat-resistant polymer tape with an adhesive for the spiral tubular heater of the present invention is, for example, the following method. Is mentioned. First, a long shape-imparting member having the same outer shape as the object to be heated (the shape may have an arbitrary shape such as a circular cross section or a rectangular shape), for example, is wound in a spiral shape on a heat-resistant rod or pipe. A heat-resistant polymer tape A with an adhesive as an inner layer, preferably an aromatic polyimide tape A with an adhesive and a tape B with an adhesive as an outer layer having the same width or a little narrower width. Aromatic polyimide tape B with an adhesive and a flexible conductive base material which provides conductivity between both ends in the longitudinal direction, preferably a tape.
A flat conductive substrate such as a fold-shaped heater is arranged. Then, in the case of a thermosetting adhesive, the solvent is dried, and at the stage of B stage, the inner layer and the outer layer of the tape are overlapped and heated to a temperature higher than the curing temperature under pressure, The adhesive is obtained by curing the adhesive to integrate the layers and then removing the spiral laminate from the elongated shape-imparting member. In the case of a thermoplastic adhesive, pressure is applied to the laminate while the inner layer and the outer layer of the tape are overlapped to heat the glass transition temperature or the melting point or higher, and then the adhesive is cooled. After being cured and laminated and integrated, the spiral laminate is obtained by removing it from the elongated shape-imparting member.

The above method can be specifically carried out as follows, for example. First, an adhesive is applied to one surface of each of the heat-resistant polymer tape A and the heat-resistant polymer tape B, which are the inner layers, to obtain a film having a dry thickness of the adhesive of 2 to 100 μm. This film is slit to 3-50 mm to produce heat-resistant polymer tapes A and B with an adhesive. This heat-resistant polymer tape A with an adhesive is wound spirally around a circular rod or pipe having a diameter of 5 to 50 mm with the adhesive surface facing outward, and both ends are fixed. Then, a conductive base material having a width narrower than that of the tape, preferably a tape-shaped heater, is spirally wound around the tape and the both ends are fixed. Next, a heat-resistant polymer tape B with an adhesive to be an outer layer is wound around so that the adhesives overlap each other, and the heat-resistant polymer tape A / adhesive /
A heater / adhesive / heat-resistant polymer tape B is formed, and preferably the periphery is pressed and fixed with a tape-shaped or linear material. The pressurization at this time can be performed at 10 kg / cm ² or less. Furthermore, after heating to a curing temperature (or plasticizing temperature) of the adhesive, preferably a temperature in the range of 150 to 400 ° C. to laminate and integrate, and after cooling, the formed laminate is removed from the rod or pipe to form a spiral. Tubular heat
Data can be obtained.

The spiral tubular heater obtained as described above may be applied to the object to be heated as it is, or may be cut into a suitable length before use (in this case,
Use by providing a separate terminal. ), And the outermost layer may be covered with a heat-resistant foam sheet or a heat-resistant porous sheet for the purpose of keeping heat. When the object to be heated has a complicated shape, the object to be heated may be covered by using a spiral tubular heater and a flat heater in combination.

[0023]

EXAMPLES Examples of the present invention will be shown below. In each of the following examples, the physical properties of the polyimide film were measured by the following methods. Water absorption (equilibrium): Measured according to ASTM D570-63 (23 ° C, RH50%, 24 hours) Tensile modulus: Measured according to ASTM D882-64T (MD) Linear expansion coefficient (50-250 ° C or 50-300 ° C):
TM is a sample that has been stress-relieved by heating at 300 ° C for 30 minutes.
Device A (tensile mode, 2g load, sample length 10mm, 2
Measured at 0 ° C / min)

Reference Example 1 54.6 kg of N, N-dimethylacetamide was added to a polymerization tank having an internal volume of 100 liters, and then 3,3 ',
4,4'-biphenyltetracarboxylic dianhydride 8.8
26 kg of paraphenylenediamine and 3.243 kg of paraphenylene diamine were added thereto, and the polymer was subjected to a polymerization reaction at 30 ° C. for 10 hours to give a logarithmic viscosity of the polymer (measurement temperature: 30 ° C., concentration: 0.5 g / 100 ml solvent, solvent: N, N-dimethyl. Acetamide)
Of 1.60 and the polymer concentration was 18% by weight to obtain a polyamic acid (imidization ratio: 5% or less) solution. In this polyamic acid solution, 0.1 parts by weight of monostearyl phosphate ester triethanolamine salt and 100 parts by weight of polyamic acid and 0.5 parts by weight (solid content basis) of an average particle size of 0 A 0.08 μm colloidal silica was added and uniformly mixed to obtain a polyamic acid solution composition. The rotational viscosity of this polyamic acid solution composition is 30.
It was 00 poise. This polyamic acid solution composition is continuously cast from the slit of the T-die mold.
A thin film of the above solution is formed by extruding on a smooth support of a drying oven, dried at 130 ° C. for 10 minutes, peeled from the support, and cured in a curing oven in a state of gripping in the width direction (200
After that, the aromatic polyimide film having a thickness of 75 μm was obtained. This film has an elastic modulus of 750 kg / mm ² and a linear expansion coefficient (50-300).
℃) 16ppm, rigidity 4.2kg, water absorption (23
C, RH 50%, 24 hours) was 0.8%.

Reference Example 2 Reference example 1 was repeated except that, in place of paraphenylenediamine, 6.04 kg of 4,4'-diaminodiphenyl ether was used and 67.6 kg of N, N-dimethylacetamide.
An aromatic polyimide film having a thickness of 75 μm was obtained in the same manner as in. This film has an elastic modulus of 370 kg / m.
m ² , linear expansion coefficient (50 to 250 ° C) of 40 pp
m, rigidity 2.1 kg, water absorption (23 ° C, RH 50%,
24 hours) was 0.9%.

Reference Example 3 In a glass separable flask having an internal volume of 2 liters,
1000 g of N-methyl-2-pyrrolidone (NMP) was put into the solution, and 73,56 g of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) was added to the solution.
(250 mmol) and diaminopolysiloxane (DA
PSi) (Toray Dow Corning Silicone, BY
16-853 U) 88 g (100 mmol) and 2,2
61.58 g (150 mmol) of -bis [4- (4-aminophenoxy) phenyl] propane (BAPP) was added, and the mixture was stirred at 60 ° C for 2 hours under a nitrogen atmosphere. After that, the temperature is further raised to 200 ° C. and water is removed while 3
The polymerization reaction was carried out for a time. Finally, the reaction solution was added to 10 liters of water, a homomixer was used for precipitation for 30 minutes, and the polymer was filtered to isolate a polymer powder. This polymer powder was washed twice in 5 liters of 2-propanol using a homomixer at 80 ° C. for 1 hour twice, and dried at 120 ° C. for 5 hours with hot air.
Vacuum-dried at ℃ for 24 hours and polyimide siloxane powder 2
10 g were obtained. This polyimidesiloxane has an inherent viscosity of 0.32 and an imidization ratio of substantially 1.
It was 00%. TH of this polyimide siloxane powder
A film was made from the F solution. The tensile elastic modulus of this film was 57 kg / mm ² , and the Tg was 190 ° C.

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

Reference Example 5 N, N-dimethylacetamide (DMAc) 1 was placed in a glass separable flask having an inner volume of 300 ml.
75.76 g was added to the solution, and a-BPDA14.
71 g (0.05 mol) and 29.23 g of 1,3-bis (4-aminophenoxy) benzene (TPE-R)
(0.1 mol) was added and the mixture was stirred at 50 ° C. for 1 hour under a nitrogen atmosphere to generate an amic acid oligomer, and then the reaction solution was heated to about 165 ° C. for 3 hours at that temperature. After stirring, an imide oligomer having an amino group at the end
Was generated. After cooling the reaction solution to 50 ° C., 11.77 g (0.12 mol) of maleic anhydride and 35 g of xylene were added, and the reaction solution was heated to 160 ° C.
The reaction mixture was stirred for 4 hours while removing xylene together with water to generate an imide oligomer having an unsaturated group at the terminal, and finally the reaction solution was cooled to room temperature (about 20 ° C.) and then poured into water to form a powder. Of the imide oligomer, and the precipitated imide oligomer powder was separated by filtration and then at 25 ° C.
Was washed twice with methanol and dried under reduced pressure to obtain a terminal-modified imide oligomer. This terminal-modified imide oligomer had an imidization ratio of substantially 100% and an inherent viscosity of 0.04.

On the other hand, in a glass separable flask having an inner volume of 300 ml, 300 g of N-methyl-2-pyrrolidone (NMP), 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a- BPDA) 29.4
2 g (0.1 mol) and 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 41.
07 g (0.1 mol) was added, and the mixture was stirred at 50 ° C. for 1 hour under a nitrogen atmosphere to generate polyamic acid, and the reaction solution was heated to about 190 ° C. and stirred at that temperature for 5 hours. An aromatic polyimide was produced. The reaction solution is extruded into a fibrous form at room temperature (about 20 ° C.) and formed into a fiber by a wet spinning method in which the reaction solution is poured into water at a temperature of room temperature or lower.
After washing twice with methanol at ℃, it was dried under reduced pressure to produce an aromatic polyimide fiber (diameter: 200 μm).
In this aromatic polyimide fiber, polyimide has an inherent viscosity of 0.41 (30 ° C.) and an imidization ratio of substantially 1
It was 00%. The imide oligomer thus obtained
Charge 50 g, 50 g of aromatic polyimide fiber and 400 g of 1,4-dioxane into a 1 liter glass container,
A uniform thermosetting adhesive solution was prepared by stirring at room temperature (about 25 ° C.) for about 2 hours. This solution composition maintained a uniform solution state even when left for 1 week. The solution composition was cast on a glass plate to form a thin film, and then the solution was mixed at 90 ° C. for 3
The film was heated and dried at 0 ° C. and 140 ° C. for 30 minutes and peeled off from the glass plate to produce a dry film which is a thermosetting curable film adhesive having a thickness of 20 μm. This dry film has a tensile modulus of 200 kg / m.
m ² and Tg were 260 ° C.

Example 1 A 75 μm aromatic polyimide film produced in Reference Example 1 was coated with a polyimidesiloxane thermosetting adhesive [85 parts of the polyimidesiloxane obtained in Reference Example 3, an epoxy resin (produced by Yuka Shell Co., Ltd., Epicote 828) 10 copies, BT
5 parts of a resin (BT2170 manufactured by Mitsubishi Gas Chemical Co., Ltd.)] in tetrahydrofuran solution (solid content concentration: 25% by weight) is applied so that the thickness after drying becomes 30 μm, and dried at 100 ° C. to obtain a polyimide film with an adhesive. This film was slit into a width of 10 mm to prepare a tape with an adhesive [water absorption rate: 0.6%].
The spiral tubular heater was produced as follows using the probe.

A tape with an adhesive of 10 mm width was spirally wound around a stainless steel rod having an outer diameter of 10 mm with the adhesive layer on the outside, then both ends were fixed, and a nichrome-made width of 2 mm was provided in the center. , Thickness 40 μm, electric resistance value 14.7
After winding a tape of Ω / m, both ends were fixed, and further, a tape with an adhesive of 10 mm width was spirally wound with the adhesive inside, and both ends were fixed. .
Furthermore, it is made of Tetoron (made by Chugai string company, TCT-0
2545) A heat-shrinkable tape (braid, width 4 mm) is wrapped in a spiral shape and heated in an oven at 100 ° C. for 1 hour, 20
After heating at 0 ° C. for 1 hour (applying pressure at this time was about 5 kg / cm ² ), the Tetron heat shrink tape was removed. After further heating at 250 ° C. for 1 hour to cure, it is allowed to cool and the spiral-shaped product as a laminate is removed from the stainless round bar, and the length is set to 100.
A cm-shaped spiral tubular heater was obtained. This spiral tubular heater was spirally wound on a stainless pipe having a diameter of 10 mm, 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 The aromatic polyimide film prepared in Reference Example 1 was replaced with the 75 μm aromatic polyimide film prepared in Reference Example 2, and a polyimidesiloxane thermosetting adhesive [Reference Example] was used. 85 parts of the polyimide siloxane obtained in 4 above, 10 parts of epoxy resin (Epoxy 828 manufactured by Yuka Shell Co., Ltd.), BT resin (BT manufactured by Mitsubishi Gas Chemical Co., Inc., BT)
2170) 5 parts] and a silane coupling agent [Toray
A tape with an adhesive [water absorption: in the same manner as in Example 1 except that 1 part of Dow Corning SH6040] was used.
0.7%] was prepared. A spiral tubular heater having a length of 100 cm was obtained in the same manner as in Example 1 except that these two kinds of tapes with an adhesive were used. This spiral tubular heater was spirally wound on a stainless pipe having a diameter of 10 mm, and a voltage of 50 V was applied to both ends. The temperature of the pipe was 153 ° C., which was uniformly maintained at a high temperature.

Example 3 On the 75 μm aromatic polyimide film produced in Reference Example 2, the adhesive solution obtained in Reference Example 5 [imide oligomer
5 parts, 5 parts of aromatic polyimide fiber, 40 parts of 1,4-dioxane] were applied so that the thickness after drying would be 25 μm, and dried at 150 ° C. to obtain a polyimide film with an adhesive. This film was slit into a width of 10 mm and a width of 9.8 mm to produce two kinds of tapes with an adhesive [both have a water absorption rate of 0.7%]. A tape having a width of 10 mm was spirally wound around a stainless steel rod having an outer diameter of 10 mm with an adhesive on the outside, and both ends were fixed, and a nichrome-made width of 2 mm, a thickness of 40 μm, and an electric resistance value of 1
After winding the tape of 4.7Ω / m, fix both ends,
On top of that, a tape with adhesive of 9.8 mm width,
The adhesive was placed inside and spirally wound, and both ends were fixed. Furthermore, a braid of polyimide fiber [polyimide fiber manufactured by Renting Co .: P84, width 4 mm]
Spirally wound and heated in an oven at 100 ° C for 1 hour, 200 ° C for 1 hour, 300 ° C for 1 hour (300
Pressurization at ° C is about 3 kg / cm ² . After that, I removed the braid. After further heating at 340 ° C for 1 hour to cure,
After cooling, the spiral-shaped product, which is a laminated body, is removed from the stainless steel round bar, and a spiral tubular heater having a length of 100 cm.
Got This spiral tubular heater was spirally wound on a stainless pipe having a diameter of 10 mm, and a voltage of 50 V was applied to both ends. The temperature of the pipe was 150 ° C. and was maintained at a high temperature uniformly.

[0034]

Since the present invention is configured as described above, it has the following effects. The heat-resistant polymer tape with an adhesive of the present invention has good heat resistance of the tape, has high rigidity, and can be bonded even when the pressure at the time of bonding is low, so that the tape has good adhesion. It is suitable for a spiral tubular heater with good heat efficiency and shape retention.

[Brief description of drawings]

FIG. 1 is a sectional view of an example of an adhesive-resistant heat-resistant polymer tape for a spiral tubular heater.

FIG. 2 shows an example of a spiral tubular heater using a heat-resistant polymer tape with an adhesive for the spiral tubular heater of the present invention, which is cut in parallel with a spiral core. FIG.

FIG. 3 is a perspective view showing an example of a spiral tubular heater using a heat-resistant polymer tape with an adhesive for the spiral tubular heater of the present invention. 1 Heat-resistant polymer tape with adhesive for spiral tubular heater 2 Heat-resistant polymer tape A 3 forming inner layer Heat-resistant adhesive 3a Heat-resistant adhesive 3b in contact with inner layer Outer layer Heat-resistant adhesive 4 in contact with a heat-resistant polymer tape B 5 for forming an outer layer Flexible conductive substrate 10 Shape-retaining spiral tubular heater

─────────────────────────────────────────────────── ─── Continuation of 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 Ube City, Yamaguchi Daiji Kogushi, No. 1978 10 Ube Industries, Ltd. Ube Chemical Factory (56) Reference JP-A-11-149978 (JP, A) JP-A-11-135236 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) H05B 3/40 C09J 7/02

Claims (4)

(57) [Claims] 1. A laminate having a structure of a heat-resistant polymer tape A forming an inner layer of a spiral material, an adhesive forming an intermediate layer and a heat-resistant polymer tape B forming an outer layer. For a shape-retaining spiral tubular heater integrally provided with a flexible conductive base material that imparts conductivity between both ends in the longitudinal direction of any one of A heat-resistant polymer tape with adhesive for a spiral tubular heater, in which a heat-resistant adhesive is provided on one side of the tape, and the adhesive can be pressure-bonded at a low pressure and the water absorption rate is 1.8% or less. -P. 2. The heat-resistant polymer tape A and the heat-resistant polymer tape B each have a thickness of 35 to 200 μm, and at least one of them has a rigidity of 0.80 kg or more. A heat-resistant polymer tape with an adhesive for the spiral tubular heater according to 1. 3. An adhesive for a spiral tubular heater according to claim 1, wherein the heat-resistant polymer tape A and the heat-resistant polymer tape B are aromatic polyimide tapes. Heat resistant polymer tape with agent. 4. The heat-resistant polymer tape with an adhesive for a spiral tubular heater according to claim 1, wherein the adhesive can be pressure-bonded at a pressure of 10 kg / cm ² or less.