JPH0976429A - Heat-shrinkable tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat-shrinkable tube using an inner layer material capable of being crosslinked by various crosslinking methods and excellent in heat- shrinkable tube capacity and the bonding capacity with various adherends. SOLUTION: A heat-shrinkable tube is constituted of a compsn. wherein an outer layer material A is composed of crosslinked polyolefin, an inner layer material (B) consists of 55-90 pts.wt. of an ethylene copolymer (a), 1-20 pts.wt. of a polyamide resin (b) and 1-25 pts.wt. of a partially sapaonified ethylene/vinyl acetate copolymer (c) and the sum total amt. of (a), (b) and (c) is 100 pts.wt. and the component (b) is 0.7-10vol. times the component (c).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a heat-shrinkable tube capable of covering and sealing various kinds of covering members and having excellent adhesion performance with an adherend and excellent practical performance. The present invention relates to a heat-shrinkable tube having excellent properties.

[0002]

2. Description of the Related Art As heat-shrinkable tubes, there are polyethylene, ethylene-based copolymers, vinyl chloride, silicone rubber and the like, which are widely used as coating materials for joints and terminals of electric wires and cables. The manufacturing method of these heat-shrinkable tubes, in order to impart heat-shrinkable properties,
It is manufactured by carrying out cross-linking such as electron beam irradiation cross-linking, chemical cross-linking and water cross-linking, followed by heating and expanding in the radial direction and cooling. Further, since the heat-shrinkable tube is required to have properties such as insulation, water resistance, sealing property, and adhesiveness, a hot-melt adhesive is applied to the inner layer or formed into two layers for use. For example, Japanese Examined Patent Publication No. 56-17218 proposes that two layers of dimer acid-based polyamide are molded on the inner surface of a polyolefin resin and electron beam crosslinking is performed. Further, Japanese Patent Publication No. 59-5097 proposes a heat-shrinkable polyolefin tube in which a polyamide-based hot-melt adhesive having a specified softening temperature is provided on the inner wall. Further, Japanese Patent Publication No. 60-2177 discloses a heat recovery article in which an ethylene / vinyl acetate copolymer having a hydrolysis rate of 50 to 90% by weight and a polyamide resin having an amine value of 0.5 to 30 are provided on a necessary portion on one side. Proposed.

Further, in JP-A-5-247426, 20 to 70% by weight of a dimer acid-based polyamide and a maleic acid-modified polyolefin resin 80 to 3 are provided on the inner surface of a rubber or plastic outer layer tube having a heat recovery property.
A heat-shrinkable tube provided with a 0 wt% hot-melt adhesive layer has been proposed.

Japanese Patent Publication No. 1-29830 discloses that
A hot melt adhesive has been proposed in which 5 to 100 parts by weight of a terpene phenol resin or rosin having an acid value of 10 or more is added to 100 parts by weight of a polyolefin obtained by copolymerizing an unsaturated carboxylic acid or an anhydride thereof.

Further, in JP-A-2-139235, an outer layer is an ethylene / vinyl acetate copolymer, and an inner layer has a vinyl acetate content of 20 to 45% by weight and a melt index of 1.
Heat shrinkable articles have been proposed that are 0-100 g / 10 min ethylene / vinyl acetate copolymers.

Further, Japanese Patent Publication No. 6-49855 discloses that
A hot-melt adhesive having a composition similar to that of the inner layer material of the present invention has been proposed.

[0007]

The inner layer material of the heat-shrinkable tube is required to be a material that does not cause peeling or blistering after heat-shrinking in order to maintain water resistance and sealing performance. further,
Recently, there has been a demand for not only easy adhesion to the outer layer material but also strong adhesion to not only plastic or metal adherends but also fluorocarbon resin-coated adherends.

However, Japanese Patent Publication No. 56-
No. 17218 and Japanese Patent Publication No. 59-5097, and dimer acid polyamides and JP-A-60-21.
Hydrolysis rate shown in Japanese Patent Publication No. 77 50-90% by weight
Ethylene / vinyl acetate copolymer with an amine value of 0.5
When using polyamide resin of 30 to 30 as the inner layer material,
Excellent adhesion to metals and fluororesins, but poor adhesion to cross-linked polyolefin forming outer layer material and adhesion to polyolefin adherend, resulting in peeling of outer layer material and inner layer material and polyolefin adhesion There is a problem that peeling from the body easily occurs.

Further, 20 to 70% by weight of a dimer acid-based polyamide and a maleic acid-modified polyolefin resin 80 to 30 disclosed in JP-A-5-247426.
The inner layer material using the heat-melting type adhesive of wt% has a problem of adhesion performance and heat resistance with the adherend such as the outer layer material and polyethylene in the same manner as above, with a compounding composition containing many dimer acid-based polyamides. In the case of a compounded composition containing a large amount of maleic acid-modified polyolefin resin, the adhesiveness to an adherend coated with a fluororesin is insufficient, so that peeling from the adherend has been a problem.

When the hot melt adhesive disclosed in Japanese Patent Publication No. 1-29830 is used as the inner layer material, the adhesiveness to the adherend coated with the fluororesin is insufficient, The peeling from the adherend has been a problem. Further, when the amount of the terpene phenol resin or rosin having an acid value of 10 or more increases, there is a problem that deformation or sagging occurs due to heat at the time of crosslinking performed by water crosslinking and chemical crosslinking.

The heat-shrinkable article comprising an ethylene / vinyl acetate copolymer having a vinyl acetate content of 20 to 45% by weight, which is disclosed in JP-A-2-139235, is excellent in the adhesive performance between the outer layer material and the inner layer material, but is a fluororesin. Since the adhesiveness to the adherend coated with is insufficient, peeling from the adherend has been a problem.

The hot-melt adhesive of JP-B-6-49855 is used as an outer layer material and a low-density polyethylene adherend when the content of the ethylene / vinyl acetate copolymer is less than 50% by weight of the whole. However, there was a problem that the adhesiveness was poor.

Therefore, the present invention is a heat-shrinkable tube which solves the above problems, can be cross-linked by various cross-linking methods, can be hermetically sealed on various coating members, and has excellent adhesive performance with an adherend. Therefore, it is an object to obtain a heat-shrinkable tube having excellent adhesiveness between the outer layer material and the inner layer material and having extremely excellent practicality.

[0014]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of extensive studies to solve the above problems in heat shrinkable tubes.
Cross-linked polyolefin as the outer layer material, ethylene copolymer as the inner layer material, polyamide resin and partially saponified ethylene /
The inventors have found that the above-mentioned problems can be solved by constituting the composition of a vinyl acetate copolymer having a specific composition, and have reached the present invention.

That is, in the present invention, (A) the outer layer material is composed of crosslinked polyolefin, (B) the inner layer material is (a) ethylene copolymer 55 to 90 parts by weight, and (b) polyamide resin 1-2.
0 parts by weight and (c) 1 to 25 parts by weight of partially saponified ethylene / vinyl acetate copolymer, (a),
To provide a heat-shrinkable tube composed of a composition in which the total amount of (b) and (c) is 100 parts by weight, and the component (b) is in the range of 0.7 to 10 times the amount of the component (c). is there.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the crosslinked polyolefin used as the outer layer material (A) is a polyolefin obtained by crosslinking uncrosslinked polyolefin by a known crosslinking method. Examples of the uncrosslinked polyolefin include high-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, polyethylene such as high-molecular-weight polyethylene and ionomer resins, ethylene / vinyl acetate copolymers, ethylene / ethyl acrylate copolymers, and the like. One or more uncrosslinked polyolefins selected from ethylene copolymers are preferably used. Further, as a known crosslinking method for crosslinking the above-mentioned uncrosslinked polyolefin,
Electron beam cross-linking, chemical cross-linking, and water cross-linking are mainly known. The above-mentioned electron beam crosslinking is a method of irradiating an uncrosslinked polyolefin tube molded product with an electron beam of 5 to 40 MRad to crosslink. With the above-mentioned chemical crosslinking, after adding a peroxide such as dicumyl peroxide to the uncrosslinked polyolefin, it is charged into a tube molding machine to obtain a tube molded product, and further heated to a temperature not lower than the decomposition temperature of the peroxide. It is known to be a method of cross-linking. For example, when dicumyl peroxide is used, it is known to cross-link at about 240 ° C. The above-mentioned water-crosslinking is the production of a water-crosslinkable silane-grafted polyolefin by adding an unsaturated silane compound such as vinyltrimethoxysilane and a small amount of peroxide to uncrosslinked polyolefin and reacting them at a temperature of about 200 ° C. Then, this is mixed with a silanol condensation catalyst such as dibutyltin dilaurate, charged into a tube molding machine to obtain a tube molded article, and then crosslinked in warm water of about 80 to 100 ° C, or JP-B-62-15580. After mixing a silanol condensation catalyst such as dibutyltin dilaurate in a water-crosslinkable silane copolymerized polyolefin consisting of ethylene and an ethylenically unsaturated silane compound described in JP-A No. 2003-242242, and after introducing it into a tube molding machine to obtain a tube molded article, It is a method of performing water crosslinking in warm water of about 80 to 100 ° C. Further, the gel fraction indicating the degree of crosslinking is preferably about 40 to 75% in any crosslinking method from the viewpoint of the property of recovering the original shape and the property of thermal expansion in the radial direction.

In the present invention, specific examples of the (a) ethylene copolymer of the (B) inner layer material include ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer,
Ethylene / propylene copolymer, ethylene / butene-1
Examples thereof include copolymers and ethylene / methacrylic acid / acrylic acid ester copolymers. Further, it is produced by a known method such as direct copolymerization or graft copolymerization of α, β-unsaturated carboxylic acid components such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, fumaric acid and their monoesters. And a carboxyl-modified ethylene copolymer. In particular, maleic anhydride is 0.
Addition of a small amount of 1 to 2% by weight has a sufficient modifying effect and is preferable. Moreover, 50 parts by weight or less of low-density polyethylene can be blended with 100 parts by weight of the above-mentioned ethylene copolymer.

The ethylene component in the ethylene copolymer is not particularly limited, but is usually 55% by weight or more, preferably more than 85% by weight, particularly preferably 85.5% by weight or more, and the upper limit is not particularly limited. However, it is preferably 98% by weight or less. When two or more ethylene copolymers having different ethylene component contents are used in combination, the ethylene component amount is
The ratio of the total amount of ethylene components to the total amount of ethylene copolymers used in combination is considered.

When the low density polyethylene is blended, the total amount of the ethylene copolymer and the low density polyethylene is treated as the amount of the ethylene copolymer, and the low density polyethylene is regarded as the ethylene component. The ethylene component content in that case is not particularly limited as described above, but is usually 55% by weight or more, preferably more than 85% by weight, particularly preferably 85.5% by weight or more. In the case of water cross-linking and chemical cross-linking, from the viewpoint of the heat resistance of deformation and sagging of the inner layer material, the blending amount of the ethylene copolymer in the inner layer material is preferably 55 to 90 parts by weight, and less than 55 parts by weight, The heat resistance of the inner layer material becomes a problem, and if it exceeds 90 parts by weight, the adhesiveness of the fluororesin to the adherend is deteriorated, which is not preferable.

In the present invention, the (b) polyamide resin of the (B) inner layer material is preferably one obtained by reacting a polycarboxylic acid such as dimer acid with an amine component. For example, adding adipic acid, azelaic acid, sebacic acid, etc. to unsaturated fatty acids such as tall oil fatty acid and soybean oil fatty acid, and further reacting with ethylenediamine, hexamethylenediamine, isophoronediamine, xylylenediamine, alkanolamine, etc. A dimer acid polyamide having a molecular weight of 2000 to 30,000 obtained by
Alternatively, polycaproamide units (nylon 6 units),
Polyundecaamide unit (nylon 11 unit), polydodecamide unit (nylon 12 unit), polyhexamethylene adipamide unit (nylon 66 unit), polyhexamethylene sebacamide unit (nylon 610 unit), dimer acid polyamide A copolymer containing at least two or more polyamide-forming components such as Nylon 6
/ Polymer of dimer acid, nylon 12 / Polyamide of dimer acid, nylon 6/66/610, nylon 6/6
6 / Dimer acid polyamide, nylon 6/66/610
Examples include copolymers such as / 11 and nylon 6/66/610/12. Further, two or more components of the above polyamide resin may be blended and used. Further, a thermoplastic polyamide resin such as a polyether ester amide copolymer may be blended and used.

The melting point of the polyamide resin is preferably 150 ° C. or lower. The content of the polyamide resin in the inner layer material is 1 to 2 with respect to 100 parts by weight of the total of (a) to (c).
It is 0 part by weight, preferably 1.5 to 18 parts by weight, and less than 1 part by weight is not preferable because the effect of the present invention is small, and when it exceeds 20 parts by weight, the peel strength from the outer layer material decreases. In the present invention, the (c) partially saponified ethylene / vinyl acetate copolymer of the inner layer material (B) is about 30 to 90%, particularly 50 to 85% of the acetic acid ester of the ethylene / vinyl acetate copolymer. What is obtained by saponifying is preferable.
Further, partially saponified ethylene / vinyl acetate copolymers containing carboxyl groups such as α, β-unsaturated carboxylic acid components acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, fumaric acid and their monoesters. Coalescence can also be used, in particular maleic anhydride is
Addition of a small amount of 2% by weight has a sufficient modifying effect and is preferable. The content of the partially saponified ethylene / vinyl acetate copolymer in the inner layer material is preferably from 1 to 25 parts by weight, and when the content is less than 1 part by weight, the effect of the present invention is small. It is not preferable because the peeling strength of is decreased. The amount of ethylene component of the partially saponified ethylene / vinyl acetate copolymer is not particularly limited, but it is preferably 55% by weight or more in order to maintain heat resistance, and the upper limit is not particularly limited, but is 98% by weight or less. Is preferred. Further, the polyamide resin (b) has a compounding ratio of 0.7 to 10 times the amount of the partially saponified ethylene / vinyl acetate copolymer (c), and a compounding ratio of less than 0.7 times the amount. However, the adhesive performance to the fluororesin is insufficient, and a compounding ratio of more than 10 times is not preferable because the peel strength between the outer layer material and the polyolefin adherend is lowered.

(B) Inner layer material (a) Ethylene copolymer,
The blending method of the (b) polyamide resin and (c) partially saponified ethylene / vinyl acetate copolymer is not particularly limited, but for example, a method of melt mixing at a melting point or higher, a blending tube forming machine And the like. The ring-and-ball type softening temperature of the composition of the melt-mixed inner layer material is 160 ° C. or higher and 50 from the heat shrinkage temperature of the outer layer material in order not to impair the heat resistance of the present invention.
It is preferable that the temperature is higher than ° C.

In the present invention, the inorganic reinforcing material which can be blended in the composition of the inner layer material is a known inorganic filler or inorganic reinforcing material, and talc, calcium silicate, titanium oxide, zinc oxide and the like are preferable. Examples of tackifiers that can be added to the composition of the inner layer material include chroman-indene resin, chroman-indene-styrene resin, terpene resin, petroleum hydrocarbon resin and rosins. The blending amount of the inorganic reinforcing material and / or the tackifier is
There is no particular limitation, but if the content is 5 parts by weight or less with respect to 100 parts by weight of the inner layer material, the inorganic reinforcing material has an effect of improving heat resistance, and the tackifier particularly has an initial adhesiveness. The effect of improving the sex is obtained.

The styrene-isoprene block copolymer, the styrene-isoprene-styrene block copolymer, the styrene-butadiene block copolymer can be added to the outer layer material and / or the inner layer material within the range of not impairing the performance of the present invention. , Styrene-butadiene-styrene block copolymer, styrene elastomer such as styrene-ethylene-butadiene-styrene block copolymer and natural rubber, butyl rubber, acrylic rubber, polyester elastomer, thermoplastic elastomer such as polyurethane elastomer and epoxy compound and Polyethylene modified with a silane compound, an ethylene-based copolymer, and the like can also be added. Further, known flame retardants, colorants, clarifiers, plasticizers, ultraviolet ray blocking agents, antiaging agents and the like can be added.

The method for obtaining the heat-shrinkable tube of the present invention is not particularly limited, but a conventionally known method can be adopted. That is, two extruders are used to form a cylindrical shape through a two-layer tube die so that the inner layer material is on the inside and the outer layer material is on the outside, and then is formed into a predetermined size and circular shape by a homing device and cooled. It can be obtained by cutting or winding it into a predetermined length through a take-up machine. If the melt viscosity of the polymer used at this time is low or the solidification time is long, in order to maintain the circular shape and size of the molten tube extruded from the die, the homing part should be cooled sufficiently by the internal pressure method, vacuum homing method, etc. The target tube-molded product can be obtained by taking into consideration such factors as adjusting the length of the cooling zone, the cooling temperature, and reducing the frictional resistance of the sliding surface so that solidification and roundness shaping can be obtained. Further, the heat-shrinkable tube is manufactured by continuously or intermittently crosslinking, heating and expanding in the radial direction and cooling. The heat-shrinkable tube thus obtained has the property of recovering its original shape by heating above the melting point of the outer layer material (heat shrinking temperature), and the inner layer material firmly adheres to the adherend. .
In addition, it is possible to manufacture a heat-shrinkable tube having a multilayer structure using another material for the intermediate layer between the outer layer material and the inner layer material of the present invention.

The present invention uses a heat-shrinkable tube composed of a composition comprising a cross-linked polyolefin as the outer layer material, an ethylene copolymer, a polyamide resin and a partially saponified ethylene / vinyl acetate copolymer as the inner layer material. By doing so, it is possible to obtain a heat-shrinkable tube which can be cross-linked by various cross-linking methods, has excellent heat-shrinkable tube performance and adhesive performance, and can be covered and sealed by various coating members.

The heat-shrinkable tube thus obtained has excellent adhesiveness to various adherends, particularly adherends whose surface is made of a fluororesin or a polyolefin resin, and is very practical.

[0028]

EXAMPLES The effects of the present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the examples,% and parts are based on weight unless otherwise specified.

Crosslinking degree (gel fraction): Extraction was carried out for 12 hours at the boiling point of xylene using a Soxhlet extractor, and the proportion of the remaining insoluble component was taken as the crosslinking degree (gel fraction).

Peeling strength between the outer layer material and the inner layer material: The heat shrinkable tube is cut into a strip shape having a length of 100 mm and a width of 5 mm in the longitudinal direction, and a part of the outer layer material and the inner layer material is forcibly peeled and then pulled. A 180 ° C peel test was performed using a tester, and the value was taken as the peel strength.

Adhesive strength between the inner layer material and the fluororesin adherend: A sheet having a thickness of 1 mm was prepared from the inner layer material using a hot press at 150 ° C., and polyvinyl fluoride (a fluororesin commercially available from DuPont Co., Ltd. Product name Tedlar TT
R20BG4) was used to bond the inner layer material with a hot press at 120 ° C, and was cut into strips with a length of 100 mm and a width of 5 mm, after forcibly peeling off a part of the interior material and the fluororesin adherend. A 180 ° C peeling test was performed using a tensile tester, and the value was taken as the adhesive strength. The hot press temperature of 120 ° C. corresponds to the general heat shrink temperature of the low density polyethylene heat shrink tube.

Adhesive strength between the inner layer material and the low-density polyethylene adherend: heat shrinkage on the low-density polyolefin adherend of a pipe made of Mitsubishi Chemical's low-density polyethylene (trade name EH-30) with an outer diameter of 7 mm After inserting the tube, 120 ℃ × 2
Heat shrink was performed for 0 minutes. A slit having a width of 4 mm was inserted in the longitudinal direction of the pipe, a part of the pipe and the heat-shrinkable tube were forcibly peeled off, and a 180 ° peeling test was performed using a tensile tester, and the value was taken as the adhesive strength.

The target value of the above adhesive strength is set to a value of 1 kg / cm or more, which is difficult to peel with a human hand.

Performance of heat shrink tubing: Temperature and humidity 40
The heat-shrinkable tube was placed in a thermo-hygrostat set to ℃ x 95% RH for 24 hours, and the heat-shrinkable tube was put into a pipe made of Mitsubishi Chemical's low-density polyethylene (trade name EH-30) with an outer diameter of 7 mm. After inserting, the sample was heat-shrinked at 120 ° C. for 20 minutes, and peeling and swelling of the end surface of the heat-shrinkable tube were observed. In addition, this test is a performance evaluation of the heat-shrinkable tube for examining whether or not the heat-shrinkable tube can be covered and sealed by the covering member. Further, as the cause of the peeling of the end surface of the heat shrinkable tube, the adhesiveness between the covering member and the inner layer material, and the cause of the blistering of the heat shrinkable tube may be the influence of water in the inner layer material.

Heat resistance: A sheet inner layer material having a thickness of 1 mm prepared using a hot press at 150 ° C. was placed in warm water at 90 ° C. for 24 hours.
It was dipped in h and the appearance before and after dipping was observed, and the presence or absence of deformation and sagging was examined. The inner layer material, which is deformed and sags, has irregularities during chemical crosslinking or water crosslinking, and cannot uniformly coat and seal the coating member, resulting in swelling and defective adhesion of the tube after heat shrinkage.

Reference Example 1 About 35% of caproamide units (6 units of nylon), about 1
5% of dodecamide unit (12 units of nylon), about 20
% Hexamethylene adipamide unit (nylon 66 unit) and about 30% hexamethylene sebacamide unit (nylon 610 unit) polyamide copolymer were produced by a known method, and the melting point was measured by a scanning calorimeter. By the way, 108 ℃
Met. Further, the relative viscosity (ηr) measured at 25 ° C. and 0.5% concentration in concentrated sulfuric acid was 1.95.

Example 1 Low density polyethylene (trade name EH-30) manufactured by Mitsubishi Chemical Co., Ltd. was placed on the outside (outer layer material) of two extruders, and ethylene / vinyl acetate manufactured by Mitsui DuPont Polychemical Co., Ltd. Polymer (trade name: Evaflex 260, vinyl acetate content 28
%) 15 parts, ethylene / vinyl acetate copolymer manufactured by Sumitomo Chemical Co., Ltd. (trade name Ebateto D2021, vinyl acetate content 10%) 62 parts, dimer acid polyamide manufactured by Henkel Hakusui Co., Ltd. (trade name Macromelt 6239) A polymer blended with 15 parts and 8 parts of a partially saponified ethylene / vinyl acetate copolymer (trade name Dumiran C-2270) manufactured by Takeda Pharmaceutical Co., Ltd. with a saponification rate of about 70% is the inner side (inner layer material). As shown in Fig. 4, the molten polymer is extruded onto a cylinder through an internal pressure tube two-layer molding die and cooled in water through a sizing plate to obtain an outer diameter of 7 mm, an inner diameter of 6 mm, an outer layer material thickness of 0.8 mm, and an inner layer material of 0.8 mm. Thickness 0.
A 2 mm tube molded product was obtained. Next, by irradiating with an electron beam of 10 Mrad to make the gel fraction of the outer layer material 57%,
The diameter was expanded 1.5 times with a diameter expansion device whose temperature was adjusted to 0 ° C. to obtain a heat-shrinkable tube (A-1).

Example 2 Two extruders were used for 100 parts of silane copolymerized low-density polyethylene (trade name: Linklon XF800T) manufactured by Mitsubishi Chemical Co., Ltd., and 100 parts of a silane-based catalyst master (trade name: Linkron manufactured by Mitsubishi Chemical Co., Ltd.). LZ013) 5 parts compounded on the outside, Example 1
A tube molded product was obtained under the same conditions as in Example 1, so that the inner layer material having the same composition as in (1) was placed inside. Then, the gel fraction of the outer layer material was adjusted to 6 by performing water crosslinking for 24 hours in a warm water tank at 90 ° C.
6%, the diameter was expanded 1.5 times with a diameter expansion device whose temperature was adjusted to 140 ° C. as in Example 1, and the heat-shrinkable tube (A-
2) was obtained.

Example 3 Two extruders were combined with 100 parts of low-density polyethylene (trade name EH-30, manufactured by Mitsubishi Chemical Corporation) and 0.5 part of dicumyl peroxide on the outside, and Example 1 was used. A tube molded product was obtained under the same conditions as in Example 1, so that the inner layer material having the same composition as in (1) was placed inside. Next, the gel fraction of the outer layer material was adjusted to 5 by passing through a heating tank at 240 ° C. for 50 seconds for chemical crosslinking.
9%, the diameter was expanded 1.5 times with a diameter expansion device whose temperature was adjusted to 140 ° C. as in Example 1, and the heat-shrinkable tube (A-
3) was obtained.

Example 4 Silane-grafted low-density polyethylene (trade name: Mordex S161) manufactured by Sumitomo Bakelite Co., Ltd. in two extruders
On the outside, a material containing 100 parts of 5 parts of a MITSUBISHI CHEMICAL CO., LTD. Tin-based catalyst master (trade name: Linklon LZ013),
A tube molded product was obtained under the same conditions as in Example 1 such that the inner layer material having the same composition as in Example 1 was placed inside. Then 90
The gel fraction of the outer layer material was adjusted to 65% by performing water crosslinking for 24 hours in a warm water tank at ℃, and the diameter was expanded to 1.5 times with the diameter expanding device whose temperature was adjusted to 140 ℃ as in Example 1. Then, a heat shrinkable tube (A-4) was obtained.

Example 5 A material in which 100 parts of silane copolymerized polyethylene (trade name: Linklon XF800T) manufactured by Mitsubishi Chemical Co., Ltd. and 5 parts of a tin-based catalyst master (trade name: Linklon LZ013) were compounded in two extruders. Outside, 15 parts of ethylene / vinyl acetate copolymer (trade name Evaflex 260) manufactured by Mitsui-DuPont Polychemical Co., Ltd., ethylene / vinyl acetate copolymer (trade name EvaTate D202 manufactured by Sumitomo Chemical Co., Ltd.)
1) 62 parts, 15 parts of the polyamide copolymer of Reference Example 1 and partially saponified ethylene / vinyl acetate copolymer manufactured by Takeda Pharmaceutical Co., Ltd. (trade name: Dumiran C-2270) 8
Example 1 so that the polymer in which the parts are blended comes inside
A tube molded product was obtained under the same conditions as above. Next, the gel fraction of the outer layer material was adjusted to 65% by performing water crosslinking for 24 hours in a warm water tank at 90 ° C., and as in Example 1, it was 1.5 times with a diameter expansion device controlled at 140 ° C. The diameter of the heat-shrinkable tube (A
-5) was obtained.

Example 6 Two extruders were used for 100 parts of silane copolymerized low-density polyethylene (trade name: Linklon XF800T) manufactured by Mitsubishi Chemical Co., Ltd., and 100 parts of a silane-based catalyst master (trade name: Linkron manufactured by Mitsubishi Chemical Co., Ltd.). LZ013), 5 parts, Sumitomo Chemical Co., Ltd. ethylene / vinyl acetate copolymer (trade name Evatate D2021)
A tube molded product was obtained under the same conditions as in Example 1 such that 25 parts by weight of the compounded material were on the outside and the inner layer material having the same composition as in Example 1 was on the inside. Next, in a warm water tank at 90 ° C, 24
Water cross-linking for a time to make the gel fraction of the outer layer material 56%,
As in Example 1, the diameter expansion device was adjusted to 140 ° C.
The diameter was expanded 5 times to obtain a heat-shrinkable tube (A-6).

Example 7 Mitsubishi Co., Ltd. silane copolymer low-density polyethylene (trade name: Linklon XF800T) in 100 parts of Mitsubishi Chemical Co., Ltd. tin-based catalyst master (trade name: Linkron) LZ013) 5 parts compounded outside, 77 parts of maleic anhydride modified ethylene / methacrylic acid / acrylic acid ester copolymer (trade name HPR, NR-301) manufactured by Mitsui DuPont Polychemical Co., Ltd., Henkel White Water (stock)
Dimer acid polyamide (trade name: Macromelt 623
9) 15 parts and partially saponified ethylene / vinyl acetate copolymer manufactured by Takeda Pharmaceutical Co., Ltd. (trade name: Dumiran C
A tube molded product was obtained under the same conditions as in Example 1 so that the polymer obtained by blending 8 parts of (2270) was on the inner side (inner layer material). Next, water cross-linking was performed for 24 hours in a warm water tank at 90 ° C. to make the gel fraction of the outer layer material 66%, and 1.5 times the same as in Example 1 with a diameter-expanding device whose temperature was adjusted to 140 ° C. The diameter was expanded to obtain a heat-shrinkable tube (A-7).

Example 8 Mitsubishi Co., Ltd. silane copolymer low density polyethylene (trade name: Linklon XF800T) in 100 parts of Mitsubishi Chemical Co., Ltd. tin-based catalyst master (trade name: Linkron) LZ013) 5 parts compounded on the outside, 15 parts Mitsui-DuPont vinyl polychemate 28%), Sumitomo Chemical Co., Ltd. ethylene / vinyl acetate copolymer (trade name EvaTate D2021, vinyl acetate content 10) %) 59 copies,
15 parts dimer acid polyamide (trade name Macromelt 6239) manufactured by Henkel Hakusui Co., Ltd., 8 parts partially saponified ethylene / vinyl acetate copolymer (trade name Dumilan C-2270) manufactured by Takeda Pharmaceutical Co., Ltd. and Fuji. Talc (trade name LMS-2) is an inorganic reinforcing material manufactured by Talc Industry Co., Ltd.
00) A tube molded product was obtained under the same conditions as in Example 1 such that the polymer obtained by blending 3 parts thereof was on the inner side (inner layer material). Then, water crosslinking was performed in a warm water tank at 90 ° C. for 24 hours to adjust the gel fraction of the outer layer material to 66%.
The diameter was expanded 1.5 times with a diameter-expanding device whose temperature was adjusted to 40 ° C. to obtain a heat-shrinkable tube (A-8).

Example 9 Two extruders were used for 100 parts of silane copolymerized low-density polyethylene (trade name: Linklon XF800T) manufactured by Mitsubishi Chemical Co., Ltd., and 100 parts of a silane-based catalyst master (trade name: Linkron manufactured by Mitsubishi Chemical Co., Ltd.). LZ013) is mixed with 5 parts of the material on the outside, and an ethylene / vinyl acetate copolymer (trade name: Evaflex 260, vinyl acetate content: 2 manufactured by Mitsui DuPont Polychemical Co., Ltd.) is used.
8%) 15 parts, Sumitomo Chemical Co., Ltd. ethylene / vinyl acetate copolymer (trade name Ebateto D2021, vinyl acetate content 10%) 59 parts, Henkel Hakusui Co., Ltd. dimer acid polyamide (trade name Macromelt 6239) ) 15 copies,
8 parts of partially saponified ethylene / vinyl acetate copolymer (trade name Dumiran C-2270) manufactured by Takeda Pharmaceutical Co., Ltd. and chroman indene styrene resin (commercial product) which is a tackifier manufactured by Nippon Steel Chemical Co., Ltd. Name Exlon N-10
0) A tube molded product was obtained under the same conditions as in Example 1 such that the polymer obtained by blending 3 parts was on the inner side (inner layer material).
Then, water crosslinking was carried out in a warm water tank at 90 ° C. for 24 hours so that the gel fraction of the outer layer material was 66%, and the gel ratio was 140% as in Example 1.
The diameter was expanded 1.5 times with a diameter expansion device whose temperature was adjusted to ° C to obtain a heat-shrinkable tube (A-9).

Example 10 Mitsubishi Co., Ltd. silane copolymerized low-density polyethylene (trade name: Linklon XF800T) in 100 parts of Mitsubishi Chemical Co., Ltd. tin-based catalyst master (trade name: Linkron) LZ013) 5 parts blended material on the outside, 77 parts ethylene / vinyl acetate copolymer manufactured by Sumitomo Chemical Co., Ltd. (trade name Evertate D2021, vinyl acetate content 10%),
15 parts of dimer acid polyamide (trade name: Macromelt 6239) manufactured by Henkel Hakusui Co., Ltd. and Takeda Pharmaceutical Co., Ltd.
A tube molded product was obtained under the same conditions as in Example 1, so that the polymer blended with 8 parts of the partially saponified ethylene / vinyl acetate copolymer (trade name Dumilan C-2270) was placed inside (inner layer material). It was Next, 2 in a warm water bath at 90 ° C
Water-crosslinking was carried out for 4 hours to make the gel fraction of the outer layer material 66%, and the diameter was expanded 1.5 times with a diameter expansion device controlled to 140 ° C. as in Example 1 to obtain a heat-shrinkable tube ( A-10) was obtained.

Example 11 Two extruders were used for 100 parts of silane copolymerized low-density polyethylene (trade name: Linklon XF800T) manufactured by Mitsubishi Chemical Co., Ltd., and 100 parts of a silane-based catalyst master (trade name: Linkron manufactured by Mitsubishi Chemical Co., Ltd.). LZ013) is mixed with 5 parts of the material on the outside, and 57 parts of an ethylene / vinyl acetate copolymer manufactured by Sumitomo Chemical Co., Ltd. (trade name: Evatate D2021, vinyl acetate content 10%),
Low density polyethylene (trade name EH-3 manufactured by Mitsubishi Chemical Corporation)
0) 20 parts, 15 parts dimer acid polyamide (trade name: Macromelt 6239) manufactured by Henkel Hakusui Co., Ltd. and partially saponified ethylene / vinyl acetate copolymer (trade name: Dumiran C-2270) manufactured by Takeda Pharmaceutical Co., Ltd. A tube molded product was obtained under the same conditions as in Example 1 so that the polymer obtained by blending 8 parts was on the inner side (inner layer material). Next, water cross-linking was performed for 24 hours in a warm water tank at 90 ° C. to make the gel fraction of the outer layer material 66%, and 1.5 times the same as in Example 1 with a diameter-expanding device whose temperature was adjusted to 140 ° C. Expand the diameter to expand the heat shrink tube (A
-11) was obtained.

Example 12 As an inner layer material, an ethylene / vinyl acetate copolymer manufactured by Mitsui DuPont Polychemical Co., Ltd. (trade name: Evaflex 2)
60, vinyl acetate content 28%) 77 parts, dimer acid polyamide manufactured by Henkel Hakusui Co., Ltd. (trade name: Macromelt 6)
239) 15 parts by weight and a partially saponified ethylene / vinyl acetate copolymer (trade name: Dumiran C-2270) manufactured by Takeda Pharmaceutical Co., Ltd. (8 parts) were used. A heat shrinkable tube (A-12) having a gel fraction of the outer layer material of 66% was obtained by the production method.

Comparative Example 1 As the inner layer material without adding the ethylene copolymer of the inner layer material composition of Example 2 as the inner layer material, dimer acid polyamide (trade name: Macromelt 6239) manufactured by Henkel Hakusui Co., Ltd.
65 parts, partially saponified ethylene / vinyl acetate copolymer manufactured by Takeda Pharmaceutical Co., Ltd. (trade name: Dumiran C-227)
0) A heat-shrinkable tube (B-1) having a gel fraction of 66% as the outer layer material was obtained by the same manufacturing method as in Example 2 except that 35 parts of a polymer was used.

Comparative Example 2 As an inner layer material without adding the dimer acid polyamide of the inner layer material composition of Example 2 as an inner layer material, an ethylene / vinyl acetate copolymer manufactured by Mitsui DuPont Polychemical Co., Ltd. (trade name: Evaflex) was used. 260, vinyl acetate content 28%) 1
5 parts, Sumitomo Chemical Co., Ltd. ethylene / vinyl acetate copolymer (trade name Evatate D2021, vinyl acetate content 1
0%) 62 parts, partially saponified ethylene / vinyl acetate copolymer manufactured by Takeda Pharmaceutical Co., Ltd. (trade name Dumilan C-
2270) A heat-shrinkable tube (B-2) having a gel fraction of 66% as the outer layer material was obtained by the same manufacturing method as in Example 2 except that 23 parts of the polymer was blended.

Comparative Example 3 As an inner layer material without adding the partially saponified ethylene / vinyl acetate copolymer of the inner layer material composition of Example 2, ethylene / acetic acid manufactured by Mitsui DuPont Polychemical Co., Ltd. was used. Vinyl copolymer (trade name: Evaflex 260,
15 parts of vinyl acetate content 28%), ethylene / vinyl acetate copolymer manufactured by Sumitomo Chemical Co., Ltd. (trade name: Evatate D2)
No. 021, vinyl acetate content 10%) 62 parts and Henkel Hakusui Co., Ltd. dimer acid polyamide (trade name Macromelt 6239) 23 parts were used, except that a blended polymer was used. A heat-shrinkable tube (B-3) having a gel fraction of 66% was obtained.

Comparative Example 4 As an inner layer material, an ethylene / vinyl acetate copolymer manufactured by Mitsui DuPont Polychemical Co., Ltd. (trade name: Evaflex 2)
Example except that a blend polymer of 60 parts, vinyl acetate content 28%) 20 parts, and Sumitomo Chemical Co., Ltd. ethylene / vinyl acetate copolymer (trade name Ebate D2021, vinyl acetate content 10%) 80 parts were used. The heat shrinkable tube (B-
4) was obtained. Comparative Example 5 In addition to using dimer acid polyamide (trade name: Macromelt 6239) manufactured by Henkel Hakusui Co., Ltd. as the inner layer material,
With the same manufacturing method as in Example 2, the gel fraction of the outer layer material was 66.
% Heat-shrink tube (B-5) was obtained.

Comparative Example 6 As an inner layer material, a partially saponified ethylene / vinyl acetate copolymer manufactured by Takeda Pharmaceutical Co., Ltd. (trade name: Dumiran C-
2270) was used, and the heat-shrinkable tube (B-) having the gel fraction of the outer layer material of 66% was manufactured by the same manufacturing method as in Example 2.
6) was obtained.

Comparative Example 7 As an inner layer material, an ethylene / vinyl acetate copolymer manufactured by Mitsui DuPont Polychemical Co., Ltd. (trade name: Evaflex 2)
60, vinyl acetate content 28%) 45 parts, dimer acid polyamide manufactured by Henkel Hakusui Co., Ltd. (trade name: Macromelt 6)
239) 30 parts and a partially saponified ethylene / vinyl acetate copolymer (trade name: Dumilan C-2270) manufactured by Takeda Pharmaceutical Co., Ltd. 25 parts were used in the same manner as in Example 2 except that a polymer blended was used. A heat shrinkable tube (B-7) having a gel fraction of the outer layer material of 66% was obtained by the production method.

Comparative Example 8 As an inner layer material, 45 parts of an ethylene / vinyl acetate copolymer manufactured by Sumitomo Chemical Co., Ltd. (trade name: Evertate D2021, vinyl acetate content: 10%), dimer acid polyamide manufactured by Henkel Hakusui Co., Ltd. Name Macromelt 6239) 30 parts and partially saponified ethylene produced by Takeda Pharmaceutical Co., Ltd./
Vinyl acetate copolymer (trade name Dumilan C-2270)
Example 2 except that a polymer blended with 25 parts was used.
A heat shrinkable tube (B-8) having a gel fraction of the outer layer material of 66% was obtained by the same manufacturing method as described above.

Comparative Example 9 As an inner layer material, 95 parts of an ethylene / vinyl acetate copolymer manufactured by Sumitomo Chemical Co., Ltd. (trade name: Evertate D2021, vinyl acetate content: 10%), dimer acid polyamide manufactured by Henkel Hakusui Co., Ltd. (commercial product) Macromelt 6239) 3 parts and partially saponified ethylene / vinyl acetate copolymer (trade name Dumiran C-2270) manufactured by Takeda Pharmaceutical Co., Ltd. 2
A heat-shrinkable tube (B-9) having a gel fraction of 66% as the outer layer material was obtained by the same manufacturing method as in Example 2 except that a polymer obtained by blending parts was used.

Comparative Example 10 77 parts of an ethylene / vinyl acetate copolymer (trade name: Evatate D2021, vinyl acetate content 10%) manufactured by Sumitomo Chemical Co., Ltd. as an inner layer material, and a mixing ratio of a polyamide resin were partially saponified. For ethylene / vinyl acetate copolymer,
5 parts of dimer acid polyamide (trade name: Macromelt 6239) manufactured by Henkel Hakusui Co., Ltd. and a partially saponified ethylene / vinyl acetate copolymer manufactured by Takeda Pharmaceutical Co., Ltd. Name Dumiran C-227
0) A heat shrinkable tube (B-10) having a gel fraction of 66% as the outer layer material was obtained by the same production method as in Example 2 except that a polymer obtained by blending 18 parts was used.

Comparative Example 11 77 parts of an ethylene / vinyl acetate copolymer (trade name: Evatate D2021, vinyl acetate content 10%) manufactured by Sumitomo Chemical Co., Ltd. as an inner layer material, and a mixing ratio of a polyamide resin were partially saponified. For ethylene / vinyl acetate copolymer,
A dimer acid polyamide (trade name: Macromelt 6239) manufactured by Henkel Hakusui Co., Ltd. with a compounding ratio exceeding 10 times.
5 parts and partially saponified ethylene / vinyl acetate copolymer manufactured by Takeda Pharmaceutical Co., Ltd. (trade name: Dumiran C-22
70) Other than using a polymer blended with 1.5 parts,
With the same manufacturing method as in Example 2, the gel fraction of the outer layer material was 66.
% Heat-shrink tube (B-11) was obtained.

The amount of ethylene component in the ethylene / vinyl acetate copolymer which is the component (a) of the inner layer material of the present invention used in Examples and Comparative Examples, the adhesiveness between the inner layer material and the outer layer material, the inner layer material and the fluororesin, and The adhesion with the low-density polyethylene adherend was evaluated, the heat resistance of deformation or sagging in warm water was evaluated, and the heat-shrinkable tube performance was measured. The results are shown in Table 1.

[Table 1]

From Table 1, the inner layer material of the heat-shrinkable tube obtained in the example has an adhesiveness of 1 kg / cm or more with the outer layer material, the fluororesin and the low-density polyethylene adherend, and is excellent in the adhesiveness. It was Moreover, the obtained heat-shrinkable tube was also excellent in heat-shrinkable tube performance. Furthermore, there was no deformation or sagging in warm water, and it was excellent in heat resistance. However,
The inner layer material of Example 12 can be used if it is a production method by electron beam crosslinking, but is inferior in heat resistance. The inner layer material not containing the ethylene copolymer of Comparative Example 1 was inferior in the adhesiveness to the outer layer material and the low-density polyethylene adherend and the heat-shrinkable tube performance, and the polyamide resin of Comparative Example 2 and Comparative Example 3 was blended. The inner layer material that does not contain the partially saponified ethylene / vinyl acetate copolymer is inferior in adhesion to the outer layer material, the fluororesin and the low density polyethylene adherend and the heat shrinkable tube performance. The inner layer material of Comparative Example 4 only with the ethylene copolymer was inferior in adhesiveness to the fluororesin, and the inner layer material of Comparative Example 5 only with the polyamide resin was excellent in adhesiveness to the outer layer material and the low-density polyethylene adherend. The inner layer material which is inferior in heat resistance and heat-shrinkable tube performance and which is only partially saponified ethylene / vinyl acetate copolymer of Comparative Example 6 has an adhesive property with an outer layer material, a fluororesin and a low density polyethylene adherend. Inferior in heat resistance and heat-shrinkable tube performance, the inner layer materials of Comparative Examples 7 and 8 containing 45 parts of the vinyl acetate content of 28% and the ethylene / vinyl acetate copolymer having a content of 10% of less than 50 parts were used. , Inferior adhesion to outer layer material and low-density polyethylene adherend, heat resistance and heat-shrinkable tube performance, and compounding amount of ethylene / vinyl acetate copolymer of Comparative Example 9 was 90.
The inner layer material containing 95 parts by weight or more was inferior in adhesiveness to the fluororesin adherend. The inner layer material having a blending ratio of less than 0.7 times that of the partially saponified ethylene / vinyl acetate copolymer of Comparative Example 10 had poor adhesion to the fluororesin adherend. The inner layer material of Comparative Example 11 in which the compounding ratio of the polyamide resin exceeds 10 times that of the partially saponified ethylene / vinyl acetate copolymer has excellent adhesiveness to the fluororesin adherend. However, the adhesiveness between the outer layer material and the low-density polyethylene adherend and the heat-shrinkable tube performance were poor.

From the results of Examples and Comparative Examples, the heat-shrinkable tube of the present invention can be crosslinked by various crosslinking methods,
It is clear that the heat shrinkable tube performance and the adhesive performance are excellent.

[0062]

INDUSTRIAL APPLICABILITY The present invention uses a cross-linked polyolefin as the outer layer material,
By using a heat shrinkable tube composed of a composition comprising an ethylene copolymer, a polyamide resin and a partially saponified ethylene / vinyl acetate copolymer as the inner layer material, it is possible to crosslink by various crosslinking methods. Since a heat-shrinkable tube having excellent heat-shrinkable tube performance and adhesiveness and capable of covering and sealing various coating members can be obtained, it is expected to be used for various applications as a heat-shrinkable tube.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 29, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 27/28 102 B32B 27/28 102 27/34 27/34 C08L 23/08 C08L 23/08 LDM LDM // B29K 23:00 105: 02 B29L 9:00 23:00

Claims (18)

[Claims] 1. An outer layer material (A) comprises a cross-linked polyolefin, and an inner layer material (B) (a) an ethylene copolymer 55-90.
Parts by weight, (b) 1 to 20 parts by weight of polyamide resin and (c) 1 to 25 parts by weight of partially saponified ethylene / vinyl acetate copolymer, and a total of (a), (b), and (c). 100 parts by weight, component (b) is 0.7 of component (c)
A heat-shrinkable tube composed of a composition in the range of 10 to 10 times. 2. The heat-shrinkable tube according to claim 1, wherein the crosslinked polyolefin of the outer layer material (A) is a water-crosslinked polyolefin. 3. The heat-shrinkable tube according to claim 2, wherein the crosslinked polyolefin of the outer layer material (A) is obtained by crosslinking a silane-grafted polyolefin. 4. The heat shrinkage according to claim 2, wherein the crosslinked polyolefin of the outer layer material (A) comprises a crosslinked silane copolymerized polyolefin obtained by copolymerizing ethylene and an ethylenically unsaturated silane compound. tube. 5. The (A) outer layer material is a water-crosslinked polyolefin 10.
The heat-shrinkable tube according to claim 2, which contains 50 parts by weight or less of a non-crosslinkable polyolefin with respect to 0 parts by weight. 6. The heat-shrinkable tube according to claim 1, wherein the outer layer material (A) is made of a crosslinked polyolefin crosslinked with an electron beam. 7. The heat-shrinkable tube according to claim 1, wherein the outer layer material (A) is a cross-linked polyolefin cross-linked with a peroxide. 8. (a) The ethylene copolymer is an ethylene / vinyl acetate copolymer, an ethylene / ethyl acrylate copolymer, an ethylene / propylene copolymer, an ethylene / butene-1 copolymer and an ethylene methacrylic acid acrylic ester. The heat-shrinkable tube according to claim 1, wherein the heat-shrinkable tube is one or more kinds selected from copolymers. 9. The heat-shrinkable tube according to claim 1 or 8, wherein the ethylene copolymer (a) is an ethylene copolymer modified with maleic anhydride. 10. An ethylene copolymer (a) having an ethylene component content of more than 85% by weight.
The heat-shrinkable tube according to any one of 1. 11. The heat-shrinkable tube according to claim 1, wherein 50 parts by weight or less of low-density polyethylene is further mixed with 100 parts by weight of the ethylene copolymer (a). 12. The heat-shrinkable tube according to claim 1, wherein the polyamide resin (b) comprises a dimer acid-based polyamide resin and / or a polyamide copolymer. 13. The saponification ratio of the acetic ester portion of (c) the partially saponified ethylene / vinyl acetate copolymer is 30 to 9.
The heat-shrinkable tube according to claim 1, wherein the heat-shrinkable tube is made of 9% ethylene / vinyl acetate copolymer. 14. The partially saponified ethylene / vinyl acetate copolymer (c) according to claim 1, wherein the partially saponified ethylene / vinyl acetate copolymer comprises a carboxyl group-containing partially saponified ethylene / vinyl acetate copolymer. Heat shrink tube. 15. The composition according to claim 1, which comprises 5 parts by weight or less of an inorganic reinforcing material and / or a tackifier based on 100 parts by weight of the composition of the inner layer material (B). Heat shrink tube. 16. The heat-shrinkable tube according to claim 14, wherein the inorganic reinforcing material is one or more of talc, calcium silicate, titanium oxide and zinc oxide. 17. The tackifier is a chroman indene resin,
The heat-shrinkable tube according to claim 15, comprising one or more of chroman-indene-styrene resin, terpene resin, rosins, and petroleum hydrocarbon resin. 18. The heat-shrinkable tube according to claim 1, which is used by being adhered to a fluororesin adherend, an adherend whose surface is coated with a fluororesin, and / or a polyolefin resin adherend.