WO2019003527A1

WO2019003527A1 - Heat recovery article and covered body covered by said heat recovery article

Info

Publication number: WO2019003527A1
Application number: PCT/JP2018/012198
Authority: WO
Inventors: 太郎藤田; 西川　信也; 遼太福本; 智山崎; 翔太町中; 修司東; 晃一郎狩野
Original assignee: 住友電工ファインポリマー株式会社; 住友電気工業株式会社
Priority date: 2017-06-27
Filing date: 2018-03-26
Publication date: 2019-01-03
Also published as: WO2019003319A1

Abstract

The heat recovery article according to one embodiment of the present invention is a cylindrical heat recovery article equipped with a substrate layer, wherein the water vapor permeability is 0.1 g/m2∙day or less when the average thickness of the substrate layer after shrinkage is 100 μm.

Description

Heat recovery article and cover coated with the heat recovery article

The present invention relates to a heat recovery article and a cover coated with the heat recovery article.
This application claims the priority based on PCT International Application No. PCT / JP2017 / 023644 filed on June 27, 2017, and incorporates all the contents described in the PCT International Application.

Products having low resistance to water vapor, such as food, medical equipment, batteries containing lithium ions, displays made of organic EL, liquid crystal, etc. as materials, need to prevent the intrusion of water vapor during storage or use.

On the other hand, a barrier label comprising a substance layer having high water vapor barrier properties and an adhesive layer has been proposed (see Japanese Patent Application Laid-Open No. 5-123378). This barrier label is in the form of a sheet, and is affixed to the periphery of a container for containing the above-mentioned product having low resistance to water vapor. And, the barrier label reduces the penetration of water vapor into the container.

Unexamined-Japanese-Patent No. 5-123378

The heat recovery article according to one aspect of the present invention is a cylindrical heat recovery article provided with a base material layer, and the water vapor transmission rate is 0.1 g when the average thickness of the base material layer after shrinkage is 100 μm. / M ² · day or less.

FIG. 1 is a perspective view of a heat recovery article according to an embodiment of the present invention.

[Problems to be solved by the present disclosure]
The barrier label described in the above-mentioned publication adheres a sheet-like label to the periphery of the container, and therefore can not avoid the entry of water vapor from the joint of the end. Further, since the barrier label of the above-mentioned publication is attached by the adhesive layer, water vapor easily infiltrates due to a lack of adhesion or peeling at the curved surface portion of the container. Therefore, it can not be said that the barrier label described in the above publication has a sufficiently high water vapor penetration preventing effect.

The present invention has been made based on the circumstances as described above, and provides a heat recovery article which is easy to coat and has a high water vapor penetration preventing effect, and a cover coated with the heat recovery article. The purpose is

[Effect of the present disclosure]
The heat recovery article according to one aspect of the present invention is easy to coat and has a high water vapor penetration preventing effect. Therefore, the cover coated with the heat recovery article is less susceptible to the penetration of water vapor into the interior.

Description of the embodiment of the present invention
The heat recovery article according to one aspect of the present invention is a cylindrical heat recovery article provided with a base material layer, and the water vapor transmission rate is 0.1 g when the average thickness of the base material layer after shrinkage is 100 μm. / M ² · day or less.

The heat recovery article coats the coated object by shrinkage, so that the coating is easy and the heat recovery article adheres to the object to be coated. In addition, the heat recovery article is cylindrical and thus has no seam. For this reason, by covering with the said heat recovery article, a crevice does not produce easily between the heat recovery article concerned and a covering subject, and it can control the penetration of water vapor. Moreover, since the water vapor transmission rate when the average thickness of the base material layer after shrinkage is 100 μm is equal to or less than the above-mentioned upper limit, the water vapor which permeates through the heat recovery article can also be reduced. Therefore, the heat recovery article is easy to coat and has a high water vapor penetration preventing effect.

The main component of the base layer is preferably polychlorotrifluoroethylene. Because polychlorotrifluoroethylene has a low water vapor transmission rate, it can further reduce the water vapor that permeates through the heat recovery article.

When the main component of the base layer is polychlorotrifluoroethylene, the base layer may further contain a fluororubber. When the base material layer further contains a fluororubber, the elastic modulus of the base material layer is reduced and the elongation is increased, so that the heat recovery article is easily expanded. Further, by blending fluororubber with polychlorotrifluoroethylene, it is possible to suppress the progress of crystallization of polychlorotrifluoroethylene at the time of heating. Therefore, by containing the polychlorotrifluoroethylene as the main component of the base material layer and further containing a fluororubber, the heat recovery article can maintain its water vapor barrier property and function (in particular, tensile elongation) by heating. Etc.) can be suppressed.

It is preferable that the content rate of the said fluororubber in the resin component contained in the said base material layer is 10 to 50 mass%. When the base material layer contains polychlorotrifluoroethylene as the main component and further contains a fluororubber, the content ratio of the fluororubber in the resin component contained in the base layer is within the above range The crystallization of polychlorotrifluoroethylene can be better suppressed while minimizing the decrease in water vapor barrier properties of the heat recovery article, and the mechanical properties of the heat recovery article can be easily maintained.

In the heat recovery article, the water vapor transmission rate is preferably 0.04 g / m ² · day or less. When the water vapor transmission rate of the heat recovery article is 0.04 g / m ² · day or less, it is possible to further reduce the water vapor that permeates through the heat recovery article.

The base layer may be crosslinked. By crosslinking the constituent material of the base layer in this manner, the heat resistance is improved.

It is preferable that the crosslinking of the base material layer be crosslinking by electron beam irradiation. Electron beam irradiation crosslinking can increase the production efficiency because the crosslinking time is short.

It is preferable that the crosslinking of the base material layer be crosslinking via a crosslinking aid. By using a crosslinking aid, extrusion processability is improved and crosslinking efficiency is enhanced. For this reason, by making the crosslinking of the above-mentioned base material layer into crosslinking via a crosslinking auxiliary agent, the heat resistance is further improved and the processability is improved, so the gap between the heat recovery article and the object to be coated Can be more difficult to occur. Therefore, the penetration of water vapor can be further suppressed.

The heat recovery article may have a multilayer structure, and at least one layer of the multilayer structure may be constituted by the base layer. With such a configuration, it is possible to impart further different properties to the heat recovery article by the other layers while enhancing the penetration prevention effect of water vapor by the base material layer.

The covering according to another aspect of the present invention is covered by the heat recovery article.

The covering is covered by the heat recovery article, so that the water vapor is less likely to penetrate inside. Accordingly, the coating is suitably used as a coating for products with low resistance to water vapor, such as food, medical devices, batteries containing lithium ions, and displays using organic EL, liquid crystals, etc. as materials.

Here, the “water vapor permeability” is a value measured in accordance with JIS-K7129 (2008) Appendix C. “The water vapor transmission rate when the average thickness of the base material layer after shrinkage is 100 μm” means the water vapor transmission rate of the base material layer after shrinkage, and then the water vapor transmission rate is the average thickness of the base material layer Refers to proportionally converted value per 100 μm based on The term "main component" means a component having the highest content, for example, a component having a content of 50% by mass or more, preferably 90% or more. In addition, a "resin component" refers to the substance which consists of a high molecular compound, and is the concept containing rubber | gum and an elastomer.

Details of the Embodiment of the Present Invention
Hereinafter, embodiments of a heat recovery article according to the present invention and a cover coated with the heat recovery article will be described in detail with reference to the drawings.

[Heat recovery article]
The heat recovery article of FIG. 1 is cylindrical and comprises a substrate layer 1.

<Base layer>
The base material layer 1 is a cylindrical tube whose diameter is reduced by heating.

Examples of the main component of the base material layer 1 include polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), high density polyethylene (HDPE), and the like. Among them, polychlorotrifluoroethylene is preferable from the viewpoint of water vapor permeability. These resins may be used alone or in combination of two or more.

When the main component of the base material layer 1 is PCTFE, the base material layer 1 may further contain fluororubber. When the base material layer 1 further contains a fluororubber, the elastic modulus of the base material layer 1 is decreased and the elongation is increased, so that the heat recovery article is easily expanded. Further, by blending fluororubber with PCTFE, the progress of crystallization of PCTFE can be suppressed at the time of heating. Therefore, by containing PCTFE as the main component of the base material layer 1 and further containing a fluororubber, the heat recovery article can maintain its water vapor barrier property and function by heating (especially, machine such as tensile elongation) Of the physical characteristics) can be suppressed. Moreover, in the range which does not impair the effect of this invention, the base material layer 1 may contain other resin, another elastomer, etc.

Examples of the fluororubber include vinylidene fluoride rubber, tetrafluoroethylene-propylene rubber, tetrafluoroethylene-perfluoromethyl vinyl ether rubber and the like. These fluororubbers may be used alone or in combination of two or more.

When the main component of the base layer 1 is PCTFE, the lower limit of the content of the fluororubber in the resin component contained in the base layer 1 is preferably 10% by mass, and more preferably 20% by mass. . As a maximum of a content rate of the above-mentioned fluororubber in a resin ingredient contained in the above-mentioned base material layer 1, 50 mass% is preferred and 40 mass% is more preferred. If the content ratio of the fluororubber in the resin component contained in the base material layer 1 does not reach the above lower limit, there is a possibility that the suppressing effect on the crystallization of PCTFE may be insufficient. On the other hand, when the content rate of the said fluororubber exceeds the said upper limit, there exists a possibility that the water-vapor-barrier fall of the base material layer 1 and by extension, the said heat recovery articles | goods may fall.

The base material layer 1 may be crosslinked. By crosslinking the constituent material of the base layer 1, the heat resistance and the water vapor barrier property of the heat recovery article can be improved. Examples of the crosslinking method include methods such as crosslinking by electron beam irradiation, chemical crosslinking, and thermal crosslinking. Among them, electron beam irradiation crosslinking is preferable because the crosslinking time is short and the production efficiency is high. When electron beam irradiation crosslinking is performed, the irradiation dose is preferably 40 kGy or more and 80 kGy or less.

In addition, it is preferable that the crosslinking of the base layer 1 be crosslinking via a crosslinking aid. By using a crosslinking aid, extrusion processability is improved and crosslinking efficiency is enhanced. For this reason, by making crosslinking of the base material layer 1 into crosslinking via a crosslinking aid, the heat resistance is further improved and the processability is improved, so the gap between the heat recovery article and the object to be coated Can be more difficult to occur. Therefore, the penetration of water vapor can be further suppressed.

As said crosslinking adjuvant, an oxime compound, an acrylate or a methacrylate compound, a vinyl compound, an allyl compound, a maleimide compound etc. are mentioned, for example. In addition, a crosslinking adjuvant can be used individually or in combination of 2 or more types.

Examples of the oxime compound include p-quinonedioxime, p, p'-dibenzoylquinone dioxime and the like.

Examples of the acrylate or methacrylate compound include diethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, acrylic acid / zinc oxide mixture, allyl acrylate, allyl Examples include methacrylate, trimethacrylic isocyanurate and the like.

Examples of the vinyl compound include divinylbenzene, divinyltoluene, divinylpyridine and the like.

Examples of the allyl compound include hexamethylenediallyl nadiimide, diallyl itaconate, diallyl phthalate, diallyl isophthalate, diallyl monoglycidyl isocyanurate, triallyl cyanurate, triallyl isocyanurate and the like.

Examples of the maleimide compound include N, N'-m-phenylenebismaleimide, N, N '-(4,4'-methylenediphenylene) dimaleimide and the like.

Among these, from the viewpoint of effectively promoting the crosslinking reaction, triallyl isocyanurate (TAIC) of allyl compound, diallyl monoglycidyl isocyanurate (DA-MGIC) of allyl compound, and trimethylolpropane triacrylate (TMPTA) of acrylate compound. Is preferred.

The average inner diameter and the average thickness of the base material layer 1 are appropriately selected in accordance with the application and the like. The average inner diameter of the base material layer 1 before thermal contraction can be, for example, 1 mm or more and 60 mm or less. Moreover, as an average internal diameter after the heat contraction of the base material layer 1, it can be 30% or more and 50% or less of the average internal diameter before heat contraction, for example. Moreover, as average thickness before shrinkage | contraction of the base material layer 1, it can be set as 0.1 mm or more and 5 mm or less, for example. The average thickness of the base material layer 1 after contraction changes in accordance with the contraction rate.

The upper limit of the water vapor permeability when the average thickness of the base material layer 1 after shrinkage is 100 μm is 0.1 g / m ² · day, more preferably 0.08 g / m ² · day, 0. 04 g / m ² · day is more preferable, and 0.01 g / m ² · day is particularly preferable. If the water vapor transmission rate exceeds the above upper limit, the effect of the heat recovery article against invading water vapor may be insufficient. On the other hand, the lower limit of the water vapor permeability is not particularly limited and is preferably as low as possible, but it is usually about 0.003 g / m ² · day.

As a minimum of heat contraction temperature of substrate layer 1, 80 ° C is preferred and 100 ° C is more preferred. On the other hand, as a maximum of heat contraction temperature of substrate layer 1, 200 ° C is preferred and 180 ° C is more preferred. If the heat shrinkable temperature of the base material layer 1 is less than the above lower limit, the heat recovery article may be softened when used under a high temperature environment, and a gap may be generated to facilitate the penetration of water vapor. On the contrary, when the thermal contraction temperature of the substrate layer 1 exceeds the upper limit, there is a possibility that the object to be coated may be damaged by high heat when the thermal recovery article is thermally shrunk, and the thermal energy for heating is unnecessarily large. And the cost of the coating may increase.

As a maximum of 2% secant modulus of substrate layer 1, 1000MPa is preferred, 800MPa is more preferred, and 500MPa is still more preferred. When the 2% secant modulus exceeds the above upper limit, the flexibility of the heat recovery article is insufficient, and a gap with the object to be coated is easily formed when the object to be coated is covered, and thus the penetration prevention effect of water vapor May be insufficient. On the other hand, the lower limit of the 2% secant modulus of the base material layer 1 is not particularly limited, but is usually about 100 MPa. The 2% secant modulus is a value measured based on ASTM-D5223-92.

In addition, a filler may be added to the base material layer 1 for the purpose of enhancing the water vapor barrier property. Moreover, you may add a flame retardant for the purpose of improving a flame retardance. Furthermore, other additives may be added to the base layer 1 as required. Examples of such additives include antioxidants, copper inhibitors, lubricants, colorants, heat stabilizers, ultraviolet light absorbers and the like.

(Filler)
As the filler, talc, silica, mica, clay, carbon, alumina, magnesium carbonate, calcium carbonate, zinc carbonate, zinc oxide, zinc oxide, zinc borate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, calcium hydroxide, titanium oxide, Montmorillonite, cellulose nanofibers and the like can be mentioned.

As a minimum of content of a filler in base material layer 1, 0.1 mass part is preferred to 100 mass parts of resin components, and 1 mass part is more preferred. On the other hand, as an upper limit of content of the said filler, 100 mass parts is preferable with respect to 100 mass parts of resin components, and 80 mass parts is more preferable. If the content of the filler is less than the above lower limit, the effect of providing the water vapor barrier property may be insufficient. Moreover, when content of the said filler exceeds the said upper limit, there exists a possibility that the toughness and elongation of the said heat recovery articles | goods may fall.

(Flame retardants)
As a flame retardant, chlorinated flame retardants such as chlorinated paraffin, chlorinated polyethylene, chlorinated polyphenyl and perchloropentacyclodecane, 1,2-bis (2,3,4,5,6-pentabromophenyl) Ethane, ethylenebispentabromobenzene, ethylenebispentabromodiphenyl, tetrabromoethane, tetrabromobisphenol A, hexabromobenzene, decabromobiphenyl ether, tetrabromophthalic anhydride, polydibromophenylene oxide, hexabromocyclodecane, ammonium bromide And other brominated flame retardants, triallyl phosphate, alkylallyl phosphate, alkyl phosphate, dimethyl phosphonate, phosphorylate, halogenated phosphorylate ester, trimethyl phosphate, tributyl phosphate Acetate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, triphenyl phosphate, tris (chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-) Dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (bromochloropropyl) phosphate, bis (2,3-dibromopropyl) 2,3-dichloropropyl phosphate, bis (chloropropyl) monooctyl phosphate, Phosphoric acid salts such as polyphosphonates, polyphosphates, aromatic polyphosphates, dibromoneopentyl glycol, aluminum tris (diethyl phosphinate), etc. And phosphorus compounds, phosphonate type polyols, phosphate type polyols, polyols such as halogen elements, melamine cyanurate, triazine, isocyanurate, nitrogen compounds such as urea and guanidine, silicone polymers, ferrocene, fumaric acid, maleic acid, etc. Other compounds may be mentioned. Among these, halogen-based flame retardants such as bromine-based flame retardants and chlorine-based flame retardants are preferable. The bromine-based flame retardant and the chlorine-based flame retardant may be used alone or in combination of two or more.

As a minimum of content of a flame retardant in

base material layer

1, 1 mass part is preferred to 100 mass parts of resin components, and 5 mass parts is more preferred. On the other hand, as an upper limit of content of a flame retardant, 100 mass parts is preferred to 100 mass parts of resin components, and 80 mass parts is more preferred. If the content of the flame retardant is less than the above lower limit, the effect of imparting flame retardancy may not be obtained. Moreover, when content of the said flame retardant exceeds the said upper limit, there exists a possibility that the toughness and elongation of the said heat recovery articles | goods may fall.

(Antioxidant)
Examples of the antioxidant include phenol compounds, amine compounds, hindered amine compounds, hindered phenol compounds, salicylic acid derivatives, benzophenone compounds, benzotriazole compounds and the like, and particularly hindered amine compounds excellent in the crosslinking inhibitory effect. The compounds are preferably used. As the antioxidant, in addition to those described above, sulfur compounds and phosphite ester compounds can be used alone or in combination.

As a phenol type compound used as an antioxidant, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tetrakis- [methylene-3- (3′5′-di] -Tert-Butyl-4'-hydroxyphenyl) propionate] methane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 6- (4-hydroxy-3) And 3,5-di-tert-butylanilino) -2,4-bis (octylthio) -1,3,5-triazine.

Examples of amine compounds used as an antioxidant include 4,4 ′-(α, α-dimethylbenzyl) diphenylamine, polymers of 2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-2, 2,4-trimethyl-1,2-dihydroquinoline, N- (1,3-dimethylbutyl) -N'-phenyl-1,4-phenylenediamine, N-isopropyl-N'-phenyl-1,4-phenylene Diamine etc. can be mentioned.

The lower limit of the content of the antioxidant in the base material layer 1 is preferably 1 part by mass, and more preferably 1.5 parts by mass with respect to 100 parts by mass of the resin component. On the other hand, as an upper limit of content of the said antioxidant, 30 mass parts is preferable with respect to 100 mass parts of resin components, and 20 mass parts is more preferable. If the content of the antioxidant is less than the above lower limit, the base material layer 1 is easily oxidized, and the heat recovery article may be deteriorated. Conversely, if the content of the antioxidant exceeds the above upper limit, bloom and bleed may occur.

[Method for producing heat recovery article]
The heat recovery article can be manufactured, for example, by a manufacturing method including an extrusion molding step and a diameter expansion step. Each process will be described below.

<Extrusion molding process>
In the extrusion molding step, a base material layer forming material for forming the base material layer 1 is extrusion molded using a melt extrusion molding machine to form an extrusion molded article.

The base material layer-forming material may be prepared, for example, by adding other resin components such as fluororubber, a cross-linking aid, a flame retardant and various additives to the resin as the main component of the base layer 1, if necessary. It can be prepared by mixing by machine. As the melt mixer, known ones such as an open roll, a Banbury mixer, a pressure kneader, a single-shaft mixer, a multi-shaft mixer and the like can be used.

An extrusion-molded article is formed by extruding the above-mentioned base material layer-forming material using a known melt extruder. Specifically, extrusion is performed using an extrusion die having a cylindrical space for extruding a layer corresponding to the base material layer 1. This gives an extruded product. In the extrusion molding step, the heat resistance may be improved by crosslinking the constituent material of the base material layer forming material.

The dimensions of the extrusion can be designed according to the application and the like. The average inner diameter of the extrusion-molded product is, for example, 0.4 mm or more and 30 mm or less, and the maximum thickness is 0.4 mm or more and 10 mm or less.

The die temperature in the extrusion molding step is not particularly limited, but can be, for example, a temperature higher by 10 ° C. or more and 100 ° C. or less than the melting point of the resin material forming the base material layer 1.

The lower limit of the extrusion linear velocity in the extrusion molding step is preferably 5 m / min, and more preferably 8 m / min. If the extrusion linear velocity is less than the lower limit, the productivity of the heat recovery article may be insufficient. On the other hand, the upper limit of the extrusion linear velocity is not particularly limited, but is usually about 15 m / min.

<Diameter expansion process>
In the diameter expansion step, the extruded product is expanded in diameter to obtain a heat recovery article.

The expanded diameter of the extrusion-molded product is expanded to a predetermined inner diameter by a method such as introducing compressed air inside while the extrusion-molded product is heated to the glass transition temperature or more, and then cooled to fix the shape. It is done by Such diameter expansion of the extrusion-molded product is performed, for example, such that the inner diameter of the extrusion-molded product is 2 or more and 4 or less. Thus, the heat recovery article is obtained by expanding and fixing the shape of the extrusion-molded product.

[Covered]
The covering is configured by covering the object to be covered with the heat recovery article.

The object to be covered with the cover is not particularly limited, and examples thereof include food, medical devices, batteries including lithium ion and the like, and displays using organic EL and liquid crystal as materials. Among them, medical devices and batteries are preferable, and those used for wearable applications are particularly preferable. Since these are particularly in an environment susceptible to water vapor and have low resistance to water vapor, the coating of the heat recovery article is highly effective in preventing the intrusion of water vapor.

The said coating can be manufactured, for example by the manufacturing method provided with a covering object insertion process, a heat recovery article heating process, and a cooling process.

First, in the covering object insertion step, the heat recovery article is covered so as to cover the covering object. Specifically, the object to be coated is inserted from the end of the heat recovery article having a cylindrical shape.

Next, in the heat recovery article heating step, the heat recovery article is heated and thermally shrunk.

Examples of the heating method include a method of heating the heat recovery article with a heat gun or the like. The heating temperature is determined by the heat shrinkage temperature of the heat recovery article, and is, for example, 100 ° C. or more and 200 ° C. or less. Further, the heating time may be any time as long as the heat recovery article contracts sufficiently, and can be, for example, 10 seconds to 15 minutes.

Further, in the heat recovery article heating step, the coated object may be sealed inside the heat recovery article by heat shrinking both ends of the heat recovery article and closing the both ends. By sealing the object to be coated inside the heat recovery article in this way, it is possible to more reliably prevent the entry of water vapor.

Finally, in the cooling step, the heat recovery article after heat contraction is cooled. The cooling method is not particularly limited. For example, cooling by natural standing or forced cooling by cold air can be used. This cooling can fix the shape of the heat recovery article.

〔advantage〕
The heat recovery article coats the coated object by shrinkage, so that the coating is easy and the heat recovery article adheres to the object to be coated. In addition, the heat recovery article is cylindrical and thus has no seam. For this reason, by covering with the said heat recovery article, a crevice does not produce easily between the heat recovery article concerned and a covering subject, and it can control the penetration of water vapor. Moreover, since the water vapor transmission rate is 0.1 g / m ² · day or less when the average thickness of the base material layer 1 after shrinkage is 100 μm, the heat recovery article penetrates the heat recovery article. Invasive water vapor can also be reduced. Therefore, the heat recovery article is easy to coat and has a high water vapor penetration preventing effect.

Other Embodiments
It should be understood that the embodiments disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is not limited to the configuration of the above embodiment, but is shown by the claims, and is intended to include all modifications within the meaning and scope equivalent to the claims.

The heat recovery article of the present invention may have a multilayer structure, and at least one layer of the multilayer structure may be constituted by the above-mentioned base material layer. For example, the heat recovery article of the present invention may comprise an adhesive layer laminated to the inner circumferential surface of the base layer. This adhesive layer is for enhancing the adhesion between the adhered portion of the object to be coated and the substrate layer, and for improving the effect of suppressing the penetration of water vapor.

As a main component of this adhesive layer, polyolefin, polyamide etc. can be used, for example. The polyamide may be crosslinked by electron beam irradiation or the like. In addition, the adhesive layer may contain additives such as a viscosity characteristic improver, a deterioration inhibitor, a flame retardant, a lubricant, a colorant, a heat stabilizer, an ultraviolet absorber, and an adhesive.

The average thickness and the average length of the adhesive layer are determined so that the amount of adhesive capable of filling the inside of the base material layer after shrinkage can be secured, and the object to be covered can be stored inside the heat recovery article. Be done. From such a viewpoint, for example, the average thickness of the adhesive layer can be 5% or more and 90% or less of the average thickness of the base material layer. The average length of the adhesive layer can be equivalent to the average length of the base layer.

The heat recovery article comprising the base layer and the adhesive layer can be formed, for example, by extruding the base layer and the adhesive layer separately. In the heat recovery article in this case, the adhesive layer is disposed on the inner peripheral surface of the base layer expanded after extrusion molding, and this is adhered to the object to be coated and then the base layer is shrunk. used.

Further, although the method of sealing the coated object inside the heat recovery article by heating and shrinking both ends of the heat recovery article has been described in the above embodiment, even if the both ends are sealed using an adhesive layer Good.

Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to the following examples.

[Manufacturing of heat recovery articles]
Three types of base material layer forming materials of the material A, the material B, and the material C described below were prepared.

(Material A)
As a material A, PCTFE (Neoflon PCTFE M-300P manufactured by Daikin Industries, Ltd.) was prepared.

(Material B)
As material B, 100 parts by weight of PCTFE was heated and melted by a roll mixer at a set temperature of 220 ° C., and 5 parts by weight of TAIC (manufactured by Nippon Kasei Co., Ltd.) was kneaded as a crosslinking aid and pelletized.

(Material C)
As material C, polyethylene (Tafmer DF110, manufactured by Mitsui Chemicals, melting point 94 ° C., MFR (190 ° C., 2.16 kgf) = 1.2 g / 10 min) was prepared.

(Material D)
As material D, 80 parts by mass of PCTFE (Aclar (registered trademark) UltRx 6000, manufactured by Honeywell) and 20 parts by mass of tetrafluoroethylene-propylene rubber (AFLAS (registered trademark) 150 CS, manufactured by Asahi Glass) as fluororubber are compounded at 260 ° C. The resin obtained by kneading was prepared.

(Material E)
As material E, 60 parts by mass of PCTFE (Aclar (registered trademark) UltRx 6000, manufactured by Honeywell) and 40 parts by mass of tetrafluoroethylene-propylene rubber (AFLAS (registered trademark) 150 CS, manufactured by Asahi Glass) as fluororubber are blended, 260 ° C. The resin obtained by kneading was prepared.

<No. 1>
The material A was used as a base material layer forming material, and an extrusion-formed product was formed by extrusion. For extrusion, a die for extrusion having a diameter of 8 mm and a diameter of 7.5 mm was used. In addition, the outer diameter of the molded object extruded by this shaping | molding die was 6 mm, and the internal diameter was 4 mm. Moreover, extrusion molding was performed at a die temperature of 220 ° C. and a linear velocity of 10 m / min using an extrusion molding machine with a cylinder diameter of 50 mmφ. After extrusion, an electron beam was irradiated at an irradiation dose of 60 kGy for crosslinking.

The resulting extrusion-molded product was sealed using heat and expansion machines, while applying internal pressure while heating and sealing the both ends, and then air-cooling and fixing its shape. The diameter expansion temperature was 120 ° C., and the diameter was increased until the inner diameter reached 12 mm, and the average thickness was 100 μm. Thus, No. 1 heat recovery article was obtained.

<No. 2>
No. 6 was produced except that no electron beam irradiation was performed and no crosslinking was performed. In the same manner as No. 1, No. Two heat recovery articles were produced.

<No. 3>
No. 1 was used except that the material B was used as a base material layer forming material. In the same manner as No. 1, No. Three heat recovery articles were produced.

<No. 4>
No. 6 was produced except that no electron beam irradiation was performed and no crosslinking was performed. In the same manner as No. 3, no. Four heat recovery articles were produced.

<No. 5>
The material A is used as a material for forming a base layer, No. 2 having a base layer in the outer layer and an adhesive layer in the inner layer by two-layer extrusion molding. Five heat recovery articles were produced. In addition, polyethylene (Tafmer DF810 made by Mitsui Chemicals, melting point = 66 ° C., MFR (190 ° C., 2.16 kgf) = 1.2 g / 10 min) was used as the adhesive layer forming material. For extrusion, a die for extrusion having a diameter of 8 mm and a diameter of 7.5 mm was used. In addition, the outer diameter of the molded object extruded by this shaping | molding die was 6 mm, and the internal diameter was 5.8 mm. The ratio of the average thickness of the substrate layer to the adhesive layer was 1: 1. Moreover, extrusion molding was performed at a die temperature of 220 ° C. and a linear velocity of 10 m / min using an extrusion molding machine with a cylinder diameter of 50 mmφ. Except for the above, no. In the same manner as No. 1, No. Five heat recovery articles were produced.

<No. 6>
No. 4 was used except that the material C was used as a base material layer forming material. In the same manner as No. 1, No. Six heat recovery articles were produced.

<No. 7>
No. 1 was used except that the material D was used as a base material layer forming material. No. 2 in the same manner as No. 2. 7 heat recovery articles were produced.

<No. 8>
No. 1 was used except that the material E was used as the base material layer forming material. No. 2 in the same manner as No. 2. Eight heat recovery articles were produced.

[Manufacture of a covering]
No. 1 to No. Using the heat recovery article of No. 8, the coated object was covered as a 5 mmφ aluminum rod, and the coated body was manufactured by heat shrinking at a temperature of 120 ° C.

As a result of visual observation of the appearance, in any of the coverings, the heat recovery article was in close contact with the object to be covered without a gap. In particular, no. No. 5 had good adhesion to the object to be coated. From this, it is considered that the penetration of water from the gap between the coating and the object to be coated can be suppressed in the coating using any of the heat recovery articles.

[Production of evaluation sheet]
No. 1 to No. For the purpose of evaluating the characteristics of the heat recovery article of No. 8, No. 8 1 to No. A sheet of the same configuration as 8 was prepared. The sheet was produced with a press apparatus at a temperature of 220 ° C., a preheating time of 5 minutes, and a pressurizing time of 10 minutes in a thickness of 100 mm × 100 mm × 100 μm. No. 1, No. 3 and No. As for No. 6, in the same manner as in the production of the heat recovery article, crosslinking was performed by irradiating an electron beam at an irradiation dose of 60 kGy.

[Evaluation]
(Water vapor permeability)
Thus obtained No. 1 to No. With respect to the sheet of No. 8, the water vapor transmission rate was measured by a method called differential pressure method with reference to JIS-K7129 (2008) Appendix C. The environmental conditions were a temperature of 40 ° C. and a humidity of 95%. The results are shown in Table 1.

(Tensile elongation residual rate)
The above No. 1 to No. No. 8 out of 8 sheets. 2, No. 7 and No. For the sheet No. 8, test pieces were prepared from the sheet according to JIS-K7127 (1995), and the tensile elongation E1 of the sheet was measured using an autograph “AG-1” manufactured by Shimadzu Corporation. The sheets were then heated to 175 ° C. for 5 minutes. Subsequently, test pieces were similarly produced from the sheet after heating, and the tensile elongation E2 of the sheet after heating was measured in the same manner. No. 2, No. 7 and No. The tensile elongation residual ratio (%) was determined for each of the eight sheets according to the following equation. The results are shown in Table 1.
Tensile elongation residual ratio (%) = (E2 / E1) × 100

From Table 1, No. 1 in which the thickness of the base material layer is 100 μm. 1 to No. 4 and No. 4 7 to No. It is understood that No. 8 has a water vapor permeability of less than 0.1 g / m ² · day and is good. In addition, No. 1 in which the thickness of the base material layer is 50 μm. Also in 5, the water vapor transmission rate is less than 0.1 g / m ² · day, and when the thickness is 100 μm, it can be said that the water vapor transmission rate is 0.1 g / m ² · day or less. On the other hand, no. In No. 6, the water vapor permeability exceeded 0.1 g / m ² · day. From this, when the average thickness of the base material layer is 100 μm, the No. 1 water vapor transmission rate is 0.1 g / m ² · day or less. 1 to No. In the case of the covering using the heat recovery article of No. 5, while the water vapor which permeates through the heat recovery article can be suppressed, no. It is considered that the coating using the heat recovery article of No. 6 can not sufficiently suppress permeation and infiltration of water vapor.

In more detail, the electron beam irradiated crosslinked No. 1 and No. 1 No. 3 heat recovery articles are No. 2 and No. The water vapor transmission rate is low for the heat recovery article of 4. From this, it is understood that the water vapor barrier property of the heat recovery article can be improved by electron beam crosslinking the constituent material of the base material layer.

In addition, No. 1 blended with fluoro rubber. 7 and No. In No. 8, no. Compared with 2, the tensile elongation residual rate after heating is large while the increase in the water vapor permeability numerical value is suppressed. From this, it is understood that, by using the base material layer in which the fluorocarbon rubber is further contained in PCTFE, it is possible to obtain a heat-recoverable article having a low water vapor transmission rate and suppressing functional deterioration even when heated.

From the above, the No. 1 water vapor transmission rate was 0.1 g / m ² · day or less. 1 to No. 5 and No. 5 7 to No. It can be seen that in the case of a coating coated with the heat recovery article of No. 8, it is difficult for water vapor to penetrate into the object to be coated.

1 Base layer

Claims

A cylindrical heat recovery article comprising a substrate layer, comprising:
The heat recovery article whose water vapor transmission rate is 0.1 g / m 2 · day or less when the average thickness of the base material layer after shrinkage is 100 μm.
The heat recovery article according to claim 1, wherein the main component of the substrate layer is polychlorotrifluoroethylene.
The heat recovery article according to claim 2, wherein the base material layer further contains a fluororubber.
The heat recovery article according to claim 3, wherein a content ratio of the fluororubber in a resin component contained in the base material layer is 10% by mass or more and 50% by mass or less.
The heat recovery article according to any one of claims 1 to 4, wherein the water vapor transmission rate is 0.04 g / m 2 · day or less.
The heat recovery article according to any one of claims 1 to 5, wherein the base material layer is crosslinked.
The heat recovery article according to claim 6, wherein the crosslinking of the base material layer is crosslinking by electron beam irradiation.
The heat recovery article according to claim 6 or 7, wherein the crosslinking of the base material layer is crosslinking via a crosslinking coagent.
Has a multilayer structure,
The heat recovery article according to any one of claims 1 to 8, wherein at least one layer of the multilayer structure is constituted by the base material layer.
A cover coated with the heat recovery article according to any one of the preceding claims.