WO2013111773A1 - テープ材用支持フィルムおよびテープ材 - Google Patents
テープ材用支持フィルムおよびテープ材 Download PDFInfo
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- WO2013111773A1 WO2013111773A1 PCT/JP2013/051284 JP2013051284W WO2013111773A1 WO 2013111773 A1 WO2013111773 A1 WO 2013111773A1 JP 2013051284 W JP2013051284 W JP 2013051284W WO 2013111773 A1 WO2013111773 A1 WO 2013111773A1
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- tape material
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- film
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/728—Hydrophilic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2555/00—Personal care
- B32B2555/02—Diapers or napkins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2429/00—Presence of polyvinyl alcohol
- C09J2429/001—Presence of polyvinyl alcohol in the barrier layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24851—Intermediate layer is discontinuous or differential
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
Definitions
- the present invention relates to a support film for tape material, and more particularly to a support film for tape material having barrier properties and a tape material using the same.
- a tape material in which an adhesive layer is formed on one surface of a sheet-like or film-like support is widely used for various uses such as medical use and industrial use.
- a plasticizer or the like may be blended in addition to the adhesive material.
- the material of the support there is a concern about the adverse effect of the plasticizer adsorbing. Therefore, it is preferable that at least the surface in contact with the adhesive layer is provided with a barrier property.
- a gas barrier film described in Patent Document 1 is known as a film material having barrier properties.
- a barrier coating layer is formed by applying a barrier coating agent in which a layered inorganic compound montmorillonite and a water-soluble polymer compound are mixed on one surface of a plastic base film.
- the tape material may be used in harsh environments such as being in contact with liquid or being immersed in a state where it is affixed to an object.
- the gas barrier film described in Patent Document 1 since the gas barrier film described in Patent Document 1 is not originally intended for use in such an environment, it cannot be said that the adhesion between the support and the barrier coat layer is sufficient. Therefore, when the gas barrier film described in Patent Document 1 is applied to the tape material as it is, peeling occurs between the support and the barrier coat layer, and a situation such that the harsh use environment cannot be sufficiently tolerated occurs. There is a problem.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a support film for tape material and a tape material that can be used while maintaining good barrier properties even under harsh environments.
- One embodiment of the present invention is a tape material support film used for a tape material, comprising a film-like support made of polyurethane, polyvinyl alcohol, and a layered inorganic compound, and formed on one surface of the support A barrier layer, and an undercoat layer provided between the support and the barrier layer and in close contact with the support and the barrier layer.
- the saponification degree of the polyvinyl alcohol is preferably set to 70% or more.
- the layered inorganic compound is preferably montmorillonite. Furthermore, in one aspect of the present invention, it is preferable that printing is performed on the undercoat layer.
- the tape material according to one aspect of the present invention preferably includes the support film for a tape material of the present invention and an adhesive layer formed on the barrier layer and on the surface opposite to the support.
- the barrier property can be satisfactorily maintained even when the tape is attached to an object or is stretched after being attached.
- FIG. 3 is a diagram showing a procedure of an experiment for examining the relationship between the degree of saponification of a water-soluble polymer compound and the adhesion between a support and a barrier layer. It is a figure which shows one procedure of the same experiment. It is a figure which shows one procedure of the same experiment. It is a figure which shows one procedure of the same experiment. It is a figure which shows one procedure of the same experiment. It is a figure which shows one procedure of the same experiment. It is a figure which shows one procedure of the same experiment.
- the tape material of the first embodiment includes the support film for tape material of the present invention (hereinafter simply referred to as “support film”), and is for industrial use, packaging use, protection use, label use, masking use, paper use. It can be used as an adhesive tape in various fields such as sanitary materials such as diapers, medical use such as adhesive bandages and transdermal administration, cosmetic use, and home use. Furthermore, the following uses are mentioned as a typical example.
- An adhesive tape for locking the packaging material is used as the packaging tape material. This adhesive tape can be stretched so that it does not break or damage the packaging material even when a force is applied during transportation in a packaged state. Can be held well.
- the outside of the tape material is not contaminated during transportation or the like.
- a medical tape material when affixed to a human body, an animal, or the like, it can follow the elongation accompanying the movement of the human body and the like, and unintended peeling hardly occurs.
- the barrier property can be satisfactorily maintained in a state where the tape material is stretched, an active ingredient such as a plasticizer does not leak to the outside of the tape material, and an excellent performance as a medical tape material is obtained. be able to.
- FIG. 1 is a cross-sectional view in the thickness direction of the tape material 1 of the first embodiment.
- the tape material 1 includes a support film 10, an adhesive layer 20 formed on one surface of the support film 10, and a peeling member 30 that covers the adhesive layer.
- the support film 10 is provided between a support 11 formed in a film shape containing polyurethane, a barrier layer 12 formed on one surface of the support 11, and the support 11 and the barrier layer 12.
- An undercoat layer 13 is provided to adhere both the support 11 and the barrier layer 12 together.
- the support 11 has flexibility and can be extended until a predetermined maximum elongation rate is obtained in which the length of the support 11 is increased by 10 percent (%) or more. A specific value of the maximum elongation rate may be set as appropriate based on the use of the tape material 1 or the like.
- the polyurethane forming the support 11 is not particularly limited, and materials conventionally used for polyurethane films can be used and can be appropriately selected depending on the application.
- polyether polyurethane polyester polyurethane, polycarbonate polyurethane and the like can be mentioned.
- polyether polyurethane or polycarbonate polyurethane is preferred.
- the material constituting polyurethane is not limited to a specific material such as the type of isocyanate forming a urethane bond, yellowing type material, non-yellowing type material, etc. And the method, the type of plasticizer used, and the like.
- the thickness of the support 11 is 10 micrometers ( ⁇ m) to 200 ⁇ m, and preferably 20 ⁇ m or more and 100 ⁇ m or less. If the thickness of the support is less than 10 ⁇ m, it is too thin and difficult to handle, and if it is more than 200 ⁇ m, the flexibility is lowered and the original flexibility is not sufficiently exhibited.
- the support 11 can include a peelable film called a release film.
- a release film When the thickness of the support 11 is thin, the support is stretched in the step of applying the barrier layer 12, and therefore, when the release film and the support (for example, polyurethane as a support) are laminated, it is manufactured. It is possible to suppress the expansion and contraction and facilitate the processing.
- the handleability of a tape material improves. This release film can be peeled off from the support after the tape material has been applied to the object, and the support 11 exhibits its original flexibility after peeling.
- the material of the release film is not particularly limited, but generally a material that can be peeled later without stretching, such as a silicone-treated PET film, a polyolefin film having good releasability, and a laminate of paper and polyethylene can be used.
- the barrier layer 12 is formed including montmorillonite, which is a layered inorganic compound, and polyvinyl alcohol (PVA), which is a water-soluble polymer compound.
- the crystal structure of montmorillonite forms a layered structure having a basic structure of three layers including two tetrahedral sheets and one octahedral sheet.
- the cation of the tetrahedral sheet is only Si, and the cation Al of the octahedral sheet is partially substituted with Mg.
- the unit crystal layer has a negative charge, and cations such as Na + , K + , Ca 2+ , Mg 2+ , H + are present between the crystal layers to match the negative charge of the unit crystal layer. Intrusion compensation.
- the type of these cations can be used without any particular limitation.
- the barrier layer 12 is formed by applying a barrier coating agent prepared by adding montmorillonite to an aqueous solution in which PVA is dissolved in water and then adding a lower alcohol, by a gravure coating method, a roll coating method, or the like. can do.
- the content of montmorillonite in the barrier layer 12 is set in the range of 2 weight percent (wt%) to 22 wt%. Although details will be described later, when the content is less than 2 wt%, it is difficult to ensure sufficient barrier properties. On the other hand, if the content exceeds 22 wt%, the effect of montmorillonite on the properties of the barrier layer 12 such as flexibility and stretchability becomes too large, and as a result, it becomes impossible to follow the shape change of the support due to elongation, cracks, etc. It tends to occur.
- the undercoat layer 13 is formed on the surface of the support 11 on which the barrier layer 12 is provided by coating or the like.
- the material of the undercoat layer 13 may be appropriately determined in view of the materials of the support and the barrier layer from the viewpoint of improving the adhesion between the support and the barrier layer.
- the support 11 is polyurethane
- the water-soluble resin includes water-dispersible resins such as emulsions and dispersions in addition to the water-soluble resin.
- water-soluble resins include, for example, polymerizable unsaturated carboxylic acids such as methacrylic acid and itaconic acid or polymerizable unsaturated carboxylic acid anhydrides thereof, and methacrylic acid such as methyl methacrylate and ethyl methacrylate.
- polyurethane resin, polyester resin, acetic acid which can introduce a hydrophilic component into its own molecular structure and can select anionic resin, cationic resin, nonionic resin, etc. by selecting the charge of the hydrophilic component
- Vinyl resins, styrene resins, shellac resins, polyamide resins and modified products thereof can be used with excellent coatability and adhesion.
- polyurethane resins are particularly preferable because they are excellent in flexibility and expand and contract following the support.
- a water-based ink prepared by adding a pigment or an additive to a water-soluble resin can also be used as an undercoat layer.
- the undercoat layer may be formed by printing the entire surface of a single color ink, or as an undercoat layer on which various information such as the manufacturer or product identification code is printed using a plurality of colors of ink. Also good.
- water-soluble resins there are natural products such as starch and dextrin, and synthetic products such as acrylates and polyethylene oxides, but these are not preferable because the adhesion is not obtained when the support is made of a urethane material. .
- the method is not limited as long as it can be uniformly applied over the entire surface, and the method such as roll coating method, gravure coating method, die coating method, etc. Can be used.
- the coating amount of the water-soluble resin may be, for example, 0.1 to 10 g / m 2 , and 1 to 3 g / m 2 is particularly preferable. Below 0.1 g / m 2 , the uniform coatability and adhesion as the undercoat layer will be impaired. At 10 g / m 2 and above, the undercoat layer will become hard and antagonize the flexibility of the support. This is not practical because the load on the undercoat layer increases.
- the barrier layer 12 is formed after the undercoat layer 13 is formed.
- the coating weight is preferably 0.1 ⁇ 10g / m 2, particularly preferably 0.5 ⁇ 3g / m 2.
- PVA is a polymer compound having a hydroxyl group obtained by saponification of polyvinyl acetate (hydrolysis treatment with alkali).
- the undercoat layer 13 improves the adhesion between the barrier layer 12 and the support 11 and prevents the above situation, so that the saponification degree of PVA is 95.5%.
- the adhesiveness of the barrier layer 12 and the support body 11 is suitably hold
- the degree of saponification is smaller than 70%, the barrier layer 12 is easily dissolved in water, and as a result, the water resistance of the support film 10 and the tape material 1 is lowered. Therefore, when a tape material is used for an industrial tape material, a packaging tape material, a protective tape material or the like, it is assumed that the tape material is affected by rainwater outdoors. In addition, if the tape material is used for sanitary material tape materials such as paper diapers, medical tape materials such as adhesive bandages or transdermal administration, cosmetic tape materials, household tape materials, etc. It is assumed that it will be affected when using water. Therefore, in the tape material used for these applications, the saponification degree of PVA is preferably 70% or more.
- the adhesive layer 20 is configured by mixing a plasticizer with an adhesive base material, and is formed on the barrier layer 12 by coating or the like on the surface opposite to the support 11.
- the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer 20 is not particularly limited. Natural rubber, synthetic isoprene rubber, recycled rubber, styrene-butadiene rubber (SBR), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene Rubber polymers such as block copolymers (SBS), polyisobutylene, SEBS, and SEPS, acrylic polymers such as (meth) acrylate copolymers having (meth) acrylate esters as main monomers, silicone Various materials such as rubber, silicone resin, silicon polymer such as dimethylsiloxane and diphenylsiloxane, polyvinyl ether, polyvinyl ester, EVA, and polyester can be used.
- plasticizers including petroleum oils (paraffinic process oil, naphthenic process oil, aromatic process oil, etc.), dibasic acid esters (dibutyl phthalate, dioctyl phthalate, etc.), liquid rubber (polybutene, liquid Isoprene, liquid polyisobutylene, etc.), vegetable oils (castor oil, tall oil, etc.), liquid fatty acid esters (isopropyl myristate, hexyl laurate, diethyl sebacate, diisopropyl sebacate, etc.), triacetin, sorbitan fatty acid esters, Various plasticizers such as sugar fatty acid esters, fatty acid glycerin esters, and surfactants can be used.
- plasticizers such as sugar fatty acid esters, fatty acid glycerin esters, and surfactants can be used.
- tackifiers may be blended in order to increase the tackiness.
- rosin, modified rosin, rosin resin such as rosin ester, terpene resin, aromatic modified terpene resin, hydrogenated terpene resin, terpene resin such as terpene phenol resin, aliphatic petroleum resin, aromatic petroleum resin
- examples thereof include petroleum resins such as copolymerized petroleum resins, hydrogenated petroleum resins, and DCPD petroleum resins, styrene resins, substituted styrene resins, xylene resins, phenol resins, and chroman indene resins.
- an antioxidant, a filler, a crosslinking agent, an ultraviolet absorber, a colorant, a flame retardant, a conductive agent, a foaming agent and the like may be added depending on the use of the tape material.
- the plasticizer causes the barrier layer 12 to be used. It is suppressed suitably that it transfers to the support body 11 exceeding it.
- the polyurethane constituting the support 11 easily adsorbs the plasticizer, and when the plasticizer is absorbed, the deterioration of the support 11 due to the plasticizer moving to the support 11 becomes a problem.
- the tape material 1 not only when the support 11 is not stretched but also when the barrier layer 12 is stretched until a stretch rate of 20% (indicating that the length after stretching increases by 20%) is obtained. The barrier property is suitably maintained.
- the tape material 1 can suitably prevent the above-described problem caused by the plasticizer not only during storage before use but also during use when it is attached to an object.
- the specific montmorillonite content rate of the tape material 1 can be easily set by the preliminary test etc. using the plasticizer to be used. The relationship between the barrier property against a part of the plasticizer and the montmorillonite content in the tape material 1 will be described later.
- the peeling member 30 is a member that protects the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer 20 until sticking to an object, and various known release papers can be suitably used. In addition, when the tape material 1 is wound around the core material in a roll shape, the peeling member 30 is not necessarily provided.
- MN montmorillonite
- the content of MN in the barrier layer is changed in 8 steps of 1 wt%, 2 wt%, 10 wt%, 18 wt%, 22 wt%, 25 wt%, 30 wt%, and 37 wt%, and the sample of the support film is changed. Eight types were produced.
- the both ends of the evaluation piece 100A reinforced with the sheet 101 were fixed to the chuck portion of the tensile tester. As shown in FIG. 3, the portion not covered with the sheet 101 was stretched at a stretching speed of 300 mm (mm / min) per minute until a predetermined stretching ratio was obtained.
- the elongation rate was set in five stages: 0%, 5%, 10%, 20%, and 30%.
- each evaluation piece 100A is removed from the tensile tester, and as shown in FIG. 4, each evaluation piece 100A is placed on the black acrylic plate 110 with the PET sheet 111 coated with silicone on the surface. The layer was fixed with the top side. At this time, it operated so that air might not enter between evaluation piece 100A and PET sheet 111 as much as possible.
- plasticizer After attaching the evaluation piece 100A to the acrylic plate 110, as shown in FIG. 5, two drops (about 0.08 grams) of plasticizer are dropped onto each evaluation piece 100 with a dropper, and a length of 50 mm is used using a cotton swab 112. Stretched.
- the plasticizer four types of isopropyl myristate (IPM), triacetin (TA), glyceryl monoisostearate (MGIS), and sorbitan monooleate (SMO) were used. After standing at room temperature for 30 minutes, the plasticizer was wiped off, and the degree of swelling of the support was visually evaluated.
- FIG. 6 to FIG. 9 are optical micrographs of the support film after performing an elongation operation with an elongation rate of 20% on the evaluation pieces having an MN content of 10 wt%, 18 wt%, 25 wt%, and 30 wt%, respectively. .
- MN 10 wt% and 18 wt% no significant change in appearance is observed, but at MN 25 wt% and 30 wt%, wrinkles due to swelling are observed.
- an adhesive layer (adhesive layer coating amount: 100 g / m 2 ) containing a base material and a plasticizer was formed on the barrier layer.
- a base material two types, a rubber base material and an acrylic base material, were used, and a total of five types of adhesive layer materials were prepared by combining a plurality of types of plasticizers.
- the adhesive layer was formed in each sample using each adhesive layer material, and the adhesive layer was covered with the peeling member, and the sample of the tape material was produced.
- the combination of the base material and the plasticizer in each adhesive layer material is as follows (% of the plasticizer indicates the content). Rubber base (IPM 20%, MGIS 10%, SMO 10%, SMO 20%), acrylic base (IPM 20%, TA 10%, MGIS 10%, SMO 10%).
- the MN content in the barrier layer 12 is set within the range of 2 wt% or more and 22 wt% or less, the plasticity is obtained both when the support film is not stretched and when the support film is stretched by 20%. It was shown that the barrier property of the support film can be ensured to such an extent that the transfer of the agent to the support is sufficiently suppressed.
- the adhesive tape 122 was cut out to 30 mm ⁇ 100 mm.
- a PET sheet 121 coated with silicone is attached to one end of the cut out adhesive tape 122 in the longitudinal direction, and then attached to the barrier layer of the sample 120 as shown in FIG. b.
- the adhesive tape 122 and the PET sheet 121 are cut out to a size of 25 mm ⁇ 90 mm as shown in FIG. c.
- two double-sided tapes 131 each having a size of 25 mm ⁇ 90 mm were attached to the acrylic plate 130 side by side.
- the support side of the cut-out adhesive tape 122 is brought into contact with the double-sided tape 131, and the cut-out adhesive tape 122 is bonded so as to cover the two double-sided tapes 131 attached to the acrylic plate.
- a part of the double-sided tape 131 protruding from the adhesive tape 122 is cut off and removed from the acrylic plate 130.
- a 50 mm ⁇ 100 mm reinforcing tape 132 is prepared, and as shown in FIG. 14, the reinforcing tape 132 is attached to the end of the adhesive tape 122 not bonded to the sample 120 so that the PET sheet 121 is sandwiched in the thickness direction.
- the evaluation piece 140 is produced.
- the evaluation piece 140 is immersed in hot water of 40 ° C.
- the entire adhesive tape 122 is placed in hot water.
- the evaluation piece 140 is pulled up from the hot water and lightly wiped off the moisture before being set in a tensile tester.
- the acrylic plate 130 is fixed to one chuck, and the end of the reinforcing tape 132 not bonded to the PET sheet is fixed to the other chuck.
- the evaluation piece is pulled at a tensile speed of 300 mm / min, and the measurement is finished when the adhesive tape 122 is completely peeled off from the support.
- the average value of the tension value N of the tensile tester in the range of the tensile amount from 10 mm to 30 mm was defined as the water-resistant adhesion.
- Three evaluation pieces were prepared for each sample to evaluate the water-resistant adhesion of the support film.
- undercoat layers were each coated on one surface of the support 11 by a 2.0 g / m 2 gravure coating method.
- Two types of barrier layer materials were uniformly applied thereon by a 2.2 g / m 2 gravure coating method to form a barrier layer, thereby preparing eight types of samples.
- the support 11 was subjected to corona treatment, and two types of the barrier layer materials were applied at 2.2 g / m 2 without an undercoat layer to obtain a comparative example.
- the support film using an acrylic resin for the undercoat layer when IPM, TA, and MGIS are used, no swelling is observed in the extended support until the extension rate of the support film reaches 10%. The migration of the plasticizer was suppressed. It was estimated that the support film using acrylic resin for the undercoat layer was inferior in elasticity of the film compared to the support film using urethane resin for the undercoat layer, and the barrier layer may have cracked. . However, if the support film can be expanded and contracted up to 10%, it can be used practically without any problems in many applications. On the other hand, regarding SMO, swelling of the support was observed regardless of the elongation rate of the support film, and it was considered that the plasticizer used in the tape material of the present invention may not be preferable.
- the barrier property is preferably improved even when the support film is extended to an extension ratio of 20%. Can be held.
- the barrier property is suitably maintained both when the tape material is not stretched and when the tape material is stretched to 20%, and the plasticizer of the adhesive layer is transferred to the support.
- the tape material to be prevented can be configured.
- the support film and the tape material can be constructed with improved adhesion between the support and the barrier layer and excellent water-resistant adhesion.
- the saponification degree of PVA is preferably 70% or more and 98.5% or less, and among the completely saponified PVA, PVA having a saponification degree exceeding 98.5% can also be used.
- PVA with a saponification degree of 95.5% or more is excellent in barrier properties, but may not have sufficient adhesion to urethane and water resistance, but this is achieved by providing an undercoat layer on the support film and tape material. As a result, it is possible to construct a support film and a tape material that can withstand more various use conditions.
- the technical scope of the present invention is not limited to the above-described embodiment, and combinations of the constituent elements of each embodiment are possible without departing from the spirit of the present invention. It is possible to change, to make various changes to each component, or to delete.
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- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Vascular Medicine (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
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- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Medicinal Preparation (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
本願は、2012年1月27日に、日本に出願された特願2012-015962号に基づき優先権を主張し、その内容をここに援用する。
また、本発明の一態様においては、前記層状無機化合物がモンモリロナイトであることが好ましい。
さらに、本発明の一態様においては、前記下引き層には印刷が施されていることが好ましい。
第一実施形態のテープ材は、本発明のテープ材用支持フィルム(以下、単に「支持フィルム」と称する。)を含んでおり、工業用、包装用、保護用、ラベル用、マスキング用、紙オムツ等の衛生材料用、絆創膏や経皮投与用等の医療用、化粧用、家庭用等の各種分野において、粘着テープ等として利用可能である。
さらに、代表的具体例として次の用途が挙げられる。包装用のテープ材としては、包装材料を係止するための粘着テープが用いられる。この粘着テープは、伸長可能なことにより、包装された状態で輸送等により力が加わった場合であっても、破断したり、包装材料を傷つけることがなく、また、伸長された状態でバリア性を良好に保持することができる。このため、輸送等の際に、テープ材の外部を汚染することがない。医療用のテープ材としては、人体や動物等に貼付した場合に、人体等の動作に伴う伸長に追従することができ、意図しない剥離が生じにくい。また、テープ材が伸長された状態でバリア性を良好に保持することができることで、可塑剤等、有効成分がテープ材の外部に漏れ出ることがなく、医療用テープ材として優れた性能を得ることができる。
支持体11は、柔軟性を有し、支持体11の長さが10パーセント(%)以上増加する所定の最大伸長率が得られるまで伸長可能である。具体的な最大伸長率の値は、テープ材1の用途等に基づいて適宜設定されてよい。本実施形態において、支持体11を形成するポリウレタンは、特に限定されず、従来ポリウレタンフィルムに用いられている材料が利用でき、用途によって適宜選択できる。たとえばポリエーテル系ポリウレタン、ポリエステル系ポリウレタン、ポリカーボネート系ポリウレタン等が挙げられる。耐水性が必要な用途では、ポリエーテル系ポリウレタンまたはポリカーボネート系ポリウレタンが好ましい。
また、ポリウレタンを構成する材料は、ウレタン結合を形成するイソシアネートの種類や、黄変タイプの材料、無黄変タイプの材料等についても特定の材料には限定されず、用途、使用に際して保管する期間や方法、使用する可塑剤の種類等に応じて適宜選択できる。
支持体11の厚さは、10マイクロメートル(μm)~200μmであり、20μm以上100μm以下とされるのが好ましい。支持体の厚さが10μm未満では薄すぎて取扱いが困難であり、200μmより厚いと柔軟性が低下して本来の柔軟性が充分発揮されない。
支持体11の厚みが薄い場合には、バリア層12を塗布する工程で、支持体が伸びてしまうので、離型フィルムと支持体(支持体として、例えば、ポリウレタン)を積層した状態で製造すると、伸縮を抑え加工し易くすることができる。また、支持体11をテープ材に加工した後は、離型フィルムによりテープ材の剛性が補強されるため、テープ材の取り扱い性が向上する。この離型フィルムは、テープ材を対象物に貼付した後に支持体から剥離することができ、剥離後は支持体11が本来の柔軟性を発揮する。
離型フィルムの材料は特に限定されないが、一般にシリコーン処理したPETフィルムや、剥離性の良いポリオレフィンフィルム、紙とポリエチレンの積層体など、伸び縮みせず後で剥離可能な材料を使うことが出来る。
モンモリロナイトは、鉱物学的には2八面体型含水層状珪酸塩鉱物で、理想的には次の化学式で表現される。
(Al2-yMgy)Si4O10(OH)2・(M+,M1/2 2+)y・nH2O ただし、y=0.2~0.6、M:交換性陽イオンNa、K、Ca、Mg、Hなど、n :層間水の量。
モンモリロナイトの結晶構造は、2枚の四面体シートと1枚の八面体シートからなる3層を基本構成とした層状構造を形成する。四面体シートの陽イオンはSiのみで、八面体シートの陽イオンのAlが一部Mgに置換されている。このため、単位結晶層は負の電荷を帯びており、その単位結晶層の負電荷に見合うように結晶層間にNa+、K+、Ca2+、Mg2+、H+などの陽イオンが入り込み補償されている。本発明では、これら陽イオンの種類は特に限定されることなく使用できる。
また、水溶性樹脂に顔料や添加剤を加え調製した水性インキも下引き層として使うことが可能である。これら水性インキを用いた場合は、単色インキの全面印刷により下引き層を形成してもよいし、複数色のインキを用いて製造元や製品識別コード等の各種情報が印刷された下引き層としてもよい。
なお、水溶性樹脂としては、でんぷんやデキストリン等の天然物やアクリル酸塩やポリエチレンオキシド等の合成物もあるが、これらは支持体がウレタン系材料からなる場合、密着性が得られず好ましくない。
バリア層12は、下引き層13の形成後に形成する。バリア層12を塗工により形成する場合、塗工量は0.1~10g/m2が好ましく、0.5~3g/m2が特に好ましい。
ただし、ケン化度が70%よりも小さくなると、バリア層12が水に溶けやすくなる結果、支持フィルム10およびテープ材1の耐水性が低下する。そのため、テープ材が、工業用テープ材、包装用テープ材、保護用テープ材等に用いられる場合は、戸外での雨水の影響を受けることが想定される。また、テープ材が紙オムツ等の衛生材料用テープ材、絆創膏や経皮投与用等の医療用テープ材、化粧用テープ材、家庭用テープ材等に用いられる場合は、汗の影響や生活上で水を用いる際の影響を受けることが想定される。したがって、これらの用途に用いるテープ材においては、PVAのケン化度を70%以上とするのが好ましい。
粘着層20に用いられる粘着剤に特に制限はなく、天然ゴム、合成イソプレンゴム、再生ゴム、スチレン・ブタジエンゴム(SBR)、スチレン-イソプレン-スチレンブロック共重合体(SIS)、スチレン-ブタジエン-スチレンブロック共重合体(SBS)、ポリイソブチレン、SEBS、SEPS等のゴム系高分子、(メタ)アクリル酸エステル類を主モノマーとする(メタ)アクリル酸エステル共重合体等のアクリル系高分子、シリコーンゴム、シリコーン樹脂、ジメチルシロキサン、ジフェニルシロキサン等のシリコン系高分子、ポリビニルエーテル系、ポリビニルエステル系、EVA系、ポリエステル系等の各種材料を用いることができる。
また、テープ材の用途に応じて、抗酸化剤、充填剤、架橋剤、紫外線吸収剤、着色剤、難燃剤、導電剤、発泡剤等が加えられてもよい。
一般に、支持体11を構成するポリウレタンは、可塑剤を吸着等しやすく、可塑剤を吸収した場合、可塑剤が支持体11に移行することによる支持体11の変質等が問題となる。しかしながら、テープ材1では、支持体11の非伸長時はもちろん、伸長率20%(伸長後の長さが20%増加することを指す)が得られるまで伸長されたときにおいてもバリア層12のバリア性が好適に保持される。その結果、テープ材1は、使用前の保存時だけでなく、対象物に貼り付けられる使用時においても可塑剤による上記問題を好適に防止することができる。なお、テープ材1の具体的なモンモリロナイト含有率は、使用する可塑剤を用いた予備試験等により、容易に設定することができる。テープ材1における、一部の可塑剤に対するバリア性とモンモリロナイト含有率との関係については後述する。
(1-1 サンプルの作成)
支持体として、厚さ20μmのポリエーテル系ポリウレタン製の支持体を用いた。支持体の一方の面に、MNとPVA(ケン化度80%)とを混合したバリアコート剤を、1.0g/m2均一に塗布することによりバリア層を形成した。これを基本構成として、バリア層におけるMNの含有率を、1wt%、2wt%、10wt%、18wt%、22wt%、25wt%、30wt%、および37wt%の8段階変化させ、支持フィルムのサンプルを8種類作製した。
作製した8種類のサンプル100を、図2に示すように25ミリメートル(mm)×120mmの大きさに切り出した。切り出したサンプル100について、引張試験機での操作をしやすくするため、切り出したサンプル100の長手方向両端部の両面に厚さ50μmのポリエチレンテレフタレート(PET)製のシート101を両面テープで貼り付け、評価片100Aを作製した。シート101で評価片100Aを覆う部分の長手方向における長さは10mmとした。各評価片100Aにおいて、シート101に覆われない部分の長手方向の長さは100mmに設定した。
IPM、TA、およびSMOについては、MN含有率1wt%、10wt%、18wt%、22wt%、25wt%、30wt%、および37wt%の評価片100Aを用いて検討した。MGISについては、MN含有率2wt%、10wt%、および22wt%の評価片100Aを用いて検討した。
結果を表1に示す。IPM、TA、およびMGISについては、MN含有率が22wt%以下の場合、すべての伸長率において支持体の膨潤を認めず、可塑剤の移行が抑制されていた。一方、SMOについては、MN含有率、伸長率にかかわらず支持体に膨潤が認められ、本発明のフィルム材に用いる可塑剤としては好ましくない場合があると考えられた。実験に用いた各可塑剤の溶解度パラメータ(SP値、フェダーズ法による)は、IPMで8.5、TAで10.2、MGISで10.76、SMOで11.76であった。支持フィルムのバリア性を考慮すると、支持体の膨潤を抑制する効果の点で、SP値が高い可塑剤を用いた支持フィルムよりも、SP値が低い可塑剤を用いた支持フィルムが優れている傾向が推測された。
図6から図9は、それぞれMN含有率10wt%、18wt%、25wt%、および30wt%の評価片に対して、伸長率20%の伸長操作を行ったあとの支持フィルムの光学顕微鏡写真である。MN10wt%および18wt%では、外観に大きな変化は見られないが、MN25wt%および30wt%では膨潤によるシワが見られる。
(2-1 サンプルの作成)
支持体として、実験1と同様の材料を用い、支持体の一方の面に、MNとPVA(ケン化度80%)とを混合したバリアコート剤を1.0g/m2均一に塗布することによりバリア層を形成した。バリア層におけるMNの含有率を、1wt%、2wt%、4wt%、10wt%、18wt%、22wt%、25wt%、30wt%、および37wt%の9段階設定し、支持フィルムのサンプルを9種類作製した。
a.非伸長時における安定性試験
10平方センチメートルに切り出したテープ材サンプルを、伸長操作を行わずに60℃で1週間保存した。
b.伸長時における安定性試験
幅30mm、長さ50mmに切り出したテープ材サンプルを、剥離部材を除去してから長さ方向に伸長率20%の伸長操作を1回行った後、60℃で3日間保存した。
いずれの場合も、保存後の各テープ材サンプルにおいて、実験1と同様に、支持体におけるシワ発生の有無により支持フィルムのバリア性を評価した。実験2における評価は、膨潤によるシワを認めない:優、わずかに膨潤によるシワを認めるが、品質に問題ない程度である:良、膨潤によるシワが認められ、使用に耐えない:不良の3段階とした。また、表2において不実施の箇所については、「無し」と記載した。
結果を表2に示す。バリア層のMN含有率が2wt%、10wt%、および18wt%の場合、非伸長時および20%伸長時のいずれにおいても支持体にシワを認めず支持フィルムのバリア性が良好に保たれていることが示唆された。
また、実験1で好ましくない場合があると考えられたSMOについても、バリア層におけるMNの含有率や粘着層における可塑剤の含有率等を適切に設定することにより、支持体への可塑剤の移行を充分抑制できることが確認された。
(3-1 サンプルの作製)
支持体は実験1と同一とし、バリア層に使用するPVAのケン化度を、80%、90%、95.5%、及び98.5%(完全ケン化)の4段階設定した。各ケン化度のPVAとMNとを混合してバリアコート剤を調製し、実験1と同様の量および方法で塗布してバリア層を形成し、支持フィルムのサンプル120を作製した。バリア層におけるMNの含有率は10wt%とした。
a.粘着テープ122を30mm×100mmに切り出した。切り出した粘着テープ122の長手方向の一方の端部にシリコーンを塗布したPETシート121を貼り付けてから、図11に示すように、サンプル120のバリア層に貼り付ける。
b.粘着テープ122及びPETシート121を、サンプル120ごと図12に示すような25mm×90mmの大きさに切り出す。
c.図13に示すように、アクリル板130に25mm×90mmの両面テープ131を2本並べて貼り付けた。さらに、切り出した粘着テープ122の支持体側と両面テープ131とを接触させ、切り出した粘着テープ122を、アクリル板に貼り付けた2本の両面テープ131を覆うように接着する。粘着テープ122からはみ出した両面テープ131の一部は切り落としてアクリル板130から除去する。
d.50mm×100mmの補強テープ132を準備し、図14に示すように、サンプル120に接着されていない粘着テープ122の端部に、PETシート121を厚さ方向に挟むように補強テープ132を貼り付けて評価片140を作製する。
e.評価片140を40℃の温湯に浸けて30分間放置する。このとき、粘着テープ122の全体を湯の中に位置させる。
f.30分経過したら評価片140を温湯から引き上げ、水分を軽く拭き取ってから引張試験機にセットする。このとき、図15に示すように、一方のチャックにアクリル板130を固定し、他方のチャックに補強テープ132のPETシートに接着されていない端部を固定する。
g.評価片を300mm/minの引張速度で牽引し、粘着テープ122が支持体から完全に剥がれた時点で測定を終了する。引張量10mmから30mmの範囲における引張試験機の張力値Nの平均値を耐水密着力とした。サンプルごとに3つの評価片を作製して支持フィルムの耐水密着力を評価した。
結果を表3に示す。PVAのケン化度が95.5%以下の評価片では、張力値Nの平均値が10ニュートン(N)以上であり、良好な耐水密着力を示したが、ケン化度98.5%の評価片では、著しく耐水密着性が低下した。
(4-1 サンプルの作製)
下引き層の材料としてウレタン樹脂水溶液とアクリル樹脂水溶液を準備した。更にそれぞれに白色顔料を配合した白インキ2種類を準備し、計4種類準備した。また、バリア層の材料として、ケン化度90%と98.5%のPVAにMN10wt%を配合し、計2種類の水溶液を準備した。
支持体11として、厚さ20μmのポリエーテル系ポリウレタン製の支持体を用いた。支持体11の一方の面に、4種類の下引き層をそれぞれ2.0g/m2グラビアコート法で塗工した。その上に2種類のバリア層材料を、2.2g/m2グラビアコート法で均一に塗布することによりバリア層を形成し8種類のサンプルを作成した。
また、上記の支持体11にコロナ処理を施し、下引き層なしで2種類の上記バリア層材料を2.2g/m2塗工し比較例とした。
A.粘着テープ接着評価法
10cm×5cmにカットしたサンプルのウレタン面を両面テープ(寺岡製作所製770K、30mm幅)でアクリル板に貼り付けた。さらに、サンプルのバリア層面にセロテープ(登録商標)(コクヨマーケティング株式会社製PB-TP1835-10、18mm幅)を長さ5cm貼り付けた後、セロテープを一気に手で引き剥がしバリア層の剥離の有無を確認した。
B.耐水密着性評価
耐水密着性については実験3と同様の手順にて行った。
結果を表4に示す。比較例で示す通り、支持フィルムに下引き層がなく、バリア層のPVAが高ケン化度(98.5%)の場合、支持体との密着性が得られず実用性がない。一方、支持フィルムに上述の下引き層を形成することでPVAケン化度によらず実用上十分な密着性が得られる。また、下引き層を形成した支持フィルムは耐水密着性も5N/25mm以上あり、水が触れる用途や、使用者が皮膚に貼り付けた状態で風呂に入る場合等でも十分な耐性があると考えられた。更に、支持フィルムに顔料を含むインキを用いて下引き層を形成しても十分な効果が得られることが確認された。
(5-1 サンプルの作製)
実験4と同様に4種類の下引き層材料と2種類のバリア層材料を組み合わせて8種類のサンプルを作成した。また実験4と同様に支持フィルムに下引き層を形成しない2種類の比較例(下引き層なし)を作成した。
(5-2 実験手順)
作製した計10種類のサンプルについて、実験1と同様の手順で行った。
結果を表5に示す。下引き層にウレタン系樹脂を用いた支持フィルムにおいては、IPM、TA、およびMGISを用いた場合は、支持フィルムの伸長率が30%となるまで伸長したすべての支持体に膨潤が観察されず、支持体への可塑剤の移行が抑制されていた。したがって、これらの可塑剤を用いてウレタン系樹脂を下引き層に用いた場合、相当な伸縮が加わる用途でも十分使用できると考えられた。一方、SMOについては、伸長率にかかわらず支持体に膨潤が認められ、本発明のテープ材に用いる可塑剤としては好ましくない場合があると考えられた。
また、下引き層にアクリル系樹脂を用いた支持フィルムにおいては、IPM、TA、およびMGISを用いた場合は、支持フィルムの伸長率が10%となるまで伸長した支持体に膨潤を認めず、可塑剤の移行が抑制されていた。下引き層にアクリル系樹脂を用いた支持フィルムでは、下引き層にウレタン系樹脂を用いた支持フィルムに比べ皮膜の伸縮性が劣り、バリア層にクラックが入った可能性があると推測された。しかし、支持フィルムが10%まで伸縮可能であれば多くの用途で実用上は問題なく使用できると考えられる。一方、SMOについては、支持フィルムの伸長率にかかわらず支持体に膨潤が認められ、本発明のテープ材に用いる可塑剤としては好ましくない場合があると考えられた。
例えば、本発明の支持フィルムおよびテープ材においては、PVAのケン化度を上述の範囲に設定することは必須ではない。したがって、テープ材の使用環境がそれほど過酷でない等の場合は、ケン化度の値が上述の範囲外であるPVAや他の水溶性高分子化合物がバリア層に用いられてもよい。
10 テープ材用支持フィルム
11 支持体
12 バリア層
13 下引き層
20 粘着層
Claims (5)
- テープ材に用いられるテープ材用支持フィルムであって、
ポリウレタンからなるフィルム状の支持体と、
ポリビニルアルコールと層状無機化合物とを含み、前記支持体の一方の面に形成されたバリア層と、
前記支持体と前記バリア層との間に設けられ、前記支持体と前記バリア層とを密着させる下引き層と、
を備えることを特徴とするテープ材用支持フィルム。 - 前記ポリビニルアルコールのケン化度は、70パーセント以上に設定されていることを特徴とする請求項1に記載のテープ材用支持フィルム。
- 前記層状無機化合物がモンモリロナイトであることを特徴とする請求項1または2に記載のテープ材用支持フィルム。
- 前記下引き層に印刷が施されていることを特徴とする請求項1から3のいずれか一項に記載のテープ材用支持フィルム。
- 請求項1から4のいずれか一項に記載のテープ材用支持フィルムと、
前記バリア層上であって前記支持体とは反対の面に形成された粘着層と、
を備えるテープ材。
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CN201380006230.2A CN104066578B (zh) | 2012-01-27 | 2013-01-23 | 带材料用支承膜和带材料 |
EP13741400.9A EP2799229B1 (en) | 2012-01-27 | 2013-01-23 | Supporting film for tape and tape |
ES13741400.9T ES2611910T3 (es) | 2012-01-27 | 2013-01-23 | Película de soporte para cinta y cinta |
JP2013555283A JP6002692B2 (ja) | 2012-01-27 | 2013-01-23 | テープ材用支持フィルムおよびテープ材 |
KR1020147020522A KR101943144B1 (ko) | 2012-01-27 | 2013-01-23 | 테이프재용 지지 필름 및 테이프재 |
US14/339,487 US9163164B2 (en) | 2012-01-27 | 2014-07-24 | Support film for tape and tape |
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US14/339,487 Continuation US9163164B2 (en) | 2012-01-27 | 2014-07-24 | Support film for tape and tape |
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EP (1) | EP2799229B1 (ja) |
JP (1) | JP6002692B2 (ja) |
KR (1) | KR101943144B1 (ja) |
CN (1) | CN104066578B (ja) |
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KR20190034208A (ko) | 2016-08-04 | 2019-04-01 | 도판 인사츠 가부시키가이샤 | 테이프재용 지지 필름, 테이프재, 및 테이프재용 지지 필름의 제조 방법 |
KR20190034194A (ko) | 2016-08-04 | 2019-04-01 | 도판 인사츠 가부시키가이샤 | 테이프재용 지지 필름 및 테이프재 |
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KR20190034194A (ko) | 2016-08-04 | 2019-04-01 | 도판 인사츠 가부시키가이샤 | 테이프재용 지지 필름 및 테이프재 |
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US20190254880A1 (en) * | 2016-09-15 | 2019-08-22 | Nitto Denko Corporation | Laminate patchable living body |
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Also Published As
Publication number | Publication date |
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CN104066578A (zh) | 2014-09-24 |
TW201338982A (zh) | 2013-10-01 |
CN104066578B (zh) | 2015-11-25 |
EP2799229B1 (en) | 2016-10-26 |
TWI541131B (zh) | 2016-07-11 |
US9163164B2 (en) | 2015-10-20 |
JP6002692B2 (ja) | 2016-10-05 |
US20140329063A1 (en) | 2014-11-06 |
KR101943144B1 (ko) | 2019-01-28 |
EP2799229A4 (en) | 2015-08-05 |
KR20140128304A (ko) | 2014-11-05 |
ES2611910T3 (es) | 2017-05-11 |
EP2799229A1 (en) | 2014-11-05 |
JPWO2013111773A1 (ja) | 2015-05-11 |
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