WO2013065579A1 - ポリオレフィン系フィルム - Google Patents
ポリオレフィン系フィルム Download PDFInfo
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- WO2013065579A1 WO2013065579A1 PCT/JP2012/077620 JP2012077620W WO2013065579A1 WO 2013065579 A1 WO2013065579 A1 WO 2013065579A1 JP 2012077620 W JP2012077620 W JP 2012077620W WO 2013065579 A1 WO2013065579 A1 WO 2013065579A1
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- film
- release layer
- layer
- adhesive
- resin
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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- 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
- B32B2307/748—Releasability
Definitions
- the present invention relates to a polyolefin film.
- the polyolefin film of the present invention is a member such as a prism sheet used for optical applications, a synthetic resin plate (for example, for building materials), a stainless plate (for example, for building materials), an aluminum plate, a decorative plywood, a steel plate, It can be used for glass plates, home appliances, precision machines, etc.
- the polyolefin-based film protects the surface of the automobile body during production, protects the product from being scratched when stacked, stored, transported, or transported in the manufacturing process, and the product. Can be suitably used for protecting from scratches during secondary processing (for example, bending or pressing).
- the above-mentioned coverings have been diversified, and not only those with a smooth coating surface but also many surface irregularities can be seen.
- Examples of the covering having surface irregularities include a prism type lens portion of a prism sheet used for an optical member.
- the adhesive layer has a high adhesive force so that the adhesive force can be obtained even if the contact area is small. Can be considered.
- styrene-based elastomer or olefin-based elastomer that exhibits high adhesive strength as a main component, but if the adhesive strength of the adhesive layer is increased, the film When the film is stored in a roll state and then fed out of the film, blocking occurs, causing problems such as partial stretching or deformation of the film.
- a general temperature for extruding a polypropylene resin using a T die or the like on one side of a base material layer made of a polypropylene resin is a release layer containing 50 wt% or more of an ⁇ -olefin copolymer having 4 or more carbon atoms.
- the problem to be solved by the present invention is that the adhesive film is stored in a roll state while showing strong adhesive strength to the covering and can be used for various coverings. It is an object of the present invention to provide a self-adhesive surface protective film which is less prone to problems such as partial elongation or deformation and has excellent processability of the film. That is, an object of the present invention is to provide a polyolefin-based film having good releasability and film-forming properties without causing surface roughness transfer and without suppressing adhesiveness.
- the present inventors have found that the above-mentioned problems can be solved by setting the compounding ratio and surface roughness of the resin used in the release layer within a predetermined range, and have achieved the present invention.
- the resin constituting the release layer contains at least a block copolymer of propylene and ethylene and an ⁇ -olefin (co) polymer having 4 or more carbon atoms, and the ⁇ -olefin (co) having 4 or more carbon atoms.
- the blending amount of the polymer is 5% by weight or more and less than 35% by weight in the resin component constituting the release layer, and a cohesive layer is coextruded on one side of the base material layer made of polypropylene resin and on the opposite side.
- the release layer has a surface roughness (SRa) of 0.20 ⁇ m or more and 0.50 ⁇ m or less.
- the ⁇ -olefin copolymer having 4 or more carbon atoms is preferably a 4-methylpentene-1 (co) polymer.
- the MFR (230 ° C., 2.16 Kgf) of the polypropylene resin is 1.0 to 15 g / 10 min.
- the adhesive layer it is preferable that at least a styrene elastomer is used for the adhesive layer, and the MFR (230 ° C., 2.16 Kgf) of the styrene elastomer is 0.5 to 20 g / 10 min.
- the polyolefin-based film according to the present invention exhibits a strong adhesive force to the covering and can be used for various coverings, but when the adhesive film is stored in a roll state and then the film is fed out, the film is partially It has the advantage that the film is not easily stretched or deformed, and is excellent in processability of the film. That is, according to the present invention, it is possible to provide a polyolefin-based film having good releasability and film-forming properties without causing surface roughness transfer and without suppressing adhesiveness.
- FIG. 1 is a schematic diagram of a measurement sample.
- the polyolefin-based film of the present invention requires a base material layer mainly composed of a polypropylene-based resin.
- the polypropylene-based resin used here include crystalline polypropylene, random copolymerization of propylene and a small amount of ⁇ -olefin, block More specifically, the crystalline polypropylene resin contains n-heptane-insoluble isotactic propylene homopolymer or propylene in an amount of 60% by weight or more, which is used in ordinary extrusion molding.
- the base material layer preferably contains 50% by weight or more of propylene units, more preferably 60% by weight or more. If the propylene content is less than 50% by weight, the film may have a low feeling and may be difficult to handle.
- the insolubility of n-heptane is indicative of the crystallinity of polypropylene and at the same time indicates safety.
- n-heptane insolubility (at 25 ° C., 60 ° C. according to Ministry of Health and Welfare Notification No. 20 in February 1982). It is a preferred embodiment to use one that is compatible with an elution amount of 150 ppm or less (30 ppm or less when the operating temperature exceeds 100 ° C.)).
- the ⁇ -olefin copolymerization component of the copolymer of propylene and other ⁇ -olefins includes ⁇ -olefins having 2 to 8 carbon atoms such as ethylene, 1-butene, 1-pentene, 1-hexene, 4 C4 or higher ⁇ -olefins such as -methyl-1-pentene are preferred.
- the copolymer is preferably a random or block copolymer obtained by polymerizing one or more of the ⁇ -olefins exemplified above with propylene.
- the melt flow rate (MFR: 230 ° C., 2.16 Kgf) of the polypropylene resin used is preferably in the range of 1.0 to 15 g / 10 minutes, more preferably in the range of 2.0 to 10.0 g / 10 minutes. Further, two or more kinds of copolymers of propylene and other ⁇ -olefins can be mixed and used. Furthermore, the waste film produced when the film obtained in the present invention is processed into a product can be re-granulated as a recovered raw material and added to the base material layer. By using the recovered raw material, the production cost can be reduced.
- the pressure-sensitive adhesive layer of the polyolefin film of the present invention can be used as long as it is a known pressure-sensitive adhesive, but is preferably a styrene-based elastomer or an olefin-based elastomer. In order to express particularly high adhesive strength, a styrene-based elastomer can be preferably used. Further, a polyolefin-based resin, a tackifying resin, and a softening agent can be mixed as necessary for controlling the adhesive strength.
- Styrenic elastomers are ABA type block polymers such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene copolymer-styrene, styrene-ethylene / propylene copolymer-styrene, styrene -Butadiene block, styrene-isoprene, styrene-ethylene / butylene copolymer, AB block polymer such as styrene-ethylene / propylene copolymer, styrene random copolymer such as styrene-butadiene rubber, and hydrogenation thereof You can list things.
- the melt flow rate (MFR: 230 ° C., 2.16 Kgf) of the styrene elastomer used is preferably in the range of 0.5 to 20 g / 10 minutes, more preferably in the range of 2.0 to 15.0 g / 10 minutes.
- the range of 3 to 10 g / 10 min is more preferable, and the range of 4 to 7 g / 10 min is particularly preferable.
- the styrene-based elastomer is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, still more preferably 75% by weight or more, preferably in the pressure-sensitive adhesive layer (resin component constituting the pressure-sensitive adhesive layer). Is not more than 100% by weight, more preferably not more than 99% by weight, still more preferably not more than 98% by weight, still more preferably not more than 97% by weight.
- the styrene component in the styrene-based elastomer is desirably 5% by weight or more and 30% by weight or less. If it is less than 5% by weight, granulation at the time of producing the resin becomes difficult, and if it exceeds 30% by weight, the adhesive strength is lowered and it becomes difficult to obtain the required adhesive strength.
- the styrene component in the styrene elastomer is preferably 10% by weight to 25% by weight, more preferably 10% by weight to 20% by weight, and still more preferably 10% by weight to 15% by weight.
- the component other than the styrene component in the styrene elastomer is preferably composed of components such as ethylene and butylene, and the amount of the component other than the styrene component is preferably 70 to 95% by weight, more preferably in the styrene elastomer. Is 75 to 90% by weight, more preferably 80 to 90% by weight, still more preferably 85 to 90% by weight.
- the olefin elastomer examples include an ⁇ -olefin polymer or copolymer having 2 to 20 carbon atoms, and a copolymer of ethylene and an unsaturated carboxylic acid or an unsaturated carboxylic acid ester.
- the melt flow rate (MFR: 230 ° C., 2.16 Kgf) of the olefin elastomer used is preferably in the range of 0.5 to 20 g / 10 minutes, more preferably in the range of 2.0 to 10.0 g / 10 minutes.
- the polyolefin-based resin is not particularly limited, and is a crystalline polypropylene, a copolymer of propylene and a small amount of ⁇ -olefin, a low density polyethylene, a high density polyethylene, a copolymer of ethylene and a small amount of ⁇ -olefin, an ethylene and a non-olefin.
- a copolymer with a saturated carboxylic acid or an unsaturated carboxylic acid ester, polystyrene and the like can be mentioned.
- the base material layer is composed of a polypropylene resin
- a polypropylene resin can be suitably used from the viewpoint of melt viscosity and the like.
- the melt flow rate (MFR: 230 ° C., 2.16 Kgf) of the polyolefin resin used is preferably in the range of 1.0 to 100.0 g / 10 minutes, more preferably in the range of 2.0 to 30.0 g / 10 minutes.
- the range of 2 to 10 g / 10 min is more preferable, and the range of 2 to 7 g / 10 min is particularly preferable.
- the blending amount of the polyolefin resin in the adhesive layer is preferably 25% by weight or less. When the blending amount of the polyolefin resin exceeds 25% by weight, the adhesive strength is lowered depending on the resin used, and sufficient adhesive strength cannot be obtained.
- the blending amount of the polyolefin resin is preferably 5% by weight or more. If it is less than 5% by weight, the adhesive force to the release layer becomes too strong, and the range of selection of the release layer may be reduced.
- the blending amount of the polyolefin resin is more preferably 6% by weight or more and 20% by weight or less, and further preferably 6% by weight or more and 15% by weight or less.
- the tackifying resin examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, alicyclic hydrocarbon resins, terpene resins, coumarone / indene resins, styrene resins, rosin resins, and the like. Hydrocarbon resins (eg petroleum resins) are preferred.
- the molecular weight of the tackifying resin is not particularly limited and can be set appropriately.However, if the molecular weight is small, there is a risk of causing material transfer from the adhesive layer to the adherend or heavy peeling, while the molecular weight is large. Therefore, the number average molecular weight of the tackifying resin is preferably about 1,000 to 100,000, since the effect of improving the adhesive force tends to be poor.
- the amount of tackifying resin in the adhesive layer is preferably in the range of 5 wt% to 30 wt%.
- the blending amount of the tackifying resin exceeds 30% by weight, the melt viscosity becomes extremely low due to the low molecular weight of the tackifying resin, and the main component is a polypropylene resin when performing coextrusion film formation using a T-die or the like. Lamination with the base material layer may be difficult. Moreover, there exists a possibility that it may not contribute to the adhesive force change of an adhesion layer as the compounding quantity of tackifying resin in an adhesion layer is less than 5 weight%.
- the amount of the tackifying resin is more preferably 6% by weight or more and 25% by weight or less, still more preferably 6% by weight or more and 20% by weight or less, still more preferably 6% by weight or more and 15% by weight or less, particularly Preferably they are 6 weight% or more and 10 weight% or less.
- the softening agent examples include low molecular weight diene polymers, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene and derivatives thereof, and polybutene.
- the molecular weight of the softening agent is not particularly limited and can be set appropriately, but if the molecular weight is small, there is a risk of causing material transfer from the adhesive layer to the adherend or heavy peeling, while the molecular weight is large.
- the number average molecular weight of the softening agent is preferably about 1,000 to 100,000 because the effect of improving the adhesive force tends to be poor.
- the tackifying resin and softening agent used in the adhesive layer are liquids or powders depending on the type, and there are things that contaminate the extruder during extrusion. Since such a problem is improved by using a tackifier resin or softener as a masterbatch with a polyolefin resin, it is preferable to use a tackifier resin or softener as a masterbatch with a polyolefin resin.
- the adhesive strength of the polyolefin-based film of the present invention is preferably in the range of 200 to 900 cN / 25 mm with respect to the acrylic plate at 23 ° C. in consideration of use in various coatings.
- the adhesive strength can be appropriately set by changing the resin composition, thickness, etc. of the adhesive layer.
- the adhesive force is more preferably 300 cN / 25 mm or more and 900 cN / 25 mm or less, and still more preferably 400 cN / 25 mm or more and 800 cN / 25 mm or less.
- the polyolefin film of the present invention may contain known additives as necessary.
- a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light resistance agent, an impact resistance improvement agent and the like may be contained.
- the low molecular weight substance on the surface of the adhesive layer is preferably less than 1 mg / m 2 .
- the measurement of the low molecular weight substance on the surface of the adhesive layer was carried out by the following procedure. After the surface of the adhesive layer is washed with an organic solvent that does not erode the resin constituting the adhesive layer such as ethanol, the organic solvent is removed from the cleaning solution with an evaporator, and the residue obtained by weighing the residue is washed.
- the polyolefin-based film of the present invention forms a release layer on the surface opposite to the adhesive layer laminated on one side of the base material layer. Even when the film is stored in a roll state and then fed out, problems such as partial stretching or deformation of the film hardly occur, and the processability of the film is excellent. In order to prevent blocking between films even when the films are stacked, it is effective to form surface irregularities on the release layer to reduce the contact area with the adhesive layer.
- a propylene-ethylene block copolymer can be suitably used.
- the surface roughness can be increased by increasing the molecular weight of the ethylene-propylene rubber in the propylene-ethylene block copolymer or increasing the amount of ethylene. Further, the surface roughness can be further increased by mixing an incompatible resin with the propylene-ethylene block copolymer. Further, in the extrusion process, the surface roughness can be further increased by reducing the shear rate applied to the resin or increasing the residence time.
- a homopolypropylene resin can be mixed with a propylene-ethylene block copolymer to reduce the surface roughness.
- an ⁇ -olefin (co) polymer having 4 or more carbon atoms such as 4-methylpentene-1 (co) polymer can be preferably used.
- Other examples include low-density polyethylene, high-density polyethylene, a copolymer of ethylene and a small amount of ⁇ -olefin, a copolymer of ethylene and vinyl acetate, polystyrene, a polyester-based resin, and a polyamide-based resin.
- 4-methylpentene-1 (co) polymer not only roughens the surface like a mat, but also improves the peelability by lowering the surface free energy of the film surface.
- the surface irregularity can be achieved by adding the above-mentioned incompatible resin to homopropylene or random polypropylene.
- a propylene-ethylene block copolymer when used, the production machine base can be changed. The uneven state hardly changes depending on the melt-kneading conditions during film formation, and stable production is possible.
- the blending amount of the ⁇ -olefin (co) polymer having 4 or more carbon atoms in the release layer is in the range of 5 wt% to 35 wt%.
- the release layer is extruded onto one side of the base material layer made of polypropylene resin by using a T die or the like.
- the film forming property of the release layer is deteriorated.
- the blending amount of the ⁇ -olefin (co) polymer having 4 or more carbon atoms is less than 5% by weight, it does not contribute to the improvement of the release force of the release layer.
- the blending amount of the ⁇ -olefin (co) polymer having 4 or more carbon atoms is preferably 7% by weight or more and 33% by weight or less.
- the molecular weight of the ⁇ -olefin (co) polymer having 4 or more carbon atoms may cause a substance transfer from the release layer to the adhesive layer if the molecular weight is small.
- the molecular weight is preferably about 10,000 to 1,000,000.
- the weight ratio of propylene-ethylene block copolymer to 4-methylpentene-1 (co) polymer in the release layer is , Preferably 95/5 to 65/35, more preferably 93/7 to 67/33.
- the average surface roughness SRa of the release layer surface is preferably 0.20 ⁇ m or more and 0.50 ⁇ m or less. By doing so, blocking resistance and the protection performance of a to-be-adhered body can be improved.
- the surface roughness of the release layer is lower than 0.20 ⁇ m, the feeding property of the film is deteriorated when the film is in a roll form.
- the surface roughness of the release layer is higher than 0.50 ⁇ m, the surface irregularities of the release layer may be transferred to the surface of the adhesive layer, and the adhesive force may be significantly reduced.
- the surface unevenness of the release layer is more preferably a surface having an average surface roughness SRa of 0.25 ⁇ m or more and 0.45 ⁇ m or less.
- the haze of the film in which the release layer having such a surface roughness is laminated is 20% or more and 80% or less.
- the haze of the film is more preferably 30% or more, and in order to make it easier to find foreign matter with a foreign matter detector during film formation, More preferably, it is 70% or less.
- the peeling force of the pressure-sensitive adhesive surface of the polyolefin-based film of the present invention with respect to the release surface is preferably in the range of 200 cN / 25 mm or less at 23 ° C. from the viewpoint of the film payout property when the pressure-sensitive adhesive film is in roll form.
- the peeling force can be appropriately set by changing the addition amount and surface roughness of the ⁇ -olefin copolymer having 4 or more carbon atoms in the release layer.
- the lower limit of the peeling force with respect to the release surface of the adhesive surface of the polyolefin film is about 1 cN / 25 mm as a practical value, and further about 5 cN / 25 mm.
- the thickness of the adhesive layer of the polyolefin film in the present invention is preferably 1 ⁇ m or more and less than 30 ⁇ m.
- the thickness of the adhesive layer is preferably 2 ⁇ m or more and 20 ⁇ m or less, more preferably 3 ⁇ m or more and 15 ⁇ m or less, and particularly preferably 4 ⁇ m or more and 8 ⁇ m or less.
- the thickness of the base material layer of the polyolefin film of the present invention is preferably 5 ⁇ m or more and less than 100 ⁇ m, more preferably 10 ⁇ m or more and less than 75 ⁇ m, and further preferably 15 ⁇ m or more and less than 40 ⁇ m.
- the thickness of the base material layer is less than 5 ⁇ m, there is a problem that the waist feeling is weak, wrinkles etc. are easily formed when pasted to a covering as a protective film, and sufficient adhesive strength cannot be obtained. If it is above, the film is disadvantageous in terms of cost.
- the thickness of the release layer of the polyolefin film in the present invention is preferably 1 ⁇ m or more and less than 30 ⁇ m.
- the thickness of the release layer is preferably 2 ⁇ m or more and 20 ⁇ m or less, more preferably 3 ⁇ m or more and 15 ⁇ m or less, and particularly preferably 4 ⁇ m or more and 8 ⁇ m or less.
- the polyolefin film of the present invention is composed of a base material layer, an adhesive layer, and a release layer containing the above resin component, and each layer may be one layer or two or more layers as long as the effect of the present invention is exhibited. Good.
- the resin constituting each layer may be sent to a feed block type T-die while being in a molten state using, for example, a single-screw or twin-screw extruder, and laminated and extruded to form a polyolefin film having at least three layers.
- the temperature of the extruder of each layer may be appropriately adjusted in consideration of the molding temperature of the components used in each layer in order to bring each layer into a molten state.
- the temperature of the T die may be the same as the above temperature.
- the take-up speed from the T die to the casting roll may be a speed at which each layer has a suitable thickness, for example, 10 m / min to 50 m / min, preferably 10 m / min to 30 m / min.
- the polyolefin film of the present invention is preferably in the form of a roll in terms of handling.
- the upper limit of the width and the winding length of the film roll is not particularly limited, but from the viewpoint of ease of handling, the width is generally 1.5 m or less, and the winding length is preferably 6000 m or less when the film thickness is 30 ⁇ m.
- a winding core a plastic core and metal cores, such as 3 inches, 6 inches, and 8 inches, can usually be used.
- the polyolefin film of the present invention is a member such as a prism sheet used for optical applications, a synthetic resin plate (for example, for building materials), a stainless steel plate (for example, for building materials), an aluminum plate, a decorative plywood, a steel plate, It can be used for glass plates, home appliances, precision machines, etc.
- the polyolefin film of the present invention protects the surface of the automobile body during production, protects against damage when stacking, storing, transporting, and transporting articles in the manufacturing process, and It can be used to protect an article from scratches during secondary processing (for example, bending or pressing).
- the present invention will be further described with reference to examples.
- the present invention is not limited to the following examples without departing from the gist thereof.
- the evaluation method of the physical property in a following example and a comparative example is as follows.
- 180 degree peeling means holding the peeling angle between the acrylic plate and the film at the time of measuring the resistance value at the time of peeling at 180 degrees.
- a schematic diagram of the measurement sample is shown in FIG. The measurement was performed three times for one sample, and the average value was defined as the adhesive strength of the sample.
- a test piece of 150 mm in the winding direction at the time of film production and 25 mm in a direction perpendicular thereto is cut out, and the release surface of the test piece attached to the adhesive surface and the acrylic plate with a double-sided adhesive tape is used.
- a release surface using a rubber roll having a mass of 2000 g (with a spring hardness of 80 Hs on the roller surface and a width of 45 mm and a diameter (including the rubber layer) of 95 mm covered with a rubber layer having a thickness of 6 mm).
- the test piece was reciprocated once at a speed of 5 mm / second and pressed.
- haze was measured using a haze meter (NDH-2000) manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with the optical property test method for JIS-K-7105 plastic.
- Example 1 Preparation of base material layer 100 wt% of a homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, MFR: 7.5 g / 10 min) was melt extruded at 240 ° C. with a 120 mm ⁇ single-screw extruder to obtain a base material layer.
- a homopolypropylene resin manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, MFR: 7.5 g / 10 min
- Styrene elastomer (Asahi Kasei Chemicals: Tuftec (registered trademark) H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min) 85 wt% and homopolypropylene resin (Sumitomo Chemical: FS2011DG3, MFR: 2.5 g / 10 min) ) 7.5 wt% and petroleum resin (Arakawa Chemical Industries, Ltd .: Alcon (registered trademark) P125) 7.5 wt% were melt extruded at 220 ° C. with a 90 mm ⁇ single screw extruder to form an adhesive layer.
- Example 2 The adhesive layer and the base material layer were the same as in Example 1, but the release layer was changed to the following content, and a three-kind three-layer unstretched film was obtained by the same production method as in Example 1.
- release layer 76 wt% of propylene-ethylene block copolymer (manufactured by Nippon Polypropylene: BC3HF) and 24 wt% of polymethylpentene (manufactured by Mitsui Chemicals: RT31) were melt-extruded at 250 ° C. by a 90 mm ⁇ single screw extruder to obtain a release layer.
- Example 3 With the base material layer remaining in Example 1, the adhesive layer and the release layer were changed to the following contents, and an unstretched film of 3 types and 3 layers was obtained by the same production method as Example 1.
- Styrene elastomer (Asahi Kasei Chemicals: Tuftec (registered trademark) H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min), petroleum resin (Arakawa Chemical Industries: Alcon (registered trademark) P125) and homopolypropylene resin (Adhesive layer obtained by melting and extruding (Sumitomo Chemical: FS2011DG3, MFR: 2.5 g / 10 min) at a ratio of 80 / 7.5 / 12.5 wt% at 220 ° C.
- Example 4 With the base material layer remaining in Example 1, the adhesive layer and the release layer were changed to the following contents, and an unstretched film of 3 types and 3 layers was obtained by the same production method as Example 1.
- Styrene elastomer (Asahi Kasei Chemicals: Tuftec (registered trademark) H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min) and homopolypropylene resin (Sumitomo Chemical: FS2011DG3, MFR: 2.5 g / 10 min)
- the mixture at a ratio of 90/10 wt% was melt-extruded at 240 ° C.
- Example 1 With the base material layer remaining in Example 1, the adhesive layer and the release layer were changed to the following contents, and an unstretched film of 3 types and 3 layers was obtained by the same production method as Example 1.
- Styrenic elastomer (Asahi Kasei Chemicals: Tuftec (registered trademark) H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min) 100 wt% is melt-extruded at 240 ° C with a 90 mm ⁇ single-screw extruder to form an adhesive layer It was.
- Example 1 The base material layer and the adhesive layer were the same as in Example 1, but the release layer was changed to the following content, and a three-kind three-layer unstretched film was obtained by the same production method as in Example 1. (Production of release layer) 100% by weight of propylene-ethylene block copolymer (manufactured by Nippon Polypropylene: BC4FC) was melt extruded at 250 ° C. with a 90 mm ⁇ single-screw extruder to obtain a release layer.
- propylene-ethylene block copolymer manufactured by Nippon Polypropylene: BC4FC
- Example 2 The base material layer and the adhesive layer were the same as in Example 1, but the release layer was changed to the following content, and a three-kind three-layer unstretched film was obtained by the same production method as in Example 1.
- release layer 96 wt% of propylene-ethylene block copolymer (manufactured by Nippon Polypropylene: BC4FC) and 4 wt% of polymethylpentene (manufactured by Mitsui Chemicals: RT31) were melt-extruded at 250 ° C. with a 90 mm ⁇ single screw extruder to obtain a release layer.
- the films obtained in Examples 1 to 4 have a practically sufficient adhesive force when used as a protective film, and are peeled off when the film is fed out as a roll without surface roughness transfer.
- the film forming property was also good.
- the films obtained in Comparative Examples 1 and 2 and 4 were not necessarily good in peelability when the film was fed out as a roll.
- the film obtained in Comparative Example 5 had severe surface roughness from the release layer to the adhesive layer.
- the film-forming property was poor and a film that could withstand the evaluation could not be obtained.
- all the films obtained in the comparative examples were inferior in quality and low in practicality.
- the polyolefin film of the present invention is used for synthetic resin plates (for example, for building materials), stainless steel plates (for example, for building materials), aluminum plates, decorative plywood, steel plates, glass plates, home appliances, precision machines, etc. Can do.
- the polyolefin-based film of the present invention protects the surface of the automobile body during production, protects against scratches when stacking, storing, transporting, and transporting articles in the manufacturing process, and It can also be suitably used to protect the article from scratches during secondary processing (for example, bending or pressing), and greatly contributes to the industry.
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明のポリオレフィン系フィルムは、ポリプロピレン系樹脂を主成分とする基材層を必要とし、ここで用いるポリプロピレン系樹脂としては、結晶性ポリプロピレン、プロピレンと少量のα-オレフィンとのランダム共重合、ブロック共重合体等を挙げることができ、さらに詳しくは、結晶性ポリプロピレン樹脂として、通常の押出成形などで使用するn-へプタン不溶性のアイソタクチックのプロピレン単独重合体又はプロピレンを60重量%以上含有するプロピレンと他のα-オレフィンとの共重合体を挙げることができ、このプロピレン単独重合体あるいはプロピレンと他のα-オレフィンとの共重合体を、単独又は混合して使用することができる。基材層にはプロピレン単位が50重量%以上含まれていることが好ましく、さらには60重量%以上含まれていることが好ましい。プロピレンが50重量%未満であると、フィルムに腰感がなくなり、取り扱いが困難になることがある。
ここで、n-ヘプタン不溶性とは、ポリプロピレンの結晶性を指標すると同時に安全性を示すものであり、本発明では、昭和57年2月厚生省告示第20号によるn-ヘプタン不溶性(25℃、60分抽出した際の溶出分が150ppm以下〔使用温度が100℃を超えるものは30ppm以下〕)に適合するものを使用することが好ましい態様である。
本発明のポリオレフィン系フィルムの粘着層は、公知の粘着剤であれば使用することが可能であるが、スチレン系エラストマーやオレフィン系エラストマーであることが好ましい。特に高い粘着力を発現させるためにはスチレン系エラストマーが好適に用いることができる。また、粘着力のコントロールのために必要に応じポリオレフィン系樹脂、粘着付与樹脂、軟化剤を混合することもできる。
使用するスチレン系エラストマーのメルトフローレート(MFR:230℃、2.16Kgf)は、0.5~20g/10分の範囲が好ましく、2.0~15.0g/10分の範囲がより好ましく、3~10g/10分の範囲がさらに好ましく、4~7g/10分の範囲が特に好ましい。
ここで、粘着層表面の低分子量物質の測定は、次の手順にて実施した。粘着層表面をエタノール等の粘着層を構成する樹脂を侵食しない有機溶剤を用いて洗浄後、その洗浄液から有機溶剤をエバポレーター等で除去した後、その残渣を秤量して求めた数値を洗浄した粘着層表面の表面積で割り、求めた。ここで、残渣が1mg/m2以上存在すると粘着層表面と被着体表面の間に異物が存在する事となり、接触面積を減らし、ファンデルワールス力を低下させる原因となる為、粘着力が低下し好ましくない。添加剤を添加する場合は、高分子型等の添加剤を選択したり、添加量及び添加方法を検討するなどして、粘着層への移行、転写がない様にすることが必要である。
本発明のポリオレフィン系フィルムは、基材層の片面に積層された粘着層とは反対面に離型層を形成するが、そうすることよってフィルム同士を重ねてもフィルム同士のブロッキングが少なく、特にフィルムをロール状態で保管し、その後フィルムを繰出す際にも、フィルムが部分的に伸長したり、変形する等の問題が起き難く、フィルムの加工適性に優れる。フィルム同士を重ねてもフィルム同士のブロッキングが発生しないようにするには、離型層に表面凹凸を形成させ、粘着層との接触面積を小さくすることが有効である。
なお、ホモプロピレンやランダムポリプロピレンに上記の非相溶な樹脂を添加することで表面の凹凸を達成することもできるが、プロピレン-エチレンブロック共重合体を用いる場合には、生産機台の変更や製膜時の溶融混練条件により凹凸状態が変わりにくく、安定した生産が可能である。
このとき、離形層の表面凹凸は、表面の平均表面粗さSRaで0.25μm以上、0.45μm以下となる様な表面にすることがより好ましい。
なお、ポリオレフィン系フィルムの粘着面の離型面に対する剥離力の下限は現実的な値として1cN/25mm程度、さらには5cN/25mm程度である。
このとき、粘着力を大きくする場合は、その粘性を考慮し、厚みを大きくするのが好ましい。粘着層の厚みを大きくすることにより、被着体との接触面積が大きくなりやすい。粘着層の厚さは、2μm以上、20μm以下であることが好ましく、さらに3μm以上、15μm以下が好ましく、特に4μm以上、8μm以下が好ましい。
このとき、離型層の厚さは、2μm以上、20μm以下であることが好ましく、さらに3μm以上、15μm以下が好ましく、特に4μm以上、8μm以下が好ましい。
JIS-Z-0237(2000)粘着テープ・粘着シート試験方法に準拠して下記の方法にて測定した。
被着体として、アクリル板(三菱レイヨン(株)製:アクリライト(登録商標)3mm厚)50mm×150mmを準備し、試験片として、フィルム製造時の巻き取り方向に150mm、それとは直交する方向に25mmの試験片を切り出し、質量2000gのゴムロール(ローラ表面のスプリング硬さ80Hs、厚さ6mmのゴム層で被覆された、幅45mm、直径(ゴム層を含む)95mmのもの)を用いて、被着体と試験片を5mm/秒の速さで、1往復させて圧着した。圧着後、温度23℃、相対湿度65%の環境下で30分放置したものを(株)島津製作所製「オートグラフ(登録商標)」(AGS-J)を用いて、300mm/分の速度で180度剥離した際の抵抗値を粘着力[cN/25mm]とした。180度剥離とは、剥離時の抵抗値を測定する際のアクリル板とフィルムの剥離角度を180度に保持することを意味する。
測定の際は測定試料のつかみ代として厚み190μm、サイズ25mm×170mmのポリエステルシートを準備し、粘着フィルムとアクリル板を圧着した測定試料の粘着フィルム側の端に、のり代15mmの幅でセロハンテープにて貼り付けて、測定の際のつかみ代とした。測定試料の模式図を図1に示す。測定は一つのサンプルに関して3回実施し、その平均値をそのサンプルの粘着力とした。
アクリル板(三菱レイヨン(株)製:アクリライト(登録商標)3mm厚)50mm×150mm全面に両面接着テープ(日東電工(株)製:No.535A)を貼付け、両面接着テープの他面に試験片の粘着面が来るように150mm(フィルム製造時の巻き取り方向)×50mm(フィルム製造時の巻き取り方向とは直交方向)の試験片を貼付けた。
新たに試験片として、フィルム製造時の巻き取り方向に150mm、それとは直交する方向に25mmの試験片を切り出し、その粘着面とアクリル板に両面接着テープを介し貼付けた試験片の離型面を重ね合わせた後、質量2000gのゴムロール(ローラ表面のスプリング硬さ80Hs、厚さ6mmのゴム層で被覆された、幅45mm、直径(ゴム層を含む)95mmのもの)を用いて、離型面と試験片を5mm/秒の速さで、1往復させて圧着した。圧着後、温度23℃、相対湿度65%の環境下で30分放置したものを(株)島津製作所製「オートグラフ(登録商標)」(AGS-J)を用いて、300mm/分の速度で180度剥離した際の抵抗値を剥離力[cN/25mm]とした。
測定の際は測定試料のつかみ代として厚み190μm、サイズ25mm×170mmのポリエステルシートを準備し、150mm×25mmの試験片の端に、のり代15mmの幅でセロハンテープにて貼り付けて、測定の際のつかみ代とした。測定は一つのサンプルに関して3回実施し、その平均値をそのサンプルの剥離力とした。
(株)小坂研究所製の接触式三次元中心面表面粗計(型式ET-30HK)を用いて、離型層の表面の中心面平均粗さ(SRa)を次の条件で触針法により測定した。条件は下記の通りであり、3回の測定の平均値をもって値とした。
触針先端半径:0.5μm
触針圧:20mgf
カットオフ値:80μm
測定長:1000μm
測定速度:100μm/秒
測定間隔:2μm
JIS-K-7105プラスチックの光学的特性試験方法に準拠して日本電色工業製のヘイズメーター(NDH-2000)を用いて測定した。
KEYENCE製のデジタルマイクロスコープ(VHX-200F)を用いて倍率100倍でフィルム粘着面のデジタル画像を撮影した。離型層からの転写がそれほど起きていないものを○、ひどいものを×とした。
フィルムを製膜する際に均一な厚みで製膜できているものを○、できていないものを×とした。
(基材層の作製)
ホモポリプロピレン樹脂(住友化学製:FLX80E4、MFR:7.5g/10min)100wt%を120mmφ単軸押出し機にて240℃で溶融押出しして基材層とした。
(粘着層の作製)
スチレン系エラストマー(旭化成ケミカルズ製:タフテック(登録商標)H1221、スチレン共重合比12wt%、MFR:4.5g/10min)85wt%とホモポリプロピレン樹脂(住友化学製:FS2011DG3、MFR:2.5g/10min)7.5wt%と石油樹脂(荒川化学工業製:アルコン(登録商標)P125)7.5wt%を90mmφ単軸押出し機にて220℃で溶融押出しして粘着層とした。
(離型層の作製)
プロピレン-エチレンブロックコポリマー(日本ポリプロピレン製:BC4FC)92wt%とポリメチルペンテン(三井化学製:RT31)8wt%を90mmφ単軸押出し機にて250℃で溶融押出しして離型層とした。
(フィルムの作製)
基材層、粘着層、離型層それぞれが各押出し機にて溶融された状態のまま、245℃の3層Tダイ(フィードブロック型、リップ幅850mm、リップギャップ1mm)内で積層押出しを行った。押出したフィルムを温度30℃のキャスティングロールへ20m/min速度で引取り、冷却固化して基材層厚みが28μm、粘着層厚みが6μm、離型層厚みが6μmの3種3層未延伸フィルムを得た。
粘着層、基材層は実施例1のまま、離型層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(離型層の作製)
プロピレン-エチレンブロックコポリマー(日本ポリプロピレン製:BC3HF)76wt%とポリメチルペンテン(三井化学製:RT31)24wt%を90mmφ単軸押出し機にて250℃で溶融押出しして離型層とした。
基材層は実施例1のまま、粘着層、離型層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
スチレン系エラストマー(旭化成ケミカルズ製:タフテック(登録商標)H1221、スチレン共重合比12wt%、MFR:4.5g/10min)と石油樹脂(荒川化学工業製:アルコン(登録商標)P125)とホモポリプロピレン樹脂(住友化学製:FS2011DG3、MFR:2.5g/10min)を80/7.5/12.5wt%の比率で混合したものを、90mmφ単軸押出し機にて220℃で溶融押出しして粘着層とした。
(離型層の作製)
プロピレン-エチレンブロックコポリマー(日本ポリプロピレン製:BC3HF)92wt%とポリメチルペンテン(三井化学製:RT31)8wt%を90mmφ単軸押出し機にて250℃で溶融押出しして離型層とした。
基材層は実施例1のまま、粘着層、離型層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
スチレン系エラストマー(旭化成ケミカルズ製:タフテック(登録商標)H1221、スチレン共重合比12wt%、MFR:4.5g/10min)とホモポリプロピレン樹脂(住友化学製:FS2011DG3、MFR:2.5g/10min)を90/10wt%の比率で混合したものを、90mmφ単軸押出し機にて240℃で溶融押出しして粘着層とした。
(離型層の作製)
プロピレン-エチレンブロックコポリマー(日本ポリプロピレン製:BC3HF)92wt%とポリメチルペンテン(三井化学製:RT31)8wt%を90mmφ単軸押出し機にて250℃で溶融押出しして離型層とした。
基材層は実施例1のまま、粘着層、離型層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
スチレン系エラストマー(旭化成ケミカルズ製:タフテック(登録商標)H1221、スチレン共重合比12wt%、MFR:4.5g/10min)100wt%を、90mmφ単軸押出し機にて240℃で溶融押出しして粘着層とした。
(離型層の作製)
プロピレン-エチレンブロックコポリマー(日本ポリプロピレン製:BC4FC)68wt%とポリメチルペンテン(三井化学製:RT31)32wt%を90mmφ単軸押出し機にて250℃で溶融押出しして離型層とした。
基材層、粘着層は実施例1のまま、離型層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(離型層の作製)
プロピレン-エチレンブロックコポリマー(日本ポリプロピレン製:BC4FC)100wt%を90mmφ単軸押出し機にて250℃で溶融押出しして離型層とした。
基材層、粘着層は実施例1のまま、離型層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(離型層の作製)
プロピレン-エチレンブロックコポリマー(日本ポリプロピレン製:BC4FC)96wt%とポリメチルペンテン(三井化学製:RT31)4wt%を90mmφ単軸押出し機にて250℃で溶融押出しして離型層とした。
基材層、粘着層は実施例1のまま、離型層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得ようとしたが、厚み精度が悪く評価に耐えうるようなフィルムを得ることができなかった。
(離型層の作製)
プロピレン-エチレンブロックコポリマー(日本ポリプロピレン製:BC3HF)50wt%とポリメチルペンテン(三井化学製:RT31)50wt%を90mmφ単軸押出し機にて250℃で溶融押出しして離型層とした。
基材層、粘着層は実施例1のまま、離型層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(離型層の作製)
プロピレン-エチレンブロックコポリマー(日本ポリプロピレン製:BC3HF)75wt%とポリメチルペンテン(三井化学製:RT31)6wt%とホモポリプロピレン樹脂(住友化学製:FLX80E4、MFR:7.5g/10min)19wt%を90mmφ単軸押出し機にて250℃で溶融押出しして離型層とした。
基材層、粘着層は実施例1のまま、離型層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(離型層の作製)
プロピレン-エチレンブロックコポリマー(日本ポリプロピレン製:BC4FC)64wt%とポリメチルペンテン(三井化学製:RT31)16wt%と低密度ポリエチレン樹脂(宇部興産製:R300)20wt%を90mmφ単軸押出し機にて250℃で溶融押出しして離型層とした。
2:ポリエステルシート
3:アクリル板
4:セロハンテープ
5:粘着フィルム
6:下部チャック
7:引っ張る方向
Claims (4)
- 離型層を構成する樹脂がプロピレンとエチレンのブロック共重合体と炭素数4以上のα-オレフィン(共)重合体を少なくとも含み、炭素数4以上のα-オレフィン(共)重合体の配合量が離型層を構成する樹脂成分中5重量%以上35重量%未満であり、ポリプロピレン系樹脂からなる基材層の片面に粘着層を、反対面に離形層を共押出により積層してなり、離型層の表面粗さ(SRa)が0.20μm以上0.50μm以下であることを特徴とするポリオレフィン系フィルム。
- 前記炭素数4以上のα-オレフィン(共)重合体が4-メチルペンテン-1系(共)重合体である請求項1に記載のポリオレフィン系フィルム。
- 前記ポリプロピレン系樹脂のMFRが(230℃、2.16Kgf)が1.0~15g/10分である請求項1又は2に記載のポリオレフィン系フィルム。
- 前記粘着層にスチレン系エラストマーを少なくとも使用し、そのスチレン系エラストマーのMFR(230℃、2.16Kgf)が0.5~20g/10分である請求項1~3のいずれかに記載のポリオレフィン系フィルム。
Priority Applications (2)
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CN201280052780.3A CN103889715B (zh) | 2011-10-31 | 2012-10-25 | 聚烯烃系膜 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015194059A1 (ja) * | 2014-06-18 | 2015-12-23 | 東洋紡株式会社 | 自己粘着性表面保護フィルム |
WO2019134120A1 (en) * | 2018-01-05 | 2019-07-11 | Baxter International Inc | Multi-layer articles and methods for producing the same |
CN113613890A (zh) * | 2019-03-29 | 2021-11-05 | 东丽薄膜先端加工股份有限公司 | 层叠膜 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6851721B2 (ja) * | 2016-02-18 | 2021-03-31 | リンテック株式会社 | 保護フィルム付き透明導電膜積層用フィルム、および透明導電性フィルムの製造方法 |
JP2017146492A (ja) * | 2016-02-18 | 2017-08-24 | リンテック株式会社 | 保護フィルム付き透明導電膜積層用フィルム、および透明導電性フィルムの製造方法 |
JP6858938B2 (ja) * | 2016-12-16 | 2021-04-14 | 東レフィルム加工株式会社 | 離型フィルムおよび保護フィルム |
KR102607556B1 (ko) * | 2018-04-16 | 2023-11-29 | 도레이 필름 카코우 가부시키가이샤 | 적층 필름 |
JP7238290B2 (ja) * | 2018-08-03 | 2023-03-14 | 東洋紡株式会社 | 積層フィルム。 |
CN109554137B (zh) * | 2018-12-04 | 2021-08-17 | 宁波激智科技股份有限公司 | 一种高粘保护膜及其制备方法 |
JP7306228B2 (ja) | 2019-11-08 | 2023-07-11 | 三菱ケミカル株式会社 | 積層フィルム、フレキシブルプリント基板工程用積層フィルム |
CN113122160A (zh) * | 2021-04-29 | 2021-07-16 | 东莞市金恒晟新材料科技有限公司 | 一种新型热增粘保护膜的制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004162048A (ja) * | 2002-10-25 | 2004-06-10 | Mitsubishi Chemicals Corp | 離型剤および離型シート |
JP2008081709A (ja) * | 2006-09-29 | 2008-04-10 | Mitsui Chemical Fabro Inc | 表面保護フィルム |
JP2008265302A (ja) * | 2007-03-22 | 2008-11-06 | Japan Polypropylene Corp | プロピレン系表面保護用フィルム |
JP2011042761A (ja) * | 2009-08-24 | 2011-03-03 | Toyobo Co Ltd | 粘着フィルム |
JP2011042757A (ja) * | 2009-08-24 | 2011-03-03 | Mitsui Chemicals Inc | 表面保護フィルム |
WO2011122287A1 (ja) * | 2010-03-31 | 2011-10-06 | 東レフィルム加工株式会社 | 表面保護フィルム |
JP2012087164A (ja) * | 2010-10-15 | 2012-05-10 | Dic Corp | 表面保護フィルム |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1720310A (zh) * | 2002-10-25 | 2006-01-11 | 三菱化学株式会社 | 脱模剂及脱膜片材 |
WO2011096350A1 (ja) * | 2010-02-02 | 2011-08-11 | 三井化学東セロ株式会社 | 表面保護フィルム |
KR20120112848A (ko) * | 2010-02-02 | 2012-10-11 | 미쓰이 가가쿠 토세로 가부시키가이샤 | 표면 보호 필름 |
-
2012
- 2012-10-25 KR KR1020147011150A patent/KR101983418B1/ko active IP Right Grant
- 2012-10-25 WO PCT/JP2012/077620 patent/WO2013065579A1/ja active Application Filing
- 2012-10-25 CN CN201280052780.3A patent/CN103889715B/zh not_active Expired - Fee Related
- 2012-10-29 TW TW101139900A patent/TWI565590B/zh not_active IP Right Cessation
- 2012-10-30 JP JP2012239505A patent/JP6056378B2/ja active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004162048A (ja) * | 2002-10-25 | 2004-06-10 | Mitsubishi Chemicals Corp | 離型剤および離型シート |
JP2008081709A (ja) * | 2006-09-29 | 2008-04-10 | Mitsui Chemical Fabro Inc | 表面保護フィルム |
JP2008265302A (ja) * | 2007-03-22 | 2008-11-06 | Japan Polypropylene Corp | プロピレン系表面保護用フィルム |
JP2011042761A (ja) * | 2009-08-24 | 2011-03-03 | Toyobo Co Ltd | 粘着フィルム |
JP2011042757A (ja) * | 2009-08-24 | 2011-03-03 | Mitsui Chemicals Inc | 表面保護フィルム |
WO2011122287A1 (ja) * | 2010-03-31 | 2011-10-06 | 東レフィルム加工株式会社 | 表面保護フィルム |
JP2012087164A (ja) * | 2010-10-15 | 2012-05-10 | Dic Corp | 表面保護フィルム |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015194059A1 (ja) * | 2014-06-18 | 2015-12-23 | 東洋紡株式会社 | 自己粘着性表面保護フィルム |
CN106459684A (zh) * | 2014-06-18 | 2017-02-22 | 东洋纺株式会社 | 自粘合性表面保护薄膜 |
JPWO2015194059A1 (ja) * | 2014-06-18 | 2017-04-20 | 東洋紡株式会社 | 自己粘着性表面保護フィルム |
WO2019134120A1 (en) * | 2018-01-05 | 2019-07-11 | Baxter International Inc | Multi-layer articles and methods for producing the same |
US11826990B2 (en) | 2018-01-05 | 2023-11-28 | Baxter International Inc. | Multi-layer articles and methods for producing the same |
CN113613890A (zh) * | 2019-03-29 | 2021-11-05 | 东丽薄膜先端加工股份有限公司 | 层叠膜 |
CN113613890B (zh) * | 2019-03-29 | 2023-10-24 | 东丽薄膜先端加工股份有限公司 | 层叠膜 |
Also Published As
Publication number | Publication date |
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JP6056378B2 (ja) | 2017-01-11 |
CN103889715B (zh) | 2015-09-02 |
KR101983418B1 (ko) | 2019-05-28 |
CN103889715A (zh) | 2014-06-25 |
TWI565590B (zh) | 2017-01-11 |
JP2013116626A (ja) | 2013-06-13 |
TW201325899A (zh) | 2013-07-01 |
KR20140085464A (ko) | 2014-07-07 |
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